The application claims the benefit of U.S. provisional application No. 63/359,965 (filed on 7.11, 2022), which is incorporated herein by reference in its entirety.
Detailed Description
The disclosures of all cited patent and non-patent documents are incorporated herein by reference in their entirety.
The term "a/an" as used herein is intended to encompass one/one or more/plural (i.e., at least one/one) of the cited features.
All ranges, if present, are inclusive and combinable unless otherwise specified. For example, when a range of "1 to 5" (i.e., 1-5) is recited, the recited range should be interpreted to include the ranges "1 to 4", "1 to 3", "1-2 and 4-5", "1-3 and 5", and the like. Unless expressly indicated otherwise, the numerical values of the various ranges in this disclosure are stated as approximations as if the minimum and maximum values within the stated ranges were both preceded by the word "about". In this way, slight variations above and below the ranges can typically be used to achieve substantially the same results as values within these ranges. Moreover, the disclosure of these ranges is intended as a continuous range including each value between the minimum and maximum values.
Every maximum numerical limitation given throughout this specification is intended to include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
It is to be appreciated that certain features of the disclosure, which are, for clarity, described above and below in the context of aspects/embodiments, may also be provided in combination in a single element. Conversely, various features of the disclosure that are, for brevity, described in the context of a single aspect/embodiment, may also be provided separately or in any subcombination.
The term "polysaccharide" (or "glycan (glycan)") means a polymeric carbohydrate molecule composed of long chains of monosaccharide units joined together by glycosidic bonds and which upon hydrolysis produces the constituent monosaccharides and/or oligosaccharides of the polysaccharide. The polysaccharides herein may be linear or branched, and/or may be homopolysaccharides (composed of only one type of constituent monosaccharides) or heteropolysaccharides (composed of two or more different constituent monosaccharides). Examples of polysaccharides herein include dextran (polydextrose) and soybean polysaccharide.
"Dextran" herein is a class of polysaccharides that are polymers of glucose (polydextrose). The dextran may comprise, for example, about, or at least about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 weight percent of glucose monomer units. Examples of glucans herein are alpha-glucan and beta-glucan.
The terms "alpha-glucan", "alpha-glucan polymer", and the like are used interchangeably herein. Alpha-glucan is a polymer comprising glucose monomer units linked together by alpha-glycosidic linkages. In typical aspects, the glycosidic linkages of the α -glucan herein are about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% of the α -glycosidic linkages. Examples of α -glucan polymers herein include α -1, 3-glucan, α -1, 4-glucan, and α -1, 6-glucan.
The terms "beta-glucan", "beta-glucan polymer", and the like are used interchangeably herein. Beta-glucan is a polymer comprising glucose monomer units linked together by beta-glycosidic linkages. In typical aspects, the glycosidic linkages of the β -glucan herein are about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% β -glycosidic linkages. Examples of beta-glucan polymers herein include beta-1, 3-glucan, beta-1, 4-glucan, and beta-1, 6-glucan.
Unless otherwise indicated, the term "saccharide" and other like terms refer herein to mono-and/or di-saccharides/oligosaccharides. Herein, "disaccharide" refers to a carbohydrate having two monosaccharides linked by glycosidic linkages. "oligosaccharide" herein may refer to a carbohydrate having, for example, 3 to 15 monosaccharides linked by glycosidic linkages. Oligosaccharides may also be referred to as "oligomers". Monosaccharides (e.g., glucose and/or fructose) contained within a disaccharide/oligosaccharide may be referred to as "monomeric units," "monosaccharide units," or other like terms.
The terms "alpha-1, 3-glucan", "poly alpha-1, 3-glucan", "alpha-1, 3-glucan polymer" and the like are used interchangeably herein. The alpha-1, 3-glucan is an alpha-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are alpha-1, 3. In some aspects, the α -1, 3-glucan comprises about, or at least about 90%, 95%, or 100% of α -1,3 glycosidic linkages. Most or all of the other linkages in the α -1, 3-glucan herein (if present) are typically α -1,6, although some linkages may also be α -1,2 and/or α -1,4. The α -1, 3-glucan herein is typically water insoluble.
The terms "alpha-1, 6-glucan", "poly alpha-1, 6-glucan", "alpha-1, 6-glucan polymer", "dextran" and the like herein refer to water-soluble alpha-glucans comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are alpha-1, 6. In some aspects, the α -1, 6-glucan comprises about, or at least about 90%, 95%, or 100% of α -1, 6-glycosidic linkages. Other linkages that may be present in alpha-1, 6-glucan include alpha-1, 2, alpha-1, 3, and/or alpha-1, 4 linkages.
The terms "alpha-1, 4-glucan", "poly alpha-1, 4-glucan", "alpha-1, 4-glucan polymer" and the like are used interchangeably herein. The alpha-1, 4-glucan is an alpha-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are alpha-1, 4. In some aspects, the α -1, 4-glucan comprises about, or at least about 90%, 95%, or 100% of α -1, 4-glycosidic linkages. Most or all of the other linkages in the α -1, 4-glucan herein, if present, are typically α -1,6 (typically forming branches), but may also be α -1,2 and/or α -1,3. Examples of α -1, 4-glucan herein include amylose, amylopectin, and starch.
The terms "beta-1, 4-glucan", "poly beta-1, 4-glucan", "beta-1, 4-glucan polymer", "cellulose", and the like are used interchangeably herein. Beta-1, 4-glucan is a water-insoluble beta-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein about 100% of the glycosidic linkages are beta-1, 4. Beta-1, 4-glucan may be as disclosed, for example, in U.S. patent application publication No. 2018/0334696.
The terms "beta-1, 3-glucan", "poly beta-1, 3-glucan", "beta-1, 3-glucan polymer" and the like are used interchangeably herein. Beta-1, 3-glucan is beta-glucan comprising glucose monomer units linked together by glycosidic linkages, wherein at least about 50% of the glycosidic linkages are beta-1, 3. In some aspects, the beta-1, 3-glucan comprises about, or at least about 90%, 95%, or 100% beta-1, 3 glycosidic linkages. Most or all of the other linkages in beta-1, 3-glucan herein, if present, are typically beta-1, 6 (typically forming branches). Beta-1, 3-glucan can be as disclosed, for example, in U.S. patent application publication No. 2014/0287919 and Stone, b.a. (2009,Chemistry ofBeta-Glucans [ beta-glucan Chemistry ], edited by Antony Bacic et al, chemistry, biochemistry, and Biology of 1-3 Beta Glucans and Related Polysaccharides[1-3 beta glucan and related polysaccharide Chemistry, biochemistry and Biology, academic press, burlington, ma), which is incorporated herein by reference.
The terms "soy polysaccharide" and "soy fiber" are used interchangeably herein and refer to high molecular weight, water insoluble polysaccharide materials that can be obtained from soybeans. Typically, the soybean polysaccharide is obtained from the cell wall structural components of soybean. The soy polysaccharide herein may be as disclosed, for example, in U.S. patent application publication No. 2018/0079732, which is incorporated herein by reference.
The "alpha-1, 2 branch" (and similar terms) as referred to herein typically comprises glucose alpha-1, 2-linked to a dextran backbone, and thus, the alpha-1, 2 branch herein may also be referred to as an alpha-1, 2,6 bond. The alpha-1, 2 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).
The "alpha-1, 3 branch" (and similar terms) as referred to herein typically comprises glucose alpha-1, 3-linked to a dextran backbone, and thus, the alpha-1, 3 branch herein may also be referred to as an alpha-1, 3,6 bond. The alpha-1, 3 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).
The "alpha-1, 4 branch" (and similar terms) as referred to herein typically comprises glucose alpha-1, 4-linked to a dextran backbone, and thus, the alpha-1, 4 branch herein may also be referred to as an alpha-1, 4,6 bond. The α -1,4 branch herein typically has one glucose group (which may optionally be referred to as side chain glucose).
The branching percentage in the polysaccharide herein refers to the percentage of all bonds in the polysaccharide that represent branching points. For example, the percentage of alpha-1, 3 branches in alpha-glucan herein refers to the percentage of all bonds in glucan that represent alpha-1, 3 branch points. Unless otherwise indicated, the percentages of bonds disclosed herein are based on the total bonds of the polysaccharide, or the portions specifically referred to for the disclosure in the polysaccharide.
The terms "bond", "glycosidic bond (glycosidic linkage)", "glycosidic bond (glycosidicbond)", and the like refer to a covalent bond that links sugar monomers within a sugar compound (oligosaccharide and/or polysaccharide). Examples of glycosidic linkages include 1,6- α -D-glycosidic linkages (also referred to herein as "α -1,6" linkages), 1,3- α -D-glycosidic linkages (also referred to herein as "α -1,3" linkages), 1,4- α -D-glycosidic linkages (also referred to herein as "α -1,4" linkages), and 1,2- α -D-glycosidic linkages (also referred to herein as "α -1,2" linkages).
The glycosidic bond profile (profile) of a polysaccharide or derivative thereof may be determined using any method known in the art. For example, a method employing Nuclear Magnetic Resonance (NMR) spectroscopy (e.g., 13CNMR and/or1 H NMR) may be used to determine the bond pattern. These and other methods that may be used are disclosed, for example, in Food Carbohydrates:chemistry, physical Properties, and Applications [ food carbohydrates: chemistry, physical properties, and Applications ] (S.W.Cui, chapter 3, S.W.Cui, structural Analysis of Polysaccharides [ structural analysis of polysaccharides ], taylor & Francis Group LLC [ Taylor Francis group Co., ltd., florida, bokapton, 2005), which are incorporated herein by reference.
The term "molar substitution" (m.s.) as used herein refers to the number of moles of organic groups per monomer unit of the polysaccharide derivatives herein. It should be noted that the molar substitution value of the polysaccharide derivative may for example have a very high upper limit, for example of hundreds or even thousands.
The "molecular weight" of a polysaccharide or polysaccharide derivative herein may be expressed as a weight average molecular weight (Mw) or a number average molecular weight (Mn), in daltons (Da) or grams/mole. Alternatively, the molecular weight may be expressed as DPw (weight average degree of polymerization) or DPn (number average degree of polymerization). The molecular weight of the smaller polysaccharide polymer, such as an oligosaccharide, may optionally be provided as "DP" (degree of polymerization), which refers only to the number of monomers contained within the polysaccharide, which may also characterize the molecular weight of the polymer based on a single molecule. Various means for calculating these different molecular weight measurements are known in the art, such as using High Pressure Liquid Chromatography (HPLC), size Exclusion Chromatography (SEC) or Gel Permeation Chromatography (GPC).
As used herein, mw may be calculated as Mw = Σ NiMi2/Σ NiMi, where Mi is the molecular weight of a single chain i and Ni is the number of chains having that molecular weight. In addition to SEC, the Mw of the polymer may be determined by other techniques such as static light scattering, mass spectrometry, MALDI-TOF (matrix assisted laser Desorption/ionization time of flight), small angle X-ray or neutron scattering, or ultracentrifugation. As used herein, mn can be calculated as mn=Σ NiMi/Σni, where Mi is the molecular weight of chain i and Ni is the number of chains having that molecular weight. In addition to SEC, mn of a polymer can be determined by various quantitative methods such as vapor pressure osmosis, by spectroscopic methods such as proton NMR, proton FTIR, or end group determination by UV-Vis. As used herein, DPw and DPn can be calculated from Mw and Mn, respectively, by dividing them by the molar mass of one monomer unit M1. In the case of unsubstituted dextran polymers, M1 =162. In the case of substituted (derivatized) dextran polymers, M1＝162+Mf x DoS, where Mf is the molar mass of the substituent group and DoS is the degree of substitution (average number of substituent groups per one glucose unit of the dextran polymer).
"Polysaccharide derivative" (and like terms) herein (e.g., dextran derivative such as an alpha-or beta-dextran derivative) typically refers to a polysaccharide that has been substituted with at least one type of organic group (e.g., acyl groups herein). The degree of substitution (DoS) of the polysaccharide derivatives herein can be up to about 3.0 (e.g., about 0.001 to about 3.0). The organic group as acyl group herein is attached to the polysaccharide derivative via an ester bond. Precursors of polysaccharide derivatives herein typically refer to the underivatized polysaccharide (which may also be referred to as the polysaccharide portion of the derivative) used to prepare the derivative. The organic groups used herein as acyl groups may be positively charged (cationic) or hydrophobic, and in general, the cationic charge may be such as that present when the organic groups are in the aqueous compositions herein, also taking into account the pH of the aqueous composition (in some aspects, the pH may be 4-10 or 5-9, or any pH as disclosed herein).
The term "degree of substitution" (DoS, or DS) as used herein refers to the average number of hydroxyl groups substituted with one or more types of organic groups per monomer unit of the polysaccharide derivative. DoS of polysaccharide derivatives herein may be stated with reference to DoS of a particular substituent or to the overall DoS, which is the sum of DoS values of different substituent types (e.g., if mixed esters). Unless otherwise disclosed, when DoS is not mentioned for a particular substituent type, it is meant to be a total DoS.
The terms "dextran ester derivative", "dextran ester compound", "dextran ester" and the like are used interchangeably herein. Dextran ester derivatives herein are typically dextran that has been esterified with one or more cationic (positively charged) organic groups (i.e., cationic acyl groups) and one or more hydrophobic organic groups (i.e., hydrophobic acyl groups) such that the derivative has a DoS of up to about 3.0 with all of these organic groups. Such dextran esters may optionally be characterized herein as amphiphilic dextran esters by having one or more different hydrophilic organic groups (in particular, one or more cationic organic groups) and one or more different hydrophobic organic groups. Dextran ester derivatives are herein referred to as "esters" because they comprise the substructure-CG -O-CO-C-, wherein "-CG -" represents a carbon atom of a monomer unit of the dextran ester derivative (e.g. glucose) (wherein such carbon atom is bonded to the hydroxyl [ -OH ] group in the polysaccharide precursor of the ester), and wherein "-CO-C-" is comprised in the acyl group.
The term "hydrophobic" herein may characterize a substituent organic group (substituent acyl) that is non-polar and has little or no affinity for water and tends to repel water.
The term "hydrophilic" herein may characterize a substituent organic group (substituent acyl) that is polar and has an affinity for interaction with a polar solvent, in particular with water or with other polar groups. Hydrophilic groups tend to attract water. Cationic organic groups (cationic acyl groups) herein are examples of hydrophilic organic groups.
In some aspects, the terms "esterification", "esterification reaction composition", and the like refer to a reaction comprising at least dextran, two or more esterifying agents, and typically a solvent as disclosed herein. The reaction is subjected to suitable conditions (e.g., solvent, time, temperature) for esterification of the hydroxyl groups of the glucose monomer units of the dextran with at least one cationic organic group (cationic acyl) and at least one hydrophobic organic group (hydrophobic acyl) provided by the esterifying agent, thereby producing the amphiphilic dextran ester compound/derivative.
The terms "aqueous liquid", "aqueous fluid", "aqueous conditions", "aqueous environment", "aqueous system" and the like as used herein may refer to water or an aqueous solution. The "aqueous solution" herein may comprise one or more dissolved salts, wherein the maximum total salt concentration may be about 3.5wt% in some embodiments. Although the aqueous liquids herein typically comprise water as the sole solvent in the liquid, the aqueous liquid may optionally comprise one or more other solvents (e.g., polar organic solvents) miscible in water. Thus, the aqueous solution may comprise a solvent having at least about 10wt% water.
For example, an "aqueous composition" herein has a liquid component comprising about or at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 99, or 100wt% water. Examples of aqueous compositions include, for example, mixtures, solutions, dispersions (e.g., suspensions, colloidal dispersions), and emulsions. In some embodiments, the pH of the aqueous composition is between about 2 and about 11 (e.g., between about 4 and about 9).
As used herein, the term "colloidal dispersion" refers to a heterogeneous system having a dispersed phase and a dispersion medium, i.e., microscopically dispersed insoluble particles suspended in another substance (e.g., an aqueous composition such as water or an aqueous solution). Examples of colloidal dispersions herein are hydrocolloids. The terms "dispersant (dispersant)" and "dispersion agent" are used interchangeably herein to refer to a material that facilitates the formation and/or stabilization of a dispersion. "dispersing" herein refers to the act of preparing a dispersion of a material in an aqueous liquid. As used herein, the term "latex" (and like terms) refers to a dispersion of one or more types of polymer particles in water or an aqueous solution. In some aspects, the latex is an emulsion comprising dispersed particles. An "emulsion" herein is a dispersion of tiny droplets of one liquid in another liquid in which the droplets are insoluble or immiscible (e.g., a non-polar substance such as an oil or other organic liquid such as an alkane, in a polar liquid such as water or an aqueous solution).
In some aspects of the disclosure, dextran ester derivatives may provide stability to the dispersion or emulsion. "stability" (or "stable" property) of a dispersion or emulsion herein is the ability of dispersed particles of the dispersion or liquid droplets (emulsion) dispersed in another liquid to remain dispersed (e.g., about or at least about 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or 100wt% of the particles of the dispersion or liquid droplets of the emulsion are in a dispersed state) for a period of about or at least about 0.5, 1,2, 4, 6, 9, 12, 18, 24, 30, or 36 months, for example, after the initial preparation of the dispersion or emulsion. The stable dispersion or emulsion may resist complete creaming, settling, flocculation, and/or coalescence of the dispersed/emulsified material.
The dextran ester derivatives herein are "soluble", "water soluble" (and like terms) herein dissolved (or significantly dissolved) in water or other aqueous conditions, optionally wherein the aqueous conditions are further characterized by having a pH of 4-9 (e.g., pH 6-8) and/or a temperature of about 1 ℃ to 130 ℃ (e.g., 20 ℃ -25 ℃). In contrast, dextran ester derivatives that are "insoluble", "water insoluble", etc. are insoluble under these conditions. In some aspects, less than 1.0 gram (e.g., an undetectable amount) of the aqueous insoluble glucan ester derivative is dissolved in 1000 milliliters of such aqueous conditions (e.g., water at 23 ℃).
The term "viscosity" as used herein refers to a measure of the degree to which a fluid (aqueous or non-aqueous) resists forces that tend to cause it to flow. Various viscosity units that may be used herein include, for example, centipoise (cP, cps) and pascal seconds (pa·s). One centipoise is one percent of one poise, which is equal to 0.100kg·m-1·s-1. In some aspects, the viscosity can be reported as an "intrinsic viscosity" (IV, η in dL/g), which term refers to a measure of the viscosity contribution of the dextran polymer to a liquid (e.g., solution) comprising the dextran polymer. IV measurements herein may be obtained, for example, using any suitable method, as disclosed in U.S. patent application publication nos. 2017/0002335, 2017/0002336, or 2018/0340199, or Weaver et al (j. Appl. Polym. Sci. [ journal of applied polymer science ] 35:1631-1637) or Chun and Park (macromol. Chem. Phys. [ large part chemistry and physics ] 195:701-711), which are incorporated herein by reference in their entirety. For example, IV can be measured in part by dissolving dextran polymer (optionally at about 100 ℃ for at least 2,4, or 8 hours) in DMSO with about 0.9 to 2.5wt% (e.g., 1,2, 1-2 wt%) LiCl. IV herein may optionally be used as a relative measure of molecular weight.
The terms "polar organic solvent" and "water miscible organic solvent" (and similar terms) are used interchangeably herein. The polar organic solvent can be dissolved in water or an aqueous solution. Thus, the polar organic solvent does not separate into different phases when added to water or aqueous solutions. The polar organic solvent contains carbon and at least one heteroatom (i.e., a non-carbon or non-hydrogen atom) such as oxygen, nitrogen, sulfur, or phosphorus. This is in contrast to non-polar organic solvents which typically contain only carbon and hydrogen atoms. Polar organic solvents typically have a dielectric constant greater than about 4. The polar organic solvent contains dipoles due to polar bonds.
The term "aprotic polar organic solvent" (and similar terms) herein refers to a polar organic solution that does not have suitably labile hydrogen atoms that can form hydrogen bonds. Aprotic polar organic solvents do not contain hydrogen atoms bonded to atoms having electronegative properties, e.g., no O-H, N-H, or S-H bonds are present.
The term "protic polar organic solvent" (and similar terms) herein refers to a polar organic solution having one or more suitably labile hydrogen atoms that can form hydrogen bonds. The protic polar organic solvents typically contain a hydrogen atom bonded to an atom having electronegative properties, e.g., the presence of one or more O-H, N-H, and/or S-H bonds.
The term "home care product" and similar terms typically refer to products, goods, and services related to the treatment, cleaning, care, and/or conditioning of the home and its interior. The foregoing includes, for example, having a chemical, composition, product, or combination thereof applied to such care.
The terms "fabric," "textile," "cloth," and the like are used interchangeably herein to refer to a woven material having a network of natural and/or man-made fibers. Such fibers may be in the form of, for example, threads or yarns.
"Fabric care composition" and like terms refer to any composition suitable for treating fabrics in some manner. Examples of such compositions include laundry detergents and fabric softeners, which are examples of laundry care compositions.
Typically, a "detergent composition" herein comprises at least a surfactant (detergent compound) and/or a builder. "surfactant" herein refers to a substance that tends to reduce the surface tension of a liquid in which the substance is dissolved. Surfactants can be used, for example, as detergents, wetting agents, emulsifiers, foaming agents and/or dispersants.
The terms "heavy duty detergent", "general purpose detergent", and the like are used interchangeably herein to refer to detergents that can be used to routinely wash white and colored textiles at any temperature. The terms "light duty detergent", "fine fabric detergent" and the like are used interchangeably herein to refer to detergents useful for treating fine fabrics such as viscose, wool, silk, ultra fine fibers or other fabrics requiring special care. "Special care" may include, for example, conditions using excess water, low agitation, and/or no bleaching.
The terms "fabric softener," "fabric conditioner," and the like herein refer to a composition (such as in liquid or solid form) that deposits lubricant and/or other surface modifying ingredients onto fabric, for example, to help maintain the softness of the fabric and/or to provide other beneficial characteristics (e.g., lubricity, antistatic properties, anti-cling, and/or wrinkle resistance) to the fabric. The fabric softener herein is typically applied to the fabric after it has been laundered with a laundry detergent, usually while the fabric is being rinsed.
The term "personal care product" and similar terms typically refer to products, goods, and services related to the treatment, cleaning, cleansing, care, or conditioning of a person. The foregoing includes, for example, having a chemical, composition, product, or combination thereof applied to such care.
An "oral care composition" herein is any composition suitable for treating soft or hard surfaces in the oral cavity, such as teeth (dental or teeth) and/or gingival surfaces.
The terms "ingestible product," "ingestible composition," and the like refer to any substance that may be orally administered (i.e., through the mouth) alone or with another substance, whether or not intended for consumption. Thus, ingestible products include food/beverage products. By "food product/beverage product" is meant any edible product intended for human or animal consumption (e.g., for nutritional purposes), including solid, semi-solid, or liquid. "food" herein may optionally be referred to as, for example, "foodstuff (foodstuff)", "food product", or other similar terms. "non-edible product" ("non-edible composition") refers to any composition that can be ingested through the oral cavity, except for food or beverage consumption purposes. Examples of non-edible products herein include supplements, nutraceuticals, functional food products, pharmaceutical products, oral care products (e.g., dentifrices, mouthwashes) and cosmetics such as sweetened lipsticks. "pharmaceutical product (pharmaceutical product)", "drug", "medicament" or "drug" or similar terms herein refer to a composition that is used to treat a disease or injury and that can be enterally or parenterally administered.
The term "medical product" and similar terms typically refer to products, goods, and services related to diagnosis, treatment, and/or care of a patient.
The term "industrial product" and similar terms typically refer to products, goods, and services used in an industrial and/or institutional environment, but are typically not used by an individual consumer.
The terms "flocculant", "flocculation reagent", "flocculation composition", "agglomeration agent" and the like herein refer to substances that promote agglomeration/coalescence of insoluble particles suspended in water or other aqueous liquids, thereby making such particles easier to remove by sedimentation/sedimentation, filtration, granulation, and/or other suitable means. Flocculation of the particles may typically be performed during removal/separation of the particles from the aqueous suspension. In some aspects, dextran ester derivatives may be used as flocculants.
The terms "film," "sheet," and similar terms herein refer to a thin material that is generally visually continuous. The film may be included as a layer or coating on the material, or may be separate (e.g., not attached to the surface of the material; stand alone). As used herein, "coating" (and like terms) refers to a layer covering a surface. The term "uniform thickness" as used herein to characterize a film or coating may, for example, refer to (i) a continuous region that is at least 20% of the total film/coating area, and (ii) has a standard deviation of thickness less than about 50 nm. The term "continuous layer" means a layer of the composition applied to at least a portion of a substrate, wherein a dried layer of the composition covers greater than or equal to 99% of the surface on which the layer has been applied, and wherein the layer has less than 1% of the voids exposing the surface of the substrate. 99% of the surface to which the layer has been applied does not include any areas of the substrate to which the layer has not yet been applied. In some aspects, the coatings herein may form a continuous layer. Coating compositions (and like terms) herein refer to all solid components forming a layer on a substrate, such as dextran ester derivatives herein and optionally pigments, surfactants, dispersing agents, binders, crosslinking agents, and/or other additives.
In some aspects, the terms "fiber", "fiber (fibers)" and the like herein refer to both short fibers (short length fibers) and long fibers. The fibers herein may comprise alpha-1, 3-glucan, natural fibers (e.g., cellulose, cotton, wool, silk), or synthetic fibers (e.g., polyester), or any other type of material disclosed herein that may form fibers.
As used herein, the terms "fibrid," "glucan fibrid," "fibrillated glucan," and the like may refer to non-granular, fibrous, or film-like glucan particles, wherein at least one of the three dimensions is of a small magnitude relative to the largest dimension. In some aspects, the glucan fibrids can have a fibrous and/or sheet-like structure with a relatively large surface area when compared to the glucan fibers. The surface area of fibrids herein may be, for example, about 5 to 50 meters2 per gram of material, with a largest dimension of about 10 to 1000 microns and a smallest dimension of 0.05 to 0.25 microns (aspect ratio of largest dimension to smallest dimension of 40 to 20000).
The terms "nonwoven", "nonwoven product", "nonwoven web" and the like herein refer to a web of individual fibers or filaments that are typically interlaid, in a random or non-identifiable manner. This is in contrast to woven or knitted fabrics which have a distinguishable network of fibers or filaments. In some aspects, the nonwoven product comprises a nonwoven web bonded or attached to another material, such as a substrate or backing. In some aspects, the nonwoven may further contain a binder or adhesive (reinforcing agent) that binds adjacent nonwoven fibers together. The nonwoven binder or adhesive may be applied to the nonwoven, for example, in dispersion/latex, solution, or solid form, and the treated nonwoven is then typically dried.
The term "coating" (and similar terms) herein is a type of coating composition that is a dispersion of pigments in a suitable liquid (e.g., an aqueous liquid) that can be used to form an adherent coating when spread over a surface as a thin coating. Such as a coating applied to a surface, may provide coloring/decoration, protection, and/or treatment (e.g., a primer) to the surface. In some aspects, the coating may optionally be characterized as a latex or latex coating due to further inclusion of dispersed particles.
The "composite" herein comprises two or more components including the compositions of the present disclosure (e.g., dextran ester derivatives). Typically, the components of the composite resist separation, and one or more of the components exhibit enhanced and/or different properties than their individual properties outside of the composite (i.e., the composite is not just a mixture, which is generally easily separated from its original components). The composite materials herein are typically solid materials and may be manufactured via, for example, extrusion or molding processes.
The terms "sequence identity", "identity", and the like as used herein with respect to polypeptide amino acid sequences (e.g., polypeptide amino acid sequences of glucosyltransferases) are as defined and determined in U.S. patent application publication No. 2017/0002336, which is incorporated herein by reference.
As a feature of certain embodiments, various polypeptide amino acid sequences are disclosed herein. Variants of these sequences having at least about 70% -85%, 85% -90%, or 90% -95% identity to the sequences disclosed herein may be used or cited. Alternatively, the variant amino acid sequence may have at least 70％、71％、72％、73％、74％、75％、76％、77％、78％、79％、80％、81％、82％、83％、84％、85％、86％、87％、88％、89％、90％、91％、92％、93％、94％、95％、96％、97％、98％、99％、 or 99.5% identity to a sequence disclosed herein. The variant amino acid sequence has the same function/activity as the disclosed sequence, or has at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the function/activity of the disclosed sequence.
The compositions herein, which are "dry" or "dried", typically have less than 6wt%, 5wt%, 4wt%, 3wt%, 2wt%, 1wt%, 0.5wt%, or 0.1wt% water contained therein.
The terms "volume percent (percent by volume)", "volume percent (vol 1%)," volume percent (v/v%), "and the like are used interchangeably herein. The volume percent of solute in a solution can be determined using the formula [ (solute volume)/(solution volume) ] x 100%.
The terms "weight percent (percent by weight)", "weight percent (WEIGHT PERCENTAGE, wt%)," weight-weight percent (weight-WEIGHT PERCENTAGE,% w/w), and the like are used interchangeably herein. Weight percent refers to the percentage of a material on a mass basis when the material is included in a composition, mixture, or solution.
The terms "weight/volume percent," "w/v%," and the like are used interchangeably herein. The weight/volume percent can be calculated as (((mass of material [ g ]))/(total volume of material plus liquid in which material is placed [ mL ])) x 100%. The material may be insoluble in the liquid (i.e., is a solid phase in the liquid phase, such as in the case of a dispersion), or soluble in the liquid (i.e., is a solute dissolved in the liquid).
The term "isolated" means a substance (or process) in a form that does not exist in nature or in an environment that does not exist in nature. Non-limiting examples of isolated materials include any dextran ester derivative disclosed herein. It is believed that the embodiments disclosed herein are synthetic/artificial (impossible to manufacture or practice except for human intervention/participation), and/or have non-naturally occurring properties.
The term "increased" as used herein may refer to an amount or activity that is at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 50%, 100%, or 200% greater than the amount or activity compared to the increased amount or activity. The terms "increased," "elevated," "enhanced," "greater than," "improved," and the like are used interchangeably herein.
Some aspects of the present disclosure relate to a composition comprising an ester derivative of dextran, wherein the dextran has a degree of substitution (DoS) of up to about 3.0 substituted with at least one cationic organic group (cationic acyl) attached to the dextran ester. Cationic dextran ester derivatives/compounds are thus disclosed. However, some aspects relate to a composition comprising an ester derivative of dextran, wherein the dextran has a DoS up to about 3.0 substituted with at least two organic groups attached to the dextran individual esters, wherein (i) at least one of the organic groups is a cationic organic group, and (ii) at least one of the organic groups is a hydrophobic organic group. By "individual ester linkages" is meant that at least two organic groups of (i) and (ii) are each linked to dextran via their own respective ester linkages. Since dextran ester derivatives can be characterized in some aspects as having at least one cationic ester group and at least one hydrophobic ester group, dextran esters of this type can optionally be characterized as amphiphilic.
The dextran ester derivative herein may be, for example, an alpha-dextran ester derivative. The glycosidic linkages of the α -glucan ester derivatives herein are typically about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% α -glycosidic linkages. Examples of suitable alpha-glucan ester derivatives include ester derivatives of alpha-1, 3-glucan, alpha-1, 6-glucan and alpha-1, 4-glucan.
In some aspects, the α -glucan ester comprises about or at least about 50%, 60%, 70%, 80%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% α -1, 3-glycosidic linkages (i.e., the ester is an α -1, 3-glucan ester). Thus, in some aspects, the α -glucan ester has about or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% glycosidic linkages that are not α -1, 3. Typically, glycosidic linkages other than alpha-1, 3 are mostly or entirely alpha-1, 6. In some aspects, the α -glucan esters have no branching points or have branching points of less than about 5%, 4%, 3%, 2%, or 1% (as a percentage of glycosidic linkages in the α -glucan).
In some aspects, the DPw, DPn, or DP of the α -glucan portion of the α -1, 3-glucan ester can be about, at least about, or less than about 2、3、4、5、6、7、8、9、10、15、25、50、75、100、150、200、300、400、500、600、700、800、900、1000、1100、1200、1300、1400、1500、1600、1700、1800、1900、2000、2500、3000、3500、 or 4000.DPw, DPn or DP may optionally be expressed as a range between any two of these values. For example only, DPw, DPn, or DP may be about 50-1600、100-1600、200-1600、300-1600、400-1600、500-1600、600-1600、700-1600、50-1250、100-1250、200-1250、300-1250、400-1250、500-1250、600-1250、700-1250、50-1000、100-1000、200-1000、300-1000、400-1000、500-1000、600-1000、700-1000、50-900、100-900、200-900、300-900、400-900、500-900、600-900、700-900、600-800、 or 600-750. By way of further example only, DPw, DPn, or DP may be about 15-100、25-100、35-100、15-80、25-80、35-80、15-60、25-60、35-60、15-55、25-55、35-55、15-50、25-50、35-50、35-45、35-40、40-100、40-80、40-60、40-55、40-50、45-60、45-55、45-50、15-35、20-35、15-30、 or 20-30. By way of further example only, DPw, DPn, or DP may be about 100-600, 100-500, 100-400, 100-300, 200-600, 200-500, 200-400, or 200-300. In some aspects, the α -glucan portion of the α -1, 3-glucan ester can have a high molecular weight as reflected by a high Intrinsic Viscosity (IV), for example, the IV can be about or at least about 6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、6-8、6-7、6-22、6-20、6-17、6-15、6-12、10-22、10-20、10-17、10-15、10-12、12-22、12-20、12-17、 or 12-15dL/g (for comparison purposes, it is noted that an IV of α -glucan having at least 90% (e.g., about 99% or 100%) α -1,3 linkages and a DPw of about 800 has an IV of about 2-2.5 dL/g). IV herein can be measured as with, for example, an a-glucan polymer dissolved in DMSO having about 0.9 to 2.5wt% (e.g., 1,2, 1-2 wt%) LiCl. The molecular weight of the α -1, 3-glucan esters herein can be calculated, for example, based on any of the foregoing α -1, 3-glucan DPw, DPn, or DP values, further considering the DoS of the esters and the type of ester group(s), such molecular weight can be about, at least about, or less than about calculated value (such a mode of molecular weight calculation can be applied to any of the other polysaccharide/glucan ester derivatives disclosed herein).
The α -1, 3-glucan moiety of the α -1, 3-glucan ester derivatives herein can be as disclosed (e.g., molecular weight, keymap, and/or method of manufacture) for example in U.S. patent nos. 7000000, 8871474, 10301604, or 10260053, or U.S. patent application publication nos. 2019/0112456、2019/0078062、2019/0078063、2018/0340199、2018/0021238、2018/0273731、2017/0002335、2015/0232819、2015/0064748、2020/0165360、2020/0131281 or 2019/0185893, each of which are incorporated herein by reference. The alpha-1, 3-glucan may be produced, for example, by an enzymatic reaction comprising at least water, sucrose, and a glucosyltransferase enzyme that synthesizes alpha-1, 3-glucan. It is contemplated that the glycosyltransferases, reaction conditions and/or methods useful for producing insoluble α -glucan can be as disclosed in any of the foregoing references.
In some aspects, the glucosyltransferases used to produce the α -1, 3-glucan moiety of the α -1, 3-glucan ester derivatives herein may comprise amino acid sequences that are at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5%, 99%, or 99.5% identical to, and have glucosyltransferase activity, either amino acid residues 55-960 of SEQ ID NO:4, residues 54-957 of SEQ ID NO:65, residues 55-960 of SEQ ID NO:30, residues 55-960 of SEQ ID NO:28, or residues 55-960100% identical to SEQ ID NO:20, and have glucosyltransferase activity, as disclosed in U.S. patent application publication No. 2019/0078063. It should be noted that a glucosyltransferase comprising amino acid residues 55-960 of SEQ ID NO:2, 4, 8, 10, 14, 20, 26, 28, 30, 34, or SEQ ID NO:4, residues 54-957 of SEQ ID NO:65, residues 55-960 of SEQ ID NO:30, residues 55-960 of SEQ ID NO:28, or residues 55-960 of SEQ ID NO:20 may synthesize insoluble alpha-glucan comprising at least about 90% (about 100%) of the alpha-1, 3 linkages.
In some aspects, the α -glucan ester comprises about or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% α -1, 6-glycosidic linkages (i.e., the ester is an α -1, 6-glucan ester, or a dextran ester). In some aspects, the substantially linear dextran sulfate may contain 5%, 4%, 3%, 2%, 1%, 0.5% or less glycosidic branches (linear dextran sulfate has 100% alpha-1, 6 linkages). The glycosidic branches from dextran sulfate, if present, are typically short, one (side chain), two, or three glucose monomers in length. In some aspects, dextran sulfate may contain about, or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% of alpha-1, 4, alpha-1, 3, and/or alpha-1, 2 glycosidic linkages. Typically, such bonds exist entirely or almost entirely as branching points from the α -1, 6-glucan.
For example, the dextran moiety of the dextran sulfate derivatives herein can have alpha-1, 2, alpha-1, 3, and/or alpha-1, 4 branches. In some aspects, about, at least about, or less than about 1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、30％、35％、40％、45％、50％、2-25％、2-20％、2-15％、2-10％、5-25％、5-20％、5-15％、5-10％、7-13％、8-12％、9-11％、10-25％、10-20％、10-15％、10-22％、12-20％、12-18％、14-20％、14-18％、15-18％、 or 15-17% of all glycosidic linkages of the branched dextran sulfate are alpha-1, 2, alpha-1, 3, and/or alpha-1, 4 glycosidic branching linkages. The length of such branches is typically mostly (> 90% or > 95%) or all (100%) of a single glucose monomer. In some aspects, a dextran having an α -1, 2-branch may be enzymatically produced according to the procedures in U.S. patent application publication nos. 2017/0218093 or 2018/0282385 (both of which are incorporated herein by reference), wherein, for example, an α -1, 2-branching enzyme such as GTFJ1 8T1 or GTF9905 may be added during or after dextran production. In some aspects, any other enzyme known to produce an alpha-1, 2-branch may be used. Dextran having an alpha-1, 3-branch may be prepared, for example, as disclosed in Vuillemin et al (2016, J.biol Chem. [ J.Biochem. ] 291:7687-7702) or International patent application publication No. WO 2021/007464, which is incorporated herein by reference.
The dextran moiety of the dextran sulfate derivatives herein can have a DPw, DPn, or DP of, for example, about, at least about, or less than about 2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、35、40、45、50、85、90、95、100、105、110、150、200、250、300、400、500、1000、1500、2000、2500、3000、4000、5000、6000、8-20、8-30、8-100、8-500、3-4、3-5、3-6、3-7、3-8、4-5、4-6、4-7、4-8、5-6、5-7、5-8、6-7、6-8、7-8、90-120、95-120、100-120、105-120、110-120、115-120、90-115、95-115、100-115、105-115、110-115、90-110、95-110、100-110、105-110、90-105、95-105、100-105、90-100、95-100、90-95、85-95、85-90、5-100、5-250、5-500、5-1000、5-1500、5-2000、5-2500、5-3000、5-4000、5-5000、5-6000、10-100、10-250、10-500、10-1000、10-1500、10-2000、10-2500、10-3000、10-4000、10-5000、10-6000、25-100、25-250、25-500、25-1000、25-1500、25-2000、25-2500、25-3000、25-4000、25-5000、25-6000、50-100、50-250、50-500、50-1000、50-1500、50-2000、50-2500、50-3000、50-4000、50-5000、50-6000、100-100、100-250、100-400、100-500、100-1000、100-1500、100-2000、100-2500、100-3000、100-4000、100-5000、100-6000、250-500、250-1000、250-1500、250-2000、250-2500、250-3000、250-4000、250-5000、250-6000、300-2800、300-3000、350-2800、350-3000、500-1000、500-1500、500-2000、500-2500、500-2800、500-3000、500-4000、500-5000、500-6000、600-1550、600-1850、600-2000、600-2500、600-3000、750-1000、750-1250、750-1500、750-2000、750-2500、750-3000、750-4000、750-5000、750-6000、900-1250、900-1500、900-2000、1000-1250、1000-1400、1000-1500、1000-2000、1000-2500、1000-3000、1000-4000、1000-5000、1000-6000、 or 1100-1300. In some aspects, the molecular weight (e.g., mw or Mn) of the dextran moiety of the dextran sulfate derivative can be about, at least about, or less than about 0.1、0.125、0.15、0.175、0.2、0.24、0.25、0.5、0.75、1、2、3、4、5、6、7、8、9、10、20、30、40、50、60、70、80、90、100、110、120、130、140、150、160、170、180、190、200、0.1-0.2、0.125-0.175、0.13-0.17、0.135-0.165、0.14-0.16、0.145-0.155、10-80、20-70、30-60、40-50、50-200、60-200、70-200、80-200、90-200、100-200、110-200、120-200、50-180、60-180、70-180、80-180、90-180、100-180、110-180、120-180、50-160、60-160、70-160、80-160、90-160、100-160、110-160、120-160、50-140、60-140、70-140、80-140、90-140、100-140、110-140、120-140、50-120、60-120、70-120、80-120、90-120、90-110、100-120、110-120、50-110、60-110、70-110、80-110、90-110、100-110、50-100、60-100、70-100、80-100、90-100、 or 95-105 million daltons. In some aspects, the molecular weight (e.g., mw or Mn) of the dextran moiety of the dextran sulfate derivative can be, for example, about, at least about, or less than about 1、5、7.5、10、12.5、15、20、30、40、50、60、70、80、90、100、150、200、250、300、400、500、600、700、800、900、1000、1250、1500、1750、2000、1-2000、1-1000、1-500、1-400、1-300、1-200、1-100、1-50、10-2000、10-1000、10-500、10-400、10-300、10-200、10-100、10-50、20-2000、20-1000、20-500、20-400、20-300、20-200、20-100、20-50、30-2000、30-1000、30-500、30-400、30-300、30-200、30-100、30-50、40-2000、40-1000、40-500、40-400、40-300、40-200、40-100、40-50、50-2000、50-1000、50-500、50-400、50-300、50-200、100-2000、100-1000、100-500、100-400、100-300、100-200、200-2000、20-1000、200-500、200-400、200-300、7.5-10、7.5-12.5、7.5-15、7.5-20、7.5-30、10-12.5、10-15、10-20、10-30、15-25、15-30、40-60、45-55、190-210、 or 290-310kDa. The molecular weight of dextran esters herein may be calculated, for example, based on any of the foregoing dextran DPw, DPn, DP, or daltons values, further considering DoS of the esters and the type of ester group or groups, and such molecular weight may be about, at least about, or less than about any of the above molecular weight values or ranges. For example, any of the foregoing DPw, DPn, DP, or daltons values, may characterize the dextran herein before, or after, the dextran has been optionally branched (e.g., α -1,2 and/or α -1, 3).
The dextran moiety of the dextran ester derivatives herein may be as disclosed (e.g., molecular weight, bond/branching pattern, production method) for example in U.S. patent application publication nos. 2016/012445, 2017/0218093, 2018/0282385, 2020/0165360, or 2019/0185893, each of which is incorporated herein by reference. In some aspects, the ester-derivatized dextran herein may be dextran produced in a suitable reaction comprising a Glucosyltransferase (GTF) 0768 (SEQ ID NO:1 or2 of US 2016/012445), GTF 8117, GTF 6831, or GTF 5604 (these latter three GTF enzymes are SEQ ID NOs: 30, 32 and 33 of US2018/0282385, respectively) or a GTF comprising an amino acid sequence that is at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% identical to the amino acid sequence of GTF 0768, GTF 8117, GTF 6831, or GTF 5604.
In some aspects, the α -glucan portion of the α -glucan ester derivative can be in the form of a graft copolymer, such as disclosed in U.S. patent application publication nos. 2020/0165360, 2019/0185893, or 2020/013681, which are incorporated herein by reference. The graft copolymer may comprise dextran (as a backbone) and alpha-1, 3-glucan (as one or more side chains) wherein the latter component has been grafted onto the former component, typically such graft copolymer is produced by using dextran or alpha-1, 2-and/or alpha-1, 3-branched dextran as a primer for alpha-1, 3-glucan synthesis by alpha-1, 3-glucan-producing glucosyltransferase as described above. One or more of the α -1, 3-glucan side chains of the α -glucan graft copolymer herein may be α -1, 3-glucan as disclosed herein. The dextran backbone of the α -glucan graft copolymer herein may be dextran or α -1, 2-and/or α -1, 3-branched dextran as disclosed herein. In some aspects, the α -glucan graft copolymer may comprise (A) an α -1, 6-glucan backbone (100% of the α -1, 6-linkages prior to branching of the α -1,2 and/or α -1, 3) that has been branched (e.g., the backbone comprises a total of about 82% -86% of the α -1,6 linkages and about 14% -18% of the α -1,2 and/or α -1,3 linkages) and (ii) has a Mw of about 15-25, 15-22.5, 17-25, 17-22.5, 18-22, or 20kDa with about 10% -22% (e.g., about 12% -18%, 14% -18%, 15% -17%, or 16%) of the α -1,2 and/or α -1,3 linkages (i.e.g., the α -1,2,6 and/or α -1,3,6 linkages), and (B) is a water-insoluble copolymer of one or more (e.g., two, three, five, six, 3, or more of the α -1,2 and/or 3) side chains.
In some aspects, the α -glucan ester comprises about or at least about 50%, 60%, 70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% α -1, 4-glycosidic linkages (i.e., the ester is an α -1, 4-glucan ester). Thus, in some aspects, the α -1, 4-glucan ester has about or less than about 50%, 40%, 30%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0% glycosidic linkages that are not α -1, 4. Examples of α -1, 4-glucan herein include amylose, amylopectin, and starch. For example, alpha-1, 4-glucan such as starch may be derived from vegetable (e.g., potato, tapioca, pea, palm) or cereal (e.g., corn, wheat, rice, barley) sources.
In some aspects, the DPw, DPn, or DP of the α -1, 4-glucan portion of the α -1, 4-glucan ester derivative can be about, at least about, or less than about 10、25、50、75、100、150、200、300、400、500、600、700、800、900、1000、1100、1200、1 300、1400、1500、1600、1700、1800、1900、2000、2500、3000、3500、 or 4000.DPw, DPn or DP may optionally be expressed as a range between any two of these values. In some aspects, the DPw, DPn, or DP of the α -1, 4-glucan portion of the α -1, 4-glucan ester derivative may be as disclosed above for α -1, 3-glucan or α -1, 6-glucan.
The dextran ester derivative herein may be, for example, a beta-dextran ester derivative. The glycosidic linkages of the β -glucan ester derivatives herein are typically about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% β -glycosidic linkages. Examples of suitable beta-glucan ester derivatives include ester derivatives of beta-1, 3-glucan (e.g., laminarin, euglena, curdlan), beta-1, 4-glucan (cellulose), and beta-1, 6-glucan. In some aspects, the glucan esters herein are not beta-glucan esters, and/or do not contain beta-glycosidic linkages.
In some aspects, the beta-glucan ester comprises about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% beta-1, 4-glycosidic linkages (i.e., the ester is a beta-1, 4-glucan ester). In some aspects, the DPw, DPn, or DP of the β -1, 4-glucan portion of the β -1, 4-glucan ester derivative can be about or at least about 10、15、20、25、30、35、40、45、50、75、100、150、200、300、400、500、600、700、800、900、1000、1100、1200、1300、1400、1500、1600、1700、1800、1900、2000、2500、3000、3500、 or 4000.DPw, DPn, or DP may optionally be expressed as a range between any two of these values (e.g., 1000-2000, 1300-1700, 1400-1600). In some aspects, the DPw, DPn, or DP of the beta-1, 4-glucan portion of the beta-1, 4-glucan ester derivative may be as disclosed above for alpha-1, 3-glucan or alpha-1, 6-glucan. In some aspects, the glucan esters herein are not beta-1, 4-glucan esters, and/or do not contain beta-1, 4-glycosidic linkages.
In some aspects, the beta-glucan ester comprises about or at least about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% beta-1, 3-glycosidic linkages (i.e., the ester is a beta-1, 3-glucan ester). In some aspects, for example, the DPw, DPn, or DP of the beta-1, 3-glucan portion of the beta-1, 3-glucan ester derivative can be about, at least about, or less than about 3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、40、50、60、70、80、90、100、150、200、300、400、500、600、700、800、900、1000、1100、1200、1300、1400、1500、1600、1700、1800、1900、2000、2500、3000、3500、4000、3-15、3-20、3-25、3-30、5-15、5-20、5-25、5-30、10-15、10-20、10-25、10-30、15-17、15-18、15-19、15-20、15-21、15-22、15-23、15-24、15-25、15-30、16-17、16-18、16-19、16-20、16-21、16-22、16-23、16-24、16-25、16-30、17-18、17-19、17-20、17-21、17-22、17-23、17-24、17-25、17-30、20-25、20-30、 or 25-30. In some aspects, the DPw, DPn, or DP of the beta-1, 3-glucan portion of the beta-1, 3-glucan ester derivative may be as disclosed above for alpha-1, 3-glucan or alpha-1, 6-glucan.
In some additional or alternative aspects herein, the ester derivative may be a soy polysaccharide ester derivative. In some aspects, the soy polysaccharide portion of the soy polysaccharide ester derivative may be as disclosed in U.S. patent application publication No. 2018/0079732, which is incorporated herein by reference. Thus, any feature of the present disclosure with respect to dextran ester derivatives can likewise characterize embodiments in which soybean polysaccharide ester derivatives are used, insofar as the skilled artisan deems appropriate. For example, the term "dextran ester derivative" (and similar terms) as used in the present disclosure may optionally be replaced with the term "soybean polysaccharide ester derivative" within the scope of what the skilled artisan deems appropriate.
In some aspects of the disclosure, the ester derivatives of the polysaccharide/dextran may have a degree of substitution (DoS) of up to about 3.0 (e.g., 0.001 to 3.0) substituted with at least two organic groups attached to the dextran individual esters, wherein (i) at least one of the organic groups is a cationic organic group (cationic acyl group) and (ii) at least one of the organic groups is a hydrophobic organic group (hydrophobic acyl group). However, in some aspects, the ester derivatives of the polysaccharide/dextran may have a DoS up to about 3.0 (e.g., 0.001 to 3.0) substituted with at least one cationic organic group (cationic acyl) attached to the polysaccharide/dextran ester.
DoS (or, optionally, "total DoS" in this regard) of the glucan substituted with at least one cationic organic group and at least one hydrophobic organic group herein can be, for example, about, at least about, or up to about 0.001、0.0025、0.005、0.01、0.02、0.025、0.03、0.04、0.05、0.06、0.07、0.075、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、 or 3.0 (DoS can optionally be expressed as a range between any two of these values). Some examples of DoS ranges herein include 0.005-2.0、0.005-1.9、0.005-1.8、0.005-1.7、0.005-1.6、0.005-1.5、0.005-1.25、0.005-1.0、0.005-0.9、0.005-0.8、0.005-0.7、0.005-0.6、0.005-0.5、0.01-2.0、0.01-1.9、0.01-1.8、0.01-1.7、0.01-1.6、0.01-1.5、0.01-1.25、0.01-1.0、0.01-0.9、0.01-0.8、0.01-0.7、0.01-0.6、0.01-0.5、0.01-0.25、0.01-0.1、0.03-2.0、0.03-1.9、0.03-1.8、0.03-1.7、0.03-1.6、0.03-1.5、0.03-1.25、0.03-1.0、0.03-0.9、0.03-0.8、0.03-0.7、0.03-0.6、0.03-0.5、0.03-0.25、0.03-0.1、0.05-2.0、0.05-1.9、0.05-1.8、0.05-1.7、0.05-1.6、0.05-1.5、0.05-1.25、0.05-1.0、0.05-0.9、0.05-0.8、0.05-0.7、0.05-0.6、0.05-0.5、0.1-2.0、0.1-1.9、0.1-1.8、0.1-1.7、0.1-1.6、0.1-1.5、0.1-1.25、0.1-1.0、0.1-0.9、0.1-0.8、0.1-0.7、0.1-0.6、0.1-0.5、0.15-2.0、0.15-1.9、0.15-1.8、0.15-1.7、0.15-1.6、0.15-1.5、0.15-1.25、0.15-1.0、0.15-0.9、0.15-0.8、0.15-0.7、0.15-0.6、0.15-0.5、0.2-2.0、0.2-1.9、0.2-1.8、0.2-1.7、0.2-1.6、0.2-1.5、0.2-1.25、0.2-1.0、0.2-0.9、0.2-0.8、0.2-0.7、0.2-0.6、0.2-0.5、0.25-2.0、0.25-1.9、0.25-1.8、0.25-1.7、0.25-1.6、0.25-1.5、0.25-1.25、0.25-1.0、0.25-0.9、0.25-0.8、0.25-0.7、0.25-0.6、0.25-0.5、0.3-2.0、0.3-1.9、0.3-1.8、0.3-1.7、0.3-1.6、0.3-1.5、0.3-1.25、0.3-1.0、0.3-0.9、0.3-0.8、0.3-0.7、0.3-0.6、0.3-0.5、0.4-2.0、0.4-1.9、0.4-1.8、0.4-1.7、0.4-1.6、0.4-1.5、0.4-1.25、0.4-1.0、0.4-0.9、0.4-0.8、0.4-0.7、0.4-0.6 and 0.4-0.5.
DoS of a glucan substituted with at least one cationic organic group herein can be, for example, about, at least about, or up to about 0.001、0.0025、0.005、0.01、0.02、0.025、0.03、0.04、0.05、0.06、0.07、0.075、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、 or 3.0 (DoS can optionally be expressed as a range between any two of these values). Some examples of DoS ranges herein include 0.005-2.0、0.005-1.9、0.005-1.8、0.005-1.7、0.005-1.6、0.005-1.5、0.005-1.25、0.005-1.0、0.005-0.9、0.005-0.8、0.005-0.7、0.005-0.6、0.005-0.5、0.01-2.0、0.01-1.9、0.01-1.8、0.01-1.7、0.01-1.6、0.01-1.5、0.01-1.25、0.01-1.0、0.01-0.9、0.01-0.8、0.01-0.7、0.01-0.6、0.01-0.5、0.01-0.25、0.01-0.1、0.03-2.0、0.03-1.9、0.03-1.8、0.03-1.7、0.03-1.6、0.03-1.5、0.03-1.25、0.03-1.0、0.03-0.9、0.03-0.8、0.03-0.7、0.03-0.6、0.03-0.5、0.03-0.25、0.03-0.1、0.05-2.0、0.05-1.9、0.05-1.8、0.05-1.7、0.05-1.6、0.05-1.5、0.05-1.25、0.05-1.0、0.05-0.9、0.05-0.8、0.05-0.7、0.05-0.6、0.05-0.5、0.1-2.0、0.1-1.9、0.1-1.8、0.1-1.7、0.1-1.6、0.1-1.5、0.1-1.25、0.1-1.0、0.1-0.9、0.1-0.8、0.1-0.7、0.1-0.6、0.1-0.5、0.15-2.0、0.15-1.9、0.15-1.8、0.15-1.7、0.15-1.6、0.15-1.5、0.15-1.25、0.15-1.0、0.15-0.9、0.15-0.8、0.15-0.7、0.15-0.6、0.15-0.5、0.2-2.0、0.2-1.9、0.2-1.8、0.2-1.7、0.2-1.6、0.2-1.5、0.2-1.25、0.2-1.0、0.2-0.9、0.2-0.8、0.2-0.7、0.2-0.6、0.2-0.5、0.25-2.0、0.25-1.9、0.25-1.8、0.25-1.7、0.25-1.6、0.25-1.5、0.25-1.25、0.25-1.0、0.25-0.9、0.25-0.8、0.25-0.7、0.25-0.6、0.25-0.5、0.3-2.0、0.3-1.9、0.3-1.8、0.3-1.7、0.3-1.6、0.3-1.5、0.3-1.25、0.3-1.0、0.3-0.9、0.3-0.8、0.3-0.7、0.3-0.6、0.3-0.5、0.4-2.0、0.4-1.9、0.4-1.8、0.4-1.7、0.4-1.6、0.4-1.5、0.4-1.25、0.4-1.0、0.4-0.9、0.4-0.8、0.4-0.7、0.4-0.6 and 0.4-0.5.
DoS of a glucan substituted with at least one cationic organic group herein can be, for example, about, at least about, or up to about 0.001、0.0025、0.005、0.01、0.02、0.025、0.03、0.04、0.05、0.06、0.07、0.075、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、 or 3.0 (DoS can optionally be expressed as a range between any two of these values). Some examples of DoS ranges herein include 0.005-2.0、0.005-1.9、0.005-1.8、0.005-1.7、0.005-1.6、0.005-1.5、0.005-1.25、0.005-1.0、0.005-0.9、0.005-0.8、0.005-0.7、0.005-0.6、0.005-0.5、0.01-2.0、0.01-1.9、0.01-1.8、0.01-1.7、0.01-1.6、0.01-1.5、0.01-1.25、0.01-1.0、0.01-0.9、0.01-0.8、0.01-0.7、0.01-0.6、0.01-0.5、0.01-0.25、0.01-0.1、0.03-2.0、0.03-1.9、0.03-1.8、0.03-1.7、0.03-1.6、0.03-1.5、0.03-1.25、0.03-1.0、0.03-0.9、0.03-0.8、0.03-0.7、0.03-0.6、0.03-0.5、0.03-0.25、0.03-0.1、0.05-2.0、0.05-1.9、0.05-1.8、0.05-1.7、0.05-1.6、0.05-1.5、0.05-1.25、0.05-1.0、0.05-0.9、0.05-0.8、0.05-0.7、0.05-0.6、0.05-0.5、0.1-2.0、0.1-1.9、0.1-1.8、0.1-1.7、0.1-1.6、0.1-1.5、0.1-1.25、0.1-1.0、0.1-0.9、0.1-0.8、0.1-0.7、0.1-0.6、0.1-0.5、0.15-2.0、0.15-1.9、0.15-1.8、0.15-1.7、0.15-1.6、0.15-1.5、0.15-1.25、0.15-1.0、0.15-0.9、0.15-0.8、0.15-0.7、0.15-0.6、0.15-0.5、0.2-2.0、0.2-1.9、0.2-1.8、0.2-1.7、0.2-1.6、0.2-1.5、0.2-1.25、0.2-1.0、0.2-0.9、0.2-0.8、0.2-0.7、0.2-0.6、0.2-0.5、0.25-2.0、0.25-1.9、0.25-1.8、0.25-1.7、0.25-1.6、0.25-1.5、0.25-1.25、0.25-1.0、0.25-0.9、0.25-0.8、0.25-0.7、0.25-0.6、0.25-0.5、0.3-2.0、0.3-1.9、0.3-1.8、0.3-1.7、0.3-1.6、0.3-1.5、0.3-1.25、0.3-1.0、0.3-0.9、0.3-0.8、0.3-0.7、0.3-0.6、0.3-0.5、0.4-2.0、0.4-1.9、0.4-1.8、0.4-1.7、0.4-1.6、0.4-1.5、0.4-1.25、0.4-1.0、0.4-0.9、0.4-0.8、0.4-0.7、0.4-0.6 and 0.4-0.5.
For example, any of the aforementioned DoS values and/or ranges of (i) at least one cationic group and (ii) at least one hydrophobic group may be optionally combined to characterize the DoS characteristics of the dextran ester derivatives herein. In some aspects, any of the foregoing values and/or ranges of total DoS may be optionally combined with any of the foregoing DoS values and/or ranges of (i) at least one cationic group and/or (ii) at least one hydrophobic group.
Regarding the polysaccharide ester derivatives herein as dextran derivatives, for example, the total DoS of the dextran ester derivatives may be no higher than 3.0 due to the presence of up to three hydroxyl groups in the glucose monomer units of the dextran. It will be appreciated by those skilled in the art that since the dextran ester derivatives as disclosed herein have DoS (e.g., between about 0.001 to about 3.0) of at least one type of organic group (acyl) used in the ester linkage (e.g., at least two types of organic groups in the ester linkage, wherein at least one group is a cationic group and at least one group is a hydrophobic group), all substituents of the dextran ester derivatives cannot be hydroxyl only.
The polysaccharide/dextran ester derivatives of the present disclosure may be substituted with at least one cationic organic group (cationic acyl) herein attached to the polysaccharide/dextran ester. For example, dextran derivatives as disclosed herein may be derivatized with one, two, three, or more different types of esterified cationic organic groups herein. In some aspects, at least one ester-linked cationic organic group comprises structure I:
Wherein R1、R2 and R3 are each independently a group comprising at least one carbon atom. The positions of R1、R2 and R3 in structure I are generally not particularly important and are not intended to initiate any particular stereochemistry.
With respect to the wavy line (variable cross section) of structure I, since the cationic organic group is ester-linked to the dextran derivative herein, and is thus a cationic acyl group, it is understood that the-n+r1R2R3 moiety of structure I is bound to the glucose monomer unit of the dextran derivative via a carbonyl group (-CO-) via one or more carbon atoms. The (chain of) one or more carbon atoms may be referred to herein as-Rc -. Carbonyl groups link the-Rc-N+R1R2R3 portion of the organic group to the oxygen atom of the now substituted hydroxyl group (i.e., the hydrogen atom is now replaced by an acyl group). Thus, structure I may optionally be described as-CO-Rc-N+R1R2R3. When bound to a glucose monomer unit of dextran, it can be described as-CG-OG-CO-Rc-N+R1R2R3, where-CG -represents a glucose monomer unit carbon atom and-OG -represents an oxygen atom of the now substituted glucose unit hydroxyl group.
In some aspects, Rc (above) comprises one (e.g., -CH2), two (e.g., -CH2CH2), three (e.g., -CH2CH2CH2), four (e.g., -CH2CH2CH2CH2), five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty-one, twenty-two, or more carbon atoms. For example, Rc may be fully or partially saturated. For example, Rc may be linear. For example, structure I may be described as -CO-CH2-N+R1R2R3、-CO-CH2CH2-N+R1R2R3、-CO-CH2CH2CH2-N+R1R2R3、 or-CO-CH2CH2CH2CH2-N+R1R2R3.
For example, Rc may have one or more substitutions with a hydroxyl group (the hydrogen atom is replaced with another group). In some aspects, Rc may comprise-CH2 CH (OH) -, for example, structure I comprising such Rc may be described as -CO-CH2CH(OH)-CH2-N+R1R2R3、-CO-CH2CH(OH)-CH2CH2-N+R1R2R3、-CO-CH2CH(OH)-CH2CH2CH2-N+R1R2R3、 or -CO-CH2CH(OH)-CH2CH2CH2CH2-N+R1R2R3.
For example, Rc may have one or more branches. In some aspects, Rc may comprise-CHRs-(CH2)p -, where Rs is the side chain and p is 0, 1, 2, or 3. For example, Rs may be-CH3、-CH2CH3、-CH2CH2CH3, or-CH2CH2CH2CH3. For example, Rs can be-CH2CH2CH2CH2-N+H3 (i.e., lysine side chain )、-CH2CH2CH2CH2-N+(CH3)3、CH2CH2-NH-C(N+H2)-NH2、-CH2CH2CH2-NH-C(N+H2)-NH2(, i.e., arginine side chain), or-CH2 -IMD (i.e., histidine side chain, CH2 bonded to imidazole ring [ IMD ] carbon-4).
In some aspects, such as in any of the above structures/formulas, R1、R2 and R3 may each be such that R1、R2 and R3 may each be independently selected from, for example, -CH3、-CH2CH3、-CH2CH2CH3, or-CH2CH2CH2CH3 (e.g., R1、R2 and R3 may each be-CH3). In some aspects, each of R1、R2 and R3 may be independently selected from monohydroxy or dihydroxy substituted forms of any of these aforementioned C1-C4 alkyl groups (e.g., hydroxyethyl, such as-CH2CH2 OH or-CH2(OH)CH3). In some aspects, each of R1、R2 and R3 may be independently selected from any of the foregoing C1-C4 alkyl groups and monohydroxy or dihydroxy substituted versions thereof. In some aspects, R1 and R2 may be independently selected from any of the foregoing C1-C4 alkyl groups and monohydroxy or dihydroxy substituted versions thereof (e.g., R1 and R2 may be-CH3) and R3 may be, for example, R3 may be saturated or unsaturated. for example, R3 may be linear or branched. R3 can be, for example, an alkyl group, such as- (CH2)nCH3) where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, or 23 (e.g., C6-C22, C12-14, C10-C16, or C8-C18 alkyl), as appropriate, R3 can alternatively be an unsaturated form of any of these alkyl groups. In some aspects, R3 can be -CH2CH2CH2-NH-CO-CH2CH2CH2-(CH2)n-CH2CH2CH2CH3, where n is 0, 2,4,6, or 10.
As discussed above, it should be apparent that in some aspects, the cationic organic group may comprise structure II:
Wherein R1、R2 and R3 are each independently selected from groups comprising at least one carbon atom (e.g., any of R1、R2 and R3 above). For illustrative purposes only, Rc in Structure II is-CH2 -. Examples of structure II herein have R1、R2 and R3, each of which is-CH3. It is understood that structure II is a cationic acyl group, additional examples of structure II herein include acyl groups of any of the betaine compounds decyl amidopropyl betaine, caprylyl betaine, cetyl amidopropyl betaine, cetyl betaine, cocoamidoethyl betaine, cocoamidopropyl betaine, decyl amidopropyl betaine, decyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropylbetaine, oleyl betaine, palmitoamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, undecyl betaine, undecylenamidopropyl betaine.
The polysaccharide/dextran ester derivatives of the present disclosure may be substituted with at least one hydrophobic organic group (hydrophobic acyl group) herein attached to the polysaccharide/dextran ester. For example, dextran derivatives as disclosed herein may be derivatized with one, two, three, or more different types of esterified hydrophobic acyl groups herein. The hydrophobic acyl group may be represented as-CO-R ', where R' is hydrophobic and comprises a chain having at least one carbon atom, and the carbonyl (-CO-) of the acyl group is attached to the polysaccharide/dextran monomer (e.g., glucose) via the oxygen atom of the monomer. R' may be, for example, linear, branched, or cyclic. R' may be saturated or unsaturated, and/or contain, for example, up to 29 carbon atoms.
In some aspects, a hydrophobic acyl group may be referred to as a "Cn acyl group" (or other similar terms) where n is an integer of 2 or greater and represents the number of carbon atoms in the acyl group, including the carbonyl carbon atom. The Cn acyl group is typically linear and may be saturated or unsaturated. The first carbon of the Cn acyl group (carbon-1) is its carbonyl carbon. In some aspects, the Cn acyl group can be acetyl (C2), propionyl (C3), butyryl (C4), Pentanoyl (C5), hexanoyl (C6), heptanoyl (C7), octanoyl (C8), nonanoyl (C9), decanoyl (C10), undecanoyl (C11), dodecanoyl (C12), Tridecyl (C13), tetradecyl (C14), pentadecyl (C15), hexadecyl (C16), Heptadecanoyl (C17), octadecanoyl (C18), nonadecanoyl (C19), eicosanoyl (C20), Eicosanoyl (C21), docosanoyl (C22), tricosanoyl (C23), tetracosanoyl (C24), Cyclopentadecanoyl (C25), hexacosanoyl (C26)、C27、C28、C29, or C30 acyl). These specific Cn acyl groups are saturated. Some of the acyl groups listed above are commonly known as acetyl (acetyl or ethanoyl group), propionyl (propionyl or propanoyl group), butyryl (butyryl or butanoyl group), pentanoyl (valeryl or pentanoyl group), hexanoyl (caproyl or hexanoyl group), heptanoyl (enanthyl or heptanoyl group), octanoyl (caprylyl or octanoyl group), Nonanoyl (pelargonyl or nonanoyl group), decanoyl (capryl or decanoyl group), lauroyl (dodecanoyl), myristyl (tetradecanoyl), palmitoyl (hexadecanoyl), stearyl (octadecanoyl), arachidyl (eicosanoyl), behenyl (behenoyl), lignoceryl (tetracosanoyl), and ceryl (hexaceryl). In some aspects, the acyl group may be a C10 to C14 acyl group, meaning that the acyl group may be any of C10、C11、C12、C13, or C14 acyl groups (thus, this particular Cn range nomenclature applies to the other Cn ranges herein). In some aspects, the acyl group may be C2 to C26、C4 to C20、C6 to C18、C8 to C18、C10 to C18、C12 to C18、C6 to C16、C8 to C16、C10 to C16、C12 to C16、C6 to C14、C8 to C14、C10 to C14、C12 to C14、C6 to C12、C8 to C12, Or a C10 to C12 acyl group.
In some aspects, the hydrophobic acyl groups may be unsaturated. The unsaturated acyl group may contain, for example, one, two, three, four, five, six, or more double bonds. In some aspects, the unsaturated acyl group may comprise one or more double bonds spanning the acyl groups of carbons (i) 4 and 5), (ii) 5 and 6, (iii) 6 and 7, (iv) 8 and 9, (v) 9 and 10, (vi) 11 and 12, (vii) 12 and 13, (viii) 14 and 15, (ix) 15 and 16, (x) 16 and 17, (xi) 17 and 18, and/or (xii) 18 and 19, wherein the carbon number is counted from the carbonyl carbon of the acyl group (i.e., carbon-1). Some suitable combinations of double bonds of acyl groups are reflected in the following list of unsaturated acyl groups. Although the double bond of an acyl group may be in cis or trans orientation herein, it is typically in cis orientation. In some aspects, the unsaturated acyl groups may be derived (derivable) from fatty acids. Examples of the unsaturated acyl group herein include (11Z, 14Z) -eicosadienoyl, (11Z, 14Z, 17Z) -eicosatrienoyl, (4Z) -hexadecenoyl, (4Z, 7Z,10Z,13Z, 16Z) -docosapentaenoyl, (4Z, 7Z,10Z,13Z,16Z, 19Z) -docosahexaenoyl, (5Z, 8Z,11Z,14Z, 17Z) -eicosapentaenoyl, (5Z, 9Z, 12Z) -octadecatrienoyl, (5Z, 9Z,12Z, 15Z) -octadecatrienoyl, (6Z, 9Z,12Z, 15Z) -octadecatrienoyl, (7Z, 10Z) -hexadecadienoyl, (7Z, 10Z, 13Z) -hexadecatrienoyl, (7Z, 10Z,13Z, 16Z) -docosatetraenoyl (7Z, 10Z,13Z,16Z, 19Z) -docosapentaenoyl, (8E, 10E, 12Z) -octadecatrienoyl, (8Z, 11Z, 14Z) -eicosatrienoyl, (8Z, 11Z,14Z, 17Z) -eicosatetraenoyl, (9Z) -octadec-9-en-12-alkynoyl, (9Z, 11E, 13E) -octadecatrienoyl, (9Z, 11E, 13Z) -octadec-9, 11, 13-trienoyl, (9Z, 12E) -hexadecadienoyl, (9Z, 12E) -octadecadienoyl, (9Z, 12Z) -octadec-9, 12-dien-6-ynoyl, (9Z, 12Z, 15Z) -octadec-9, 12, 15-trien-6-ynoyl, (Z) -tetradec-7-enoyl, cis, cis-tetradec-5, 8-dienoyl, cis-tetradec-5-enoyl, arachidonyl, docosenoyl dodecenoyl group dodecene (dodecene) acyl group oleoyl, myristenoyl, octadeca-9-alkynoyl octadecenoyl, palmitoyl, and oleoyl.
In some aspects, the hydrophobic acyl group may comprise an aryl group. For example, an aryl acyl group may include a benzoyl group (-CO-C6H5), which may also be referred to as a benzoate group. In some aspects, an aryl acyl group can comprise a benzoyl group substituted with at least one halogen ("X"; e.g., cl, F), alkyl, haloalkyl, ether, cyano, or aldehyde group, or a combination thereof, such as represented by structures III (a) through III (r) below:
in some aspects, the hydrophobic acyl groups may comprise branched groups. Examples of branched acyl groups herein include 2-methylpropanoyl, 2-methylbutanoyl, 2-dimethylbropionyl, 3-methylbutanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2-dimethylbutyryl, 2, 3-dimethylbutyryl, 3-dimethylbutyryl, 2-ethylbutyryl and 2-ethylhexanoyl.
In some aspects, the polysaccharide/dextran ester derivatives of the present disclosure can be characterized as mixed esters due to the inclusion of at least one cationic ester group herein and at least one hydrophobic ester group herein. By way of example only, the mixed glucan ester can comprise one or both of betaine acyl groups herein (e.g., structure II, wherein R1、R2 and R3 are each-CH3) (e.g., doS is about 0.01-0.12, 0.03-0.1, 0.04-0.09, or 0.05-0.09) and (i) C10 to C14 acyl groups herein (e.g., C12 acyl groups such as lauroyl) and/or (II) aryl acyl groups herein (e.g., benzoyl) as hydrophobic acyl groups (e.g., doS is about 0.2-1.0, 0.3-0.9, 0.4-0.8, or 0.5-0.8), and optionally such mixed glucan ester can further comprise acetyl groups (e.g., doS is about 0.02-0.3). In some aspects, such dextran esters may comprise alpha-1, 2-and/or alpha-1, 3-branched (e.g., about 15% -25% branched) alpha-1, 6-dextran (e.g., about 10-70, 20-60, or 30-50 kDa) as its dextran component. While in some aspects the polysaccharide/dextran ester derivative does not contain any other type of substituent groups than ester groups, in other aspects one or more other types of substituent groups may be present.
Hydrophobic acyl groups of polysaccharide/dextran ester derivatives herein may be as disclosed, for example, in U.S. patent application publication nos. 2014/0187767, 2018/0155455, or 2020/0308371, or international patent application publication No. WO 2021/252575, each of which is incorporated herein by reference.
In some alternative aspects, the polysaccharide/dextran as disclosed herein may be derivatized with anionic organic groups and hydrophobic ester groups (i.e., anionic organic groups in place of or in addition to cationic ester groups). The hydrophobic ester group can be as disclosed herein (e.g., an ester group comprising an aryl group, such as benzoyl) for example. The anionic organic groups are typically linked to the polysaccharide/glucan via ether or ester linkages, and may optionally be characterized as anionic ether groups or anionic ester groups. Examples of suitable anionic groups herein include carboxyalkyl groups (e.g., carboxymethyl groups), which are examples of ether groups, and groups derived from cyclic organic anhydrides (e.g., succinate groups), which are examples of ester groups. By way of example only, the polysaccharide/glucan derivatives herein may have (i) carboxymethyl ether and benzoyl ester groups, or (ii) succinic acid ester and benzoyl ester groups. Suitable anionic groups may be as disclosed, for example, in U.S. patent application publication nos. 2014/0179913, 2016/0304629, 2020/0002646, 2021/0253977, 2018/0155455, or 2023/0192905, or international patent application publication nos. WO 2021/247810, WO 2022/178073, or WO 2022/178075, which are incorporated herein by reference. In the foregoing alternative aspect, doS of a glucan having an anionic organic group herein can be as disclosed herein for, for example, a hydrophobic ester group or a cationic ester group.
In some alternative aspects, the polysaccharide/dextran as disclosed herein may be derivatized with anionic organic groups and cationic ester groups (i.e., anionic organic groups replace hydrophobic ester groups or anionic organic groups in addition to hydrophobic ester groups). The cationic ester group can be as disclosed herein (e.g., a cationic ester group comprising structure I herein), for example. The anionic organic groups are typically linked to the polysaccharide/glucan via ether or ester linkages, and may optionally be characterized as anionic ether groups or anionic ester groups. Examples of suitable anionic groups herein include carboxyalkyl groups (e.g., carboxymethyl groups), and groups derived from cyclic organic anhydrides (e.g., succinate groups). By way of example only, the polysaccharide/dextran derivatives herein may have (I) carboxymethyl ether and structure I ester groups, or (ii) succinic acid esters and structure I ester groups. Suitable anionic groups may be as disclosed, for example, in the above-mentioned patent application references. In the foregoing alternative aspect, doS of a glucan having an anionic organic group herein can be as disclosed herein for, for example, a hydrophobic ester group or a cationic ester group.
Some aspects of the disclosure relate to a method of producing an ester derivative of dextran herein. Such a process (ester derivatization process/reaction, or esterification process/reaction) may comprise (a) contacting a glucan with at least two esterifying agents, wherein at least one of the esterifying agents comprises a cationic organic group (cationic acyl group), wherein at least one of the esterifying agents comprises a hydrophobic organic group (hydrophobic acyl group), wherein at least one cationic organic group and at least one hydrophobic organic group are esterified to the glucan, thereby producing an ester derivative of the glucan, wherein the ester derivative of the glucan has a degree of substitution (DoS) of up to about 3.0 substituted with the cationic organic group and the hydrophobic organic group, and (b) optionally separating the ester derivative of the glucan produced in step (a). Thus, any glucan or other polysaccharide as disclosed herein can be added to the esterification process to produce any ester derivative herein.
For example, the esterification agent used in the ester derivatization process of the present disclosure can be a carboxylic acid comprising any cationic acyl group as disclosed herein. It is understood that the terminal carbonyl (-CO-) of a cationic acyl group is the carbonyl of the-COOH group of a carboxylic acid comprising a cationic acyl group, and that the term "terminal" is used herein as distinguished from any internal carbonyl group of an acyl group as disclosed herein, if present. The carboxylic acid may be provided as a salt with an anion such as chloride, fluoride, or bromide, wherein the anion is counter-balanced with one or more N+ moieties of the carboxylic acid.
The esterification agent used in the ester derivatization process of the present disclosure may be, for example, a carboxylic acid comprising any hydrophobic acyl group as disclosed herein. It is understood that the terminal carbonyl (-CO-) of a hydrophobic acyl group is the carbonyl of the-COOH group of a carboxylic acid comprising a hydrophobic acyl group.
The esterification agent used in the ester derivatization process of the present disclosure may be, for example, an acyl halide (acid halide) comprising any acyl group as disclosed herein. The halide of the acyl halide herein may be, for example, chloride, fluoride, or bromide. In some aspects, the esterification agent used in the ester derivatization process can be, for example, an anhydride comprising any acyl group as disclosed herein. Some illustrative examples of anhydrides include aroyl anhydride (aroyl anhydride) (e.g., benzoic anhydride [ benzoyl anhydride ]), acetic anhydride, propionic anhydride, and butyric anhydride.
The concentration of the esterifying agent (for cationic or hydrophobic esterification) in the esterification reaction herein may be, for example, about 10, 25, 50, 75, 100, 125, 150, 175, 200, 10-200, 25-100, 10-25, 100-200, or 150-200g/L.
The step of contacting the glucan with at least one esterifying agent is typically performed under substantially anhydrous conditions. The substantially anhydrous esterification reaction herein contains no water or less than about 0.05wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.0wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、 or 2.0wt% water. The solvent used to contact the dextran with the at least one esterifying agent may be, for example, a non-aqueous solvent in which the dextran typically may be dissolved. In some aspects, the non-aqueous solvent may be an organic solvent comprising N, N-dimethylacetamide (DMAc) (optionally with about 0.5% -5% LiCl), dimethylsulfoxide (DMSO), N-Dimethylformamide (DMF), pyridine, SO2/Diethylamine (DEA)/DMSO, liCl/1.3-dimethyl-2-imidazolidinone (DMI), DMSO/tetrabutylammonium fluoride Trihydrate (TBAF), N-methylpyrrolidone, dichloromethane, and/or N-methylmorpholine-N-oxide (NMMO). A dehydrating agent (e.g., tosyl chloride or dicyandiamide) may optionally be included in the contacting step herein.
For example, the contacting step may be performed in one esterification reaction ("one pot" reaction). In some aspects of the one-pot reaction, at least one cationic esterifying agent and at least one hydrophobic esterifying agent may be provided simultaneously in the reaction, or these agents may be provided sequentially to the reaction (e.g., one or more hydrophobic esterifying agents may be added first followed by one or more cationic esterifying agents, or vice versa). In some aspects, the contacting step may be performed in at least two separate reactions, wherein at least one of the reactions uses at least one cationic esterifying agent, and at least one of the reactions uses at least one hydrophobic esterifying agent. The ester product of the first reaction may optionally be isolated before entering another reaction. In some aspects, one or more reactions for cationic esterification may be performed, after which the ester product enters one or more reactions for hydrophobic esterification (or vice versa).
For example, the concentration of dextran in the esterification reactions herein may be about or at least about 10、25、50、75、100、150、200、250、300、10-300、10-250、10-200、10-50、25-300、25-250、25-200、25-50、150-300、150-250、 or 150-200g/L. The temperature of the esterification reaction herein may be, for example, about 50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、50℃-150℃、50℃-140℃、50℃-130℃、60℃-150℃、60℃-140℃、60℃-130℃、70℃-150℃、70℃-140℃、70℃-130℃、60℃-80℃、 or 110 ℃ to 130 ℃. In some aspects, the esterification reaction may be conducted for about 1, 2, 3, 4, 5, 6, 7, 8, 1-8, 2-8, 1-6, or 2-6 hours. In some aspects, the pH of the esterification reaction can be about 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, or 12.
The esterified glucan derivatives produced in one or more of the esterification reactions herein can optionally be isolated. In some aspects, such products may be first precipitated from the reaction. Precipitation may be performed by adding an excess (e.g., at least 2-3 volumes of the reaction volume) of alcohol (e.g., 100% or 95% concentration) (e.g., methanol, ethanol, isopropanol) or other solvent (e.g., acetonitrile, ethyl acetate) to the reaction. The precipitated product may then be separated using a filter funnel, centrifuge, filter press, or any other method or apparatus that allows for the removal of liquid from solids. The isolated product may be dried, such as by vacuum drying, air drying, or freeze drying.
In some aspects, the esterified glucan derivative product can be isolated by steps including a reaction in which the completion is filtered by ultrafiltration (e.g., with a5 or 10 molecular weight cut-off filter), or a diluted form thereof. Optionally, the completed reaction or diluted form thereof may first be periodically filtered (i.e., not ultrafiltered), and the filtrate may then be subjected to ultrafiltration. The concentrated liquid obtained by ultrafiltration may then be dried to its component solids, such as by freeze-drying, or the solids may be precipitated from the liquid and then dried (e.g., freeze-dried).
The esterified glucan derivative products herein can optionally be washed one or more times with a liquid that does not readily dissolve the product after precipitation or drying. For example, the dextran ester product may be washed with alcohol, acetone, aromatic compounds, or any combination of these, depending on the solubility of the ester product therein (where lack of solubility is desirable for washing). In general, solvents comprising an organic solvent (e.g., 95% -100%) such as an alcohol are preferred for washing the dextran ester derivative product.
Any of the above esterification reactions can be repeated using the dextran ester derivative products herein as starting materials for further modification. Such further modification may be with the same esterifying agent as used in the first reaction, or with a different esterifying agent.
The compositions as disclosed herein comprising at least one dextran ester derivative herein may be, for example, aqueous compositions (e.g., solutions or dispersions such as colloidal dispersions) or dry compositions. In some aspects, the compositions herein may comprise about, at least about, or less than about 0.01、0.05、0.1、0.2、0.25、0.3、0.4、0.5、0.6、0.7、0.75、0.8、0.9、1.0、1.2、1.25、1.4、1.5、1.6、1.75、1.8、2.0、2.25、2.5、3.0、3.5、4.0、4.5、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、96、97、98、99、 or 99.5wt% or w/v% dextran ester derivative. The composition may comprise, for example, a range between any two of these wt% or w/v% values (e.g., ,5-50、5-45、5-40、5-35、5-30、5-25、5-20、5-15、5-10、1-20、1-15、1-10、1-7.5、1-5、2-20、2-15、2-10、2-7.5、2-5、3-20、3-15、3-10、3-7.5、 or 3-5wt% or w/v%). The liquid component of the aqueous composition may be an aqueous fluid such as water or an aqueous solution. The solvent of the aqueous solution is typically water, or may comprise, for example, about, or at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 98, or 99wt% water, or as disclosed below. In some aspects, the compositions herein may comprise, or be in the form of, a solution, dispersion (e.g., emulsion), mixture, wet cake, or wet powder, dry powder, extrudate, composite, film/coating, fiber, or fibrid.
In some aspects, the solvent of the compositions herein comprises water and, for example, at least about 40% (v/v or w/w) of one or more polar organic solvents. In some aspects, the solvent comprises about, or at least about 40、41、42、43、44、45、46、47、48、49、50、51、52、53、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、96、97、40-90、40-80、40-70、40-60、50-90、50-80、50-70、50-60、60-90、60-80、60-70、70-90、70-80、40-70、40-60、75-85、 or 85-95v/v% or w/w% of one or more polar organic solvents. The balance of the solvent is typically only water (e.g., a solvent having about 75v/v% polar organic solvent has about 25v/v% water), but may optionally contain (e.g., less than 2,1, 0.5, or 0.25 v/v%) one or more other liquids other than polar organic solvent. The solvent herein may optionally be characterized as an aqueous solvent in view of its water content. Although the solvents herein typically comprise one type of polar organic solvent, two, three or more polar organic solvents may optionally be included, in which respect the polar organic solvent concentration is typically the concentration of a combination of polar organic solvents.
In some aspects, the polar organic solvent may be protic. Examples of the protic polar organic solvents herein include alcohols (e.g., methanol, ethanol, isopropanol, 1-propanol, t-butanol, n-butanol, isobutanol), methylformamide, and formamide. Further examples of protic polar organic solvents herein include n-butanol, ethylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, glycerol, 1, 2-propanediol, and 1, 3-glycerol.
In some aspects, the polar organic solvent may be aprotic. Examples of aprotic polar organic solvents herein include acetonitrile, dimethyl sulfoxide, acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, propylene carbonate, and sulfolane. Additional examples of aprotic polar organic solvents herein include hexamethylphosphoramide, dimethyl imidazolidinone (1, 3-dimethyl-2-imidazolidinone), dioxane, nitromethane, and butanone. In general, esters, ketones and aldehyde solvents that do not have acidic hydrogen atoms are other examples of aprotic polar organic solvents herein.
The aqueous compositions herein may have a viscosity of, for example, about, at least about, or less than about 1、5、10、100、200、300、400、500、600、700、1000、2000、3000、4000、5000、6000、7000、8000、9000、10000、15000、1-300、10-300、25-300、50-300、1-250、10-250、25-250、50-250、1-200、10-200、25-200、50-200、1-150、10-150、25-150、50-150、1-100、10-100、25-100、 or 50-100 centipoise (cps). For example, the viscosity may be measured as with the aqueous compositions herein at any temperature between about 3 ℃ to about 80 ℃ (e.g., 4 ℃ to 30 ℃, 15 ℃ to 25 ℃). The viscosity is typically measured as at atmospheric pressure (about 760 torr) or at a pressure of + -10% thereof. The viscosity may be measured using, for example, a viscometer or rheometer, and may optionally be measured, for example, at a shear rate (rotational shear rate) of about 0.1, 0.5, 1.0, 5, 10, 50, 100, 500, 1000, 0.1-500, 0.1-100, 1.0-500, 1.0-1000, or 1.0-100s-1 (1/s) or about 5, 10, 20, 25, 50, 100, 200, or 250rpm (revolutions per minute).
For example, a composition as disclosed herein may have a turbidity of about, or less than about 1500、1400、1300、1200、1100、1000、900、800、700、600、500、400、300、280、260、240、220、200、190、180、170、160、150、140、130、120、110、100、90、80、70、60、50、45、40、35、30、25、20、18、16、14、12、10、9、8、7、6、5、4、3、2、1、1-250、1-200、1-150、1-100、1-50、1-20、1-15、1-10、1-5、2-250、2-200、2-150、2-100、2-50、2-20、2-15、2-10、2-5、10-250、10-200、10-150、10-100、10-50、 or 10-20NTU (nephelometric turbidity units). Any of these NTU values may optionally be relative to the α -glucan ester derivative and solvent component portion of the compositions herein. In some aspects, it is contemplated that any of these NTU levels will (continuously) last for about, at least about, or up to about 0.5, 1,2,4, 6, 8, 10, 20, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, or 360 days, or 1,2, or 3 years (typically starting from initial preparation). Any suitable method may be used to measure turbidity, such as the method disclosed in Progress in Filtration and Separation [ filtration and separation progress ] (version: 1, chapter 16. Turbidity: measurement of filtrate and supernatant quality.
In some aspects, the aqueous component of the aqueous composition has no (detectable) dissolved sugar, or about 0.1-1.5, 0.1-1.25, 0.1-1.0, 0.1-75, 0.1-0.5, 0.2-0.6, 0.3-0.5, 0.2, 0.3, 0.4, 0.5, or 0.6wt% dissolved sugar. Such dissolved sugars may include, for example, sucrose, fructose, leuconostoc disaccharide, and/or soluble glucose-oligosaccharides. In some aspects, the aqueous solution component of the aqueous composition may have, for example, one or more salts/buffers (e.g., na+, C1-, naCl, phosphate, tris, citrate) (e.g., 0.1, 0.5, 1.0, 2.0, or 3.0 wt.%) and/or a pH of about 4.0、4.5、5.0、5.5、6.0、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10.0、10.5、4.0-10.0、4.0-9.0、4.0-8.0、5.0-10.0、5.0-9.0、5.0-8.0、6.0-10.0、6.0-9.0、 or 6.0-8.0. In some aspects, esters of insoluble glucan such as those herein (e.g., alpha-1, 3-glucan having a DP >8 or > 9) are insoluble under aqueous conditions (e.g., at a concentration of at least about 0.5wt% or 1.0 wt%) having a pH of at least about 10, 10.5, or 11.
In some aspects, for aqueous compositions that are aqueous dispersions (e.g., emulsions) of particles of dextran esters of the present disclosure, the particles are dispersed in about or at least about 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98%, 99%, or 100% of the volume of the dispersion. In some aspects, it is contemplated that such a level of dispersion (e.g., emulsion) will last for about, at least about, or up to about 0.5, 1, 2, 4, 6, 8, 10, 20, 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, or 360 days, or for a period of 1, 2, or 3 years (typically starting from the initial preparation of the dispersion).
The temperature of the compositions herein may be, for example, about, at least about, or up to about 0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、5℃-50℃、20℃-25℃、20℃-30℃、20℃-40℃、30℃-40℃、40℃-130℃、40℃-125℃、40℃-120℃、70℃-130℃、70℃-125℃、70℃-120℃、80℃-130℃、80℃-125℃、80℃-120℃、60℃-100℃、60℃-90℃、70℃-100℃、70℃-90℃、75℃-100℃、75℃-90℃、 or 75-85 ℃.
In some aspects, the compositions herein may be non-aqueous (e.g., dry compositions). Examples of such embodiments include powders, granules, microcapsules, flakes, or any other form of particulate matter. Other examples include larger compositions such as pellets, sticks, cores, beads, tablets, sticks, or other agglomerates, or ointments or lotions (or any other form of non-aqueous or dry composition herein). The non-aqueous or dry composition typically has about or no more than about 12, 10, 8, 6, 5, 4, 3, 2, 1.5, 1.0, 0.5, 0.25, 0.10, 0.05, or 0.01wt% water contained therein. In some aspects (e.g., those involving laundry or dishwashing detergents), the dry compositions herein may be provided in sachets or pouches.
In some aspects, the compositions herein comprising dextran ester derivatives may be detergent compositions. Examples of such compositions are disclosed herein as detergents for dishwashing and as detergents for fabric care.
In some aspects, the compositions herein may comprise one or more salts, such as sodium salts (e.g., naCl, na2SO4). Other non-limiting examples of salts include those having (I) aluminum, ammonium, barium, calcium, chromium (II or III), copper (I or II), iron (II or III), hydrogen, lead (II), lithium, magnesium, manganese (II or III), mercury (I or II), potassium, silver, sodium, strontium, tin (II or IV), or zinc cations, and (II) acetate, borate, bromate, bromide, carbonate, chlorate, chloride, chlorite, chromate, cyanamide, cyanide, dichromate, dihydrogen phosphate, ferricyanide, ferrocyanide, fluoride, bicarbonate, hydrogen phosphate, bisulfate, hydrogen sulfide, bisulfite, hydride, hydroxide, hypochlorite, iodate, iodide, nitrate, nitride, nitrite, oxalate, oxide, perchlorate, permanganate, peroxide, phosphate, phosphide, phosphite, silicate, stannate, stannous salt, sulfate, sulfide, sulfite, tartrate, or thiocyanate anions. Thus, for example, any salt having a cation from (i) above and an anion from (ii) above may be in the composition. The salt may be present in the aqueous compositions herein in wt%, for example, or at least about.01,.025,.05,.075,.1,.25,.5,.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.5, 3.0, 3.5,.01-3.5,.5-2.5, or.5-1.5 wt% (such wt% values typically refer to the total concentration of one or more salts).
The compositions herein may optionally contain one or more enzymes (active enzymes). Examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipolytic enzymes), xylanases, lipases, phospholipases, esterases (e.g., aryl esterases, polyester enzymes), perhydrolases, cutinases, pectinases, pectin lyases, mannanases, keratinases, reductases, oxidases (e.g., choline oxidases), phenol oxidases, lipoxygenases, ligninases, pullulanases, tannase, pentosanases, malates (malanases), beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, metalloproteinases, amadoriases (amadoriase), glucoamylases, arabinofurannases, phytases, isomerases, transferases, nucleases, and amylases. If one or more enzymes are included, they may be included in the compositions herein in an amount of, for example, about 0.0001 to 0.1wt% (e.g., 0.01 to 0.03 wt%) of the active enzyme (e.g., calculated as pure enzyme protein). In fabric care or automatic dishwashing applications, the enzymes (e.g., any of the above, such as cellulases, proteases, amylases, and/or lipases) herein may be present, for example, in an aqueous composition (e.g., wash liquor, grey water) in which the fabric or dish is treated at a concentration of from a minimum of about 0.01 to 0.1ppm total enzyme protein, or from about 0.1 to 10ppb total enzyme protein (e.g., less than 1 ppm) to a maximum of about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000ppm total enzyme protein.
In some aspects, the dextran ester derivative and/or the composition comprising such derivative is biodegradable. After 15, 30, 45, 60, 75, or 90 days of testing, for example, such biodegradability may be determined as by the carbon dioxide evolution test method (OECD guideline 301B, incorporated herein by reference) to be about, at least about, or at most about 5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％、90％、5％-60％、5％-80％、5％-90％、40％-70％、50％-70％、60％-70％、40％-75％、50％-75％、60％-75％、70％-75％、40％-80％、50％-80％、60％-80％、70％-80％、40％-85％、50％-85％、60％-85％、70％-85％、40％-90％、50％-90％、60％-90％、 or 70% -90%, or any value between 5% and 90%. It is contemplated that such biodegradability may be about, at least about, or up to about 10%, 25%, 50%, 75%, 100%, 150%, 200%, 250%, 500%, 750%, or 1000% higher than the biodegradability of the material in question.
The compositions may comprise one, two, three, four or more different dextran ester derivatives herein and optionally at least one non-derivatized dextran (e.g., as disclosed herein). For example, the composition may comprise at least one type of dextran ester derivative and at least one type of dextran, and in some aspects the latter may be (or can be) a precursor compound of the former. In some aspects, there is no non-derivatized alpha-glucan (e.g., a precursor compound).
The composition comprising at least one dextran ester derivative as disclosed herein may be in the form of, for example, a household care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), a medical product, or a pharmaceutical product, such as described in any one of U.S. patent application publication nos. 2018/0022834、2018/0237816、2018/0230241、20180079832、2016/0311935、2016/0304629、2015/0232785、2015/0368594、2015/0368595、2016/0122445、2019/0202942、 or 2019/0309096, or international patent application publication No. WO 2016/133734, which are incorporated herein by reference in their entirety. In some aspects, the composition may comprise at least one component/ingredient of a home care product, personal care product, industrial product, pharmaceutical product, or ingestible product (e.g., a food product) as disclosed in any of the foregoing publications and/or as disclosed herein.
It is believed that in some aspects, the compositions may be used to provide one or more of the physical properties of, for example, thickening, freeze/thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, adhesion, suspension, dispersion, gelation, or reduced mineral hardness to personal care products, pharmaceutical products, household products, industrial products, or ingestible products (e.g., food products).
The personal care products herein are not particularly limited and include, for example, skin care compositions, cosmetic compositions, antifungal compositions, and antibacterial compositions. The personal care products herein may be in the form of, for example, lotions, creams, pastes, balms, ointments, pomades, gels, liquids, combinations of these, and the like. The personal care products disclosed herein may comprise at least one active ingredient, if desired. Active ingredients are generally considered to be ingredients that cause the desired pharmacological effect.
In some aspects, a skin care product may be applied to the skin to address skin damage associated with lack of moisture. Skin care products may also be used to address the visual appearance of skin (e.g., reduce the appearance of flaking, cracking, and/or red skin) and/or the feel of skin (e.g., reduce the roughness and/or dryness of skin while improving the softness and microminiaturization of skin). Typically, the skin care product may comprise at least one active ingredient for treating or preventing skin disorders, providing a cosmetic effect, or providing a moisturizing benefit to the skin, such as zinc oxide, petrolatum, white petrolatum, mineral oil, cod liver oil, lanolin, polydimethylsiloxane, stearin, vitamin a, allantoin, calamine, kaolin, glycerin or colloidal oatmeal, and combinations of these. The skin care product may comprise, for example, one or more natural moisturizing factors such as ceramide, hyaluronic acid, glycerol, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, glycosphingolipids, urea, linoleic acid, glycosaminoglycans, mucopolysaccharides, sodium lactate, or sodium pyrrolidone carboxylate. Other ingredients that may be included in the skin care product include, but are not limited to, glycerides, almond oil, canola oil, squalane, squalene, coconut oil, corn oil, jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter, soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol esters, wax esters, fatty acids, and orange peel oil. In some aspects, the skin care product may be an ointment, lotion, or disinfectant (e.g., hand disinfectant).
The personal care products herein may also be in the form of, for example, cosmetics, lipsticks, mascaras, rouges, foundations, blushes, eyeliners, lip pencils, lip colors, other cosmetics, sunscreens, sun blocks, nail polishes, nail conditioners, temporary tattoo inks, body washes (back gels), shower gels (shower gel), body washes, facial washes, lip sticks, skin creams, cold creams, skin lotions, body sprays, soaps, body scrubs, exfoliants (exfoliant), astringents, nape lotions (scruffing lotion), depilatories, permanent wave solutions (PERMANENT WAVING so1 ution), anti-dandruff formulations, antiperspirant compositions, deodorants, shaving products, pre-shave products, post-shave products, cleaners, skin gels, hair dyes (ring), dentifrice compositions, toothpastes, or mouthwashes. Examples of personal care products (e.g., cleansers, soaps, scrubs, cosmetics) include carriers or exfoliants (e.g., jojoba beads [ jojoba ester beads ]) (e.g., about 1-10, 3-7, 4-6, or 5 wt.%), such agents can optionally be dispersed within the product.
In some aspects, the personal care product may be a hair care product. Examples of hair care products herein include shampoos, hair conditioners (leave-in or rinse-out), nutritional hair lotions, hair dyes, hair coloring products, hair shine products, hair care essences, hair anti-frizziness products, hair bifurcation repair products, mousses (e.g., hair styling mousses), hair sprays (e.g., hair styling sprays), and hair setting gels (e.g., hair styling gels). In some embodiments, the hair care product may be in the form of a liquid, paste, gel, solid, or powder. Hair care products as disclosed herein typically comprise one or more of anionic surfactants such as sodium polyoxyethylene lauryl ether sulphate, cationic surfactants such as stearoyl trimethylammonium chloride and/or distearoyl trimethylammonium chloride, nonionic surfactants such as glycerol monostearate, sorbitan monopalmitate and/or polyoxyethylene cetyl ether, humectants such as propylene glycol, 1, 3-butylene glycol, glycerol, sorbitol, pyroglutamate, amino acids and/or trimethylglycine, hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane and/or olefin oligomers, higher alcohols such as stearyl alcohol and/or cetyl alcohol, lipid-rich agents, anti-dandruff agents, disinfectants, anti-inflammatory agents, crude drugs, water-soluble polymers such as methylcellulose, hydroxycellulose and/or partially deacetylated crustaceans, preservatives such as p-hydroxybenzoates, ultraviolet light absorbers, pearlescent agents, pH adjusting agents, fragrances and pigments.
In some aspects, the composition may be a hair care composition, such as a hair styling (style) or hair styling (setting) composition (e.g., hair gel or lotion, hair mousse/foam) (e.g., aerosol hair gel, non-aerosol pump hair gel, injection (spritze), foam, cream (freme), paste, non-flowing (non-runny) gel, mousse, pomade, hairspray (1 acquer), hair wax). Hair styling/styling compositions/formulations that may be adapted to comprise at least one dextran ester derivative herein may be as disclosed, for example, in US 20090074697、WO 1999048462、US20130068849、JP H0454116A、US 5304368、AU 667246B2、US 5413775、US 5441728、US 5939058、JP 2001302458A、US 6346234、US20020085988、US 7169380、US 20090060858、US20090326151、US20160008257、WO 2020164769、 or US20110217256, which are incorporated herein by reference in their entirety. Hair care compositions such as hair styling/styling compositions may comprise one or more ingredients/additives as disclosed in any of the foregoing references, and/or one or more of the following: fragrances/perfumes, aromatherapy essences, herbs, infusion, antimicrobial agents, irritants (e.g., caffeine), essential oils, hair dyes, colorants or coloring agents, anti-graying agents, antifoaming agents, sunscreens/UV blockers (e.g., benzophenone-4), vitamins, antioxidants, surfactants or other wetting agents, mica, silica, metal flakes or other sparkling effect materials, conditioning agents (e.g., volatile or non-volatile silicone fluids), and, Antistatic agents, opacifiers, viscosity-reducing agents (DETACKIFYING AGENT), penetrants, preservatives (e.g., phenoxyethanol, ethylhexyl glycerol, benzoate, diazo alkyl urea (diazolidinyl urea), iodopropynyl butylcarbamate), emollients (e.g., panthenol, isopropyl myristate), rheology modifying or thickening polymers (e.g., acrylate/methacrylamide copolymers, polyacrylic acid [ e.g., CARBOMER ]), emulsified oil phases, petrolatum, fatty alcohols, glycols and polyols, emulsifiers (e.g., PEG-40 hydrogenated castor oil), Oleyl alcohol polyether-20), humectants (e.g., glycerol, octanediol), silicone derivatives, proteins, amino acids (e.g., isoleucine), conditioning agents, chelating agents (e.g., EDTA), solvents (e.g., see below), monosaccharides (e.g., dextrose), disaccharides, oligosaccharides, pH stabilizing compounds (e.g., aminomethylpropanol), film forming agents (e.g., acrylate/hydroxy ester acrylate copolymers, polyvinylpyrrolidone/vinyl acetate copolymers, triethyl acetate), aerosol propellants (e.g., C3-C5 alkanes such as propane, Isobutane, or n-butane, monoalkyl ethers, dialkyl ethers, such as di (C1-C4 alkyl) ethers [ e.g., dimethyl ether ]), and/or any other suitable material herein. Dextran ester derivatives as used in hair styling/shaping compositions herein may act as, for example, hair fixatives/styling agents (typically non-permanent hair fixatives, but permanent), and optionally are the only hair fixatives in the composition. Optional additional hair fixatives herein include PVP (polyvinylpyrrolidone), octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer, AMPHOMER, or any film former as listed above.
The total amount of the one or more dextran ester derivatives in the hair care compositions, such as hair styling/styling compositions herein, may be, for example, about, at least about, or less than about 0.5wt％、1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、0.5-15wt％、0.5-10wt％、0.5-5wt％、0.5-2wt％、1-15wt％、1-10wt％、1-5wt％、1-2wt％、2.5-7.5wt％、3-7wt％、 or 4-6wt%. For example, the hair styling/shaping composition may comprise a solvent comprising water and optionally a water-miscible (typically polar) organic compound (e.g., liquid or gas), such as an alcohol (e.g., ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol), an alkylene glycol alkyl ether, and/or a mono-or dialkyl ether (e.g., dimethyl ether). If an organic compound is included, it may constitute, for example, about 10%, 20%, 30%, 40%, 50%, or 60% (balance water) by weight or volume of the solvent. For example, the amount of solvent in the hair styling/styling compositions herein may be about 50-90wt%, 60-90wt%, 70-90wt%, 80-90wt%, 50-95wt%, 60-95wt%, 70-95wt%, 80-95wt%, or 90-95wt%.
Examples of hair styling gel formulations herein may comprise about 90-95wt% (e.g., about 92 wt%) of a solvent (e.g., any of the herein), 0.3-1.0wt% (e.g., about 0.5 wt%) of a thickener (e.g., polyacrylic acid), 0.1-0.3wt% (e.g., about 0.2 wt%) of a chelating agent (e.g., EDTA) (optional), 0.2-1.0wt% (e.g., about 0.5 wt%) of a humectant (e.g., glycerin), 0.01-0.05wt% (e.g., about 0.02 wt%) of a UV blocker (e.g., benzophenone-4) (optional), 0.05-0.3wt% (e.g., about 0.1 wt%) of a preservative (e.g., diazo alkyl urea) (optional), 0.5-1.2wt% (e.g., about 0.8 wt%) of an emulsifier (e.g., oleyl alcohol polyether-20), 0.1-0.3wt% (e.g., about 0.2 wt%) of an aromatic/fragrance (e.g., about 0.2 wt%), 0.2-1.5 wt% (e.g., about 0.5 wt%) of a methyl alcohol (e.g., about 7 wt%) of a stabilizing compound as a hair setting compound, and/or a stabilizing derivative thereof.
Examples of hair styling gel formulations herein may comprise about 0.2-1.0wt% (e.g., about 0.5 wt%) of a pH stabilizing compound (e.g., aminomethylpropanol), 0.1-0.3wt% (e.g., about 0.2 wt%) of a fragrance/perfume (optional), 0.05-0.12wt% (e.g., about 0.08 wt%) of a surfactant (e.g., an ethoxylated polydimethylsiloxane polyol), 0.05-0.12wt% (e.g., about 0.08 wt%) of a conditioning agent (e.g., cyclomethicone) (optional), 0.05-0.3wt% (e.g., about 0.2 wt%) of a preservative (e.g., sodium benzoate) (optional), 15-20wt% (e.g., about 17 wt%) of water, 30-40wt% (e.g., about 65 wt%) of an alcohol (e.g., ethanol), 40-60wt% (e.g., about 45 wt%) of a propellant (e.g., dimethyl ether, or a mixture of dimethyl ether and C3-C5 alkane [ e.g., propane ] and isobutane ], and about 2-4wt% (e.g., 2 wt%) of a dextran as a fixing derivative.
Some aspects of the present disclosure relate to hair that has been treated with a hair care composition herein (e.g., a hair styling/styling composition, shampoo, or conditioner). For example, the hair may comprise dextran ester derivatives on its surface, such as in a film/coating of the hair, and/or adsorbed or otherwise deposited on the hair surface, and optionally, one or more other ingredients of the hair care compositions herein may also be present. Typically, hair as disclosed herein, such as hair having a coating comprising an alpha-glucan ester, does not exhibit macroscopic flaking (i.e., little or no noticeable flaking).
Various examples of personal care formulations comprising at least one dextran ester derivative as disclosed herein are disclosed in (1-3) below.
(1) A hair conditioner composition comprises cetyl alcohol (1-3%), isopropyl myristate (1-3%), and hydroxyethyl cellulose250HHR, 0.1-1%), dextran derivative (0.1-2%), potassium salt (0.1-0.5%),II preservative (0.5%, obtained from International Temp Co., ltd. (International Specialty Products)), and the balance being water.
(2) A hair shampoo composition comprises 5-20% Sodium Lauryl Ether Sulfate (SLES), 1-2% cocamidopropyl betaine, 1-2% sodium chloride, 0.1-2% dextran ester derivative, antiseptic (0.1-0.5%), and water for the rest.
(3) A skin emulsion composition comprises 1-5% glycerol, 1-5% glycol stearate, 1-5% stearic acid, 1-5% mineral oil, 0.5-1% acetylated lanolin98 0.1-0.5 Cetyl alcohol, 0.2-1% triethanolamine, 0.1-1wt%II preservative, 0.5-2wt% dextran ester derivative, and the balance being water.
The pharmaceutical products herein may be in the form of, for example, emulsions, liquids, elixirs, gels, suspensions, solutions, creams, or ointments. Furthermore, the pharmaceutical products herein may be in the form of any of the personal care products disclosed herein, such as antibacterial or antifungal compositions. The pharmaceutical product may further comprise one or more pharmaceutically acceptable carriers, diluents, and/or pharmaceutically acceptable salts. The compositions herein may also be used, for example, in capsules, tablets, tablet coatings, and as excipients for medicaments and pharmaceuticals.
Household and/or industrial products herein may be in the form of, for example, dry wall tape joint compounds, mortars, grouts, cementitious gypsum, spray gypsum, cementitious stucco, adhesives, pastes, wall/ceiling modifiers, binders and processing aids for tape casting, extrusion molding, injection molding and ceramics, spray adhesives and suspension/dispersion aids for pesticides, herbicides and fertilizers, fabric care products such as fabric softeners and laundry detergents, hard surface cleaners, air fresheners, polymer emulsions, latexes, gels such as water based gels, surfactant solutions, coatings such as water based coatings, protective coatings, adhesives, sealants and caulks, inks such as water based inks, metal working fluids, films or coatings, or emulsion based metal cleaning fluids for electroplating, phosphating, galvanization and/or general metal cleaning operations. In some aspects, the compositions herein are included in fluids as viscosity modifiers and/or drag reducers, such uses including, for example, downhole operations/fluids (e.g., hydraulic fracturing and enhanced oil recovery).
Some aspects herein relate to (i) a brine, such as seawater, or (ii) an aqueous solution having one or a combination of about 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 2.5-4.0, 2.75-4.0, 3.0-4.0, 2.5-3.5, 2.75-3.5, 3.0-4.0, or 3.0-3.5wt% salt (e.g., including at least NaCl), having at least one water-soluble dextran ester derivative as disclosed herein. The concentration of dextran ester derivative in such water of (i) or (ii) may be, for example, about, at least about, or less than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 0.1-0.6, 0.1-0.5, 0.1-0.4, 0.1-0.3, or 0.1-0.2wt%. Despite the relatively high salt concentration in such aqueous compositions, it is contemplated that in some aspects the dextran ester derivative may remain fully or mostly in solution and provide viscosity. Such a solution of (i) or (ii) as adjusted by viscosity of the dextran ester derivative herein may be in a system (e.g., any system herein, such as a downhole operation) in which such a solution is used at the time of its use.
Examples of ingestible products herein include foods, beverages, animal feeds, animal health and/or nutrition products, and/or pharmaceutical products. The intended use of the composition as disclosed herein in an ingestible product may be, for example, to provide texture, to increase bulk, and/or to thicken.
Additional examples of the use of the compositions of the present disclosure for ingestible products include use as bulking, binding, and/or coating ingredients, carriers for coloring agents, flavoring/perfuming agents, and/or high intensity sweeteners, spray drying adjuvants, bulking, thickening, dispersing, and/or emulsifying agents, and ingredients for promoting moisture retention (humectants). Illustrative examples of products that may be prepared with the compositions herein include food products, beverage products, pharmaceutical products, nutritional products, and sports products. Examples of beverage products herein include concentrated beverage mixes, carbonated beverages, non-carbonated beverages, fruit flavored beverages, fruit juices, teas, coffee, nectar, powdered beverages, liquid concentrates, dairy beverages, ready-to-drink (RTD) products, smoothies, alcoholic beverages, flavored waters, and combinations thereof. Examples of food products herein include baked goods (e.g., bread), confectionary, frozen dairy products, meats, artificial/synthetic/cultured meats, cereal products (e.g., breakfast cereals), dairy products (e.g., yogurt), condiments (e.g., mustard, tomato catchup, mayonnaise), snack bars, soups, sauces, mixes, prepared foods, infant foods, dietary preparations, peanut butter, syrups, sweeteners, food coatings, pet foods, animal feeds, animal health and nutrition products, dried fruits, sauces, gravies, jams/jellies, dessert products, spreads, batter, breadcrumbs, seasoning mixes, frostings, and the like. In some aspects, the compositions herein may provide or enhance foaming of beverages such as milk beverages, non-dairy alternative beverages (e.g., "vegetarian" milk such as soy milk, almond milk, or coconut milk), dairy creamers (DAIRY CREAMER), and/or non-dairy creamers (e.g., for hot beverages such as coffee [ e.g., cappuccino) ], tea [ e.g., chai teas) ].
The compositions comprising dextran ester derivatives herein may be included in personal care products, pharmaceutical products, household products, industrial products, or ingestible products (e.g., food products), for example, in amounts that provide the desired thickening and/or dispersibility. Examples of the concentration or amount of the disclosed compositions in the product are any of the weight percentages provided herein.
In some aspects, the composition comprising at least one dextran ester derivative herein may be in the form of or comprise a fabric care composition. For example, the fabric care composition may be used for hand washing, machine washing, and/or other purposes, such as soaking and/or pretreatment of fabrics. The fabric care composition may take the form of, for example, a laundry detergent, a fabric conditioner, any product added during washing, rinsing or drying, a unit dose or spray. The fabric care composition in liquid form may be in the form of an aqueous composition. In other embodiments, the fabric care composition may be in a dry form, such as a granular detergent or dryer added fabric softener sheet. Other non-limiting examples of fabric care compositions may include general purpose or heavy duty detergents in particulate or powder form, general purpose or heavy duty detergents in liquid, gel or paste form, liquid or dry fine fabric (e.g., delicate laundry) detergents, cleaning aids such as bleach additives, "soil release sticks" or pretreatments, substrate-containing products such as dry and wet wipes, pads or sponges, sprays and mists, water soluble unit dose articles. As further examples, the compositions herein may be in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granule, tablet, capsule, bead or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment pouch, or multi-compartment pouch.
The detergent compositions herein may be in any useful form, such as powders, granules, pastes, bars, unit doses, or liquids. The liquid detergent may be aqueous, typically comprising up to about 70wt% water and 0wt% to about 30wt% organic solvent. The liquid detergent may also be in the form of a compact gel type containing only about 30wt% water.
The detergent composition (e.g., a composition of a fabric care product or any other product herein) typically comprises one or more surfactants, wherein the surfactants are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, semi-polar nonionic surfactants, and mixtures thereof. In some embodiments, the surfactant is present at a level of from about 0.1% to about 60%, and in alternative embodiments, from about 1% to about 50%, and in still further embodiments, from about 5% to about 40%, by weight of the detergent composition. Typically, the detergent will contain from 0wt% to about 50wt% of an anionic surfactant such AS Linear Alkylbenzene Sulfonate (LAS), alpha Olefin Sulfonate (AOS), alkyl sulfate (fatty Alcohol Sulfate) (AS), alcohol ethoxy sulfate (AEOS or AES), secondary Alkane Sulfonate (SAS), alpha-sulfo fatty acid methyl ester, alkyl-or alkenyl succinic acid or soap. Additionally, the detergent composition may optionally contain from 0wt% to about 40wt% of a nonionic surfactant, such as an alcohol ethoxylate (AEO or AE), carboxylated alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, or polyhydroxy alkyl fatty acid amide (as described, for example, in WO 92/06154, which is incorporated herein by reference).
The detergent compositions herein may optionally comprise one or more detergent builders or builder systems. In some aspects, oxidized alpha-1, 3-glucan may be included as a co-builder, and the oxidized alpha-1, 3-glucan compounds used herein are disclosed in U.S. patent application publication No. 2015/0259439. In some aspects incorporating at least one builder, the cleaning composition comprises at least about 1%, from about 3% to about 60%, or even from about 5% to about 40% builder by weight of the composition. Examples of builders include alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicate, alkaline earth metal and alkali metal carbonate, aluminosilicate, polycarboxylic acid compounds, ether hydroxy polycarboxylic acid esters, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, and carboxymethyl oxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acid, such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, along with polycarboxylic acids (polycarboxylate) such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid (oxydisuccinic acid), polymaleic acid, benzene 1,3, 5-tricarboxylic acid, carboxymethyl oxysuccinic acid, and soluble salts thereof. Additional examples of detergent builders or complexing agents include zeolites, bisphosphates, triphosphates, phosphonates, citrates, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTMPA), alkyl or alkenyl succinic acids, soluble silicates or layered cinnamates (e.g., SKS-6 from Helrst company (Hoechst)).
In some embodiments, the builder forms water-soluble hard ion complexes (e.g., chelating builders), such as citrates and polyphosphates (e.g., sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixed sodium tripolyphosphate and potassium tripolyphosphate, etc.). It is contemplated that any suitable builder will be useful in the present disclosure, including those known in the art (see, e.g., EP 2100949).
In some embodiments, suitable builders may include phosphate builders and non-phosphate builders. In some embodiments, the builder is a phosphate builder. In some embodiments, the builder is a non-phosphate builder. The builder may be used at a level of from 0.1% to 80%, or from 5% to 60%, or from 10% to 50% by weight of the composition. In some embodiments, the product comprises a mixture of phosphate and non-phosphate builder. Suitable phosphate builders include the mono-, di-, tri-or oligomeric polyphosphates, including alkali metal salts, including sodium salts, of these compounds. In some embodiments, the builder may be Sodium Tripolyphosphate (STPP). In addition, the composition may comprise carbonates and/or citrates, preferably citrates, which help to achieve neutral pH compositions. Other suitable non-phosphate builders include homopolymers and copolymers of polycarboxylic acids and partially or fully neutralized salts thereof, monomeric polycarboxylic acids and hydroxycarboxylic acids and salts thereof. In some embodiments, salts of the above compounds include ammonium and/or alkali metal salts, i.e., lithium, sodium and potassium salts, including sodium salts. Suitable polycarboxylic acids include acyclic, cycloaliphatic, heterocyclic and aromatic carboxylic acids, wherein in some embodiments they may contain at least two carboxyl groups, which are in each case separated from one another, in some cases by no more than two carbon atoms.
The detergent compositions herein may comprise at least one chelating agent. Suitable chelating agents include, but are not limited to, copper, iron, and/or manganese chelating agents and mixtures thereof. In embodiments where at least one chelating agent is used, the composition comprises from about 0.1% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the composition.
The detergent compositions herein may comprise at least one deposition aid. Suitable deposition aids include, but are not limited to, polyethylene glycol, polypropylene glycol, polycarboxylates, soil release polymers (such as polyethylene terephthalate), clays such as kaolin, montmorillonite, attapulgite, illite, bentonite, halloysite, and mixtures thereof.
The detergent compositions herein may comprise one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles, or mixtures thereof. Additional dye transfer inhibitors include manganese phthalocyanine, peroxidase, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles, and/or mixtures thereof; chelating agents, examples of which include ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentamethylenephosphonic acid (DTPMP), hydroxyethanediphosphonic acid (HEDP), ethylenediamine N, N' -disuccinic acid (EDDS), methylglycine diacetic acid (MGDA), diethylenetriamine pentaacetic acid (DTPA), propylenediamine tetraacetic acid (PDT A), 2-hydroxypyridine-N-oxide (HPNO), or methylglycine diacetic acid (MGDA), glutamic acid N, N-diacetic acid (N, N-dicarboxymethylglutamic acid tetrasodium salt (GLDA), nitrilotriacetic acid (NTA), 4, 5-dihydroxyisophthalic acid, citric acid and any of its salts, N-hydroxyethylethylenediamine triacetic acid (HEDTA), triethylenetetramine hexaacetic acid (TTHA), N-hydroxyethylethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediamine tetrapropionic acid (EDTP) and derivatives thereof, alone or in combination with any of the foregoing, in embodiments employing at least one dye transfer inhibitor, may comprise from about 0.0001% to about 0.01% by weight of the compositions herein, or even from about 0.1% to about 3% of the at least one dye transfer inhibiting agent.
The detergent compositions herein may comprise silicate salts. In some of these embodiments, sodium silicate (e.g., sodium disilicate, sodium metasilicate, and/or crystalline phyllosilicates) may be used. In some embodiments, the silicate is present at a level from about 1% to about 20% by weight of the composition. In some embodiments, silicate is present at a level of from about 5% to about 15% by weight of the composition.
The detergent compositions herein may comprise a dispersant. Suitable water-soluble organic materials include, but are not limited to, homo-or co-polymeric acids or salts thereof, wherein the polyacid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms.
The detergent compositions herein may additionally comprise, for example, one or more enzymes as disclosed hereinabove. In some aspects, the detergent composition may comprise one or more enzymes, each at a level of from about 0.00001% to about 10% by weight of the composition, and the balance of cleaning adjunct materials by weight of the composition. In some other aspects, the detergent composition may further comprise each enzyme at a level of from about 0.0001% to about 10%, from about 0.001% to about 5%, from about 0.001% to about 2%, or from about 0.005% to about 0.5% by weight of the composition. Enzymes contained in the detergent compositions herein may be stabilized using conventional stabilizers, for example, polyols such as propylene glycol or glycerol, sugars or sugar alcohols, lactic acid, boric acid or boric acid derivatives (e.g., aromatic borates).
In some aspects, the detergent composition may comprise one or more other types of polymers in addition to the dextran ester derivative as disclosed herein. Examples of other types of polymers useful herein include carboxymethyl cellulose (CMC), dextran, poly (vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly (vinyl alcohol) (PVA), polycarboxylic acid esters such as polyacrylates, maleic/acrylic acid copolymers, and lauryl methacrylate/acrylic acid copolymers.
The detergent compositions herein may contain a bleach system. For example, the bleaching system may comprise a source of H2O2 such as perboric acid or percarbonic acid, which may be combined with a peracid-forming bleach activator such as tetraacetylethylene diamine (TAED) or nonanoyloxybenzene sulfonate (NOBS). Alternatively, the bleaching system may comprise a peroxyacid (e.g., an amide, imide, or sulfone type peroxyacid). Still alternatively, the bleaching system may be an enzymatic bleaching system comprising a perhydrolase enzyme, such as for example the system described in WO 2005/056783.
The detergent compositions herein may also contain conventional detergent ingredients such as fabric conditioning agents, clays, suds boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, color-changing inhibitors, optical brighteners or perfumes. The pH of the detergent compositions herein (measured in use of a concentrated aqueous solution) is generally neutral or alkaline (e.g., pH from about 7.0 to about 11.0).
Examples of suitable anti-redeposition agents and/or clay soil removal agents for use in fabric care products herein include polyethoxy zwitterionic surfactants, water-soluble copolymers of acrylic or methacrylic acid and acrylic or methacrylic acid-ethylene oxide condensates (e.g., U.S. patent No. 3719647), cellulose derivatives such as carboxymethyl cellulose and hydroxypropyl cellulose (e.g., U.S. patent nos. 3597416 and 3523088), and mixtures comprising nonionic alkyl polyethoxy surfactants, polyethoxy alkyl quaternary cationic surfactants, and fatty amide surfactants (e.g., U.S. patent No. 4228044). Non-limiting examples of other suitable anti-redeposition agents and clay soil removal agents are disclosed in U.S. patent nos. 4597898 and 4891160 and international patent application publication No. WO 95/32272, which are incorporated herein by reference in their entirety.
Particular forms of detergent compositions which may be suitable for the purposes herein are disclosed, for example, in US 20090209445 A1、US 20100081598 A1、US 7001878 B2、EP 1504994 B1、WO 2001085888 A2、WO 2003089562 A1、WO 2009098659 A1、WO 2009098660A1、WO 2009112992 A1、WO 2009124160 A1、WO 2009152031A1、WO 2010059483 A1、WO 2010088112 A1、WO 2010090915A1、WO 2010135238 A1、WO 2011094687 A1、WO 2011094690A1、WO 2011127102A1、WO 2011163428A1、WO 2008000567A1、WO 2006045391 A1、WO 2006007911 A1、WO 2012027404A1、EP 1740690 B1、WO 2012059336 A1、US 6730646 B1、WO 2008087426A1、WO 2010116139A1、 and WO 2012104613A1, which are incorporated herein by reference in their entirety.
The laundry detergent compositions herein may optionally be heavy duty (general purpose) laundry detergent compositions. Exemplary heavy duty laundry detergent compositions comprise a cleaning surfactant (10% -40% wt/wt) comprising an anionic cleaning surfactant (selected from the group consisting of linear or branched or random chain, substituted or unsubstituted alkyl sulphates, alkyl sulphonates, alkyl alkoxylated sulphates, alkyl phosphates, alkyl phosphonates, alkyl carboxylates and/or mixtures thereof) and optionally a nonionic surfactant (selected from the group consisting of linear or branched or random chain, substituted or unsubstituted alkyl alkoxylated alcohols, e.g. C8-C18 alkyl ethoxylated alcohols and/or C6-C12 alkylphenol alkoxylates), wherein the weight ratio of anionic cleaning surfactant (having a hydrophilicity index (HIc) from 6.0 to 9) to nonionic cleaning surfactant is greater than 1:1. Suitable detersive surfactants also include cationic detersive surfactants (selected from the group consisting of alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and/or mixtures thereof), zwitterionic and/or amphoteric detersive surfactants (selected from the group consisting of alkanolamine sulfobetaines), amphoteric surfactants, semi-polar nonionic surfactants, and mixtures thereof.
The detergents herein, such as heavy duty laundry detergent compositions, may optionally comprise a surface-active enhancing polymer consisting of an amphiphilic alkoxylated grease cleaning polymer selected from the group consisting of alkoxylated polymers having branched hydrophilic and hydrophobic character, such as alkoxylated polyalkyleneimines (in the range of 0.05wt% to 10 wt%) and/or random graft polymers (typically comprising a hydrophilic backbone containing monomers selected from the group consisting of unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyols (such as glycerol) and mixtures thereof), and one or more hydrophobic side chains selected from the group consisting of C4-C25 alkyl groups, polypropylene, polybutenes, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acids and mixtures thereof.
The detergents herein, such as heavy duty laundry detergent compositions, may optionally include additional polymers, such as soil release polymers (including anionically end capped polyesters (e.g., SRP 1), polymers in random or block configuration comprising at least one monomer unit selected from the group consisting of sugars, dicarboxylic acids, polyols, and combinations thereof, ethylene glycol terephthalate-based polymers in random or block configuration and copolymers thereof, such as REPEL-O-TEX SF, SF-2, and SRP6, TEXCARE SRA, SRA300, SRN100, SRN170, SRN240, SRN300, and SRN325, MARLOQUEST SL), one or more anti-redeposition agents herein (0.1 wt% to 10 wt%) including carboxylate polymers, such as polymers comprising at least one monomer selected from the group consisting of acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and any mixtures thereof, vinylpyrrolidone homopolymers, and/or polyethylene glycol, molecular weights ranging from random to 100,000, and polymeric acrylate esters such as maleic acid esters/da copolymers.
The detergents herein, such as heavy duty laundry detergent compositions, may optionally further comprise saturated or unsaturated fatty acids, preferably saturated or unsaturated C12-C24 fatty acids (0 wt% to 10 wt%), deposition aids (examples of which include polysaccharides, cellulosic polymers, polydimethyl ammonium halides (DADMACs), and copolymers of DAD MAC with vinylpyrrolidone, acrylamide, imidazole, imidazoline halides, and mixtures thereof (in random or block configurations), cationic guar, cationic starch, cationic polyacrylamide, and mixtures thereof.
The detergents herein, such as heavy duty laundry detergent compositions, may optionally further comprise at least one dye transfer inhibitor, examples of which are described above.
The detergents herein, such as heavy-duty laundry detergent compositions, may optionally include a silicone or fatty acid based suds suppressor, hueing dye, calcium and magnesium cations, visual signal transduction ingredient, suds suppressor (0.001 wt% to about 4.0 wt%), and/or structurant/thickener (0.01 wt% to 5 wt%) selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, ultrafine cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof. The structuring agent (structurant) may also be referred to as structuring agent (structural agent).
For example, the detergents herein may be in the form of heavy duty dry/solid laundry detergent compositions. Such detergents may include (i) cleaning surfactants such as any of the anionic cleaning surfactants disclosed herein, any of the nonionic cleaning surfactants disclosed herein, any of the cationic cleaning surfactants disclosed herein, any of the zwitterionic and/or amphoteric cleaning surfactants disclosed herein, any of the amphoteric surfactants, any of the semi-polar nonionic surfactants, and mixtures thereof; (ii) builders such as any phosphate-free builder (e.g. zeolite builder in the range 0wt% to less than 10wt%, sodium tripolyphosphate in the range 0wt% to less than 10wt%, citric acid, citrate and nitrilotriacetic acid, any silicate (e.g. sodium or potassium silicate or sodium metasilicate in the range 0wt% to less than 10 wt%); any carbonate (e.g., sodium carbonate and/or sodium bicarbonate in the range of 0wt% to less than 80 wt%) and mixtures thereof, (iii) bleaching agents such as any photobleach (e.g., sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dyes and mixtures thereof), any hydrophobic or hydrophilic bleach activator (e.g., dodecyloxybenzene sulfonate, decanoyloxy benzene sulfonate, decanoyloxy benzoic acid or salts thereof, 3, 5-trimethylhexanoyloxy benzene sulfonate, tetraacetylethylenediamine-TAED, nonyloxy benzene sulfonate-NOBS, nitrile quaternary ammonium salts and mixtures thereof), any hydrogen peroxide (e.g., inorganic peroxyhydrate salts, examples of which include perborates, percarbonates, quaternary ammonium salts and mixtures thereof), the mono-or tetrahydrated sodium salt of a persulfate, perphosphate or persilicate), any preformed hydrophilic and/or hydrophobic peracids (e.g., percarboxylic acids and salts, percarbonic acids and salts, periodic acids and salts, peroxymonosulphuric acids and salts, and mixtures thereof), and/or (iv) any other components such as bleach catalysts (e.g., imine bleach promoters, examples of which include iminium cations and polyanions, imine zwitterionic, modified amines, modified amine oxides, N-sulphonyl imines, N-phosphonoimines, N-acyl imines, thiadiazole dioxides, perfluorinated imines, cyclic sugar ketones, and mixtures thereof), and metal-containing bleach catalysts (e.g., copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, as well as auxiliary metal cations (such as zinc or aluminum) and chelants (such as EDTA, ethylenediamine tetra (methylenephosphonic acid)).
The detergents herein, such as those used for fabric care (e.g., laundry), may be contained in, for example, a unit dose (e.g., a pouch or sachet). The unit dosage form may comprise a water-soluble outer film that completely encapsulates the liquid or solid detergent composition. A unit dose may comprise a single compartment, or at least two, three, or more (multiple) compartments. The plurality of compartments may be arranged in a stacked orientation or in a side-by-side orientation. The unit dose herein is typically a closed structure of any form/shape suitable for containing and protecting its contents without allowing the contents to be released prior to contact with water.
In some aspects, the composition comprising at least one dextran ester derivative herein may be in the form of a fabric softener or comprise a fabric softener (liquid fabric softener). Examples of such compositions are rinsing agents typically used in washing fabric-containing materials herein after cleaning the fabric-containing materials with a laundry detergent composition (e.g., laundry rinse agents, such as are used in the laundry rinse cycle in a washing machine). The concentration of dextran ester derivative in the composition (e.g., rinse agent) comprising the fabric softener may be, for example, about or at least about 20, 30, 40, 50, 60, 70, 80, 20-70, 20-60, 30-80, 30-70, 30-60, 40-80, 40-70, or 40-60ppm. The concentration of fabric softener in the composition (e.g., rinse agent) can be, for example, about or at least about 50、75、100、150、200、300、400、500、600、50-600、50-500、50-400、50-300、50-200、100-600、100-500、100-400、100-300、100-200、10-600、50-500、50-400、50-300、50-200、200-600、200-500、200-400、 or 200-300ppm. The fabric softener concentration may be based on the total fabric softener composition added (not necessarily based on separate fabric softener components), or on one or more fabric softeners in the fabric softener formulation. The fabric softener herein may further comprise, for example, one or more of a fabric softener (e.g., diethyl dimethyl ammonium chloride), an antistatic agent, a perfume, a wetting agent, a viscosity modifier (e.g., calcium chloride), a pH buffer/buffering agent (e.g., formic acid), an antimicrobial agent, an antioxidant, a radical scavenger (e.g., ammonium chloride), a chelating agent/builder (e.g., diethylenetriamine pentaacetate), an antifoaming agent/lubricant (e.g., polydimethylsiloxane), a preservative (e.g., benzisothiazolinone), and a colorant. In some aspects, the fabric softener may further comprise one or more of a fabric softener, a viscosity modifier, a pH buffer/buffering agent, a free radical scavenger, a chelating agent/builder, and an antifoaming agent/lubricant. The fabric softener may be perfume-free and/or dye-free, or in some aspects have less than about 0.1wt% perfume and/or dye. In some aspects, fabric softeners that may be suitable for use herein may be as disclosed in any of U.S. patent application publication nos. 2014/0366282, 2001/0018410, 2006/0058214, 2021/0317384, or 2006/0014655, or international patent application publication nos. WO 2007/078782、WO 1998/016538、WO 1998/012293、WO 1998007920、WO 2000/070004、WO 2009/146981、WO 2000/70005、 or WO 2013087366, which are incorporated herein by reference. Some brands of fabric softeners that may be suitable for use herein include DOWNY, DOWNY ULTRA, DOWNY INFUSIONS, ALL, SNUGGLE, LENOR and GAIN, if desired. In some aspects, liquid fabric softener products (e.g., as present prior to use in a laundry rinse cycle) can be formulated to include one or more dextran ester derivatives. In some aspects, the fabric softener may be in unit dosage, such as disclosed herein for detergents.
The compositions disclosed herein comprising at least one dextran ester derivative may be, for example, in the form of or comprise a dishwashing detergent composition. Examples of dish detergents include automatic dish detergents (typically used in dish washing machines) and hand dish detergents. The dishwashing detergent composition can, for example, be in any dry or liquid/aqueous form as disclosed herein. Components that may be included in some aspects of the dishwashing detergent composition include, for example, one or more of phosphate salts, oxygen or chlorine-based bleaches, nonionic surfactants, basic salts (e.g., metasilicate, alkali metal hydroxide, sodium carbonate), any of the active enzymes disclosed herein, corrosion inhibitors (e.g., sodium silicate), defoamers, additives that slow the removal of glaze and pattern from ceramics, perfumes, anti-caking agents (in granular detergents), starches (in tablet-based detergents), gelling agents (in liquid/gel-based detergents), and/or sand (powdered detergents).
A dishwashing detergent such as an automatic dishwasher detergent or a liquid dishwashing detergent may comprise (i) a nonionic surfactant comprising any ethoxylated nonionic surfactant, alcohol alkoxylated surfactant, epoxy-capped poly (oxyalkylated) alcohol, or amine oxide surfactant present in an amount from 0 to 10 wt.%, (ii) a builder in the range of about 5-60 wt.%, comprising any phosphate builder (e.g., mono-, di-, tri-, other oligomeric polyphosphates, sodium tripolyphosphate-STPP), any phosphate-free builder (e.g., amino acid-based compounds including methyl-glycine-diacetic acid [ MGDA ] and salts or derivatives thereof, Glutamic acid-N, N-diacetic acid [ GLDA ] and salts or derivatives thereof, iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxymethylinulin and salts or derivatives thereof, nitrilotriacetic acid [ NTA ], diethylenetriamine pentaacetic acid [ DTPA ], B-alanine diacetic acid [ B-ADA ] and salts thereof, homo-and copolymers of polycarboxylic acids and partially or fully neutralized salts thereof, monomeric polycarboxylic acids and hydroxycarboxylic acids and salts thereof in the range of 0.5 to 50% by weight, or sulphonated/carboxylated polymers in the range of about 0.1 to about 50% by weight, and (iii) drying assistants in the range of about 0.1 to about 10% by weight (e.g. polyesters, especially anionic polyesters (optionally with 3 to 6 functional groups-typically acids-which facilitate polycondensation), Together with further monomers of alcohol or ester function), polycarbonate-, polyurethane-and/or polyurea-polyorganosiloxane compounds or precursor compounds thereof, in particular of the reactive cyclic carbonate and urea type, (iv) silicates in the range from about 1% to about 20% by weight (for example sodium silicate or potassium silicate, such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates), (v) inorganic bleaching agents (for example peroxo hydrate salts such as perborates, percarbonates, perphosphates, persulfates and persilicates) and/or organic bleaching agents (for example organic peroxo acids such as diacyl-and tetraacyl peroxides, in particular diperoxodecanedioic acid, Diperoxydecanedioic acid and diperoxydischiadic acid), (vi) a bleach activator (e.g., organic peracid precursors in the range of from about 0.1 wt.% to about 10 wt.%) and/or a bleach catalyst (e.g., manganese triazacyclononane and related complexes, co, cu, mn, and Fe bipyridyl amines and related complexes, and cobalt (III) pentaamine acetate and related complexes), (vii) a metal care agent (e.g., benzotriazoles, metal salts and complexes, and/or silicates) in the range of from about 0.1 wt.% to 5 wt.%, and (viii) a glass corrosion inhibitor (e.g., magnesium, salts and/or complexes of zinc, or bismuth), and/or (ix) any of the active enzymes disclosed herein (ranging from about 0.01 to 5.0mg active enzyme per gram of automatic dishwashing detergent composition) and enzyme stabilizer components (e.g., oligosaccharides, polysaccharides, and inorganic divalent metal salts). In some aspects, the dishwashing detergent ingredient or the entire composition (but correspondingly adapted to include the dextran ester derivative herein) may be as disclosed in U.S. patent No. 8575083 or 9796951, or U.S. patent application publication No. 2017/0044468, each of which is incorporated herein by reference.
The detergents herein, such as those used for dishwashing, may be contained, for example, in unit doses (e.g., pouches or sachets) (e.g., water-soluble unit dose articles), and may be as described above for fabric care detergents, but comprise suitable dishwashing detergent compositions.
It is believed that many commercially available detergent formulations may be suitable for inclusion of dextran ester derivatives as disclosed herein. Examples of commercially available detergent formulations includeULTRAPACKS (Hangao (Henkel)),QUANTUM (Lijieshi (Reckitt Benckiser)), CLOROXTM 2PACKS (Colorox (C1 orox))) OXICLEAN MAX FORCE POWER PAKS (Church & Dlight), duwei company of cut,STAIN RELEASE、ACTIONPACS, and also a method for producing the samePODSTM (Procter & Gamble).
The compositions disclosed herein comprising at least one dextran ester derivative may be, for example, in the form of or comprise an oral care composition. Examples of oral care compositions include dentifrices, toothpastes, mouthwashes, mouth rinses, chewing gums, and edible strips (ediblestrips) that provide some form of oral care (e.g., treating or preventing cavities [ caries ], gingivitis, plaque, tartar, and/or periodontal disease). The oral care composition can also be used to treat "oral surfaces," which encompass any soft or hard surface within the oral cavity, including surfaces of the tongue, hard and soft palate, buccal mucosa, gums, and tooth surfaces. "tooth surface" herein is the surface of a natural tooth or the hard surface of an artificial dentition (including, for example, crowns, caps, fillings, bridges, dentures or dental implants).
The oral care compositions herein may comprise, for example, about 0.01-15.0wt% (e.g., -0.1-10 wt% or-0.1-5.0 wt%, -0.1-2.0 wt%) dextran ester derivatives as disclosed herein. Dextran ester derivatives included in oral care compositions can sometimes be provided therein as thickening and/or dispersing agents that can be used to impart a desired consistency and/or mouthfeel to the composition. One or more other thickening or dispersing agents may also be provided in the oral care compositions herein, such as, for example, carboxyvinyl polymers, carrageenan (e.g., L-carrageenan), natural gums (e.g., karaya gum (karaya), xanthan gum, acacia gum, tragacanth), colloidal magnesium aluminum silicate, or colloidal silica.
The oral care composition herein may be, for example, a toothpaste or other dentifrice. Such compositions, as well as any other oral care compositions herein, may additionally comprise, but are not limited to, one or more anticaries agents, antimicrobial or antibacterial agents, anticalculus or tartar control agents, surfactants, abrasives, pH adjusters, foam adjusters, humectants, flavorants, sweeteners, pigments/colorants, whitening agents, and/or other suitable components. Examples of oral care compositions to which dextran ester derivatives herein may be added are disclosed in U.S. patent application publication nos. 2006/01334025, 2002/0022006, and 2008/0057007, which are incorporated herein by reference.
Anticaries agents herein may be orally acceptable fluoride ion sources. Suitable sources of fluoride ions include, for example, fluorides, monofluorophosphates and fluorosilicates, and amine fluorides, including olafluoro (N '-octadecyltrimethylene diamine-N, N' -tris (2-ethanol) -dihydrofluoride). For example, anticaries agents may be present in an amount that provides the composition with a total of about 100-20000ppm, about 200-5000ppm, or about 500-2500ppm fluoride ions. In oral care compositions where sodium fluoride is the sole source of fluoride ion, for example, an amount of about 0.01 to 5.0wt%, about 0.05 to 1.0wt%, or about 0.1 to 0.5wt% sodium fluoride may be present in the composition.
Antimicrobial or antibacterial agents suitable for use in the oral care compositions herein include, for example, phenolic compounds (e.g., 4-allylcatechol; parabens such as benzyl parahydroxybenzoate, butyl parahydroxybenzoate, ethyl parahydroxybenzoate, methyl parahydroxybenzoate and propyl parahydroxybenzoate, 2-benzyl phenol, butylated hydroxyanisole, butylated hydroxytoluene, capsaicin, carvacrol, pyrogallol, eugenol, guaiacol, halobisphenols such as hexachlorophene (hexachlorophene) and bromochlorophenol (bromochlorophene), 4-hexylresorcinol, 8-hydroxyquinoline and its salts, salicylates such as menthyl salicylate, methyl salicylate and phenyl salicylate, phenol, pyrocatechol, N-salicylanilide, thymol, halodiphenyl ether compounds such as triclosan and triclosan monophosphate), copper (II) compounds (e.g., copper (II) chloride, fluoride, sulfate and hydroxide), zinc ion sources (e.g., zinc acetate, citrate, gluconate, glycine salt, oxide and sulfate), phthalic acid and its salts (e.g., magnesium monopotassium phthalate), octenidine, oxonium chloride, chlorhexidine (e.g., cetyl chloride, chlorhexidine, 4-N-acetyl chloride, chlorhexidine chloride, etc.), delmopinol, cinepazide), magnolia extract, grape seed extract, rosemary extract, menthol, geraniol, citral, eucalyptol, antibiotics (e.g., wo Gemeng th, amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin, clindamycin), and/or any antibacterial agents disclosed in U.S. patent No. 5776435 (incorporated herein by reference). The one or more antimicrobial agents can optionally be present at about 0.01 to 10wt% (e.g., 0.1 to 3 wt%), such as in the disclosed oral care compositions.
Anticalculus or tartar control agents suitable for use in the oral care compositions herein include, for example, phosphates and polyphosphates (e.g., pyrophosphates), polyaminopropane sulfonic Acid (AMPS), zinc citrate trihydrate, polypeptides (e.g., polyaspartic acid and polyglutamic acid), polyolefin sulfonates, polyolefin phosphates, bisphosphonates (e.g., azacycloalkane-2, 2-bisphosphonates, such as azacycloheptane-2, 2-bisphosphonic acid), N-methylazacyclopentane-2, 3-bisphosphonic acid, ethane-1-hydroxy-1, 1-bisphosphonic acid (EHDP), ethane-1-amino-1, 1-bisphosphonates, and/or phosphonoalkanoic acids and salts thereof (e.g., alkali metal and ammonium salts thereof). Useful inorganic phosphates and polyphosphates include, for example, mono-, di-and tri-sodium phosphates, sodium tripolyphosphate, tetrapolyphosphate, mono-, di-, tri-and tetra-sodium pyrophosphates, disodium dihydrogen pyrophosphate, sodium trimetaphosphate, sodium hexametaphosphate, or any of these replaced by potassium or ammonium. In certain embodiments, other useful anticalculus agents include anionic polycarboxylate polymers (e.g., polymers or copolymers of acrylic acid, methacrylic acid, and maleic anhydride, such as polyvinylmethylether/maleic anhydride copolymers). Other useful anticalculus agents include chelating agents such as hydroxycarboxylic acids (e.g., citric acid, fumaric acid, malic acid, glutaric acid, and oxalic acid and salts thereof) and aminopolycarboxylic acids (e.g., EDTA). One or more anticalculus or tartar control agents may optionally be present at about 0.01 to 50wt% (e.g., about 0.05 to 25wt% or about 0.1 to 15 wt%), e.g., in the disclosed oral care compositions.
Surfactants suitable for use in the oral care compositions herein may be, for example, anionic, nonionic or amphoteric. Suitable anionic surfactants include, but are not limited to, water soluble salts of C8-20 alkyl sulfates, C8-20 fatty acid sulfonated monoglycerides, sarcosinates, and taurates. Examples of the anionic surfactant include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl hydroxyethyl sulfonate, sodium polyethylene glycol monolauryl ether carboxylate, and sodium dodecylbenzene sulfonate. Suitable nonionic surfactants include, but are not limited to, poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides. Suitable amphoteric surfactants include, but are not limited to, derivatives of C8-20 aliphatic secondary and tertiary amines having an anionic group such as carboxylate, sulfate, sulfonate, phosphate, or phosphonate. An example of a suitable amphoteric surfactant is cocoamidopropyl betaine. The one or more surfactants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.01 to 10wt% (e.g., about 0.05 to 5.0wt% or about 0.1 to 2.0 wt%).
Abrasives suitable for use in the oral care compositions herein can include, for example, silica (e.g., silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate, and resinous abrasives (e.g., urea-formaldehyde condensate products). Examples of insoluble phosphates useful herein as abrasives are orthophosphates, polymetaphosphates and pyrophosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, beta-calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and insoluble sodium polymetaphosphate. The one or more abrasives are optionally present in the disclosed oral care compositions, for example, in a total amount of about 5-70wt% (e.g., about 10-56wt% or about 15-30 wt%). In certain embodiments, the average particle size of the abrasive is about 0.1 to 30 microns (e.g., about 1 to 20 microns or about 5 to 15 microns).
In certain embodiments, the oral care composition can comprise at least one pH adjuster. Such agents may be selected to acidify, make more basic, or buffer the pH of the composition to a pH range of about 2-10 (e.g., a pH range from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9). Examples of pH adjusters useful herein include, but are not limited to, carboxylic, phosphoric, and sulfonic acids, acidic salts (e.g., monosodium citrate, disodium citrate, monosodium malate), alkali metal hydroxides (e.g., sodium hydroxide, carbonates such as sodium carbonate, bicarbonate, sodium sesquicarbonate), borates, silicates, phosphates (e.g., monosodium phosphate, trisodium phosphate, pyrophosphate salts), and imidazoles.
Foam modulators suitable for use in the oral care compositions herein may be, for example, polyethylene glycol (PEG). High molecular weight PEG are suitable, including, for example, those having an average molecular weight of about 200000-7000000 (e.g., about 500000-5000000 or about 1000000-2500000). The one or more PEGs are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.1-10wt% (e.g., about 0.2-5.0wt% or about 0.25-2.0 wt%).
In certain embodiments, the oral care composition may comprise at least one humectant. In certain embodiments, the humectant may be a polyol, such as glycerin, sorbitol, xylitol, or low molecular weight PEG. Most suitable humectants can also be employed as sweeteners herein. The one or more humectants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 1.0 to 70wt% (e.g., about 1.0 to 50wt%, about 2 to 25wt%, or about 5 to 15 wt%).
Natural or artificial sweeteners may optionally be included in the oral care compositions herein. Examples of suitable sweeteners include dextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup (e.g., high fructose corn syrup or corn syrup solids), partially hydrolyzed starch, hydrogenated starch hydrolysates, sorbitol, mannitol, xylitol, maltitol, isomalt, aspartame, neotame, saccharin and salts thereof, dipeptide-based intense sweeteners and cyclamates. One or more sweeteners are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.005 to 5.0 wt%.
Natural or artificial flavorants may optionally be included in the oral care compositions herein. Examples of suitable flavorants include vanillin, sage, marjoram, parsley oil, spearmint oil, cinnamon oil, oil of wintergreen (methyl salicylate), peppermint oil of capsicum, clove oil, bay oil, fennel oil, eucalyptus oil, citrus oils, fruit oils, essences such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, or pineapple, flavors derived from beans and nuts such as coffee, cocoa, cola, peanut, or almond, and adsorbed and encapsulated flavorants. Also encompassed within the flavorants herein are ingredients that provide flavor and/or other sensory effects in the mouth, including cooling or warming effects. Such ingredients include, but are not limited to, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cinnamon, oxazolidinone (oxanone),Hydroxymethyl anethole, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthane-3-carboxamide, N,2, 3-trimethyl-2-isopropyl butanamide, 3- (1-menthoxy) -propane-1, 2-diol, cinnamaldehyde Glycerol Acetal (CGA) and Menthone Glycerol Acetal (MGA). One or more flavorants are optionally present in, for example, the disclosed oral care compositions in a total amount of about 0.01 to 5.0wt% (e.g., about 0.1 to 2.5 wt%).
In certain embodiments, the oral care composition can comprise at least one bicarbonate salt. Any orally acceptable bicarbonate can be used, including, for example, alkali metal bicarbonate salts such as sodium or potassium bicarbonate, and ammonium bicarbonate. For example, one or more bicarbonate salts are optionally present in the disclosed oral care compositions in a total amount of about 0.1-50wt% (e.g., about 1-20 wt%).
In certain embodiments, the oral care composition may comprise at least one whitening agent and/or colorant. Suitable whitening agents are peroxide compounds, such as any of those disclosed in U.S. patent No. 8540971, which is incorporated herein by reference. Suitable colorants herein include, for example, pigments, dyes, lakes, and agents that impart a particular luster or reflectivity, such as pearlizing agents. Specific examples of colorants useful herein include talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, aluminum magnesium silicate, silica, titanium dioxide, zinc oxide, red, yellow, brown, black iron oxide, ferric ammonium ferrocyanide, manganese violet, deep blue, titanium mica, and bismuth oxychloride. For example, one or more colorants are optionally present in the disclosed oral care compositions in a total amount of about 0.001 to 20wt% (e.g., about 0.01 to 10wt% or about 0.1 to 5.0 wt%).
Additional components that may optionally be included in the oral compositions herein include, for example, one or more enzymes (above), vitamins, and anti-binders. Examples of vitamins useful herein include vitamin C, vitamin E, vitamin B5, and folic acid. Examples of suitable anti-binders include methylparaben (solbro 1), ficin, and quorum sensing inhibitors.
Further examples of personal care, home care, and other products and ingredients herein may be any as disclosed in U.S. patent No. 8796196, incorporated herein by reference. Examples of personal care, home care, and other products and ingredients herein include perfumes, fragrances, insect repellents and pesticides, foaming agents such as surfactants, pet pesticides, pet shampoos, disinfectants, hard surface (e.g., floors, tub/shower, sink, toilet bowl, door handle/panel, glass/window, exterior or interior of car/automobile) treatments (e.g., cleaning, sanitizing, and/or coating agents), wipes and other nonwoven materials, colorants, preservatives, antioxidants, emulsifiers, emollients, oils, pharmaceuticals, flavors, and suspending agents.
The present disclosure also relates to methods of treating materials. The method comprises contacting the material with an aqueous composition comprising at least one dextran ester derivative disclosed herein.
In some aspects, the material contacted with the aqueous composition in the contact methods herein may comprise a fabric. The fabrics herein may comprise natural fibers, synthetic fibers, semisynthetic fibers, or any combinations thereof. The semisynthetic fibers herein are produced using naturally occurring materials that have been chemically derivatized, examples of which are rayon. Non-limiting examples of the types of fabrics herein include fabrics made from (i) cellulosic fibers such as cotton (e.g., suede, canvas, striped or lattice, chenille, printed cotton, corduroy, large cord, brocade, jean, flannel, striped cotton, jacquard, knit, maryland (matelass e), oxford, advanced dense cotton, poplin, pleat (pliss e), sateen, seersucker, transparent tissue, terry, twill, velvet), rayon (e.g., viscose, modal, lyocell), linen, and combinations thereof(Ii) Protein fibers such as silk, wool and related mammalian fibers, (iii) synthetic fibers such as polyester, acrylic, nylon, and the like, (iv) long plant fibers from jute, flax, ramie, coir, kapok, sisal, herceptin, abaca, hemp, and tamarix, and (v) any combination of fabrics of (i) - (iv). Fabrics comprising a combination of fiber types (e.g., natural and synthetic) include, for example, those having both cotton fibers and polyester. Materials/articles comprising one or more fabrics herein include, for example, garments, curtains, drapes, upholstery, carpets, bed fabrics, bathroom tissue, tablecloths, sleeping bags, tents, automotive interiors, and the like. Other materials include natural and/or synthetic fibers including, for example, nonwoven fabrics, liners, papers, and foams.
The aqueous composition that is contacted with the fabric may be, for example, a fabric care composition (e.g., laundry detergent, fabric softener). Thus, if the fabric care composition is used in a treatment process, the treatment process may be considered a fabric care process or a laundry process in certain embodiments. It is contemplated that the fabric care compositions herein may achieve one or more of the following fabric care benefits (i.e., surface substantive effects) of removing wrinkles, reducing fabric abrasion, resisting fabric abrasion, reducing fabric pilling, extending fabric life, maintaining fabric color, reducing fabric fading, reducing dye transfer, restoring fabric color, reducing fabric staining, releasing fabric soil, maintaining fabric shape, enhancing fabric smoothness, preventing redeposition of soil on fabric, preventing laundry graying, improving fabric hand/feel (handle) and/or reducing fabric shrinkage.
Examples of conditions (e.g., time, temperature, wash/rinse volume) for performing a fabric care or laundry process are disclosed herein in WO 1997/003161 and U.S. patent nos. 4794661, 4580421 and 5945394, which are incorporated herein by reference. In other examples, a material comprising a fabric may be contacted with an aqueous composition herein for (i) a "cold" temperature of about 15 ℃ to 30 ℃ for laundry washing or rinsing, a "warm" temperature of about 30 ℃ to 50 ℃ for about 50, 60, 70, 80, 90, 100, 110, or 120 minutes, (ii) a pH iv of at least about 10 ℃, 15 ℃,20 ℃, 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃,90 ℃, or 95 ℃ (e.g., for laundry washing or rinsing, a "warm" temperature of about 30 ℃ to 50 ℃, a "hot" temperature of about 50 ℃ to 95 ℃), (iii) a pH of at least about 2,3, 4,5, 6, 7, 8, 9, 10, 11, or 12 (e.g., a pH range of about 2 to 12 or about 3 to 11), and (e.g., a concentration of at least about 0.5, 5, 0.5% to 3.5% or any combination of salts (i) at a concentration of at least about 0.5, 0.5 to 3.5% to (i) or (i.0.5% of NaCl.
For example, the contacting step in a fabric care or laundry method may include any of a wash, soak, and/or rinse step. In still further embodiments, contacting with the material or fabric may be by any means known in the art, such as dissolving, mixing, shaking, spraying, treating, dipping, rinsing, pouring or pouring, bonding, painting, coating, applying, pasting, and/or communicating an effective amount of the dextran derivative herein with the fabric or material. In still other embodiments, the fabric may be treated with a contact to provide a surface substantive effect. As used herein, the term "fabric hand" or "feel" refers to the haptic sensory response of an individual to a fabric, which may be physical, physiological, psychological, social, or any combination thereof. In one embodiment, the fabric hand may be used to measure relative hand valuesThe system was used to measure (Nu Cybertek, inc. of Davis, calif. (Nu Cybertek, inc. Davis, calif.) (American society of textile chemists and Colorists (American Association of Textile CHEMISTS AND Colorists) [ AATCC test method "202-2012.Relative Hand Value of Textiles:Instrumental Method [ relative feel value of textile: instrumental method ]" ]).
In some aspects of treating a material comprising a fabric, the dextran ester derivative of the aqueous composition is adsorbed to the fabric. This feature is believed to make the dextran ester derivatives herein useful as anti-redeposition agents and/or anti-graying agents (e.g., in addition to their viscosity modulating effects) in fabric care compositions. The anti-redeposition or anti-graying agents herein help to prevent redeposition of stains on laundry in the wash water after the stains have been removed. In some aspects, it is further contemplated that adsorbing the dextran ester derivative herein to the fabric enhances the mechanical properties of the fabric.
Colorimetric techniques (e.g., dubois et al, 1956, anal. Chem. [ analytical chemistry ]28:350-356; And et al, 2006,Lenzinger Berichte [ Ronchigy report ]85:68-76, both incorporated herein by reference) or any other method known in the art.
Other materials that may be contacted in the above treatment methods include surfaces that may be treated with a dishwashing detergent (e.g., an automatic dishwashing detergent or a hand dishwashing detergent). Examples of such materials include surfaces of tableware, glassware, pots, pan-like ware, baking trays, cookware and flat tableware (collectively referred to herein as "foodware" (tableware)) made of ceramic materials, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, melamine, etc.) and wood. Thus, in certain embodiments, the treatment method may be considered, for example, a dishwashing method or a foodware washing method. Examples of conditions (e.g., time, temperature, wash volume) for performing the dishwashing or foodware washing methods herein are disclosed herein as well as in U.S. patent No. 8575083 and U.S. patent application publication No. 2017/0044468, which are incorporated herein by reference. In some aspects, the foodware article may be contacted with the aqueous compositions herein under a suitable set of conditions, such as any of those disclosed above with respect to contact with the fabric-containing material.
Other materials that may be contacted in the above treatment methods include oral surfaces, such as any soft or hard surfaces within the oral cavity, including surfaces of the tongue, hard and soft palate, buccal mucosa, gums, and dental surfaces (e.g., hard surfaces of natural teeth or artificial dentition such as crowns, caps, fillings, bridges, dentures, or dental implants). Thus, in certain embodiments, the treatment method may be considered, for example, an oral care method or a dental care method. The conditions (e.g., time, temperature) used to contact the oral surface with the aqueous compositions herein should be suitable for the intended purpose of making such contact. Other surfaces that may be contacted in the treatment method also include surfaces of skin systems such as skin, hair or nails (i.e., any keratin-containing tissue or material).
Thus, some aspects of the disclosure relate to materials comprising dextran ester derivatives herein (e.g., fabrics or fibers comprising products as disclosed herein, or any other materials herein, such as hair, skin, or other keratin-containing materials). Such materials may be prepared according to, for example, the material processing methods as disclosed herein. In some aspects, a material may comprise a dextran ester derivative if the dextran ester derivative is adsorbed to or otherwise in contact with the surface of the material (e.g., dextran ester contained in a coating of the material).
Some aspects of the methods of treating a material herein further comprise a drying step, wherein the material is dried after contact with the aqueous composition. The drying step may be performed directly after the contacting step, or after one or more additional steps that may follow the contacting step (e.g., drying the fabric, cutlery, or hair after washing in an aqueous composition herein, such as rinsing in water). Drying may be performed by any of several methods known in the art, such as air drying (e.g., about 20-25 ℃) or, for example, at a temperature of at least about 30 ℃, 40 ℃,50 ℃, 60 ℃,70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 170 ℃, 175 ℃, 180 ℃, or 200 ℃. The material that has been dried herein typically has less than 3wt%, 2wt%, 1wt%, 0.5wt%, or 0.1wt% water contained therein.
The aqueous composition used in the treatment methods herein may be any of the aqueous compositions disclosed herein. Examples of aqueous compositions include detergents (e.g., laundry or dish detergents), fabric softeners, aqueous dentifrices (such as toothpastes), and hair care products (such as hair styling, hair cleaning, or hair conditioning products).
Some aspects herein relate to a method of styling hair. Such a method may comprise, for example, at least steps (a) and (b), or steps (c) and (d), as follows:
(a) Contacting (e.g., coating) hair with a composition comprising a dextran ester derivative herein, thereby providing treated hair (or coated hair), and
(B) Bringing the treated hair (or the coated hair) into a desired form, or
(C) Bringing the hair into a desired form, and
(D) Contacting (e.g., coating) the hair of step (c) with a composition comprising a dextran ester derivative herein, thereby providing treated hair (or coated hair), and
(E) Optionally, removing the solvent, if any, used in step (a) or (d) to deliver the dextran ester derivative to the hair.
Such a method may optionally be characterized as a hair styling method. For example, the contacting in the hair styling method may be performed by applying/treating hair with a hair styling composition herein (e.g., gel, mousse, spray) comprising at least one dextran ester derivative. The hair to be treated in the hair styling process, in particular in step (a) or (d), may typically be wet or dry. Step (e) of removing the solvent may be performed by, for example, drying, such as by the drying methods disclosed herein (e.g., air drying or blow drying with room temperature or heated air). Drying may be performed with (or without) agitation of the treated hair, such as by combing or wiping while drying. Optionally, the styling methods herein may include the step of applying steam to the treated hair after step (b) or step (d) (but before optional step [ e ]). In some aspects, step (b) or (c) of bringing the hair into a desired form may be performed by straightening, curling, or otherwise bringing the hair into a form different from that of the hair present prior to step (a), (b), or (c). Hair styled by the styling methods herein may optionally remain in a desired form for a period of time of, for example, at least 1 day, 2 days, 3 days, 4 days, 5 days, or more without any device and/or additional material being applied to the styled hair (i.e., while in a free-standing state). Such styling reservations may be under conditions such as dry air (e.g., relative humidity 50% or less) or humid air (e.g., relative humidity greater than 50%), typically for a period of time during which the hair is not being styled or rinsed.
In some aspects, materials that can be treated with the aqueous compositions (e.g., dispersions/emulsions) herein are nonwoven products. Such treatment, which may involve application of the aqueous compositions herein (at any concentration disclosed herein), typically followed by a drying step (e.g., air drying, heat drying, vacuum drying; the drying temperature may be, for example, any suitable temperature disclosed herein), may strengthen the nonwoven product (i.e., act as a binder therefor). In some aspects, dextran ester derivatives as disclosed herein can increase the dry or wet tensile strength (measured in N/5 cm) of a nonwoven, for example, or at least about 1000%, 10000%, 100000%, or 1000000%. Accordingly, further provided herein are nonwoven products containing binders/enhancers comprising dextran ester derivatives of the present disclosure. In some aspects, the dry or wet tensile strength of a nonwoven comprising a dextran ester derivative herein may be about or at least about 10, 15, 20, 25, 50, 75, 100, 125, 130, 135, 140, 145, 150, 10-150, 15-150, 20-150, 25-150, 10-140, 15-140, 20-140, or 25-140N/5cm. The dextran ester derivative may be present in an amount of about 1,2, 5, 10, 15, 20, 25, 1-5, 1-10, 5-20, or 1-25wt% based on the total weight of the nonwoven material and the dextran ester derivative in the nonwoven product. the nonwoven product herein may be, for example, air-laid, dry-laid, wet-laid, carded, electrospun, hydroentangled, spunbond, or meltblown. In some aspects, the nonwoven product may be a polishing or scouring sheet, agricultural cover, agricultural seed strip, clothing lining, automotive headliner or upholstery, bib, cheese packaging, geotextile, coffee filter paper, cosmetic make-up removal or application, detergent pouch/sachet, fabric softener sheet, envelope, facial mask, filter, clothing pouch, thermally or electrically conductive fabric, household care wipe (e.g., for floor care, hard surface cleaning, pet care, etc.), house wrap, hygiene product (e.g., sanitary pad/towel, medical mattress), insulation, label, clothing aid, medical care or personal injury care product (e.g., bandages, and the like, Plaster bandage pads or plaster sleeves, dressings, bags, sterile overwraps, sterile packaging, surgical drapes, gowns, swabs), mops, napkins or tissues, papers, personal or baby wipes, reusable bags, roof coverings, table cloths, labels, tea or coffee bags, liners, vacuum cleaning bags, or wall coverings. In some aspects, the fibers of the nonwoven product may comprise cellulose and/or alpha-1, 3-glucan, or may comprise one or more other materials disclosed herein that may be used to form the fibers. Examples of nonwoven products, nonwoven product materials, and/or methods of producing nonwoven products and materials herein may be as disclosed in U.S. patent application publication nos. 2020/0370216, 2018/0282918, 2017/0167063, 2018/0310291, or 2010/0291213, each of which is incorporated herein by reference.
The compositions herein comprising at least one dextran ester derivative as disclosed herein may be, for example, films or coatings. In some aspects, the film or coating may be a dried film or coating comprising, for example, less than about 3, 2, 1, 0.5, or 0.1wt% water. In some aspects, the film or coating may comprise about 20-40, 20-35, 20-30, 25-40, 25-35, or 25-30wt% dextran ester derivative herein, wherein the balance of the material in the film or coating is optionally water, an aqueous solution, and/or a plasticizer. The amount of dextran ester derivative as disclosed herein in the film or coating herein may be, for example, about or at least about 1、2、3、4、5、6、7、8、9、10、11、12、13、14、1 5、1 6、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、96、97、98、99、99.5、99.9、 or 100wt%. The films or coatings herein may be produced, for example, by providing a layer of an aqueous dispersion or solution of dextran ester derivative (e.g., about 5-30, 5-25, 5-20, 10-30, 10-25, or 10-20wt% dextran ester) onto the surface/object/material and then removing all or most (> 90, 95, 98, 99 wt%) of the water from the dispersion or solution to produce the film or coating. For example, a process similar to or as disclosed in U.S. patent application publication No. 2018/0258595 (incorporated herein by reference) may be used to produce a film or coating. For example, the grammage of a coating comprising a dextran ester derivative herein on a substrate may be about or at least about 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 1-10, 1-8, 1-6, 1-5, 1-4, 1-3, or 1-2gsm (grams per square meter).
The films or coatings herein may have a thickness of, for example, about, at least about, or up to about 0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、2、2.5、5、7.5、10、15.5、15、17.5、20、22.5、25、30、35、40、45、50、75、100、150、200、0.5-1.5、0.8-1.5、1.0-1.5、0.5-1.4、0.8-1.4、 or 1.0-1.4 mils (1 mil = 0.001 inch). In some aspects, such thicknesses are uniform, and may be characterized as having a continuous area that (i) is at least 20%, 30%, 40%, or 50% of the total film/coating area, and (ii) has a standard deviation of thickness of less than about 0.06, 0.05, or 0.04 mils. In some aspects, the films or coatings herein can be characterized as thin (e.g., <2 mils). The film herein is typically a cast film.
The films or coatings herein may exhibit various degrees of transparency as desired. For example, the film/coating may be highly transparent (e.g., high light transmission and/or low haze). As used herein, optical clarity may refer, for example, to a film or coating that allows at least about 10% -99% light transmission or at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, or 99% light transmission, and/or less than 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, 2%, or 1% haze. High optical clarity may optionally refer to films/coatings having at least about 90% light transmittance and/or less than 10% haze. The light transmittance of the films/coatings herein can be measured, for example, following test ASTM D1746 (2009,Standard Test Method for Transparency of Plastic Sheeting [ standard test method for plastic sheet transparency ], ASTM International [ american society for materials and testing ], pennsylvania, west Kang Shehuo ken (West Conshohocken, PA)) (incorporated herein by reference). The haze of the films/coatings herein may be measured, for example, following test ASTM D1003-13 (2013,Standard Test Method for Haze and Luminous Transmittance ofTransparent Plastics [ standard test method for haze and light transmittance of clear plastics ], ASTM International [ american society for materials and testing ], pennsylvania, west Kang Shehuo ken (West Conshohocken, PA)) (incorporated herein by reference).
The films or coatings herein may optionally further comprise a plasticizer, such as glycerol, propylene glycol, ethylene glycol, and/or polyethylene glycol. In some aspects, other film components (in addition to the compositions herein) can be as disclosed in U.S. patent application publication nos. 2011/0151224, 2015/0191550, 20190153674, or 20210095155, or U.S. patent nos. 9688035 or 3345200, which are incorporated herein by reference in their entirety.
In some aspects, the films or coatings herein, or any suitable solid composition (e.g., composite, fiber, fibrid) may further comprise at least one crosslinking agent. The dextran ester derivatives of the present disclosure can be crosslinked (covalently) with each other and/or with at least one other component of the composition (e.g., polymer, active agent), or with a component of the substrate if the composition is applied to the substrate. However, in some aspects, the dextran ester derivative herein is not crosslinked in any way, but one or more other components of the composition are crosslinked. The crosslinking may, for example, (i) enhance the tensile strength of the film or coating composition and/or (ii) plasticize the film or coating composition. In some aspects, crosslinking may connect the film or coating to the substrate. In some cases, crosslinking agents such as dicarboxylic or polycarboxylic acids, aldehydes, or polyphenols may be used to impart both plasticity and attachment characteristics to the substrate. Suitable crosslinking reagents for preparing the compositions herein having crosslinking as described above are contemplated to include phosphorus oxychloride (POCl3), polyphosphates, sodium Trimetaphosphate (STMP), boron containing compounds (e.g., boric acid, diborates, tetraborates such as tetraborate decahydrate, pentaborates, polymeric compounds such asAlkali metal borates), polyvalent metals (e.g., titanium-containing compounds such as titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, or polyhydroxy complexes of titanium; zirconium-containing compounds such as zirconium lactate, zirconium carbonate, zirconium acetylacetonate, zirconium triethanolamine, zirconium diisopropylamine lactate, or polyhydroxy complexes of zirconium), glyoxal, glutaraldehyde, acetaldehyde, polyphenols, divinyl sulfone, epichlorohydrin, polyamide-epichlorohydrin (PAE), di-or polycarboxylic acids (e.g., citric acid, malic acid, tartaric acid, succinic acid, glutaric acid, adipic acid), dichloroacetic acid, polyamines, 1,2,7, 8-diglycidyl octane, diethylene glycol dimethyl ether (diglyme), diglycidyl ethers (e.g., diglycidyl ether itself, ethylene glycol diglycidyl ether [ EGDGE ], 1, 4-butanediol diglycidyl ether [ BDGE ], polyethylene glycol diglycidyl ethers [ PEGDE, such as PEG2000DGE ], 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol a diglycidyl ether [ bae ]), and triglycidyl ethers (e.g., trimethylolpropane). Still other examples of suitable crosslinking agents are described in U.S. patent nos. 4462917, 4464270, 4477360, and 4799550, and U.S. patent application publication No. 2008/012907, which are incorporated herein by reference in their entirety. However, in some aspects, the crosslinking reagent is not a boron-containing compound (e.g., as described above). The dextran ester derivatives herein may be crosslinked in other circumstances (e.g., in a dispersion, fiber, fibrid, or other composition disclosed herein) other than a film or coating, such as with any crosslinking agent as disclosed herein.
One or more conditioning agents may be included in the film, e.g., the coating, to enhance the feel of the film or coating. The conditioning agent may be an anionic softening agent such as a sulfated oil, soap, sulfated alcohol, and/or oil emulsion, a cationic softening agent such as a quaternary ammonium compound, a nonionic softening agent such as a polyoxyethylene derivative, a polyethylene emulsion, a wax emulsion, and/or a silicone softening agent, a natural fatty acid, an oil, a monoglyceride, a diglyceride, a polyglycerol ester, a citric acid ester, a lactic acid ester, and/or a sugar ester such as a sucrose ester and/or a sorbitan ester.
Also disclosed are articles comprising an adhesive, film, coating, or adhesive, comprising the dextran ester derivative herein in dry form. Such articles (optionally, "coated articles") include a substrate having at least one surface on which a coating, adhesive, film, or adhesive is disposed/deposited in a substantially continuous or discontinuous manner. In some aspects, the article comprises paper, leather, wood, metal, polymer, fibrous material, masonry, drywall, gypsum, and/or architectural surfaces. "architectural surface" herein is the exterior or interior surface of a building or other man-made structure. In some aspects, the article includes a porous substrate such as paper, cardboard, paperboard, corrugated board, cellulosic substrate, textile, or leather. However, in some aspects, the article may comprise a polymer, such as polyamide, polyolefin, polylactic acid, polyethylene terephthalate (PET), poly (trimethylene terephthalate) (PTT), aramid, polycycloethylene sulfide (PES), polyphenylene sulfide (PPS), polyimide (PI), polyethylenimine (PEI), polyethylene naphthalate (PEN), polysulfone (PS), polyetheretherketone (PEEK), polyethylene, polypropylene, poly (cyclic olefin), poly (cyclohexylene dimethylene terephthalate), poly (trimethylene furandicarboxylate) (PTF), or cellophane. In some aspects, the article comprising the fibrous substrate is a fiber, yarn, fabric blend, textile, nonwoven, paper, or carpet. The fibrous substrate may contain natural and/or synthetic fibers such as cotton, cellulose, wool, silk, rayon, nylon, aramid, acetate, polyurethaneurea, acrylic, jute, sisal, seaweed, coir, polyamides, polyesters, polyolefins, polyacrylonitriles, polypropylene, polyaramides, or blends thereof.
In some aspects, the films, coatings, or other compositions (e.g., composites) herein may have grease/oil and/or oxygen barrier properties. In addition to the dextran ester derivatives herein, such compositions may include one or more components as disclosed in U.S. patent application publication nos. 20190153674 or 20210095155, each of which is incorporated herein by reference. for example, films, coatings, or other compositions herein may comprise, optionally as a binder, one or more of polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl acetate, silanol-modified polyvinyl alcohol, butylene glycol vinyl alcohol copolymer (BVOH), polyurethane, starch, corn dextrin, carboxymethyl cellulose, cellulose ether, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, alginate, sodium alginate, xanthan gum, carrageenan, casein, soy protein, guar gum, synthetic polymers, styrene butadiene latex, and/or styrene acrylate latex. in some aspects, the composition used to prepare the film, coating, or other composition may comprise about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 65-85, 65-80, 70-85, or 70-80wt% of a binder or compound such as polyvinyl alcohol (or any other of the compounds cited above), and about 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2.5, 15-35, 20-35, 15-30, or 20-30wt% of a dextran ester derivative as disclosed herein. In some aspects, a composition for preparing a film, coating, or other composition can comprise a ratio of binder or compound (e.g., any of the compounds cited above, such as polyvinyl alcohol or starch) to dextran ester derivative herein of about 7:3, 7.5:2.5, 8:2, 8.5:1.5, or 9:1, based on the wt% of each of these components in the composition. In some aspects, the film, coating, or other composition does not include starch, while in other aspects, such as an oxygen barrier, may include starch (e.g., as disclosed in U.S. patent application publication No. 2011/0135912 or U.S. patent No. 5621026 or 6692801, which are incorporated herein by reference). The grease/oil barrier properties of the coating or film compositions herein may be assessed, for example, using a standard "KIT" Test following TECHNICAL ASSOCIATION OF THE PULP AND PAPER INDUSTRY (TAPPI) Test Method T-559cm-02[ pulp and paper industry association (TAPPI) Test Method T-559cm-02] (GREASE RESISTANCE TEST for paper and paperboard [ grease resistance Test for paper and paperboard ], TAPPIPRESS [ TAPPI press ], atlanta, GA, USA; incorporated herein by reference). Good grease/oil barrier/tolerance function is indicated in this test on a scale of 1 to 12 with a value close to 12. If desired, the grease/oil barrier properties and the water/aqueous liquid barrier properties can be evaluated by the Cobb test. The barriers herein may have a puffer index value of, for example, less than 20, 17.5, 15, 12.5, 10, 7.5, or 5. The oxygen barrier properties of the coatings or film compositions herein can be assessed by measuring the Oxygen Transmission Rate (OTR) of the coating, which can be determined, for example, according to ASTM F-1927-07(2007,Standard Test Method for Determination of Oxygen Gas Transmission Rate,Permeability and Permeance at Controlled Relative Humidity Through Barrier Materials Using a Coulometric Detector[ standard test methods for determining oxygen transmission rate, permeability, and permeation through barrier materials at controlled relative humidity using coulombic detectors, ASTM INTERNATICNAL [ american society for materials and testing ], pennsylvania, west Kang Shehuo ken (West Conshohocken, PA) ] (incorporated herein by reference). For example, OTR may be determined at a relative humidity of about 50% -80%, 30% -55%, 35% -50%, or 30% -80%, and/or at a temperature of about or at least about 15 ℃,20 ℃, 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃, 15 ℃ to 40 ℃, 15 ℃ to 35 ℃, 15 ℃ to 30 ℃, 15 ℃ to 25 ℃,20 ℃ to 40 ℃,20 ℃ to 35 ℃,20 ℃ to 30 ℃, or 20 ℃ to 25 ℃. Examples of substrates herein that may utilize the grease/oil and/or oxygen barrier coating include any of the foregoing substrates/surfaces, including substrates comprising cellulose (e.g., paper, paperboard, cardboard, corrugated board, textiles), polyethylene, polypropylene, polylactic acid, poly (ethylene terephthalate) (e.g., MYLAR), poly (propylene terephthalate), polyamide, polybutylene succinate, polybutylene adipate terephthalate, polybutylene succinate adipate, poly (trimethylene furandicarboxylate), synthetic and/or petroleum-based substrates, or biobased substrates. Any of the foregoing films, coatings, or other compositions may be in the form of, for example, a laminate or extruded product, and which optionally is located on any of the foregoing substrates.
In some aspects, a film, coating, or other composition (e.g., dispersion, foam, masterbatch, composite) comprising a dextran ester derivative herein may further comprise polyurethane (e.g., any as disclosed herein). Such compositions may comprise, for example, about 1,5, 10, 15, 20, 35, 30, 35, 40, 45, 50, 55, 60, 5-50, 5-45, 5-40, 5-35, 5-30, 10-60, 10-50, 10-45, 10-40, 10-35, or 10-30wt% of the dextran ester derivative herein, the balance may comprise all or predominantly (e.g., greater than 90% or 95%) of one or more polyurethanes. Such compositions may be wet (e.g., dispersions of dextran ester derivatives and polyurethanes) or dry (e.g., masterbatches of dextran ester derivatives and polyurethanes, films/coatings, laminates, foams, or extruded composites). The polyurethanes herein may have a molecular weight of, for example, about or at least about 1000, 1500, 2000, 2500, 3000, 3500, 4000, 1000-3000, 1500-3000, 1000-2500, or 1500-2500. In some examples, such compositions may be hydrolytically aged (e.g., exposed to 45 ℃ to 55 ℃, or about 50 ℃, and/or 90% -98% or about 95% relative humidity for a period of 2-4 or 3 days). In some aspects, polyurethane compositions having dextran ester derivatives herein may be heat processable and/or pressure processable, e.g., application of heat and/or pressure for pressing, molding, extrusion, or any other relevant processing step may be performed at about or at least about 90 ℃, 95 ℃,100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 130 ℃, 140 ℃, 95 ℃ to 115 ℃, or 100 ℃ to 110 ℃, and/or at a pressure of at least about 5000, 10000, 15000, 20000, or 25000 psi. Such application of heat and/or pressure may last for a period of time of, for example, at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 30 minutes. In some aspects, the extruded polyurethane composition, such as a film, may be about or at least about 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, or 100% transparent or translucent. In some aspects, any of the polyurethane compositions disclosed herein can be made by a method comprising providing an aqueous polyurethane dispersion and mixing the dextran ester derivative herein with the polyurethane dispersion. The resulting aqueous composition may be used directly to make the composition (e.g., film or coating), or it may be dried into a masterbatch that is then used to prepare the composition (e.g., by melt processing).
In some aspects, the film or coating may be in the form of an edible film or coating. In some aspects, such materials may comprise a dextran ester derivative herein and one or more components as described in U.S. patent nos. 4710228, 4543370, 4820533, 4981707, 5470581, 5997918, 8206765, or 8999413, or U.S. patent application publication No. 2005/0214414, which are incorporated herein by reference. In some aspects, the dextran ester derivatives herein replace starch and/or starch derivatives in an edible film or coating, optionally as disclosed in any of the foregoing references. The edible film or coating can be on, for example, potato products (e.g., potato strips such as french fries), other vegetables or vegetable products (e.g., zucchini, pumpkin, sweet potato, onion, okra, pepper, kidney bean, tomato, cucumber, lettuce, cabbage, carrot, broccoli, cauliflower, bean sprouts, onion, any cut form of vegetables), mushrooms, fruits (e.g., berries (such as raspberries, strawberries, or blueberries), avocados, kiwi, kumquat, oranges, apples, pears, bananas, grapefruits, cherries, papaya, lemon, lime, mango, peach, cantaloupe, any cut form of fruit), and/or nuts (peanuts, walnuts, almonds, hickory, cashew nuts, hazelnut/seeds, brazil nuts, macadamia nuts). Any other food disclosed herein (as appropriate) may have, for example, an edible coating. In some aspects, these and other food products having the edible films or coatings herein may be fried or baked, and/or the films or coatings provide tenderness, moisture retention, moisture protection, crispness, dietary fiber (in lieu of digestible starch), oxygen barrier, freshness, and/or ripening resistance. In some aspects, anti-ripening can be measured by the coating reducing (e.g., at least 25%, 50%, 75%, 80%, 85%, or 90%) the extent of release of a gaseous ripening hormone (such as ethylene) of a plant-based product (e.g., at 15-30 ℃, 15-25 ℃, or 20-25 ℃) and/or by the coating reducing the extent of softening and/or sweetening of the plant product. In some aspects, the edible coating may be prepared by applying an aqueous dispersion or solution (e.g., at 5-15, 5-12, 5-10, 7.5-15, 7.5-12, or 7.5-10wt% in water) comprising the dextran ester derivative herein to the food product and drying the dispersion or solution (e.g., by air drying, vacuum drying, and/or heating).
In some aspects, the coating composition that may be used to prepare the coatings herein may comprise any of the foregoing components/ingredients/formulations. In some aspects, the coating composition is a latex composition, such as described below.
In some aspects, the compositions herein comprising at least one dextran ester derivative as disclosed herein may be latex compositions. Examples of latex compositions herein include coatings (e.g., primers, finishes/decorators), adhesives, films, coatings, and adhesives. The formulation and/or components of the latex compositions herein (other than the compositions herein) may be as described, for example, in U.S. patent nos. 6881782, 3440199, 3294709, 5312863, 4069186, or 6297296, or U.S. patent application publication No. 2020/0263026, which are incorporated herein by reference in their entirety.
The dextran ester derivatives as disclosed herein may be present in the latex composition in any useful amount, such as about or at least about 0.01％、0.02％、0.03％、0.04％、0.05％、0.06％、0.07％、0.08％、0.09％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、15％、20％、25％、30％、40％、45％、50％、55％、60％、65％、70％、75％、0.01％-75％、0.01％-5％、5％-20％、20％-50％、 or 50% -75% by weight of all dispersed solids based on the latex.
In some aspects, the latex composition may comprise a polymer polymerized from at least one ethylenically unsaturated monomer (e.g., monoethylenically unsaturated monomer), a polyurethane, an epoxy, and/or a rubber elastomer. Examples of monoethylenically unsaturated monomers herein include vinyl monomers, acrylic monomers, allyl monomers, acrylamide monomers, unsaturated monocarboxylic acids, and unsaturated dicarboxylic acids.
Examples of suitable vinyl monomers for the polymers in the latex compositions herein include any compound having vinyl functionality (i.e., ethylenic unsaturation), such as vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate, vinyl pivalate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl butyrate, vinyl benzoate, vinyl isopropyl acetate), vinyl aromatic hydrocarbons (e.g., styrene, methyl styrene, and similar lower alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene, divinylbenzene), vinyl aliphatic hydrocarbons (e.g., vinyl chloride; vinylidene chloride; alpha olefins such as ethylene, propylene, and isobutylene; conjugated dienes such as 1, 3-butadiene, methyl-2-butadiene, 1, 3-piperylene, 2, 3-dimethylbutadiene, isoprene, cyclohexene, cyclopentadiene, and dicyclopentadiene), and vinyl alkyl ethers (e.g., methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether), but do not include compounds having acrylic functionality (e.g., acrylic acid, such as acrylic acid, acrylonitrile, and the like). In some aspects, the latex compositions herein comprise a vinyl acetate-ethylene copolymer, a carboxylated vinyl acetate-ethylene copolymer, and/or a polyvinyl acetate.
Examples of suitable acrylic monomers for the polymers in the latex compositions herein include alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, aromatic derivatives of acrylic and methacrylic acids, acrylamides, and acrylonitrile. Typically, alkyl acrylates and methacrylates (also known as alkyl esters of acrylic or methacrylic acid) have an alkyl ester moiety containing from 1 to about 18 carbon atoms per molecule, or from 1 to about 8 carbon atoms per molecule. Suitable acrylic monomers include, for example, methyl acrylate and methyl methacrylate, ethyl acrylate and ethyl methacrylate, butyl acrylate and butyl methacrylate, propyl acrylate and propyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate, decyl acrylate and decyl methacrylate, isodecyl acrylate and isodecyl methacrylate, benzyl acrylate and benzyl methacrylate, isobornyl acrylate and isobornyl methacrylate, neopentyl acrylate and neopentyl methacrylate, and 1-adamantyl methacrylate. Acids such as acrylic acid or methacrylic acid may also be used if acid functionality is desired.
In some aspects, the latex composition comprises a polyurethane polymer. Examples of suitable polyurethane polymers are those comprising polysaccharides, as disclosed in U.S. patent application publication No. 2019/0225737 (which is incorporated herein by reference). The latex comprising polyurethane may be prepared, for example, as disclosed in U.S. patent application publication number 2016/0347978, which is incorporated herein by reference, and/or comprise the reaction product of one or more polyisocyanates with one or more polyols. Useful polyols include, for example, polycarbonate polyols, polyester polyols, and polyether polyols. The polycarbonate polyurethane herein may be formed as a reaction product of a polyol (such as 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, or tetraethylene glycol) and a diaryl carbonate (such as diphenyl carbonate or phosgene). The at least one polyisocyanate herein may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a polyisocyanate having both aromatic and aliphatic groups. Examples of polyisocyanates include 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, mixtures of 2, 4-and 2, 6-toluene diisocyanate, bis (4-isocyanatocyclohexyl) methane, 1, 3-bis (1-isocyanato-1-methylethyl) benzene, bis (4-isocyanatophenyl) methane, 2,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2, 4-diisocyanatotoluene, bis (3-isocyanatophenyl) methane, 1, 4-diisocyanatobenzene, 1, 3-diisocyanato-o-xylene, 1, 3-diisocyanato-paraxylene, 1, 3-diisocyanato-metaxylene, 2, 4-diisocyanato-1-chlorobenzene, 2, 4-diisocyanato-1-nitrobenzene, 2, 5-diisocyanato-1-nitrobenzene, m-phenylene diisocyanate, hexahydrotoluene diisocyanate, 1, 5-naphthalene diisocyanate, 1-methoxy-2, 4-phenylene diisocyanate, 4 '-biphenylene methane diisocyanate, 4' -biphenylene diisocyanate, 3 '-dimethyl-4, 4' -diphenylmethane diisocyanate, 3'-4,4' -diphenylmethane diisocyanate, and 3,3 '-dimethyldiphenylmethane-4, 4' -diisocyanate. Also useful herein are polyisocyanate homopolymers comprising allophanate, biuret, isocyanurate, iminooxadiazinedione, or carbodiimide groups, for example. The polyol herein may be any polyol comprising two or more hydroxyl groups, e.g., C2 to C12 alkanediol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, isomers of butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, decanediol, and mixtures thereof, Dodecanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol (neopentyl glycol), 1, 4-bis (hydroxymethyl) cyclohexane, 1,2, 3-glycerol (glycerol), 2-hydroxymethyl-2-methyl-1, 3-propanol (trimethylolethane), 2-ethyl-2-hydroxymethyl-1, 3-propanediol (trimethylolpropane), 2-bis (hydroxymethyl) -1, 3-propanediol (pentaerythritol), 1,4, 6-octanetriol, chloropentanediol, glycerol monoalkyl ether, glycerol monoethyl ether, diethylene glycol, 1,3, 6-hexanetriol, 2-methylpropanediol, 2, 4-trimethyl-1, 3-pentanediol, Cyclohexane dimethanol, polymer polyols such as polyether polyols or polyester polyols. In some aspects, the polyol herein may be poly (oxytetramethylene) glycol, polyethylene glycol, or poly 1, 3-propanediol. In some aspects, the polyol may be a polyester polyol, such as one produced by transesterification of an aliphatic diacid with an aliphatic diol. Suitable aliphatic diacids include, for example, C3 to C10 diacids, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid. In some aspects, aromatic and/or unsaturated diacids may be used to form the polyester polyols.
In some aspects, the latex composition comprises an epoxy polymer/resin (polyepoxide), such as a bisphenol a epoxy resin, a bisphenol F epoxy resin, a phenolic epoxy resin, an aliphatic epoxy resin, or a glycidyl amine epoxy resin.
In some aspects, the latex composition comprises a rubber elastomer. In some aspects, the rubber elastomer may include one or more diene-based sulfur-vulcanizable elastomers having a glass transition temperature (Tg) of less than-30 ℃ as determined, for example, by dynamic mechanical analysis. In further examples, rubber elastomers herein include natural rubber, synthetic polyisoprene, polybutadiene rubber, styrene/butadiene copolymer rubber, ethylene propylene diene monomer rubber, hydrogenated nitrile rubber, neoprene rubber, styrene/isoprene/butadiene terpolymer rubber, butadiene/acrylonitrile rubber, polyisoprene rubber, isoprene/butadiene copolymer rubber, nitrile rubber, ethylene-acrylic rubber, butyl and halogenated butyl rubber, chlorosulfonated polyethylene, fluoroelastomers, hydrocarbon rubber, polybutadiene, or silicone rubber.
The liquid component of the latex compositions herein may be water or an aqueous solution. In some aspects, the aqueous solution of the latex may comprise an organic solvent that is miscible or immiscible with water. Suitable organic solvents herein include acetone, methyl ethyl ketone, butyl acetate, tetrahydrofuran, methanol, ethanol, isopropanol, diethyl ether, glycerol ether, hexane, toluene, dimethylacetamide, dimethylformamide, and dimethylsulfoxide.
In some aspects, the latex compositions herein may further comprise one or more additives. Examples of additives herein include dispersants, rheology aids, defoamers, foaming agents, adhesion promoters, flame retardants, bactericides, fungicides, preservatives, optical brighteners, fillers, anti-settling agents, coalescing agents, humectants, buffers, pigments/colorants (e.g., metal oxides, synthetic organic pigments, carbon black), viscosity modifiers, antifreeze agents, surfactants, binders, crosslinking agents, corrosion inhibitors, hardeners, pH adjusters, salts, thickeners, plasticizers, stabilizers, extenders, and matting agents. Examples of pigments herein include titanium dioxide (TiO2), calcium carbonate, diatomaceous earth, mica, hydrated alumina, barium sulfate, calcium silicate, clay, silica, talc, zinc oxide, aluminum silicate, nepheline syenite, and mixtures thereof. In some aspects, the latex composition is substantially free (e.g., less than 1, 0.5, 0.1, or 0.01wt% of components) of starch, starch derivatives (e.g., hydroxyalkyl starch), cellulose, and/or cellulose derivatives (e.g., carboxymethyl cellulose).
In some aspects, the latex compositions herein in the form of a coating or other coloring agent can have a Pigment Volume Concentration (PVC) of about 3% to about 80%. For example, the matte coating may have PVC in the range of about 55% -80%, the primer or basecoat may have PVC in the range of about 30% -50%, and/or the glossy colored coating may have PVC in the range of about 3% -20%. In some aspects, the coating or other coloring agent may have about 55％、60％、65％、70％、75％、80％、55％-80％、55％-75％、55％-70％、60％-80％、60％-75％、60％-70％、63％-67％、64％-66％、65％-80％、65％-75％、 or 65% -70% PVC. The PVC values herein may be, for example, values of specific pigments (or pigment mixtures) such as those disclosed above (e.g., titanium dioxide). It is believed that the compositions of the present disclosure provide one or more physical properties to the latex composition (e.g., for use as a coating or other colorant) such as opacity, less pigment needed, increased hardness, reduced tackiness, reduced gloss (i.e., providing a matte effect), increased shear strength, better abrasion resistance, improved drying time, improved fade resistance, less foaming, and/or improved hand (less tacky feel) than latex compositions that do not include the disclosed compositions.
The latex compositions herein may be applied to a substrate (above) of an article using any method known in the art. Typically, after the latex composition is applied, at least a portion of the aqueous solution is removed, such as by drying, to provide an adhesive, film, coating, or binder comprising the latex composition in dry or semi-dry form. Suitable application methods include air knife coating, bar coating, wire bar coating, spray coating, brush coating, cast coating, flexible blade coating, gravure coating, spray applicator coating, short dwell coating, slide hopper coating, curtain coating, flexographic coating, size press coating, reverse roll coating, and transfer roll coating. For example, the latex composition may be applied to at least a portion of the substrate, and may be applied in one or more coating layers/one or more times.
Some aspects herein relate to compositions comprising pigments. The pigment-containing composition can be in liquid form (e.g., an aqueous or non-aqueous composition herein) or in solid form (e.g., a dry composition herein). Examples of pigment-containing compositions herein include any of such compositions disclosed elsewhere herein (e.g., paints, primers, stains), inks, dyes (e.g., food coloring dyes, fabric coloring dyes), resins, sunscreens, and cosmetics (e.g., mascara, blush, nail polish/varnish, lipstick, lip gloss, eyeliner, foundation, eye shadow, skin decorative compositions). The pigment in the pigment-containing composition can be, for example, any pigment herein. Examples of pigments for these and/or other aspects herein include oxides of titanium (e.g., titanium dioxide), zinc, iron, zirconium, cerium, and chromium, manganese violet, ultramarine blue, chromium hydrate, prussian blue, zinc sulfide, nitroso, nitro, azo, xanthene, quinoline, anthraquinone, and/or phthalocyanine compounds, metal complex compounds, and isoindolinone, isoindoline, quinacridone, violenone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, and/or quinophthalone compounds. Additional examples of pigments useful herein are disclosed in U.S. patent application publication No. 2006/0085924 (which is incorporated herein by reference).
The compositions herein comprising at least one dextran ester derivative as disclosed herein may be in the form of a composite (e.g., a rubber composite or a polyurethane composite), such as disclosed in U.S. patent application publication nos. 2019/0225737, 2017/0362345, or 2020/0181370, which are incorporated herein by reference in their entirety. Optionally, it can be said that the composite material as disclosed herein comprises at least one polymer in addition to the dextran ester derivative of the present disclosure. One or more of the above components of the latex composition (e.g., rubber or polyurethane) may optionally be additional polymers in such composites. The additional polymer of the composite herein may be rubber, polyurethane, thermoplastic polymer, polyethylene, polypropylene, ethylene copolymer, polyvinylbutyrate, polylactic acid, polyvinyl alcohol, polyamide, polyether thermoplastic elastomer, polyester, polyether ester, ethylene vinyl alcohol copolymer, starch, cellulose, or any suitable polymer as disclosed above with respect to the latex component.
In some aspects, the rubber may be, for example, one or more of natural rubber, synthetic rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-isoprene copolymer, styrene-butadiene-isoprene terpolymer, ethylene propylene diene monomer rubber, hydrogenated nitrile rubber, silicone rubber, or neoprene. Examples of rubber-containing composites herein include tires (e.g., automobiles/bicycles; pneumatic tires; including tire treads and/or tire sidewalls), belts (e.g., conveyor belts, power transmission belts), hoses, gaskets, footwear (e.g., shoes, athletic shoes, boots; soles, cushioning, and/or aesthetic features), coatings, films, and adhesives. The rubber composites herein are typically vulcanized. In some aspects, it is contemplated that inclusion of the compositions herein in rubber-containing composites may provide advantages such as lower cost, lower density, lower energy consumption during processing, and/or better or the same performance (e.g., increased wet traction, reduced rolling resistance, lighter weight, and/or mechanical strength) than with the use of an existing filler such as carbon black or silica, and in some aspects, tires may have such performance enhancements. In some aspects, the compositions herein replace about or at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100wt% of the active filler (e.g., carbon black or silica) typically used in rubber composites such as tires. It should be noted that rubber composite tires currently on the market (not containing the compositions herein) typically contain up to about 30wt% of an active filler such as carbon black. Thus, rubber composites herein, such as tires, may comprise, for example, about or at least about 5, 10, 15, 20, 25, or 30 weight percent of a composition as disclosed herein. In some aspects, the rubber compositions herein may have a low minimum elastic torque (ML) (e.g., less than or about 0.10, 0.08, 0.06, 0.04, 0.03, or 0.02dNm [ newton-meters ]), and thus methods of mixing rubber compositions during their preparation are disclosed.
The composition comprising at least one dextran ester derivative as disclosed herein may be a paper/packaging composition or a cellulose containing fiber composition. Examples of such compositions may be any type of paper/packaging or cellulose fiber-containing composition disclosed herein, such as paper (e.g., writing paper, office paper, copying paper, kraft paper), cardboard, paperboard, corrugated board, tissue, napkins/towel, wipes, or nonwoven fabrics. The formulation and/or components of the paper/packaging compositions or cellulose fiber-containing compositions herein (except for the dextran ester derivatives herein) and the forms of these compositions may be as described in, for example, U.S. patent application publication nos. 2018/0119357, 2019/0330802, 2020/0062929, 2020/0308371, or 2020/0370216, which are incorporated herein by reference in their entirety. In some aspects, the dextran ester derivative acts as a reinforcing aid in paper or other cellulose fiber-containing compositions. It is contemplated that the ability of dextran ester derivatives to flocculate fibers and/or other insoluble materials in a papermaking process (e.g., pulp flocculation) is a means in which the dextran ester derivatives herein can be incorporated into paper or other products that are involved in flocculation in their production. However, in some aspects, dextran ester derivatives may be added as components to any of the foregoing compositions in a manner that is independent of the possible addition as a flocculation aid.
Some aspects of the present disclosure relate to a flocculation or dewatering method comprising (a) mixing at least one dextran ester derivative herein into an aqueous composition comprising suspended solids/particles whereby at least a portion of the suspended solids/particles become flocculated, and (b) optionally separating the flocculated solids/particles of (a) from the aqueous composition. Thus, in some aspects, dextran ester derivatives can be characterized as, for example, flocculants, dewatering agents, clarifiers, and/or dehazing agents. The flocculated particles of the treated composition typically settle (flocculate) or at least become more convenient for the separation procedure (e.g., filtration). Although soluble dextran ester derivatives may be used in the flocculation process, insoluble dextran ester derivatives may also be used in some aspects. Typically, dextran ester derivatives used herein for flocculation applications are (i) biodegradable and/or (ii) uncrosslinked.
For example, one, two, three, or more different types of dextran ester derivatives herein may be used in the flocculation process. In some aspects, the dextran ester derivative is the only flocculant employed, while in other aspects, the dextran ester derivative is used in conjunction with another type of flocculant (e.g., a commercially available flocculant such as acrylamide). In these latter aspects, the dextran ester derivative may constitute, for example, about or at least about 30, 40, 50, 60, 70, 80, or 90wt% of all flocculant added to the aqueous composition.
The amount of dextran derivative mixed into the aqueous composition comprising suspended solids/particles in step (a) may be, for example, about or at least about 2, 4, 6, 8, 10, 12, 14, 2-12, 2-10, 2-8, 4-14, 4-12, 4-10, 4-8, 6-14, 6-12, 6-10, 6-8, 8-14, 8-12, or 8-10g/kg (on a dry solids basis) of suspended solids. It will be appreciated that the aqueous soluble dextran ester derivative is typically dissolved in the aqueous composition after the mixing step (a). Mixing may be by any standard means.
The temperature and pH of the aqueous composition with suspended solids treated with the dextran ester derivative can be any temperature and pH as disclosed herein for the aqueous composition. In some aspects, the pH may be about 4, 5, 6, 7, 8, 9, 10, 4-10, 5-9, or 6-8, and/or the temperature may be about 1-80℃、1-70℃、1-60℃、1-50℃、1-40℃、1-30℃、5-80℃、5-70℃、5-60℃、5-50℃、5-40℃、5-30℃、15-80℃、15-70℃、15-60℃、15-50℃、15-40℃、 or 15-30 ℃. After addition of the dextran ester derivative and mixing with the aqueous composition, settling of the suspended solids may be allowed to begin for, for example, about or at least about 0.5, 1,2, 3, 4, 5, 6, 9, 12, 18, 24, 30, 36, 42, or 48 hours.
In some aspects, the percentage of initial suspended solids that settle (i.e., are no longer suspended) after treatment with the dextran ester derivative is about or at least about 30, 40, 50, 60, 70, 80, 90, 95, 96, 97, 98, 99, or 100wt%. Typically, the flocculants herein allow the settled particles to occupy less space. For example, after treatment of an aqueous composition (initially with suspended particles) with a dextran ester derivative herein, the total volume of settled particles may be about or less than about 90%, 80%, 70%, 60% or 50% of the total volume of precipitated particles settled in the aqueous composition without the aid of a flocculant, where all other conditions of each system are the same. Any suitable method may be used to determine the sedimentation volume, such as the methods described in the examples below.
In some aspects, the turbidity (i.e., the quality of the liquid as cloudy, opaque, and/or thick due to suspension), color, and/or opacity of an aqueous composition having suspended solids/particles can be reduced by about or at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or 75% when treated with a dextran ester derivative herein. Turbidity can be measured in Nephelometric Turbidity Units (NTU), for example. Any suitable method may be used to measure turbidity, such as the method disclosed in Progress in Filtration and Separation [ filtration and separation progress ] (version: 1, chapter 16. Turbidity: measurement of filtrate and supernatant quality. The color of the liquids herein may be measured using any suitable method, such as, for example, spectrocolorimetry or optocolorimetry.
In some aspects, the filterability of an aqueous composition having suspended solids/particles can be enhanced/improved when treated with the dextran ester derivatives herein. The filterability of the liquid composition may be measured using any suitable method, such as by measuring capillary suction time. In some aspects, the capillary suction time (e.g., measured in seconds) of an aqueous composition having suspended solids/particles can be reduced by about or at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 85% when treated with a dextran ester derivative herein. Any suitable method may be used to measure the capillary suction time of the liquid.
Suspended particles that can undergo flocculation herein are typically colloidal particles (i.e., stably suspended insoluble particles [ solids ]). Thus, the aqueous composition that may be subjected to the flocculation methods herein may be, for example, a colloid. The aqueous compositions comprising suspended solids/particles that may be treated with the flocculants as disclosed herein may be, for example, wastewater (e.g., municipal, industrial, agricultural wastewater), sewage/sewage, sludge (e.g., activated sludge), water from bodies of water (e.g., rivers/streams, canals, urban rivers, ponds, swamps, lakes, seas), pond water, cooling water, water containing sediment (e.g., clay sediment) and/or soil, water to be processed for drinking, or water containing fibers and/or fillers (as found in papermaking processes (e.g., pulp flocculation)). Examples of industrial wastewater come from paper mills or drilling/mining operations. In some aspects, the suspended solids can comprise microbial cells (live and/or dead), such as bacteria, yeast, and/or algae. It is contemplated that flocculation herein may be applied to aqueous compositions that exist in food or beverage manufacturing processes such as brewing (e.g., wort after fermentation thereof), cheese curd formation, or soy curd (tofu) production. Systems/operations that may incorporate the disclosed flocculation methods include, for example, wastewater/soil/sludge treatment, papermaking, water purification, soil conditioning, and/or mining/drilling/downhole operations, or any other system/operation that uses flocculation.
The flocculation methods herein optionally further comprise the step of separating the flocculated solids/particles from the treated aqueous composition. Such steps may include, for example, sedimentation/sedimentation, filtration, centrifugation, and/or decantation.
The present disclosure also relates to a method of producing a solid composition comprising at least one dextran ester derivative herein. Such methods can include at least (a) providing a non-caustic (e.g., pH 6-8 or 6-9) aqueous composition (e.g., solution or dispersion) comprising at least one dextran ester derivative as disclosed herein, (b) bringing the aqueous composition into a desired form (e.g., fiber, fibrid, film/coating, composite, extrudate), and (c) removing the liquid/solvent from the aqueous composition of step (b) to produce a solid composition comprising the dextran ester derivative. In some aspects, the ester derivatives of glucans herein as non-derivatives are insoluble under non-caustic aqueous conditions (e.g., a-1, 3-glucan having a DP >8 or > 9).
In some aspects where the non-caustic aqueous composition is a solution and the ester derivative of dextran herein as the non-derivative is insoluble under non-caustic aqueous conditions, the liquid/solvent may be removed by increasing the pH of the solution to above about 10, 10.5, 11, 11.5, or 12, thereby causing the dissolved dextran ester to precipitate out of the solution. The pH of the solution may be increased, for example, by adding/mixing a base (e.g., a metal hydroxide such as NaOH) to the solution. The precipitated dextran ester derivative from step (b), which is in the desired form/shape, may optionally be washed, for example with an organic liquid such as an alcohol (e.g. methanol, ethanol, isopropanol), and/or dried. The concentration of dextran ester derivative in the solution provided in step (a) may be as disclosed elsewhere herein, such as about or at least about 10, 12, 14, 16, 18, 20, 25, 30, 10-25, 10-20, 16-30, 16-25, or 16-20wt%.
The present disclosure also relates to a solid composition as produced by the foregoing method. Such a composition may be, for example, a fiber, fibrid, film/coating, composite, or extrudate.
Non-limiting examples of the compositions and methods disclosed herein include:
1. A composition comprising an ester derivative of dextran (dextran ester derivative), wherein the dextran has a degree of substitution (DoS) of up to about 3.0 substituted with at least two organic groups attached to the dextran individual esters, wherein (i) at least one of the organic groups is a cationic organic group, and (ii) at least one of the organic groups is a hydrophobic organic group.
2. The composition of embodiment 1 wherein the glucan is alpha-glucan.
3. The composition of embodiment 2, wherein at least about 50% of the glycosidic linkages of the α -glucan are α -1.3 linkages.
4. The composition of embodiment 2, wherein at least about 50% of the glycosidic linkages of the α -glucan are α -1,6 linkages, optionally wherein the α -glucan comprises at least 1% α -1,2 and/or α -1,3 branches.
5. The composition of embodiment 1, wherein the glucan is beta-glucan (e.g., wherein at least about 50% of the glycosidic linkages of the beta-glucan are beta-1, 3 linkages or beta-1, 4 linkages).
6. The composition of embodiment 1,2, 3, 4, or 5, wherein the dextran has a weight average degree of polymerization (DPw) of at least 6.
7. The composition of embodiments 1,2, 3, 4, 5, or 6 wherein said DoS by said at least two organic groups is at least about 0.005.
8. The composition of embodiments 1, 2, 3, 4,5, 6, or 7 wherein the DoS by the at least two organic groups is from about 0.005 to about 1.5.
9. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, or 8 wherein the DoS by the cationic organic group is from about 0.005 to about 1.5.
10. The composition of embodiments 1,2, 3, 4, 5, 6, 7, 8, or 9 wherein the DoS by the cationic organic group is from about 0.005 to about 1.0.
11. The composition of embodiments 1, 2, 3, 4, 5, 6, 7,8, 9, or 10 wherein the DoS by the cationic organic group is from about 0.005 to about 0.5.
12. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 wherein the DoS by the cationic organic group is from about 0.005 to about 0.1.
13. The composition of embodiments 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 wherein the DoS by the cationic organic group is from about 0.04 to about 0.1.
14. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 wherein the DoS by the hydrophobic organic group is from about 0.005 to about 1.5.
15. The composition of embodiments 1,2, 3, 4, 5, 6,7, 8, 9,10, 11, 12, 13, or 14 wherein the DoS by the hydrophobic organic group is from about 0.005 to about 1.0.
16. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wherein the DoS by the hydrophobic organic group is from about 0.005 to about 0.5.
17. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 wherein the DoS by the hydrophobic organic group is from about 0.4 to about 1.0.
18. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17 wherein the cationic organic group comprises the structure:
And R1、R2 and R3 are each independently a group comprising at least one carbon atom (e.g., R1、R2 and R3 are each CH3).
19. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, or 18 wherein the cationic organic group comprises the structure:
And R1、R2 and R3 are each independently a group comprising at least one carbon atom (e.g., R1、R2 and R3 are each CH3).
20. The composition of embodiments 1,2, 3,4, 5, 6,7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, or 19, wherein the hydrophobic organic group comprises a C2 to C26 acyl group (e.g., a C6 to C18 acyl group, a C8 to C16 acyl group, a C10 to C14 acyl group, or a C12 acyl group).
21. The composition of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, wherein the hydrophobic organic group comprises an aryl group (e.g., benzoyl or substituted benzoyl).
22. The composition of embodiments 1,2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21, wherein the ester derivative of dextran has a biodegradability of at least 10% after 15 days as determined by a carbon dioxide evolution test method.
23. The composition of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, wherein the composition is an aqueous composition.
24. The composition of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23, wherein the composition is a home care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), or a pharmaceutical product.
25. The composition of embodiments 1,2,3,4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 further comprising at least one surfactant.
26. The composition of embodiments 1,2, 3,4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, further comprising at least one enzyme.
27. The composition of embodiment 26, wherein the enzyme is a cellulase, protease, lipase, amylase, lipase, or nuclease.
28. The composition of examples 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27 further comprising at least one of a complexing agent, a soil release polymer, a surface activity enhancing polymer, a bleach activator, a bleach catalyst, a fabric conditioner, a clay, a foam booster, a foam inhibitor, an anti-corrosion agent, a soil suspension agent, an anti-soil redeposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightening agent, a fragrance, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a hueing dye, a visual signal transduction component, an antifoaming agent, a structuring agent, a thickening agent, an anti-caking agent, starch, sand, or a gelling agent.
29. The composition of embodiments 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28, wherein the composition is in the form of, or is contained in, a liquid, gel, powder, hydrocolloid, granule, tablet, bead, or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment pouch, or multi-compartment pouch.
30. The composition of examples 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24,25, 26, 27, 28, or 29, wherein the composition is (a) a flocculant, (b) a viscosity modifier, (c) a latex composition, (d) a pigment-containing composition, (e) a film or coating, (f) a fiber or fibrid, (g) a cosmetic product (e.g., a hair styling product), (h) a detergent composition, (i) an adhesive composition, (j) paper, or (k) any composition/product as disclosed herein.
31. A method of producing an ester derivative of dextran (dextran ester derivative), the method comprising: (a) contacting dextran with at least two esterifying agents, wherein at least one of the esterifying agents comprises a cationic organic group, wherein at least one of the esterifying agents comprises a hydrophobic organic group (optionally wherein [ i ] the contacting is performed in one reaction and the at least two esterifying agents are provided simultaneously in the reaction, or the at least two esterifying agents are provided sequentially in the reaction, or [ ii ] the contacting is performed in at least two separate reactions, wherein at least one of the reactions uses at least one esterifying agent having a cationic group and at least one of the reactions uses at least one esterifying agent having a hydrophobic group), wherein at least one cationic organic group and at least one hydrophobic organic group are esterified to the dextran, thereby producing an ester derivative of the dextran (e.g., according to examples 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 21, 20, 21, 22, wherein the at least one of the at least one cationic organic group is substituted with a cationic group, and at least one of the at least one organic group is replaced with an ester derivative of the dextran, wherein the at least one cationic organic group is replaced with an ester derivative of the dextran (a) and the step (a) is optionally substituted with an organic group of the cationic derivative of the polysaccharide).
32. A method of styling hair comprising at least steps (a) and (b), or steps (c) and (d), by (a) contacting (e.g., coating) hair with a dextran ester derivative (or a composition according to the above embodiments) according to embodiments 1,2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, thereby providing treated hair (or coated hair), and (b) bringing the treated hair (or the coated hair) in a desired form (e.g., straightening, curling, or bringing the hair in any other form than the form in which the hair existed prior to step [ a ] or [ b ]); or (c) bringing the hair in a desired form (e.g., straightening, curling, or any other form that is different from the form in which the hair was present prior to step [ c ]), and (d) contacting (e.g., coating) the hair of step (c) with a dextran ester derivative according to examples 1,2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 (or a composition according to the above examples), thereby providing treated hair (or coated hair), and (e) optionally, removing the solvent (if present) used in step (a) or (d) to deliver the dextran ester derivative to the hair.
33. A composition as described in examples 1, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, or a method as described in examples 31 or 32, but wherein "soy polysaccharide" is used in place of "dextran".
34. A method of producing a solid composition comprising at least one dextran ester derivative (such as from examples 1,2,3, 4, 5, 6,7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22), wherein the method at least comprises (a) providing a non-caustic (e.g., pH 6-8 or 6-9) aqueous composition (e.g., solution or dispersion) comprising at least one dextran ester derivative as disclosed herein, (b) bringing the aqueous composition in a desired form (e.g., fiber, fibrid, film/coating, composite, extrudate), and (c) removing a liquid/solvent of the aqueous composition of step (b) (e.g., by drying, and/or if a solution is used, by raising the pH of the solution to above about 10 to cause the dissolved dextran ester to precipitate out of solution) to produce a solid composition comprising the dextran ester derivative, and (d) optionally washing and/or drying the resulting solid composition of step (c).
35. The composition of examples 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or 33, or the method of example 32 or 34, but wherein the cationic organic ester groups are replaced with anionic organic groups, optionally wherein the anionic organic groups are linked to the dextran ether (e.g., carboxyalkyl groups such as carboxymethyl groups) or ester linkages (e.g., cyclic anhydride derivative groups such as succinate groups).
36. The composition of examples 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or 33, or the method of examples 32 or 34, but wherein the hydrophobic organic ester groups are replaced with anionic organic groups, optionally wherein the anionic organic groups are linked to the dextran ether (e.g., carboxyalkyl groups such as carboxymethyl groups) or ester linkages (e.g., cyclic anhydride derivative groups such as succinate groups).
Non-limiting examples of the compositions and methods disclosed herein include:
A composition comprising an ester derivative of dextran, wherein the dextran has a degree of substitution (DoS) up to about 3.0 substituted with at least one cationic organic group (cationic acyl) attached to the dextran ester.
The composition of embodiment 1b wherein the glucan is alpha-glucan.
The composition of embodiment 2b, wherein at least about 50% of the glycosidic linkages of the alpha-glucan are alpha-1.3 linkages.
The composition of embodiment 2b, wherein at least about 50% of the glycosidic linkages of the α -glucan are α -1,6 linkages, optionally wherein the α -glucan comprises at least 1% α -1,2 and/or α -1,3 branches.
The composition of embodiment 1b, wherein the glucan is beta-glucan.
The composition of embodiment 5b, wherein at least about 50% of the glycosidic linkages of the beta-glucan are beta-1, 3 linkages or beta-1, 4 linkages.
The composition of examples 1b, 2b, 3b, 4b, 5b, or 6b, wherein the dextran has a weight average degree of polymerization (DPw) of at least 6.
The composition of embodiments 1b, 2b, 3b, 4b, 5b, 6b, or 7b, wherein said DoS by said cationic organic group is at least about 0.005.
The composition of embodiments 1b, 2b, 3b, 4b, 5b, 6b, or 7b, wherein said DoS by said cationic organic group is at least about 0.3.
The composition of embodiments 1b, 2b, 3b, 4b, 5b, 6b, or 7b, wherein the DoS by the cationic organic group is from about 0.3 to about 2.0.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, or 10b, wherein the cationic organic group comprises the structure:
And R1、R2 and R3 are each independently a group containing at least one carbon atom.
The composition of example 11b, wherein R1、R2 and R3 are each CH3.
The composition of example 11b, wherein the cationic organic group comprises the structure:
And R1、R2 and R3 are each independently a group containing at least one carbon atom.
The composition of example 13b, wherein R1、R2 and R3 are each CH3.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, or 14b, wherein the ester derivative of dextran has a biodegradability of at least 10% after 15 days as determined by a carbon dioxide evolution test method.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, or 15b, wherein the composition is an aqueous composition.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, or 16b, wherein the composition is a household care product, a personal care product, an industrial product, an ingestible product (e.g., a food product), or a pharmaceutical product.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, or 17b further comprising at least one surfactant.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, or 18b further comprising at least one enzyme.
The composition of embodiment 19b, wherein the enzyme is a cellulase, protease, lipase, amylase, lipase, or nuclease.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, or 20b further comprising at least one of a complexing agent, a soil release polymer, a surface active enhancing polymer, a bleach activator, a bleach catalyst, a fabric conditioner, a clay, a foam booster, a foam inhibitor, an anti-corrosion agent, a soil suspension agent, an anti-soil redeposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightening agent, a fragrance, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a shading dye, a visual signal transduction component, an antifoaming agent, a structurant, a thickener, an anti-caking agent, starch, sand, or a gelling agent.
The composition of examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, 20b, or 21b, wherein the composition is in the form of, or is contained in, a liquid, gel, powder, hydrocolloid, granule, tablet, bead or lozenge, single-compartment pouch, multi-compartment pouch, single-compartment pouch, or multi-compartment pouch.
A composition as described in examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, 20b, 21b, or 22b, wherein the composition is (a) a flocculant, (b) a viscosity modifier, (c) a latex composition, (d) a pigment-containing composition, (e) a film or coating, (f) a fiber or fibrid, (g) a cosmetic product (e.g., a hair styling product), (h) a detergent composition, (i) an adhesive composition, (j) paper, or (k) any composition/product as disclosed herein.
A method of producing an ester derivative of dextran, the method comprising (a) contacting dextran in a reaction with at least one esterifying agent comprising a cationic organic group (cationic acyl group), wherein at least one cationic organic group (cationic acyl group) is esterified to the dextran thereby producing an ester derivative of the dextran (e.g., according to examples 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, or 15 b), wherein the ester derivative of dextran has a degree of substitution (DoS) of up to about 3.0 substituted with the cationic organic group (cationic acyl group), and (b) optionally, separating the ester derivative of dextran produced in step (a).
A composition as described in examples 1b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, 20b, 21b, 22b, or 23b, or a method as described in example 24b, but wherein "soy polysaccharide" is used in place of "dextran".
A method of producing a solid composition comprising at least one dextran ester derivative (such as from examples 1b, 2b, 3b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, or 15 b), wherein the method at least comprises (a) providing a non-caustic (e.g., pH 6-8 or 6-9) aqueous composition (e.g., solution or dispersion) comprising at least one dextran ester derivative as disclosed herein, (b) bringing the aqueous composition in a desired form (e.g., fiber, fibrid, film/coating, composite, extrudate), and (c) removing a liquid/solvent of the aqueous composition of step (b) (e.g., by drying, and/or if a solution is used, by raising the pH of the solution to above about 10 to cause precipitation of the dissolved dextran ester from solution) to produce a solid composition comprising the dextran ester derivative, and (d) optionally washing and/or drying the solid composition produced in step (c).
A method of styling hair comprising at least steps (a) and (b), or steps (c) and (d), by (a) contacting (e.g., coating) hair with a dextran derivative (or composition according to the above embodiments) according to embodiments 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, 20b, 21b, 22b, or 23b, thereby providing treated hair (or coated hair), and (b) causing the treated hair (or the coated hair) to be in a desired form (e.g., straightened, curled, or in any other form different from the form in which the hair existed prior to step [ a ] or [ b ]); or (c) bringing the hair of step (c) into contact (e.g., coated) with the glucan ester derivative (or composition according to the above embodiments) according to embodiments 1b, 2b, 3b, 4b, 5b, 6b, 7b, 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b, 19b, 20b, 21b, 22b, or 23b (or any other form other than the form in which the hair was present prior to step [ c ]), thereby providing treated hair (or coated hair), and (e) optionally, removing the solvent (if present) used in step (a) or (d) to deliver the dextran ester derivative to the hair.
Examples
The disclosure is further illustrated in the following examples. It should be understood that while these examples are indicative of certain aspects of the present disclosure, they are presented by way of illustration only. From the foregoing discussion and these examples, one skilled in the art can ascertain the essential characteristics of the disclosed embodiments, and without departing from the spirit and scope thereof, can make various changes and modifications to the disclosed embodiments to adapt it to various uses and conditions.
Materials/methods
Representative preparation of alpha-1, 3-glucan
Alpha-1, 3-glucan having about 100% of alpha-1, 3 glycosidic linkages can be synthesized, for example, according to the procedure disclosed in U.S. application publication No. 2014/0179913 (see, e.g., example 12 therein), which is incorporated herein by reference.
As another example, a slurry of alpha-1, 3-glucan is prepared from an aqueous solution (0.5L) containing Streptococcus salivarius gtfJ enzyme (100 units/L), sucrose (100 g/L) from OmniPur Sucrose (EM 8550), potassium phosphate buffer (10 mM) from Sigma Aldrich (SIGMA ALDRICH) and pH adjusted to 5.5 from DuPont (DuPont) as described in U.S. patent application publication No. 2013/0244188 (incorporated herein by reference)(Antimicrobial agent) (100 ppm). The resulting enzyme reaction was maintained at 20-25 ℃ for 24 hours. Since the α -1, 3-glucan synthesized in the reaction is water insoluble, a slurry is formed. Alpha-1, 3-glucan solids were then collected on a 40 micron filter paper using a buchner funnel equipped with a 325 mesh screen to form a wet cake containing about 60wt% to 80wt% water.
Representative preparation of alpha-1, 6-glucan having alpha-1, 2 branches
Methods for preparing alpha-1, 6-glucan containing varying amounts of alpha-1, 2 branches are disclosed in U.S. application publication No. 2018/0282385, which is incorporated herein by reference. Reaction parameters such as sucrose concentration, temperature and pH can be adjusted to provide a-1, 6-glucan having various levels of a-1, 2-branching and molecular weight. Representative procedures for preparing alpha-1, 6-glucan having 19% of alpha-1, 2-branches and 81% of alpha-1, 6 bonds are provided below. The glycosidic bond distribution was quantified using a 1D1 H-NMR spectrum. Additional samples of alpha-1, 6-glucan having alpha-1, 2-branches were similarly prepared. For example, one contains 32% α -1, 2-branches and 68% α -1,6 linkages, and the other contains 10% α -1, 2-branches and 90% α -1,6 linkages.
A stepwise combination of a glucosyltransferase (dextran sucrase) GTF8117 and an alpha-1, 2 branching enzyme GTFJ T1 was used to prepare a soluble alpha-1, 6-glucan having about 19% of the alpha-1, 2 branches according to the following procedure. The reaction mixture (2L) consisting of sucrose (450 g/L), GTF8117 (9.4U/mL) and 50mM sodium acetate was adjusted to pH 5.5 and stirred at 47 ℃. Aliquots (0.2-1 mL) were removed at predetermined times and quenched by heating at 90 ℃ for 15 minutes. The resulting heat treated aliquot was passed through a 0.45- μm filter. The flow-through was analyzed by HPLC to determine the concentration of sucrose, glucose, fructose, leuconostoc disaccharides, oligosaccharides and polysaccharides. After 23.5 hours, the reaction mixture was heated to 90 ℃ for 30 minutes. An aliquot of the heat treated reaction mixture was passed through a 0.45- μm filter and the flow was analyzed for soluble mono/di, oligo and polysaccharides. The main product is linear dextran with a DPw of 93.
The second reaction mixture was prepared by adding 238.2g sucrose and 210mL α -1, 2-branching enzyme GTFJ T1 (5.0U/mL) to the remaining heat treated reaction mixture obtained from the GTF8117 reaction just described above. The mixture was stirred at 30 ℃ and the volume was about 2.2L. Aliquots (0.2-1 mL) were removed at predetermined times and quenched by heating at 90 ℃ for 15 minutes. The resulting heat treated aliquot was passed through a 0.45- μm filter. The flow-through was analyzed by HPLC to determine the concentration of sucrose, glucose, fructose, leuconostoc disaccharides, oligosaccharides and polysaccharides. After 95 hours, the reaction mixture was heated to 90 ℃ for 30 minutes. An aliquot of the heat treated reaction mixture was passed through a 0.45- μm filter and the flow was analyzed for soluble mono/di, oligo and polysaccharides. The remaining heat treated mixture was centrifuged using a 1-L centrifuge bottle. The supernatant was collected and cleaned more than 200-fold using an ultrafiltration system with a 1-or 5-kDa MWCO cassette and deionized water. Drying the cleaned oligosaccharide/polysaccharide product solution. The dried samples were then analyzed by 1H-NMR spectroscopy to determine the anomeric linkages of the oligosaccharides and polysaccharides.
Example 1
Synthesis of betaine ester derivatives of insoluble alpha-glucan
This example shows the use of insoluble alpha-1, 3-glucan to produce various forms of betaine alpha-1, 3-glucan derivatives, which are soluble cationic glucan esters.
Water-insoluble alpha-1, 3-glucan (80 g [493.6mmol ]) (about 100% of alpha-1, 3 linkages) was suspended in 2.4L of N, N-dimethylacetamide. The temperature of the formulation was then raised to 120 ℃ and stirred at that temperature for two hours. After cooling to 80 ℃, 144gLiCl was added to the formulation. After cooling the formulation to 70 ℃, a clear solution was formed. Ground betaine hydrochloride (45.6 g [296.16mmo1], CAS registry number 590-46-5) (e.g., SIGMA ALDRICH catalog number B3501) was added to the solution, which was then stirred at 70℃for 10 minutes. Then, 57.6g (296.16 mmo 1) of tosyl chloride (dehydrating agent) was added to the solution, and the formulation was allowed to react at 70℃for 2 hours. A clear yellow solution formed which was then cooled to room temperature. The solid product was precipitated by adding 4L of ethanol to 1/3 of the solution, this was done in each part, after which all precipitated products were combined (a similar precipitated product could be obtained by adding 12L of ethanol to the whole solution in a larger vessel). The precipitated product betaine a-1, 3-glucan ester was washed three times with 5 liters of ethanol per wash and then dried under vacuum at 40 ℃.
The α -1, 3-glucan samples with different molecular weights (about 100% of the α -1, 3-linkages, all water insoluble) were reacted separately as described above, but with different amounts of reagents to produce betaine-modified α -1, 3-glucan ester products of different molecular weights and substitution (DoS) levels. Table 1 shows the various betaine alpha-1, 3-glucan ester products (samples A-F) that were successfully synthesized, all of which were readily soluble in neutral water at room temperature.
TABLE 1
Various water-soluble betaine alpha-1, 3-glucan ester products
Example 2
Synthesis of betaine ester derivatives of soluble alpha-glucan
This example shows the use of soluble glucan α -1, 2-branched α -1, 6-glucan to produce various forms of betaine α -1, 6-glucan derivatives, which are soluble cationic glucan esters.
Various soluble alpha-1, 2-branched alpha-1, 6-glucans were used for betaine esterification, 40kDa alpha-1, 6-glucan with 20% of alpha-1, 2 branches, 17kDa alpha-1, 6-glucan with 45% of alpha-1, 2 branches and 300kDa alpha-1, 6-glucan with 45% of alpha-1, 2 branches. In each of these α -glucans, the α -1, 6-glucan backbone (with α -1,2 branches therein) has 100% α -1,6 glycosidic linkages, and the listed molecular weights are those of the α -1, 6-glucan backbone. Each α -1, 2-branch consists of a single (side chain) glucose unit.
For betaine esterification, each of the above branched alpha-1, 6-glucan (40 g) was individually dissolved in DMAc (200 mL) at elevated temperature (110 ℃ C. To 130 ℃ C.). Betaine hydrochloride (40 g, CAS registry number 590-46-5) (e.g., SIGMA ALDRICH catalog number B3501) and dicyandiamide (> 20g, dehydrating agents) were then added to begin esterification. The uniformity of each reaction formulation was further adjusted by the addition of DI-water and/or CaCl2. Each reaction was then heated under vacuum for less than 3 hours. About 80mL of liquid was removed and the crude product was precipitated from methanol and washed several times in methanol to give the desired product (betaine-modified α -glucan ester) in quantitative yield. The products from these reactions were designated BC-2 (40 kDa α -1, 6-glucan, 20% α -1,2 branching, doS 0.02), BC-4 (40 kDa α -1, 6-glucan, 20% α -1,2 branching, doS 0.04), BC-10 (17 kDa α -1, 6-glucan, 45% α -1,2 branching, doS 0.04) and BC-11 (300 kDa α -1, 6-glucan, 45% α -1,2 branching, doS 0.04).
Example 3
Analysis of betaine alpha-1, 3-glucan ester derivatives
An aqueous solution of betaine a-1, 3-glucan ester product of table 1 was prepared and analyzed for viscosity using a Brookfield unit (spindle S03) at room temperature (about 20 ℃). High molecular weight dextran esters exhibit high viscosity levels at relatively low concentrations (see table 2, e.g., product E), which are desirable features in many applications such as industrial applications (e.g., oil and gas production, wastewater treatment), personal care, and home care. In contrast, dextran ester products having low molecular weights allow for the preparation of high solids aqueous solutions (about 15wt% or higher) (see table 2), which is a desirable feature in coating applications (e.g., paper coatings), for example, higher solids content minimizes the drying time required and improves overall process yield.
TABLE 2
Viscosity analysis of aqueous solutions of betaine alpha-1, 3-glucan ester products
A is shown in table 1.
b Concentration of dextran ester product dissolved in water.
The effect of pH on the dissolution behavior of betaine-modified alpha-1, 3-glucan in water was tested. A 20wt% solution of sample a (see table 1) in water (about 1 mL) was added to 20mL of water (water pH 13, 12, 11, or 10, respectively) containing 4000, 400, 40, or 4ppm NaOH. At pH 13 and 12, dextran esters settle out of solution as a hard polymer at the bottom (pH 13) or as a cloudy solution (pH 12). At pH 11, more dextran ester remains in solution (some cloudiness), while most, if not all, of the dextran ester remains in solution at pH 10. This dissolution behavior of betaine-modified alpha-1, 3-glucan esters is unexpected. While quaternary ammonium alpha-1, 3-glucan ethers (e.g., hydroxypropyl trimethylammonium glucan ether) become more soluble at high pH, the opposite is true for betaine alpha-1, 3-glucan esters. This behavior provides several advantages for the use of betaine alpha-1, 3-glucan esters in polymer processing. For example, dextran esters can be extruded into fibers or films from water into high pH baths. The ester chemistry can then be removed (chemically or enzymatically) if desired to produce a fully water insoluble alpha-1, 3-glucan product. Thus, betaine-modified alpha-1, 3-glucan esters allow for maintenance of a water-based processing environment to produce products comprising non-derivatized alpha-1, 3-glucan.
Biodegradability assay
Biodegradability is determined in accordance with OECD 301B rapid biodegradability CO2 escape test guidelines (see OECD,1992. Economic CO-ordination and development organization, OECD 301 rapid biodegradability. OECD chemical test guidelines, part 3-incorporated herein by reference). In this assay, the test substance (betaine dextran ester) is the only carbon and energy source and under aerobic conditions the microorganism metabolizes the test substance to produce CO2 or incorporate carbon into the biomass. The amount of CO2 produced by the test substance (corrected for CO2 evolved from the blank inoculum) is expressed as a percentage of the theoretical amount of CO2 that can be produced if the organic carbon in the test substance is fully converted to CO2 (ThCO2).
The biodegradation test of betaine alpha-1, 3-glucan ester derivatives was performed according to the OECD 301B test (above). The dextran ester samples with the highest betaine groups DoS (sample F, table 1) were analyzed for biodegradation over 28 days and the results are shown in fig. 1 and table 3.
TABLE 3 Table 3
Biodegradation of betaine alpha-1, 3-glucan ester products
Abbreviations a TOC (Total organic carbon content), AVG (average), SD (standard deviation), REL (relative to the reference)
Sample F exhibited significant biodegradability within 28 days of the initial test (fig. 1, table 3). This result is unexpected because in terms of biodegradability, the DoS (0.88) of sample F is relatively high, as such DoS levels with different bond/derivatization types (e.g., ether linked carboxymethyl or ether linked hydroxypropyl trimethylammonium groups) will typically greatly inhibit biodegradability. The enhanced biodegradability characteristics of betaine alpha-1, 3-glucan ester derivatives herein make them highly useful in applications where bioaccumulation of polymers is undesirable (e.g., aqueous environments).
Example 4
Use of betaine-modified dextran esters in cosmetic care-hair styling applications
In this example, betaine alpha-1, 3-glucan esters and betaine alpha-1, 2-branched alpha-1, 6-glucan esters were tested for their characteristics related to hair styling applications. The tests for these applications were performed with the different cationic dextran esters listed in table 4 together with a negative control (dextran derivative not used) and a positive control (cationic dextran ether).
TABLE 4 Table 4
After styling with 1:1 ethanol/water with 1wt% dextran derivative samples, the hair tresses were changed in height. Little or no change reflects effective hair styling (i.e., application of glucan derivatives maintains the curvature of the hair tresses). Reference is made to the following text.
Each test sample was completely dissolved in the ethanol/water (1:1) mixture at1 wt%. The turbidity of the solution was then measured in Nephelometric Turbidity Units (NTU) using a calibrated nephelometer (HACH 2100AN nephelometer). The solution was then poured into a petri dish and allowed to evaporate overnight at room temperature. The quality of each of the resulting films was checked. For several of the betaine-modified dextran ester samples tested (see table 4), good solubility and high quality film formation as indicated by low solution turbidity and ability to form transparent films, respectively, were observed. These features are believed to make the material useful in hair styling products-for example, may allow for clear and transparent application to the hair to provide hair styling hold while avoiding an unclean appearance.
In the curl retention test, about 1 gram of each solution (table 4) was applied to a hair tress (8 "rinboost hair sample). The resulting tress was dried at room temperature overnight, with half of the tress being rewound at an angle >90 degrees. Each hair tress was then hung in a 45 ℃ oven and heated for 3 hours. The height of the curled half of each tress was then measured and compared to the height of the tress present before hanging from it (table 4). In the control experiment, the height of the curled half of the hair tress was changed by 6.5cm. However, for several locks treated with betaine-modified dextran ester samples, the height of the curled half of the lock did not change, or changed very little (see table 4), indicating significant hair styling retention.
Example 5
Use of betaine-modified dextran esters in coatings
In this example, betaine alpha-1, 3-glucan esters were used to coat paper. The coating provides an oil/grease barrier to the paper.
Betaine alpha-1, 3-glucan ester (sample a, table 1) was applied as a solution on a paper substrate, which was prepared by dissolving betaine alpha-1, 3-glucan powder in distilled water at 10wt% or 20 wt%. For example, to prepare 50 grams of a 10wt% formulation, 5 grams of betaine dextran powder was dissolved in 45 grams of water. Each formulation was stirred using a magnetic stirrer bar at room temperature until all the powder was dissolved. Alternatively, a laboratory blender may be used if desired. The viscosity of each solution increases as the betaine dextran dissolves in water.
Once the betaine a-1, 3-glucan powder was completely dissolved, the resulting solution was applied to a foldable cardboard paper substrate (METSABOARD CLASSIC FBB,235gsm grammage, 0.425mm thickness) using an automated bar coater with a heating module (model PROCEQ ZAA 2600.A, jennel test instruments company (Zehntner Testing Instruments)). Different rods (Zehntner) were used to provide the paper substrate with the desired coating thickness and grammage: #3 rods (wet thickness of 6.9 μm, cat No. ACC 378.006) and #14 rods (wet thickness of 32.0 μm, cat No. ACC 378.032). The coating speed was set at 20mm/min and coated at room temperature. The coated paper was dried overnight at ambient conditions. Lower drying times would also be possible, and drying may optionally be carried out in an oven at, for example, 60 ℃ for 10 minutes. In one test, the program was applied to the pre-treated side of the cardboard (pre-treated by the manufacturer for printing) while the program was applied to the back side (non-printed side) of a single piece of cardboard that was otherwise retested.
The oil barrier properties of each betaine a-1, 3-glucan coated paper substrate were evaluated using a 60 second Cobb Unger oil test (ISO 535, TAPPI T441, SCAN P12, EN 20535, DIN 53132, incorporated herein by reference). The results of this analysis are shown in table 5. Papers coated with betaine a-1, 3-dextran esters using 10wt% and 20wt% solutions exhibited significant oil barrier function as compared to the negative control reference (uncoated papers) (table 5).
TABLE 5
Gsm, grams per square meter.
Example 6
Two-step process for the synthesis of amphiphilic dextran ester derivatives containing cationic and hydrophobic substituents
This example shows a two-step process using water-soluble glucan α -1, 2-branched α -1, 6-glucan to produce a multifunctional amphiphilic α -glucan ester derivative. In particular, alpha-glucan derivatives substituted with betaines, benzoyl, lauroyl and acetyl groups are produced.
Step 1. Synthesis of hydrophobic dextran ester derivatives containing benzoyl and lauroyl substituents:
Dextran powder (40 kDa alpha-1, 6-glucan with 20% alpha-1, 2 branching, 30 g) was dissolved in DMAc (150 mL) at 90 ℃. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove about 60mL of liquid. Benzoyl chloride (17 g) and lauroyl chloride (8 g) were then added, after which the reaction formulation was stirred at 90 ℃ for 1.5 hours. The resulting product benzoyl lauroyl α -1, 2-branched α -1, 6-glucan ester was precipitated and purified using ethyl acetate and obtained in quantitative yield.
Step one 2. Synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl and lauroyl substituents:
The hydrophobic α -glucan ester product (20 g) prepared in step 1 above was dissolved in DMAc (100 mL) at elevated temperature (110 ℃). Betaine hydrochloride (20 g, CAS registry number 590-46-5) (e.g., SIGMA ALDRICH catalog number B3501), dicyandiamide (20 g), and water (3 mL) were then added. The reaction formulation was distilled under vacuum at 130 ℃ for one hour to remove 40mL of liquid. The reaction was then cooled to room temperature, after which the crude product was first precipitated in acetonitrile and then dissolved in water. The resulting aqueous solution was then subjected to ultrafiltration (MWCO 5 kDa) followed by freeze-drying to yield 5.6 g of the product benzoyl lauroyl betaine a-1, 2-branched a-1, 6-glucan ester. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.07, 0.52, 0.23 and 0.13 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups are derived from DMAc solvents), respectively.
Example 7
Two-step process for the synthesis of amphiphilic dextran ester derivatives containing betaine and hydrophobic substituents
Step 1. Synthesis of hydrophobic dextran ester derivative containing benzoyl and acetyl substituents:
Dextran powder (40 kDa alpha-1, 6-glucan with 20% alpha-1, 2 branching, 200 g) was dissolved in DMAc (1000 mL) at 88 ℃. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 300mL of liquid. Benzoyl chloride (110 g) was then added, after which the reaction formulation was stirred at 88 ℃ for 2 hours. The resulting product, benzoylα -1, 2-branched α -1, 6-glucan ester, was precipitated and purified using isopropanol and obtained in quantitative yield. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.36 and 0.14 for benzoyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively.
Step one 2, synthesis of amphiphilic dextran ester derivative containing betaine, benzoyl and acetyl substituent groups:
The hydrophobic α -glucan ester product (10 g) prepared in step 1 above was dissolved in DMAc (300 mL) at elevated temperature (90 ℃). Then, betaine hydrochloride (6 g) was added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 30mL of liquid. Tosyl chloride (12 g) was then added. The final reaction formulation was heated at 75 ℃ for one hour and then cooled to room temperature, after which the desired product was precipitated in isopropanol and washed three times with isopropanol to provide benzoylacetyl betaine a-1, 2-branched a-1, 6-glucan ester. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.27, 0.34 and 0.14 for betaine, benzoyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively. The molecular weight of the final product was determined by SEC to be 10.5kDa.
Example 8
Two-step process for the synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl, lauroyl and acetyl substituents
Step 1. Synthesis of hydrophobic dextran ester derivatives containing benzoyl, lauroyl and acetyl substituents:
Dextran powder (40 kDa alpha-1, 6-glucan with 20% alpha-1, 2 branching, 120 g) was swollen in DMAc (550 mL) at 90℃for one hour. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 185mL of liquid. Benzoyl chloride (74 g) and lauroyl chloride (30 g) were then added, after which the reaction formulation was stirred at 90 ℃ for one hour 45 minutes. The resulting product benzoyl lauroyl acetyl α -1, 2-branched α -1, 6-glucan ester was precipitated and purified using isopropanol and obtained in quantitative yield. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.64, 0.12 and 0.08 for benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively.
Step one 2. Synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl, lauroyl and acetyl substituents:
the hydrophobic α -glucan ester product (10 g) prepared in step-1 above was dissolved in DMAc (300 mL) at elevated temperature (90 ℃). Then, betaine hydrochloride (6 g) was added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 30mL of liquid. Tosyl chloride (12 g) was then added. The final reaction formulation was heated at 75 ℃ for one hour and then cooled to room temperature, after which the desired product was precipitated in isopropanol and washed three times to give benzoyl lauroyl acetyl betaine a-1, 2-branched a-1, 6-glucan ester in quantitative yield. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.13, 0.34, 0.03 and 0.01 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively. The molecular weight of the final product was determined by SEC to be 11.4kDa.
Example 9
Two-step process for the synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl, lauroyl and acetyl substituents
Step 1. Synthesis of hydrophobic dextran ester derivatives containing benzoyl, lauroyl and acetyl substituents:
Dextran powder (40 kDa alpha-1, 6-glucan with 20% alpha-1, 2 branching, 120 g) was swollen in DMAc (560 mL) at 90℃for one hour. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 240mL of liquid. Benzoyl chloride (74 g) and lauroyl chloride (30 g) were then added, after which the reaction formulation was stirred at 90 ℃ for 1.5 hours. The resulting product benzoyl lauroyl acetyl α -1, 2-branched α -1, 6-glucan ester was precipitated and purified using isopropanol and obtained in quantitative yield. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.57, 0.04 and 0.10 for benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively.
Step one 2. Synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl, lauroyl and acetyl substituents:
the hydrophobic α -glucan ester product (10 g) prepared in step 1 above was dissolved in DMAc (300 mL) at elevated temperature (90 ℃). CaCl2.2H2 O (12 g) was then added. Then, betaine hydrochloride (6 g) was added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 30mL of liquid. Tosyl chloride (12 g) was then added. The final reaction formulation was heated at 75 ℃ for one hour and then cooled to room temperature, after which the desired product was precipitated in isopropanol and washed three times to give benzoyl lauroyl acetyl betaine a-1, 2-branched a-1, 6-glucan ester in quantitative yield. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.28, 0.39, 0.02 and 0.12 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively. The molecular weight of the final product was determined by SEC to be 8.1kDa.
Example 10
One pot synthesis of amphiphilic dextran ester derivatives containing cationic and hydrophobic substituents this example illustrates a one pot (single step) process using water soluble dextran alpha-1, 2 branched alpha-1, 6-dextran to produce a multifunctional amphiphilic alpha-dextran ester derivative. In particular, alpha-glucan derivatives substituted with betaines, benzoyl, lauroyl and acetyl groups are produced.
Dextran powder (40 kDa alpha-1, 6-dextran with 20% alpha-1, 2 branches, 40 g) was dissolved in DMAc (200 mL) at elevated temperature (90 ℃). CaCl2.2H2 O (12 g) was then added. Subsequently, betaine hydrochloride (40 g) and tosyl chloride (25 g) were added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 60mL of liquid. Benzoyl chloride (15 g) and lauroyl chloride (10 g) were then added to the reaction. The final reaction formulation was heated for one hour and then cooled to room temperature, after which about 200mL of ethanol was added. The soluble portion of the formulation was diluted with water and purified by ultrafiltration (MWCO 5 kDa) and then freeze-dried to yield 10.8g of the product benzoyl lauroyl betaine a-1, 2-branched a-1, 6-glucan ester. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.07, 0.27, 0.16 and 0.08 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively.
Example 11
One-pot synthesis of amphiphilic dextran ester derivative containing betaine and hydrophobic substituent group
This example shows a one-pot (single step) process using water-soluble glucan α -1, 2-branched α -1, 6-glucan to produce a multifunctional amphiphilic α -glucan ester derivative. In particular, alpha-glucan derivatives substituted with betaines, benzoyl, lauroyl and acetyl groups are produced.
Dextran powder (40 kDa α -1, 6-dextran with 20% α -1,2 branching, 20g, pre-dried overnight at 45 ℃) was swollen in DMAc (350 mL) for one hour at elevated temperature (90 ℃). After this step, betaine hydrochloride (6 g) was added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove 30mL of liquid. Benzoyl chloride (7 g) and lauroyl chloride (5 g) were then added. The resulting reaction formulation was heated for one hour. Then, tosyl chloride (25 g) was added. The final reaction formulation was stirred at 75 ℃ for an additional hour and then cooled to room temperature. Isopropanol was added to precipitate the crude product. The solid product was further washed several times with isopropanol and then dried under vacuum to give 17.6g of the product benzoyl lauroyl betaine alpha-1, 2-branched alpha-1, 6-glucan ester. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.15, 0.05, 0.01 and 0.07 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups are derived from DMAc solvents), respectively. The molecular weight of the final product was determined by SEC to be 53.9kDa.
Example 12
One-pot synthesis of amphiphilic dextran ester derivatives containing betaine, benzoyl, lauroyl and acetyl substituents
This example shows a one-pot (single step) process using water-soluble glucan α -1, 2-branched α -1, 6-glucan to produce a multifunctional amphiphilic α -glucan ester derivative. In particular, alpha-glucan derivatives substituted with betaines, benzoyl, lauroyl and acetyl groups are produced.
Dextran powder (40 kDa α -1, 6-dextran with 20% α -1,2 branching, 20g, pre-dried overnight at 45 ℃) was swollen in DMAc (350 mL) for one hour at elevated temperature (90 ℃). After this step, betaine hydrochloride (6 g) was added. The reaction formulation was distilled under vacuum at 100 ℃ for one hour to remove about 30mL of liquid. Benzoyl chloride (10 g) and lauroyl chloride (6.5 g) were then added. The resulting reaction formulation was heated for one hour. Then, tosyl chloride (12 g) was added. The final reaction formulation was stirred at 75 ℃ for an additional hour and then cooled to room temperature. Isopropanol was added to precipitate the crude product. The solid product was further washed several times with isopropanol and then dried under vacuum to give about 18g of the product benzoyl lauroyl betaine alpha-1, 2-branched alpha-1, 6-glucan ester. In particular, the product was determined by1 H-NMR analysis to have acyl DoS values of 0.20, 0.09, 0.22 and 0.19 for betaine, benzoyl, lauroyl and acetyl groups (acetyl groups derived from DMAc solvent), respectively. The molecular weight of the final product was determined by SEC to be 10.4kDa.
Example 13
Use of amphiphilic ester derivatives in cosmetic care-hair styling applications
In this example, the characteristics of amphiphilic alpha-1, 2-branched alpha-1, 6-glucan esters were tested in relation to hair styling applications. In particular, the two different amphiphilic dextran esters produced in examples 6 and 10 above (both benzoyl lauroyl betaine α -1, 2-branched α -1, 6-dextran) and a negative control (no dextran derivative was used) were tested for these applications.
Each dextran ester test sample was completely dissolved in an ethanol/water (3:1) mixture at 4 wt%. The turbidity of the solution was then measured in Nephelometric Turbidity Units (NTU) using a calibrated nephelometer (HACH 2100AN nephelometer). Turbidity measurements for each sample are listed in table 6.
In the curl retention test, about 0.5 grams of each solution was applied to a hair tress (8 "rinboost hair sample). The resulting tress was dried at room temperature overnight, with half of the tress being rewound at an angle >90 degrees. The height of the curled half of each tress is then measured and compared to the height of the tress present before it was dried. In the control experiment, the height of the curled half of the hair tress was changed by 6.0cm. As a comparison, for tresses treated with the amphiphilic dextran ester derivative produced in example 6 (step 2 product) or 10 (one pot product), the height of the curled half of each tress varied much less (table 6), indicating significant hair styling hold.
TABLE 6
A hair tresses height change after styling with 3:1 ethanol/water with 4wt% dextran ester derivative samples. Little or no change reflects effective hair styling (i.e., application of glucan derivatives maintains the curvature of the hair tresses). See above.