ALKOXYLATED ISO-NONANOLTechnical FieldThe invention relates to an alkoxylated iso-nonanol. The new alkoxylated iso-nonanol leads to improved surfactant properties and achieves improved dynamic surface tension and emulsifying ability.
BackgroundNonionic surfactants are widely used in various fields, for example household and personal care products, due to their advantages like resistance to water hardness, good oil and grease removing capability, and compatibility with other surfactants. As a large family of nonionic surfactants, alkoxylated aliphatic alcohols have been developed for several decades, which consist of a hy-drophobic group derived from an alcohol such as fatty alcohol, Guerbet alcohol or oxo alcohol, and a hydrophilic chain or segment derived from varying amounts of alkylene oxide such as eth-ylene oxide, propylene oxide and/or butylene oxide. The alkoxylated aliphatic alcohols have ex-cellent permeability, emulsification, foam and detergency properties, and are environmentally friendly due to their lower toxicity risks and higher biodegradability rates.
Notwithstanding the widespread use of alkoxylated aliphatic alcohols, the research of this type of nonionic surfactant generally focused on alkoxylated long-chain alcohol such as C12 to C18 or higher alcohols. Fewer researchers and manufacturers looked at alkoxylated alcohols with less carbon numbers, especially having branched chains, although some products are already com-mercially available, for example, alkyl polyethylene glycol ether based on C10-Guerbet alcohol and ethylene oxide manufactured and sold under LUTENSOLTM XP by BASF.
Alkoxylated aliphatic alcohols vary in wetting, foaming, detergency and other properties for their applications in cleaning products, depending on a great extent on the type of alcohol and on the type and amount of alkylene oxide adducts.
There is a need to find a new alkoxylated aliphatic alcohol nonionic surfactants which can endow desirable comprehensive properties including for example, dynamic surface tension, foaming property and emulsifying ability.
Summary of InventionIt is an object of the present invention to find an alkoxylated iso-nonanol obtained by alkoxylation of a mixture of isomeric nonanols. The obtained new alkoxylated iso-nonanol nonionic surfactant is useful in various applications, including, for example, cleaning formulations, which could exhibit a comprehensive performance with respect to dynamic surface tension property, emulsifying abil-ity property, the foaming behavior, viscosity, stability and detergency of the cleaning formulations. It was found by the inventors that the object can be achieved by an alkoxylated iso-nonanol ob-tained by alkoxylation of a mixture of isomeric nonanols, wherein the mixture of isomeric nonanols has a degree of branching (ISO index) in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4. It was found by the inventors that the object can be achieved by an alkoxylated iso-nonanol with a certain range of alkoxylation degree, which can be obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably 1.1 to 1.4. Particularly, the alkoxylated iso-nonanol is ethoxylated isononanol.
Accordingly, in the first aspect, the present invention relates to a cleaning formulation comprising an alkoxylated iso-nonanol with a degree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4. Particularly, the cleaning formulation of the present invention comprises an ethoxylated iso-nonanol with a degree of ethoxylation in the range of 1 to 20, particularly in the range of 3 to 14.
More particularly, the present invention relates to a cleaning formulation for home care cleaning, household cleaning or institutional cleaning, for example laundry detergent formulations and hard surface detergent formulations, which comprises the alkoxylated iso-nonanol as described herein.
In the second aspect, the present invention relates to use of an alkoxylated iso-nonanol with a degree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14 in a cleaning formulation, wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of iso-meric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4.
Particularly, the present invention relates to an ethoxylated iso-nonanol with a degree of ethoxy-lation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the ethoxylated iso-nonanol is obtained by ethoxylation of a mixture of isomeric nonanols having the degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.
Particularly, the present invention relates to an ethoxylated propoxylated iso-nonanol with a de-gree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the ethox-ylated propoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having the degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.
Particularly, the present invention relates to an ethoxylated propoxylated ethoxylated iso-nonanol, preferably with a degree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the ethoxylated propoxylated ethoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having the degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.
Particularly, the present invention relates to a propoxylated ethoxylated propoxylated iso-nonanol, preferably with a degree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the propoxylated ethoxylated propoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having the degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.
Detailed DescriptionThe singular forms “a” , “an” and “the” include plural referents unless the context clearly dictates otherwise. The terms “comprise (s) ” , “comprising” , etc. are used interchangeably with “contain (s) ” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements can be present. The expressions “consist (s) of” or “consisting of” or cognates can be embraced within “comprise (s) ” or “comprising” or cognates. The terms “in-clude (s) ” , “including” , etc. are to be interpreted in a non-limiting, open manner.
Herein, the term “iso-nonanol” is intended to mean an isomeric mixture of C9 oxo alcohols, which is generally produced commercially by the hydroformylation of a C8 olefin mixture.
Herein, the term “degree of alkoxylation” refers to the number of moles of alkylene oxide reacted with one mole of iso-nonanol to produce the alkoxylated iso-nonanol nonionic surfactant, and is intended to mean number average degree of alkoxylation. Similarly, the term “degree of ethoxy-lation” is intended to mean the average number of moles of ethylene oxide unit per mole of eth-oxylated iso-nonanol.
Herein, the term “degree of branching” means the sum of branching number multiplying with the proportion of the respective alkyl alcohol (nonanol) in the mixture of isomeric alkyl alcohols (iso-nonanols) . For example, the branching degree of nonanol-1 is 0; 2-ethyl-2-methylhexanol-1 is 2 and 2, 3, 4-trimethylhexanol-1 is 3. The degree of branching of the isomeric nonanols is the sum of all values which are obtained by multiplying the branching number with the proportion of the respective nonanol.
In the first aspect, the present invention provides an alkoxylated iso-nonanol with a degree of alkoxylation in the range of 1 to 20, wherein the alkoxylated iso-nonanol is obtained by alkoxyla-tion of a mixture of isomeric nonanols having a degree of branching within 1.1 to 1.5, preferably 1.1 to 1.4.
<Alkoxylated iso-nonanol>
The alkoxylated iso-nonanol according to the present invention may be represented by the for-mula:
RO- (AO) n-H (I)
wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, AO is alkyleneoxy, for example ethyleneoxy, propyleneoxy, butyleneoxy or a combination thereof, and n is a number in the range of 1 to 20,
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nona-nols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
In some embodiments, the alkoxylated iso-nonanol according to the present invention has the formula (I) wherein AO is ethyleneoxy, propyleneoxy or a combination thereof, preferably eth-yleneoxy.
In some embodiments, the alkoxylated iso-nonanol according to the present invention has the formula (I) wherein AO is ethyleneoxy, propyleneoxy or a combination thereof, preferably eth-yleneoxy, still preferably a combination of ethyleneoxy and propyleneoxy.
The polymeric segment derived from alkylene oxide in the alkoxylated iso-nonanol, for example the polymeric segment represented by “- (AO) n-” in the formula (1) , may have a block polymeric structure or a random polymeric structure when the segment is derived from two or more different alkylene oxides, for example ethylene oxide and propylene oxide.
It will be understood that “- (AO) n-” in formula (I) is just intended to represent a polymeric segment having alkyleneoxy units at a total number of “n” , which is not intended to impose any limitation of the polymeric structure. When the said segment is derived from two or more different alkylene oxides, for example, ethylene oxide and propylene oxide, the index “n” in “- (AO) n-” represents the total number of ethyleneoxy units and propyleneoxy units, irrespective of their arrangement in the segment.
It will be also understood that the alkoxylated iso-nonanol may be a mixture of alkoxylates with respect to the degree of alkoxylation. In this case, the index n in formula (I) may be a decimal number.
It will be understood that the alkoxylated iso-nonanol is a mixture of alkoxylates of iso-nonanol in view of that fact that iso-nonanol is an isomeric mixture. The alkoxylated iso-nonanol may also be a mixture of alkoxylates with respect to the degree of alkoxylation. In this case, the index n in formula (I) may be a decimal number.
Preferably, the alkoxylated iso-nonanol according to the present invention is a mixture of alkox-ylates of iso-nonanol having the same degree of alkoxylation in the range of 1 to 20, preferably in the range of 3 to 14, for example 3, 4, 5, 6, 7, 8, 9, wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
In some embodiments, the alkoxylated iso-nonanol according to the present invention is a mixture of ethoxylates of iso-nonanol having the same degree of alkoxylation in the range of 1 to 20. The ethoxylated iso-nonanol according to the present invention as described herein preferably has a degree of alkoxylation in the range of 3 to 14, for example 3, 4, 5, 6, 7, 8, 9 and 10, wherein the ethoxylated iso-nonanol is obtained by ethoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
Particularly, the alkoxylated iso-nonanol can be prepared by adding alkylene oxide, for example ethylene oxide, propylene oxide or a mixture thereof to iso-nonanol in a conventional manner in the presence of a conventional alkali catalyst, such as potassium hydroxide or sodium hydroxide.
Suitable iso-nonanol (i.e., the isomeric mixture of C9 oxo alcohols) for preparing the alkoxylated iso-nonanol according to the present invention may be commercially available, for example from BASF. The iso-nonanol prepared in accordance with known method via the hydroformylation route may also be used for preparing the alkoxylated iso-nonanol according to the present inven-tion.
In any one embodiment of the present invention, the isomeric mixture of nonanols has degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.
Generally, the method for preparing iso-nonanol involves two or more steps and starts from butenes. In a first step, the butenes are dimerized to give a mixture of isomeric octenes. The octene mixture is then hydroformylated to give C9 aldehydes and then hydrogenated to give a nonanol isomer mixture, often referred to as iso-nonanol. Details of suitable methods with respect to hydrocarbon feed as the source of butenes, catalysts, process conditions, etc. can be found in many patent applications, for example in DE19924339A1, WO 01/48049 A1 or US9090553B2.
In some preferred embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol according to the present invention may have the following composition, based on the total sum of the components of 100%by weight, as described in US9090553B2:
·from 6.0 to 16.0%by weight, preferably from 7.0 to 15.0%by weight, particularly preferably from 8.0 to 14.0%by weight, of n-nonanol;
·from 12.8 to 28.8%by weight, preferably from 14.8 to 26.8%by weight, particularly preferably from 15.8 to 25.8%by weight, of 6-methyloctanol;
·from 12.5 to 28.8%by weight, preferably from 14.5 to 26.5%by weight, particularly preferably from 15.5 to 25.5%by weight, of 4-methyloctanol;
·from 3.3 to 7.3%by weight, preferably from 3.8 to 6.8%by weight, particularly preferably from 4.3 to 6.3%by weight, of 2-methyloctanol;
·from 5.7 to 11.7%by weight, preferably from 6.3 to 11.3%by weight, particularly preferably from 6.7 to 10.7%by weight, of 3-ethylheptanol;
·from 1.9 to 3.9%by weight, preferably from 2.1 to 3.7%by weight, particularly preferably from 2.4 to 3.4%by weight, of 2-ethylheptanol;
·from 1.7 to 3.7%by weight, preferably from 1.9 to 3.5%by weight, particularly preferably from 2.2 to 3.2%by weight, of 2-propylhexanol;
·from 3.2 to 9.2%by weight, preferably from 3.7 to 8.7%by weight, particularly preferably from 4.2 to 8.2%by weight, of 3, 5-dimethylheptanol; from 6.0 to 16.0%by weight, preferably from 7.0 to 15.0%by weight, particularly preferably from 8.0 to 14.0%by weight, of 2, 5-dimethyl-heptanol;
·from 1.8 to 3.8%by weight, preferably from 2.0 to 3.6%by weight, particularly preferably from 2.3 to 3.3%by weight, of 2, 3-dimethylheptanol;
·from 0.6 to 2.6%by weight, preferably from 0.8 to 2.4%by weight, particularly preferably from 1.1 to 2.1%by weight, of 3-ethyl-4-methylhexanol;
·from 2.0 to 4.0%by weight, preferably from 2.2 to 3.8%by weight, particularly preferably from 2.5 to 3.5%by weight, of 2-ethyl-4-methylhexanol; and
·from 0.5 to 6.5%by weight, preferably from 1.5 to 6%by weight, particularly preferably from 1.5 to 5.5%by weight, of other alcohols having 9 carbon atoms.
In some embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol according to the present invention may have the following composition, based on the total sum of the com-ponents of 100%by weight:
·from 7.0 to 15.0%by weight of n-nonanol;
·from 14.8 to 26.8%by weight of 6-methyloctanol;
·from 14.5 to 26.5%by weight of 4-methyloctanol;
·from 3.8 to 6.8%by weight of 2-methyloctanol;
·from 6.3 to 11.3%by weight of 3-ethylheptanol;
·from 2.1 to 3.7%by weight of 2-ethylheptanol;
·from 1.9 to 3.5%by weight of 2-propylhexanol;
·from 3.7 to 8.7%by weight of 3, 5-dimethylheptanol; from 7.0 to 15.0%by weight, of 2, 5-dime-thyl-heptanol;
·from 2.0 to 3.6%by weight of 2, 3-dimethylheptanol;
·from 0.8 to 2.4%by weight of 3-ethyl-4-methylhexanol;
·from 2.2 to 3.8%by weight of 2-ethyl-4-methylhexanol; and
·preferably from 1.5 to 6%by weight of other alcohols having 9 carbon atoms.
In some other embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol ac-cording to the present invention may have the following composition, based on the total sum of the components of 100%by weight,
·from 8.0 to 14.0%by weight of n-nonanol;
·from 15.8 to 25.8%by weight of 6-methyloctanol;
·from 15.5 to 25.5%by weight of 4-methyloctanol;
·from 4.3 to 6.3%by weight of 2-methyloctanol;
·from 6.7 to 10.7%by weight of 3-ethylheptanol;
·from 2.4 to 3.4%by weight of 2-ethylheptanol;
·from 2.2 to 3.2%by weight of 2-propylhexanol;
·from 4.2 to 8.2%by weight of 3, 5-dimethylheptanol; from 8.0 to 14.0%by weight of 2, 5-dimethyl-heptanol;
·from 2.3 to 3.3%by weight of 2, 3-dimethylheptanol;
·from 1.1 to 2.1%by weight of 3-ethyl-4-methylhexanol;
·from 2.5 to 3.5%by weight of 2-ethyl-4-methylhexanol; and
·from 1.5 to 5.5%by weight of other alcohols having 9 carbon atoms.
According to any one embodiment of the present invention, the degree of branching indicates the sum of branching number multiplying with the proportion of the respective alkyl alcohol in the mixture of isomeric alkyl alcohol. For example, the branching degree of nonanol-1 is 0, 2-ethyl-2-methylhexanol-1 is 2 and 2, 3, 4-trimethylhexanol-1 is 3. The branching numbers of the respective nonanol can refer to the below table.
The degree of branching of the isomeric nonanols is the sum of all values which are obtained by multiplying the branching number with the proportion of the respective nonanol in the mixture of isomeric nonanols.
In a specific embodiment of the present invention, the alkoxylated iso-nonanol according to the present invention may be represented by the formula (I) :
RO- (AO) n-H (I)
wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, AO is ethyleneoxy, and n is a number in the range of 1 to 20, preferably in the range of 3 to 14, for example 3, 4, 5, 6, 7, 8, 9;
wherein the alkoxylated iso-nonanol is obtained by ethoxylation of a mixture of isomeric nona-nols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4;
wherein the obtained ethoxylated iso-nonanol has a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
In a specific embodiment of the present invention, the alkoxylated iso-nonanol according to the present invention may be represented by the formula (II) :
RO- (EO) p- (PO) q-H (II)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
p is a number in the range of 1 to 14, preferably in the range of 2 to 10, more preferably in the range of 3 to 9;
q is a number in the range of 0.5 to 9, preferably in the range of 1 to 7;
wherein the sum of p+q is a number in the range of 1 to 20, preferably in the range of 3 to 14; wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
According to some embodiments of the present invention, the alkylene oxide segment repre-sented by “- (EO) p- (PO) q-” in the formula (II) , may have a block polymeric structure or a random polymeric structure.
In a specific embodiment of the present invention, the alkoxylated iso-nonanol can be repre-sented by the formula (III) :
RO- (PO) x- (EO) y- (PO) z-H (III)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
x is a number in the range of 1 to 9, preferably in the range of 3 to 7,
y is a number in the range of 1 to 17, preferably in the range of 3 to 15;
z is a number in the range of 0.5 to 20, preferably in the range of 3 to 17;
preferably the sum of x + y + z is a number in the range of 1 to 20, preferably in the range of 3 to 14;
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
According to the abovementioned embodiment of the present invention, the alkylene oxide seg-ment represented by “- (PO) x- (EO) y- (PO) z-” in the formula (III) , may have a block polymeric struc-ture or a random polymeric structure.
In a specific embodiment of the present invention, the alkoxylated iso-nonanol can also be rep-resented by the formula (IV) :
RO- (EO) g- (PO) h- (EO) i-H (IV)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
g is a number in the range of 1 to 9, preferably in the range of 3 to 7,
h is a number in the range of 1 to 17, preferably in the range of 3 to 15;
i is a number in the range of 0.1 to 20, preferably in the range of 0.5 to 10;
preferably the sum of g + h + i is a number in the range of 1 to 20, preferably in the range of 3 to 14;
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
According to the abovementioned embodiment of the present invention, the alkylene oxide seg-ment represented by “- (EO) g- (PO) h- (EO) i-” in the formula (IV) , may have a block polymeric struc-ture or a random polymeric structure.
<Cleaning Formulation>
The present invention further relates to a cleaning formulation comprising the alkoxylated iso-nonanol as nonionic surfactant. There is no particular restriction to type of the cleaning formula-tions according to the present invention, which may be formulations designed for cleaning any soiled materials.
The alkoxylated iso-nonanol as described herein may be used in cleaning compositions such as laundry detergent compositions and industrial and institutional cleansing compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating compositions, cementitious compositions, lacquers or paints, and agrochemical formulations, preferably in laundry detergent compositions, and in fabric and home care compositions. Preferably, the alkoxylated iso-nonanol is an alkox-ylated iso-nonanol with a degree of alkoxylation in the range of 1 to 20, particularly in the range of 3 to 14, wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4. More preferably, the alkoxylated iso-nonanol is an ethoxylated iso-nonanol with a degree of ethoxyla-tion in the range of 1 to 20, particularly in the range of 3 to 14, wherein the ethoxylated iso-nonanol is obtained by ethoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4.
In some specific embodiments, the alkoxylated iso-nonanol having the formula (II) as described hereinabove may be used in cleaning compositions such as laundry detergent compositions and industrial and institutional cleansing compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating compositions, cementitious compositions, lacquers or paints, and agrochemical formulations, preferably in laundry detergent compositions, and in fabric and home care compositions.
In some specific embodiments, the alkoxylated iso-nonanol having the formula (III) as described hereinabove may be used in cleaning compositions such as laundry detergent compositions and industrial and institutional cleansing compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating compositions, cementitious compositions, lacquers or paints, and agrochemical formulations, preferably in laundry detergent compositions, and in fabric and home care compositions.
In some specific embodiments, the alkoxylated iso-nonanol having the formula (IV) as described hereinabove may be used in cleaning compositions such as laundry detergent compositions and industrial and institutional cleansing compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating compositions, cementitious compositions, lacquers or paints, and agrochemical formulations, preferably in laundry detergent compositions, and in fabric and home care compositions.
Therefore, in the third aspect, the present invention provides a cleaning composition or a fabric and home care composition comprising the alkoxylated iso-nonanol as nonionic surfactant.
The term “cleaning composition” as used herein includes compositions and formulations designed for cleansing any soiled material, which includes, but are not limited to laundry detergent compositions, industrial and institutional cleansing compositions for use of cleansing for example hard surfaces such as tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces. The term “fabric and home care compositions” includes for example fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleansing compositions, laundry additives, laundry rinse additives, wash additives, post-rinse fabric treatment compositions, ironing aids, dish washing compositions, hard surface cleansing compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in a porous substrate or nonwoven sheet, light-duty and heavy-duty liquid detergent compositions, bleaching compositions.
Various types of cleaning compositions and fabric and home care compositions are known in the art. Any conventional formulations of those compositions may be applied with including the alkoxylated iso-nonanol according to the present invention. The alkoxylated iso-nonanol according to the present invention may be used in those compositions in addition to or in place of an active or additive ingredient having a similar functional property.
In some embodiments, the present invention provides a laundry detergent composition and a fabric and home care composition comprising the alkoxylated iso-nonanol as described herein as nonionic surfactant, preferably a liquid laundry detergent composition such as a laundry care composition or a laundry washing composition, or a liquid fabric and home care composition.
The alkoxylated iso-nonanol can be used in combination with other surfactants, which may be selected from anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants, zwitterionic surfactants and any combinations thereof. The cleaning composition of the present invention may –and preferably does -further comprise from about 1%to about 70%by weight of the composition of a surfactant system.
Nonlimiting examples of anionic surfactants may include C9-C20 linear alkylbenzene sulfonates (LAS) , C10-C20 primary, branched chain and random alkyl sulfates (AS) ; C10-C18 secondary (2, 3) alkyl sulfates of the formula CH3 (CH2) x (CHOSO3-M+) CH3 and CH3(CH2) y (CHOSO3-M+) CH2CH3 where x and (y+1) are integers of at least about 7 and M is a water-solubilizing cation; unsaturated sulfates such as oleyl sulfate; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as described in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as described in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as described in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES) ; and alpha-olefin sulfonate (AOS) .
Preferable examples of suitable anionic surfactants are alkali metal and ammonium salts of C8-C12-alkyl sulfates, of C12-C18-fatty alcohol ether sulfates, of C12-C18-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-C12-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol) , of C12-C18-alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of C10-C18-alkylarylsulfonic acids, preferably of n-C10-C18-alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.
For example, an anionic surfactant selected from C10-C15-linear alkylbenzenes sulfonates, C10-C18-alkylether sulfates with 1 to 5 ethoxy units and C10-C18-alkylsulfates may be used.
The cleaning composition or the fabric and home care composition may comprise one or more anionic surfactants in an amount in the range of 1%to 50%, preferably 2%to 30%, more preferably 3%to 25%, and most preferably 5%to 25 %, based on the total weight of the composition.
Non-limiting examples of non-ionic surfactants may include C8-C18 alkyl ethoxylates, such as non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates, such as from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as described in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as described in U.S. 4,565,647; specifically alkylpolyglycosides as described in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as described in US 5,332, 528; and ether capped poly (oxyalkylated) alcohol surfactants as described in US 6,482,994 and WO 01/42408.
The non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di-and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides) .
The cleaning composition or the fabric and home care composition may comprise one or more non-ionic surfactants in an amount in the range of 1%to 50%, preferably 2%to 40%, more preferably 3%to 30%, and most preferably 5%to 25 %, based on the total weight of the composition.
Non-limiting examples of amphoteric surfactants may include water-soluble amine oxides and water-soluble sulfoxides, especially water-soluble amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides and alkyl amido propyl dimethyl amine oxides, more preferably coco dimethyl amino oxide and coco amido propyl dimethyl amine oxide. Amine oxides may have a linear or mid-branched alkyl moiety.
Typical linear amine oxides include water-soluble amine oxides containing one C8-C18-alkyl moiety and two moieties selected from C1-C3-alkyl groups and C1-C3-hydroxyalkyl groups. The amine oxides of formula R1-N (R2) (R3) O in which R1 is a C8-C18-alkyl and R2 and R3 are selected from methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C10-C18-alkyl dimethyl amine oxides and linear C8-C12-alkoxy ethyl dihydroxy ethyl amine oxides.
Typical mid-branched amine oxides have one alkyl moiety having n1 carbon atoms and one alkyl branch having n2 carbon atoms wherein the alkyl branch is located on the α or β carbon from the nitrogen. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The sum of n1 and n2 is in the range of 10 to 24, preferably from 12 to 20, and more preferably 10 to 16. The number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. Here “symmetric” means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more preferably at least 75 wt%to 100 wt%of the mid-branched amine oxides. The amine oxide further comprises two moieties, independently selected from a C1-C3-alkyl, a C1-C3-hydroxyalkyl group, or a polyethylene oxide group containing an average of 1 to 3 ethylene oxide groups.
Preferably, the amphoteric surfactants may be selected from C8-18-alkyl dimethyl aminoxides and C8-C18-alkyl di (hydroxyethyl) aminoxide.
Non-limiting examples of zwitterionic surfactants may include betaines such as alkyl betaines, alkylamidobetaines, amidazoliniumbetaines, sulfobetaines (INCI Sultaines) as well as phosphobetaines. Preferred betaines are, for example alkylbetaines and sulfobetaines. Examples of suitable alkylbetaines and sulfobetaines include (designated in accordance with INCI) : Almondamidopropyl Betaines, Apricotamidopropyl Betaines, Avocadamidopropyl Betaines, Babassuamidopropyl Betaines, Behenamidopropyl Betaines, Behenyl Betaines, Canolamidopropyl Betaines, Capryl/Capramidopropyl Betaines, Carnitine, Cetyl Betaines, Cocamidoethyl Betaines, Cocamidopropyl Betaines, Cocamidopropyl Hydroxysultaine, Coco-Betaines, Coco-Hydroxysultaine, Coco/Oleamidopropyl Betaines, Coco-Sultaine, Decyl Betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaines, Isostearamidopropyl Betaines, Lauramidopropyl Betaines, Lauryl Betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaines, Minkamidopropyl Betaines, Myristamidopropyl Betaines, Myristyl Betaines, Oleamidopropyl Betaines, Oleamidopropyl Hydroxysultaine, Oleyl Betaines, Olivamidopropyl Betaines, Palmamidopropyl Betaines, Palmitamidopropyl Betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaines, Polytetrafluoroethylene Acetoxypropyl Betaines, Ricinoleamidopropyl Betaines, Sesamidopropyl Betaines, Soyamidopropyl Betaines, Stearamidopropyl Betaines, Stearyl Betaines, Tallowamidopropyl Betaines, Tallowamidopropyl Hydroxysultaine, Tallow Betaines, Tallow Dihydroxyethyl Betaines, Undecylenamidopropyl Betaines And Wheat Germamidopropyl Betaines.
Non-limiting examples of cationic surfactants may include quaternary ammonium surfactants, which can have up to 26 carbon atoms, for example alkoxylated quaternary ammonium (AQA) surfactants as described in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as described in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as described in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as described in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as described in US 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine (APA) .
The compositions of the invention may comprise adjunct additives (also abbreviated herein as “adjuncts” ) , such adjuncts being preferably in addition to the surfactant as described hereinabove.
Suitable adjuncts may include builders, fatty acids and/or salts thereof, structurants, thickeners and rheology modifiers, clay/soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleansing agents, solubilizing agents, amphiphilic copolymers, chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated perfume, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, hueing agents, dye transfer inhibiting agents, fabric softeners, carriers, suds boosters, suds suppressors (antifoams) , color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, anti-bacterial and anti-microbial agents, preservatives, anti-oxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes, and perfumes.
In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders” . Examples of builders include complexing agents, ion-exchange compounds, dispersing agents, scale inhibiting agents and precipitating agents.
Builders may be selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.
Suitable citrates include mono-, di-and tri-alkali metal salts of citric acid, ammonium or substituted ammonium salts of citric acid, as well as citric acid. Citrates can be used as the anhydrous compound or as a hydrate, for example as trisodium citrate dihydrate. Any amount of citrates, when used, is calculated referring to anhydrous trisodium citrate.
Suitable phosphates include sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. However, it is preferred that the compositions according to the invention is free from phosphates, polyphosphates, and hydrogenphosphates.
Suitable silicates include sodium disilicate and sodium metasilicate, aluminosilicates such as for example zeolites and sheet silicates, in particular those of the formula α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.
Suitable carbonates include alkali metal carbonates and alkali metal hydrogen carbonates, preferably sodium salts.
Suitable phosphonates are hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance as the builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) . Suitable aminoalkanephosphonates are preferably ethylene diaminetetramethylenephosphonate (EDTMP) , diethylenetriaminepentamethylene-phosphonate (DTPMP) , and also their higher homologues. The phosphonates are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta-and octa-sodium salts of DTPMP.
Suitable amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylenetetraamine hexaacetate, propylene diamine tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The amino carboxylates and polycarboxylates are preferably used in the form of respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular in respective fully neutralized salts form.
The compositions according to the invention may comprise an alkali carrier. The alkali carrier can ensure, for example, a pH of at least 9 if an alkaline pH is desired. Suitable alkali carriers are for example, alkali metal carbonates, alkali metal hydrogen carbonates, and alkali metal metasilicates, and alkali metal hydroxides. Preferably the alkali metal is potassium in each case, more preferably sodium. In the present invention, a pH >7 may also be adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
The compositions according to the present invention may comprise an enzyme, preferably a detergent enzyme.
In one embodiment, the enzyme is classified as an oxidoreductase (EC 1) , a transferase (EC 2) , a hydrolase (EC 3) , a lyase (EC 4) , an isomerase (EC 5) , or a ligase (EC 6) . The EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999. Preferably, the enzyme is a hydrolase (EC 3) .
The enzyme may be selected from proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease (EC 3.4.21) , more preferably, a subtilisin protease (EC 3.4.21.62) . Alternatively, the en-zyme is an amylase (alpha and/or beta) of bacterial or fungal origin (EC 3.2.1.1 and 3.2.1.2, re-spectively) . Preferably, amylases are selected from the group of alpha-amylases (EC 3.2.1.1) .
Preferably, the protease is a protease with at least 90%sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering) . Preferably, the amylase is an amylase with at least 90%sequence identity to SEQ ID NO: 54 of WO2021032881A1.
The composition of the present invention can comprise one type of enzyme or more than one enzyme of different types, e.g., an amylase and a protease, or more than one enzyme of the same type, e.g., two or more different proteases, or mixtures thereof, e.g., an amylase and two different proteases.
The enzyme, when present, may be present in the compositions according to the present invention in an amount sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like antigreying or antipilling effects (e.g., in case of cellulases) . Preferably, the enzyme may be present in an amount of 0.00001%to 5%, preferably 0.00001%to 2%, more preferably 0.0001%to 1%, or even more preferably 0.001%to 0.5%enzyme protein based on the total weight of the compositions.
Preferably, an enzyme-containing compositions may further comprise an enzyme stabilizing system. The enzyme-containing composition may comprise 0.001%to 10%, 0.005%to 8%, or 0.01%to 6%of an enzyme stabilizing system, based on the total weight of the compositions. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.
Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, glycerol or sorbitol) , salts (preferably, CaCl2, MgCl2 or NaCl) , short chain (preferably, C1-C6) carboxylic acids or salts thereof (preferably, formic acid, formate (preferably, sodium formate) , acetic acid, acetate, or lactate) , borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA) ) , peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA) ) , peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA) , peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H) , peptide acetals, and peptide aldehyde hydrosulfite adducts.
The compositions according to the invention may further comprise a bleaching agent, which is preferably selected from sodium perborate, anhydrous or as the monohydrate or as the tetrahydrate or as the so-called dihydrate, sodium percarbonate, anhydrous or as the monohydrate, and sodium persulfate.
The compositions according to the invention may further comprise a bleach catalyst, which is preferably selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium-or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper-and ruthenium-amine complexes can also be used as bleach catalysts.
The compositions according to the invention can comprise a bleach activator, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetraacetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl-or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts ( “MMA salts” ) , trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2, 2-dioxohexahydro-1, 3, 5-triazine ( “DADHT” ) or nitrile quats (trimethylammonium acetonitrile salts) .
The compositions according to the invention may comprise a corrosion inhibitor, for example selected from triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
The compositions according to the invention may comprise some cleaning polymers and/or soil release polymers and/or anti-graying polymers.
The cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s HP20) and/or “multifunctional diamines” (for example BASF’s HP96) .
Suitable multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, more preferably 8,000 to 50,000, more preferably 10,000 to 30,000, and most preferably 10,000 to 20,000 g/mol. Suitable multifunctional polyethylene imines have 80 wt%to 99 wt%, preferably 85 wt%to 99 wt%, more preferably 90 wt%to 98 wt%, most preferably 93 wt%to 97 wt%or 94 wt%to 96 wt%ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5,000 g/mol. Preferably employed is a molecular weight from 500 to 1,000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
Suitable multifunctional diamines are typically ethoxylated C2-C12-alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2,000 to 10,000, more preferably 3,000 to 8,000, and most preferably 4,000 to 6,000 g/mol. Particularly, ethoxylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
Suitable anti-graying polymers include copolymers of acrylic or maleic acid and styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and their alkali metal salts, in particular sodium salts thereof.
The compositions according to the present invention may also comprise a complexing agent, which is preferably selected from methylglycinediacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and salts thereof. MGDA and GLDA may be present as racemate or as enantiomerically pure compounds. GLDA is preferably selected from L-GLDA or enantiomerically enriched mixtures of L-GLDA in which at least 80 mol%, preferably at least 90 mol%, of L-GLDA is present. Suitable salts are ammonium salts and alkali metal salts, particularly preferably potassium and in particular sodium salts.
The compositions according to the present invention may also comprise an antimicrobial agent and/or preservative. An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. A preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth. Examples of preservatives are as listed on pages 35 to 39 in patent application WO2021/115912 A1.
Especially of interest are the following antimicrobial agents and/or preservatives:
·4, 4’ -Dichloro-2-hydroxydiphenyl ether (Synonyms: 5-chloro-2- (4-chlorophenoxy) phenol, Diclosan, DCPP) ;
·2-Phenoxyethanol (Synonyms: Phenoxyethanol, Methylphenylglycol, Phenoxetol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, 2- (phenoxy) ethanol, 2-phenoxy-1-ethanol) ;
·2-Bromo-2-nitropropane-1, 3-diol (Synonyms: 2-bromo-2-nitro-1, 3-propanediol, Bronopol) ;
·glutaraldehyde (Synonyms: 1, 5-pentandial, pentane-1, 5-dial, glutaral, glutardialdehyde) ;
·Glyoxal (Synonyms: ethandial, oxylaldehyde, 1, 2-ethandial) ;
·2-Butyl-benzo [d] isothiazol-3-one (BBIT) ;
·2-Methyl-2H-isothiazol-3-one (MIT) ;
·2-Octyl-2H-isothiazol-3-one (OIT) ;
·5-Chloro-2-methyl-2H-isothiazol-3-one (CIT or CMIT) ;
·Mixture of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT) (Mixture of CMIT/MIT) ;
·1, 2-benzisothiazol-3 (2H) -one (BIT) ;
·Hexa-2, 4-dienoic acid (trivial name “sorbic acid” ) and its salts, e.g., calcium sorbate, sodium sorbate; potassium (E, E) -hexa-2, 4-dienoate (Potassium Sorbate) ;
·Lactic acid and its salts; L- (+) -lactic acid; especially sodium lactate;
·Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate;
·Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate;
·Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate;
·Didecyldimethylammonium chloride (DDAC) ;
·N- (3-aminopropyl) -N-dodecylpropane-1, 3-diamine (Diamine) ;
·Peracetic acid; and
·Hydrogen peroxide.
The compositions according to the invention may comprise the at least one antimicrobial agent or preservative in an amount of 0.0001 to 10%, based on the total weight of the compositions.
Preferably, the compositions according to the invention may comprise 2-phenoxyethanol in an amount of 2 ppm to 5%, preferably 0.1%to 2%, or 4, 4’ -dichloro 2-hydroxydiphenyl ether (DCPP) in an amount of 0.001%to 3%, preferably 0.002%to 1%, more preferably 0.01%to 0.6%, based on the total weight of the compositions.
Preferably, the compositions according to the invention may comprise 4, 4’ -dichloro-2-hydroxydiphenylether, preferably in an amount of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, based on the total weight of the compositions.
The compositions according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol, and/or fillers such as sodium sulfate.
Further optional ingredients may include, but are not limited to, viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.
In the fourth aspect, the present invention provides a method of preserving an aqueous cleansing composition comprising the copolymer as described herein against microbial contamination or growth, which includes adding 2-phenoxyethanol in the detergent composition.
In the fifth aspect, the present invention provides a method of cleansing a fabric or a hard surface, which includes an antimicrobial treatment of the fabric or the hard surface with a cleansing composition comprising the copolymer as described herein and 4, 4’ -dichloro-2-hydroxydiphenylether.
Aspects of the present invention will be more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.
Various types of cleaning formulations are known in the art. Any conventional formulations may be applied with including the alkoxylated iso-nonanol nonionic surfactant according to the present invention. The alkoxylated iso-nonanol nonionic surfactant according to the present invention may be used in those formulations in addition to or in place of a conventional nonionic surfactant typi-cally comprised in cleaning formulations.
Embodiments
Various embodiments (Embodiments 1 to 13) are listed below. It will be understood that the em-bodiments listed below may be combined with all aspects and other embodiments in accordance with the scope of the invention.
Embodiment 1: An alkoxylated iso-nonanol represented by the formula (I) :
RO- (AO) n-H (I)
wherein R is linear or branched C9 alkyl, preferably R is a C9-alkyl originating from iso-nonanol,
AO is alkyleneoxy, for example ethyleneoxy, propyleneoxy, butyleneoxy or a combination thereof, and
n represents degree of alkoxylation and is a number in the range of 1 to 20, wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
Embodiment 2: The alkoxylated iso-nonanol according to embodiment 1, wherein the AO is eth-yleneoxy, propyleneoxy or a combination thereof, preferably ethyleneoxy.
Embodiment 3: The alkoxylated iso-nonanol according to any of embodiments 1 to 2, wherein the alkoxylated iso-nonanol has a degree of alkoxylation in the range of 1 to 20, preferably in the range of 3 to 14, for example 3, 4, 5, 6, 7, 8, 9 and 10.
Embodiment 4: The alkoxylated iso-nonanol according to any one of embodiments 1 to 3, wherein the chemical structure is represented by the formula (II) :
RO- (EO) p- (PO) q-H (II)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
p is a number in the range of 1 to 14, preferably in the range of 2 to 10, more preferably in the range of 3 to 9;
q is a number in the range of 0.5 to 9, preferably in the range of 1 to 7;
wherein the sum of p+q represents degree of alkoxylation and is a number in the range of 1 to 20, preferably in the range of 3 to 14;
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nona-nols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
Embodiment 5: The alkoxylated iso-nonanol as defined according to any one of Embodiments 1 to 3, wherein the chemical structure is represented by the formula (III) :
RO- (PO) x- (EO) y- (PO) z-H (III)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
x is a number in the range of 1 to 9, preferably in the range of 3 to 7,
y is a number in the range of 1 to 17, preferably in the range of 3 to 15;
z is a number in the range of 0.5 to 20, preferably in the range of 3 to 17;
preferably the sum of x +y + z represents degree of alkoxylation and is a number in the range of 1 to 20, preferably in the range of 3 to 14;
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nona-nols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
Embodiment 6: The alkoxylated iso-nonanol as defined according to any one of Embodiments 1 to 3, wherein the chemical structure is represented by the formula (IV) :
RO- (EO) g- (PO) h- (EO) i-H (IV)
Wherein
R is a linear or branched C9-alkyl, preferably R is a C9-alkyl originating from iso-nonanol, PO is propyleneoxy and EO is ethyleneoxy, and
g is a number in the range of 1 to 9, preferably in the range of 3 to 7,
h is a number in the range of 1 to 17, preferably in the range of 3 to 15;
i is a number in the range of 0.1 to 20, preferably in the range of 0.5 to 10;
preferably the sum of g + h + i represents degree of alkoxylation and is a number in the range of 1 to 20, preferably in the range of 3 to 14;
wherein the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
Embodiment 7: A cleaning formulation comprising the alkoxylated iso-nonanol as defined accord-ing to any of embodiments 1 to 6.
Embodiment 8: The cleaning formulation according to embodiment 7, which is selected from laun-dry detergent compositions and industrial and institutional cleansing compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating compositions, cementitious compositions, lac-quers or paints, and agrochemical formulations.
Embodiment 9: The cleaning formulation according to embodiment 7 or 8, wherein the alkoxylated nonanol is present in the cleaning formulation in an amount varying in the range of 0.5%to 40%, preferably 1%to 35%, based on the total weight of the formulation.
Embodiment 10: The cleaning formulation according to any one of claims 7 to 9, which comprises 2-phenoxyethanol, preferably in an amount of 2 ppm to 5%, more preferably 0.1 to 2%by weight, based on the total weight of the composition.
Embodiment 11: The cleaning formulation according to any one of claims 7 to 10, which comprises 4, 4’ -dichloro-2-hydroxydiphenylether, preferably in an amount of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, based on the total weight of the composition.
Embodiment 12: The cleaning formulation according to any one of claims 7 to 11, which comprises at least one enzyme, preferably at least one enzyme selected from the group consisting of proteases, amylases, lipases, cellulases, hemicellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases.
Embodiment 13: Use of an alkoxylated iso-nonanol as defined in any of embodiments 1 to 6 in a cleaning formulation.
Examples
Aspects of the present invention will be more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.
I. Chemicals:
Iso-nonanols for preparing the inventive examples are commercially available from BASF. Iso-nonanols for preparing the comparative examples are commercially available from Exxon Mo-bil under the tradename EXXALTM 9.
II. Preparations
Inventive Examples:
Ethxoylated iso-nonanol containing 7EO was prepared in accordance with the following process.
797 g of iso-nonanol (from BASF) and 4.3 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.
After the water content is less than 1,000ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 1703g of ethylene oxide (EO) was charged into the pressure reactor at an EO flow rate of 450 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 160 ℃ to 180 ℃. After the EO charging was finished, the reaction system was kept at 170 ℃ for 1 h. After analysis and identification, the reactor is cooled down to 60℃. Afterwards, 4.1 g of acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.
Other alkoxylated iso-nonanol_nonionic surfactants were prepared by the same process, except that the iso-nonanol, ethylene oxide (EO) and KOH were charged in amounts summarized in Table 1 below.
Table 1
INA is used as abbreviation of iso-nonanol alkoxylate
Ethoxylated propoxylated iso-nonanol containing 3EO and 1 PO (Iso-C9- (EO) 3- (PO) 1) was pre-pared in accordance with the following process.
647 g of iso-nonanol (from BASF) and 2.1 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.
After the water content is less than 1,000ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 593 g of ethylene oxide (EO) was charged into the pressure reactor at an EO flow rate of 450 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 160 ℃ to 180 ℃. Then, After the EO charging was finished, the reaction system was kept at 170 ℃ for 1 h.
Then lower temp to 130 ℃. 260g of propylene oxide (PO) was charged into the pressure reactor at an PO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the PO charging was finished, the reaction system was kept at 140 ℃ for 2 h. After analysis and identification, the reactor is cooled down to 60℃. After-wards, 3.1 g of acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.
Propoxylated ethoxylated propoxylated iso-nonanol containing 5 PO, 6 EO and 3 PO (INA 563-Iso-C9- (PO) 5- (EO) 6- (PO) 3) was prepared in accordance with the following process:
649 g of iso-nonanol (from BASF) and 2.1 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.
After the water content is less than 1,000ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 1305 g of propylene oxide (PO) was charged into the pressure reactor at an PO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the PO charging was finished, the reaction system was kept at 140 ℃ for 2 h.
Then, 1188 g of ethylene oxide (EO) was charged into the pressure reactor at an EO flow rate of 450 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 160 ℃ to 180 ℃. After the EO charging was finished, the reaction system was kept at 170 ℃ for 1 h. Then the reactor is cooled down to 130℃ and PO addition of 783 g starts. The reaction temperature is controlled at 135-140℃, postcook of 1～2 hour at 140℃ is conducted to guarantee clean cap of PO.
After analysis and identification, the reactor is cooled down to 60℃. Afterwards, 2 g of acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.
Ethoxylated propoxylated ethoxylated iso-nonanol containing 5EO, 5PO and 0.5 EO (INA 550- (Iso-C9- (EO) 5- (PO) 5- (EO) 0.5) was prepared in accordance with the following process:
721 g of iso-nonanol (from BASF) and 2.2 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.
After the water content is less than 1,000ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 1100 g of EO was charged into the pressure reactor at an EO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the EO charging was finished, the reaction system was kept at 140 ℃ for 1 h.
Then, 1450 g of PO was charged into the pressure reactor at an PO flow rate of 250 g/h. After the PO charging was finished, the reaction system was kept at 140 ℃ for 1 h. Then EO addition of 110 g starts. The reaction temperature is controlled at 135-140℃, postcook of 1～2 hour at 140℃ is conducted.
After analysis and identification, the reactor is cooled down to 60℃. Afterwards, 2 g of acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.
Other alkoxylated iso-nonanol nonionic surfactants were prepared by the same process, except that the iso-nonanol, ethylene oxide (EO) , propylene oxide (PO) and KOH were charged in amounts summarized in Table 1’ below.
Table 1’
Comparative examples:
Comparative INA:
The same synthesis method was used for preparing the comparative example except that the different iso-nonanol (EXXALTM 9) was used. The ethylene oxide (EO) and KOH were charged in amounts summarized in Table 2 below.
Table 2
III. Test Methods
Degree of branching measurement and calculation
Apparatus: GC-FID
Measurement Method:
The retention time of each isomer has been identified by GC-FID. The iso-index is calculated with sum of branching number multiply with proportion. For example, the branching number for Nona-nol-1 is 1, for 2-Ethyl-2-methylhexanol-1 is 2 and for 2, 3, 4-Trimethylhexanol-1 is 3, according to the branching methyl group number. The proportion is tested via GC-FID. The lower the ISO index, the greater the linearity of the molecules in the respective fraction.
The degree of branching of the iso-nonanols for preparing the alkoxylated iso-nonanol examples is calculated as below table.
The results of the degree of branching of iso-nonanols used for preparing the inventive examples and comparative examples are in below table.
Inventive examples:
Comparative examples:
Com.: comparative
Test of Dynamic surface tension
Dynamic surface tension
The SITA science line T60 measures the dynamic surface tension of liquids up to the semi-static range. Air bubbles are generated from a capillary with known radius. The bubble pressure is measured as a function of bubble lifetime, which can be correlated to the surface tension according to the Young-Laplace equation.
Apparatus and Materials:
1. SITA T60 (Sita Messtechnik, Germany)
2. Water bath
3. Heating and stirring plate
4. Glass beakers
5. Glass vials (100 mL)
The SITA science line T60 was calibrated with DI water. Clean water samples after calibration should have a surface tension of 72.0±1.0 mN/m (depending on the quality and temperature) . Following calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.1, 1.0, 10.0 seconds) .
100ml 0.1%surfactant (ethoxylated iso-nonanol) were transferred into 100ml vials and immersed in a heated water bath to 23℃ ±1℃. The samples were equilibrated for 30 minutes in water bath. Then The samples were tested in the SITA. After each sample was tested the SITA's cleaning procedure was run, then the surface tension of DI water was checked to ensure the SITA was adequately clean. If the DI water measurements were not within 72.0±1.0 mN/m, then the cleaning procedure was run again. The surface tension (mN/m) versus bubble life time at 23℃was recorded and the experimental data is provided in below table.
Test data:
Com.: comparative
Lower dynamic surface tension values obtained by the inventive iso-nonanols means better sur-factant property than the comparative iso-nonanols having the same EO numbers (obtained by alkoxylation of iso-nonanol having higher branching degree) . The inventive iso-nonanol INA 303 comprising both EO and PO segments shows lower surface tension than comparative INA 5, INA 7 and INA 9.
Test of Emulsifying ability
Test condition: 2g/L deionized water solution by product content at 23℃
Oil types: anti-wear hydraulic oil L-HM 46# (UK CULL)
Test method:
1) 20ml oil and 20ml surfactant solution@2g/L into the 100ml graduated cylinder;
2) after inverting for 1 min, then record time stratified to 10ml.
Test data:
Com. Comparative
Longer time means better emulsification performance.
Comparative examples with much higher degree of branching show relative worse emulsifying power compared to the inventive examples comprising the same EO numbers.
The alkoxylated iso-nonanol comprising three alkoxylated segments of propoxy groups, ethoxy groups and propoxy groups, in particular INA 563 shows the best emulsifying power.
Foaming Formation &Stability (Ross Miles method) :
550 ml 2 g/L surfactant solution was prepared in DI water to test foaming formation and stability by Ross Miles method. Firstly, 50 ml surfactant solution was pre-charged into botton of the volumetric cylinder and then the rest 500 ml surfactant solution was poured into the cylinder from the top via a glass bulb. The solution was dripped from the top and recorded from the end, and the foam volume was recorded respectively after 30 seconds and 2 minutes.
The alkoxylated iso-nonanols containing both ethoxy groups and propoxy groups have obviously lower foam and acceptable emulsifying power.