Movatterモバイル変換


[0]ホーム

URL:


CN114085373A - Hyaluronic acid polyether polyol and preparation method and application thereof - Google Patents

Hyaluronic acid polyether polyol and preparation method and application thereof
Download PDF

Info

Publication number
CN114085373A
CN114085373ACN202111499793.2ACN202111499793ACN114085373ACN 114085373 ACN114085373 ACN 114085373ACN 202111499793 ACN202111499793 ACN 202111499793ACN 114085373 ACN114085373 ACN 114085373A
Authority
CN
China
Prior art keywords
hyaluronic acid
polyether polyol
reaction
acid polyether
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111499793.2A
Other languages
Chinese (zh)
Other versions
CN114085373B (en
Inventor
隋美玉
陆国太
张明峰
吕树卫
李传亮
王久龙
刘佳奇
姜明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co LtdfiledCriticalWanhua Chemical Group Co Ltd
Priority to CN202111499793.2ApriorityCriticalpatent/CN114085373B/en
Publication of CN114085373ApublicationCriticalpatent/CN114085373A/en
Application grantedgrantedCritical
Publication of CN114085373BpublicationCriticalpatent/CN114085373B/en
Activelegal-statusCriticalCurrent
Anticipated expirationlegal-statusCritical

Links

Classifications

Landscapes

Abstract

The invention discloses a hyaluronic acid polyether polyol, a preparation method and an application thereof, wherein the hyaluronic acid polyether polyol has a structure shown in a formula 1:

Description

Hyaluronic acid polyether polyol and preparation method and application thereof
Technical Field
The invention relates to hyaluronic acid polyether polyol and a preparation method and application thereof, belonging to the technical field of polyether polyol preparation.
Background
The surfactant is an indispensable chemical product in daily life of people, and is called industrial monosodium glutamate. The functions of the surfactant are various, the surfactant has the figure in the fields of textile, coating, medical, metal processing and daily use chemicals, and with the development of times and the improvement of living standard of people, people not only pursue the daily life with high cleaning force, but also pursue more surfactants with high quality, multiple functions, environmental protection and degradability. In addition, part of the high molecular weight polyether surfactant has the characteristics of quenching liquid, but the preparation of high molecular weight polyether by using small molecules is difficult to prepare, a reaction kettle of a manufacturer is required to have a large growth ratio, and the phenomenon that chain breakage is easy to occur when the molecular weight is more than 5000 and the molecular weight is difficult to grow is avoided.
Hyaluronic acid is an acidic mucopolysaccharide, which is also known by the alternative name: hyaluronic acid. Hyaluronic acid exhibits various important physiological functions in the body with its unique molecular structure and physicochemical properties, such as lubricating joints, regulating permeability of blood vessel walls, regulating proteins, regulating diffusion and operation of aqueous electrolytes, promoting wound healing, and the like. More importantly, hyaluronic acid has a special water retention effect, is the substance which is found to have the best moisture retention in nature at present, is called an ideal natural moisture retention factor, and the skin also contains a large amount of hyaluronic acid. The skin aging process of human beings also changes with the content and metabolism of hyaluronic acid, it can improve skin nutrition metabolism, make skin tender and smooth, remove wrinkle, increase elasticity, prevent aging, and is good transdermal absorption enhancer while keeping moisture. However, the conventional hyaluronic acid is solid and has poor compatibility, so that the application of the hyaluronic acid is limited.
At present, a part of research on hyaluronic acid at home and abroad relates to preparation and purification of hyaluronic acid, and the other part of the research is that hyaluronic acid is directly used as an additive to be used in cosmetics, and a precedent that ethylene oxide and propylene oxide are modified and then the hyaluronic acid is added to be used in cosmetics does not exist, for example, patent application CN104069019A of Binzhou Anhua bioengineering limited company discloses a shampoo containing hyaluronic acid, which mainly focuses on high yield of the hyaluronic acid, low protein content and high glucuronic acid content, and the hyaluronic acid is directly used as an additive to prepare shampoo, so that the compatibility of the formula of the hyaluronic acid in practical application has certain difficulty.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides hyaluronic acid polyether polyol and a preparation method thereof, wherein hyaluronic acid and derivatives thereof are used as an initiator to be combined with epoxide (EO and PO) to prepare polyether polyol, and the hyaluronic acid polyether polyol is a nonionic surfactant with excellent performance.
The method can change the hyaluronic acid and the derivatives thereof from solid to liquid, so that the hyaluronic acid and the derivatives thereof have good biocompatibility, and meanwhile, the hyaluronic acid polyether polyol is colorless and transparent, does not influence the color of any other formula when in use, and has degradability, cleanability, skin beautifying, moisturizing and moisturizing effects.
In addition, based on the characteristics of macromolecules of hyaluronic acid, the preparation method is particularly suitable for preparing high molecular weight polyether, and the high molecular weight polyether shows excellent thermal stability and cooling stability and is also suitable for being used as quenching liquid.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides hyaluronic acid polyether polyol which has a structure shown in a formula 1:
Figure BDA0003402276370000031
in the formula, m, n, p, q, x and y are all integers from 0 to 50, at least 1 of m, n, p, q, x and y is not 0, and the values of m, n, p, q, x and y can be the same or different; z is an integer of 10 to 50;
preferably, m and n are not 0 at the same time, p and q are not 0 at the same time, and x and y are not 0 at the same time;
preferably, the values of m, n, p, q, x and y are 1-30;
preferably, the value of z is 20-30.
The average molecular weight of the hyaluronic acid polyether polyol is 11000-4103000, preferably 23000-410000.
The product chroma of the hyaluronic acid surfactant is less than or equal to 30Hazen by a national standard GB/T9282 method, and the chroma is preferably less than or equal to 20 Hazen.
The light transmittance of the hyaluronic acid surfactant is more than or equal to 85% by measuring with a GBT2566-2010 method, and preferably the light transmittance is more than or equal to 90%.
The viscosity of the hyaluronic acid surfactant is 300-6000mPa.s, and the acid value is less than or equal to 0.5 mgKOH/g.
The invention also provides a preparation method of the hyaluronic acid polyether polyol shown in the formula 1, which comprises the step of reacting hyaluronic acid and derivatives thereof with ethylene oxide and/or propylene oxide in the presence of an alkaline catalyst to obtain the hyaluronic acid polyether polyol.
In the method of the present invention, the hyaluronic acid and its derivatives are selected from any one or a combination of at least two of hyaluronic acid, sodium hyaluronate, potassium hyaluronate, magnesium hyaluronate, calcium hyaluronate, and zinc hyaluronate, preferably hyaluronic acid and/or sodium hyaluronate;
preferably, the molecular weight of the hyaluronic acid and the derivatives thereof is 4000-200000g/mol, preferably 10000-100000 g/mol;
preferably, the water content of the raw material of hyaluronic acid and its derivatives is lower than 1000ppm, preferably lower than 400 ppm; preferably, the hyaluronic acid or derivative thereof is dehydrated in vacuum before reaction, the dehydration temperature is 80-130 ℃, preferably 100-120 ℃, and the dehydration time is 0.5-3h, preferably 0.5-1.5h, so that the water content is at least less than 1000 ppm.
In the method, the mass ratio of the hyaluronic acid and the derivatives thereof to the ethylene oxide and the propylene oxide is 1: 0-29: 0 to 38, ethylene oxide and propylene oxide are not both 0, preferably 1: 0.3-18: 0.4-23.
In the method of the present invention, the basic catalyst is selected from any one or a combination of at least two of alkali metal hydroxide, alkaline earth metal oxide, phosphazene catalyst, alkali metal methoxide, and alkali metal ethoxide, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, and phosphazene;
preferably, the amount of the alkaline catalyst is 0.01-0.5%, preferably 0.05-0.2% of the total mass of the hyaluronic acid and the derivatives thereof, ethylene oxide and propylene oxide.
In the method, the reaction temperature is 100-180 ℃, preferably 120-140 ℃;
in the reaction process, ethylene oxide and propylene oxide adopt a continuous feeding mode, and the pressure in the feeding process is controlled to be 0.1-0.6MPaG, preferably 0.1-0.3 MpaG; after the feeding is finished, the aging reaction is carried out for 0.5 to 3 hours, preferably 0.5 to 1.5 hours, and the reaction reaches the end point.
In the method, the reaction can be carried out in any one of a tubular reactor, a stirring kettle, a loop reactor and the like, and after the reaction is finished, gas impurities such as unreacted ethylene oxide, propylene oxide and the like are removed in vacuum;
preferably, the reaction also comprises adding acid to the reaction liquid for neutralization treatment after the reaction is finished, wherein the acid is selected from organic acids such as acetic acid, lactic acid, neodecanoic acid and the like, and acetic acid is preferred; preferably, the reaction solution is neutralized to a pH of 5 to 7, preferably 6 to 7;
preferably, the system after the reaction can be further added with inorganic acid and treated with an adsorbent, such as in some specific examples, firstly adding a certain amount of phosphoric acid to adjust to pH 4-5, then adding magnesium silicate for adsorption and stirring, then adding diatomite for adsorption and stirring, then performing pressure filtration, and obtaining the product after adsorption with pH 6-7, wherein the adsorption treatment is a routine operation in the field and is not particularly required by the invention.
The invention further provides application of the hyaluronic acid polyether polyol in the fields of washing, pharmacy, spinning, cosmetics and metal processing, and the hyaluronic acid polyether polyol is preferably used as a surfactant and quenching liquid.
Preferably, the invention provides a shower gel composition taking the hyaluronic acid polyether polyol as a surfactant and taking the application of the hyaluronic acid polyether polyol in cosmetics as an example, wherein the shower gel composition comprises the following components in parts by weight:
Figure BDA0003402276370000051
Figure BDA0003402276370000061
wherein, preferably, the humectant is sorbitol, hexaglycerol, vaseline; the essence is rose or gardenia flavor water-oil essence; the bactericide is polyhexamethylene guanidine or hydantoin; the pH regulator is citric acid or lactic acid.
The preparation method of the shower gel composition comprises the steps of weighing the components in proportion, stirring and mixing for 0.5-4h, preferably 1-2h at the temperature of 30-60 ℃ until the components are fully and uniformly mixed.
The pH value of the shower gel composition is 6.0-7.0, the viscosity of the shower gel composition is 500-6000mPa.s at 25 ℃, the light transmittance is more than or equal to 70%, and the chroma is less than or equal to 50.
Preferably, when the hyaluronic acid polyether polyol is used as a quenching liquid, the composition of the hyaluronic acid polyether polyol comprises hyaluronic acid polyether polyol, sodium benzoate and water.
Preferably, the content of the hyaluronic acid polyether polyol is 1-20%, preferably 3-10%, and the content of sodium benzoate is 0.05% -1%, preferably 0.1-0.5%, based on 100% of the total mass of the quenching liquid.
The working principle of the quenching liquid is that in the quenching process of a workpiece, once the liquid temperature around the workpiece rises above the cloud point of the solution, polymers in the quenching liquid are desolventized from the solution and suspended in the quenching liquid in a fine liquid bead form. The suspended polymer liquid beads are adhered to the surface of the workpiece by virtue of the good wettability when contacting the red hot workpiece, and the workpiece is wrapped by a water-rich coating, so that the cooling speed of water is adjusted, and the workpiece is prevented from quenching and cracking. When the workpiece is cooled down, the polymer adhered to the workpiece is re-dissolved into the quenching liquid, so that the polymer capable of being used in the quenching liquid must have high-temperature stability.
The hyaluronic acid polyether polyol is a high-molecular polymer, and the characteristic of multi-branched chain is easier in structural stability and is not easy to decompose at high temperature. According to the invention, the ether bond of the hyaluronic acid polyether polyol and water are interacted through the hydrogen bond, the hydrogen bond is broken when the liquid temperature is increased, water molecules combined on the ether group are separated, the high molecular weight polyether can be separated out from the water and adhered to the surface of a workpiece to form a polymer film, so that the cooling speed of the workpiece is slowed, and the workpiece is protected to reduce cracks. After a part of heat is brought out along with stirring, cooling circulation and steam escape, the temperature of the quenching liquid is gradually reduced, the high molecular weight polyether forms a stable aqueous solution under the action of hydrogen bonds with water again, the high molecular weight polyether is removed from the surface of the workpiece, and the high molecular weight polyether is less when the workpiece is taken out of the water, so that the stable concentration of the quenching liquid is ensured. The hyaluronic acid polyether has the characteristic of water retention, is easy to lock water and reduce evaporation capacity, so that the concentration of quenching liquid is more stable, and the replacement and supplement times are reduced.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) the hyaluronic acid polyether polyol provided by the invention enables hyaluronic acid and derivatives thereof which are solid at normal temperature to be changed into liquid, has the advantage of good fluidity, is good in solubility in a formula, is colorless and transparent, and does not generate any adverse effect on the color of the formula.
2) After the hyaluronic acid polyether polyol is modified by EO/PO, on the basis of the characteristics of good degradability, good biocompatibility, small cytotoxicity and the like of hyaluronic acid, the hyaluronic acid polyether polyol has the water retention and water supplement effects and the characteristics of a surfactant by introducing the EO/PO chain segment and controlling the molecular weight, improves the emulsifying, cleaning, foaming and wetting capabilities of a formula, and shows excellent fluidity, formula compatibility, cleaning performance and foaming performance.
3) The hyaluronic acid polyether polyol has the characteristics of high molecular weight, high stability, good water locking effect and the like, shows excellent thermal stability and cooling stability, is particularly suitable for preparing quenching liquid, and has better performance and longer service life compared with the similar products sold in the market.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
The source information of the main raw materials adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
hyaluronic acid: qingdao Wanyuan mountain biotechnology limited company, the purity is more than or equal to 99 percent;
sodium methoxide: the purity of the alatin reagent is more than or equal to 30 percent, and the alatin reagent is sodium methoxide methanol solution;
potassium methoxide: the purity of the Aladdin reagent is more than or equal to 99.5 percent, and the Aladdin reagent is powdery;
phosphazene: kyork company, the purity is more than or equal to 40 percent, and the product is a phosphazene ethanol solution;
EO, PO: wanhua chemistry, water content less than 100 ppm;
phosphoric acid: the purity of the alatin reagent is more than or equal to 85 percent, and the alatin reagent is a phosphoric acid aqueous solution;
KOH is a Chinese medicine reagent with the purity of 50 percent, and is aqueous solution;
natural fatty alcohol ether sodium sulfate (AESS 70%): zanyu technology, purity 70%, 30% water;
natural fatty alcohol ammonium sulfate (K1299%): the purity of the Hunan Lichen is more than or equal to 99 percent;
cocamidopropyl betaine: the Jinan Zhongsheng chemical industry with the purity more than or equal to 99 percent;
cocamide DEA: wuhanxin chemical industry, the purity is more than or equal to 99 percent;
humectant (sorbitol): hubei Koufole materials science and technology Limited, the purity is more than or equal to 99 percent;
essence (rose flavour): jinan PolyYili chemical Co., Ltd., the purity is more than or equal to 99 percent;
fungicide (polyhexamethylene guanidine): the purity of the Jinan Zhengquan complete chemical industry Co., Ltd is more than or equal to 95 percent;
PH adjuster (citric acid): the purity of the product is more than or equal to 99 percent.
Sodium benzoate: zhejiang Yangem biotechnology limited, the purity is more than or equal to 99%.
Secondly, the analysis and test method adopted by the embodiment of the invention comprises the following steps:
biodegradability: measured by a GB/T19277 method;
biocompatibility: measured by the GB/T16886 method;
average molecular weight: measured by the GPC method;
chroma: the determination is carried out by a national standard GB/T9282 method;
foam volume, defoaming time: measured by the GB/T12579 method;
the stain removal rate is as follows: and comparing the whiteness before and after cleaning to calculate the stain removal rate.
Viscosity: measured by the method GBT 10247-2008;
acid value: measured by the GBT12008.5 method;
light transmittance: measured by the method of GBT 2566-2010;
wetting: measured by the method of GB 11983-2008;
pH: measuring the pH of a 1% aqueous solution of the compound by using a conventional pH meter;
product characterization: measured by using a Thermo Fisher IS50 FTIR infrared spectrometer, the setting parameters are as follows: the number of scans was 16, with a scan range of 4000-.
The evaluation method of the moisturizing and water-retaining effects of the shower gel comprises the following steps:
selecting 800 volunteers 18-30 years old, randomly dividing into 8 groups, respectively trying one shower gel sample, 100 examples in each group, selecting one shower gel sample from the positions of 3cm x 3cm with almost no difference in initial skin state and initial water content of about 30% on the double forearms, testing the initial water content by using an intelligent water white detector (Shenzhen Meili Zhi science and technology Limited company), cleaning the test area by using the shower gel to-be-tested sample after the test area is smeared for 5min by the tester, measuring the water content of the test area after the test is finished without using any skin care products, measuring the water content of the test area after 1h, and averaging the water content of each group.
And (3) testing the concentration stability of the quenching liquid: the self-made quenching liquid and the outsourcing quenching liquid are respectively sent to a downstream factory for testing for one week, the initial concentration is 10 +/-0.2%, and a circulating sample is taken after 1 week of use to determine the concentration.
Example 1
Preparing hyaluronic acid polyether polyol:
adding 200g of hyaluronic acid (z is 26, the average molecular weight is 10000g/mol) and 75.2g of KOH catalyst into a reaction container, heating to 120 ℃, and vacuumizing and dehydrating for 3 hours until the water content is 430 ppm; controlling the reaction temperature to be 120 ℃, adding 3158g of ethylene oxide and 4162g of propylene oxide into a reaction vessel, feeding for 10 hours, controlling the pressure to be 0.1-0.3MPaG, aging and reacting for 3 hours after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30 minutes at 80 ℃ to remove unreacted monomers, adding 79g of 85% phosphoric acid into the reaction liquid for neutralization until the pH value is 4-5, adding 76g of magnesium silicate adsorbent into the reaction liquid for stirring for 1 hour, then adding 8g of diatomite for stirring for 20 minutes, and performing pressure filtration to obtain hyaluronic acid polyether polyol, wherein the pH value of the hyaluronic acid polyether polyol is 6.9.
The infrared spectrometer is adopted for testing, and the raw materials are 3310-3340cm-1Has a single stretching vibration peak of-NH-, and the characteristic absorption peak of the wave band of the product disappears after the reaction, and is 1101cm-1The absorption peak of C-O-C stretching vibration is enhanced. The raw material is 3350cm-1The region shows a strong absorption peak, mainly due to stretching vibration of hydroxyl groups, while the crude product (without post-treatment) is 3350cm-1And the absorption peak nearby is obviously weakened, and the hydroxyl value absorption peak at the position after neutralization is obviously enhanced, so that the product is the hyaluronic acid polyether polyol with the structure of formula 1.
The performance indexes of the pure hyaluronic acid polyether polyol product are tested according to the method disclosed by the invention, and the results are shown in table 1.
The hyaluronic acid polyether polyol is adopted to prepare the shower gel composition, and the formula comprises the following components:
68g of deionized water, 14g of natural fatty alcohol ether sodium sulfate (AESS 70%), 4g of natural fatty alcohol ammonium sulfate (K1299%), 3g of cocamidopropyl betaine, 5g of cocamide DEA, 3g of sorbitol, 0.2g of sodium chloride, 0.2g of rose essence, 0.06g of polyhexamethylene guanidine, 0.3g of citric acid and 2g of hyaluronic acid polyether polyol.
Weighing the components according to the formula, pouring the components into a stirring kettle, stirring and mixing for 1h at 40 ℃, and completely and uniformly mixing until no visible foreign matters exist to obtain the shower gel composition.
The pH, viscosity at 25 ℃, light transmittance, moisturizing and water retention of the body wash composition were measured according to the methods described above, and the results are shown in table 2.
The hyaluronic acid polyether polyol prepared in this example was tested as a quenching liquid:
the hyaluronic acid polyether polyol prepared in the example is prepared into water solutions with mass concentrations of 3%, 5%, 10% and 20%, 0.2% of sodium benzoate is added as an anticorrosive additive, a cooling performance test is performed according to the petrochemical standard SH/T0220, and the result is shown in Table 3 by comparing with a commercial PAG quenching liquid.
The stability of the quench liquid was tested in the manner described above and the results are shown in Table 4.
Example 2
Preparing hyaluronic acid polyether polyol:
adding 200g of hyaluronic acid (z is 10 and the average molecular weight is 4000g/mol) and 54.4g of sodium methoxide catalyst into a reaction container, heating to 110 ℃, and vacuumizing and dehydrating for 2 hours until the water content is 260 ppm; controlling the reaction temperature to be 160 ℃, adding 2037 g of ethylene oxide and 2685g of propylene oxide into a reaction vessel, feeding for 7 hours, controlling the pressure to be 0.1-0.3MPaG, aging and reacting for 1.5 hours after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30min at 80 ℃ to remove unreacted monomers, adding 18.5g of acetic acid into the reaction liquid to neutralize the pH value to be 6.5, and obtaining the hyaluronic acid polyether polyol.
The result of the test by adopting the infrared spectrometer test method proves that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The performance indexes of the pure hyaluronic acid polyether polyol product are tested according to the method disclosed by the invention, and the results are shown in table 1.
The hyaluronic acid polyether polyol of this example is used to prepare a body wash composition, and the formulation composition and the preparation method thereof refer to example 1, except that the hyaluronic acid polyether polyol of this example is replaced with the hyaluronic acid polyether polyol of this example, and other operations are not changed. The pH, viscosity at 25 ℃, light transmittance, moisturizing and water retention of the body wash compositions were measured and the results are shown in table 2.
The hyaluronic acid polyether polyol prepared in this example was tested as a quenching liquid: the method was as described in example 1, except that the hyaluronic acid polyether polyol of this example was replaced and the other operations were not changed. The results of the performance test are shown in tables 3 and 4.
Example 3
Preparing hyaluronic acid polyether polyol:
adding 1000g of hyaluronic acid (z is 30, the average molecular weight is 11600g/mol) and 3.2g of phosphazene catalyst into a reaction container, heating to 80 ℃, and vacuumizing and dehydrating for 0.5h until the water content is 300 ppm; controlling the reaction temperature to be 100 ℃, adding 680g of ethylene oxide and 897g of propylene oxide into a reaction vessel, feeding for 1h, controlling the pressure to be 0.1-0.3MPaG, aging and reacting for 1h after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30min at 80 ℃ to remove unreacted monomers, adding 0.4g of acetic acid into the reaction liquid, and neutralizing until the pH value is 6.6 to obtain the hyaluronic acid polyether polyol.
The result of the test by adopting the infrared spectrometer test method proves that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The performance indexes of the pure hyaluronic acid polyether polyol product are tested according to the method disclosed by the invention, and the results are shown in table 1.
The hyaluronic acid polyether polyol of this example is used to prepare a body wash composition, and the formulation composition and the preparation method thereof refer to example 1, except that the hyaluronic acid polyether polyol of this example is replaced with the hyaluronic acid polyether polyol of this example, and other operations are not changed. The pH, viscosity at 25 ℃, light transmittance, moisturizing and water retention of the body wash compositions were measured and the results are shown in table 2.
The hyaluronic acid polyether polyol prepared in this example was tested as a quenching liquid: the method was as described in example 1, except that the hyaluronic acid polyether polyol of this example was replaced and the other operations were not changed. The results of the performance test are shown in tables 3 and 4.
Example 4
Preparing hyaluronic acid polyether polyol:
adding 300g of hyaluronic acid (z is 27, the average molecular weight is 10500g/mol) and 18.8g of sodium hydroxide catalyst into a reaction container, heating to 130 ℃, and vacuumizing and dehydrating for 1h until the water content is 400 ppm; controlling the reaction temperature to be 140 ℃, adding 1531g of ethylene oxide and 2018g of propylene oxide into a reaction vessel, feeding for 5 hours, controlling the pressure to be 0.2-0.3MPaG, carrying out aging reaction for 1 hour after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30min at 80 ℃ to remove unreacted monomers, adding 29g of acetic acid into the reaction liquid to neutralize the pH value to be 6.7, and thus obtaining the hyaluronic acid polyether polyol.
The result of the test by adopting the infrared spectrometer test method proves that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The performance indexes of the pure hyaluronic acid polyether polyol product are tested according to the method disclosed by the invention, and the results are shown in table 1.
The hyaluronic acid polyether polyol of this example is used to prepare a body wash composition, and the formulation composition and the preparation method thereof refer to example 1, except that the hyaluronic acid polyether polyol of this example is replaced with the hyaluronic acid polyether polyol of this example, and other operations are not changed. The pH, viscosity at 25 ℃, light transmittance, moisturizing and water retention of the body wash compositions were measured and the results are shown in table 2.
The hyaluronic acid polyether polyol prepared in this example was tested as a quenching liquid: the method was as described in example 1, except that the hyaluronic acid polyether polyol of this example was replaced and the other operations were not changed. The results of the performance test are shown in tables 3 and 4.
Example 5
Preparing hyaluronic acid polyether polyol:
adding 1000g of hyaluronic acid (z is50, the average molecular weight is 19400g/mol) and 4.4g of potassium methoxide catalyst into a reaction vessel, heating to 100 ℃, and vacuumizing and dehydrating for 1.5h until the water content is 200 ppm; controlling the reaction temperature to be 130 ℃, adding 680g of ethylene oxide and 1345g of propylene oxide into a reaction vessel, feeding for 2h, controlling the pressure to be 0.1-0.3MPaG, aging and reacting for 1h after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30min at 80 ℃ to remove unreacted monomers, adding 3.9g of acetic acid into the reaction liquid, and neutralizing until the pH value is 6.8 to obtain the hyaluronic acid polyether polyol.
The result of the test by adopting the infrared spectrometer test method proves that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The performance indexes of the pure hyaluronic acid polyether polyol product are tested according to the method disclosed by the invention, and the results are shown in table 1.
The hyaluronic acid polyether polyol of this example is used to prepare a body wash composition, and the formulation composition and the preparation method thereof refer to example 1, except that the hyaluronic acid polyether polyol of this example is replaced with the hyaluronic acid polyether polyol of this example, and other operations are not changed. The pH, viscosity at 25 ℃, light transmittance, moisturizing and water retention of the body wash compositions were measured and the results are shown in table 2.
The hyaluronic acid polyether polyol prepared in this example was tested as a quenching liquid: the method was as described in example 1, except that the hyaluronic acid polyether polyol of this example was replaced and the other operations were not changed. The results of the performance test are shown in tables 3 and 4.
Comparative example 1
The hyaluronic acid polyether polyol was prepared according to the method of example 4, except that: the hyaluronic acid butane polyether was prepared by replacing 1531g of ethylene oxide and 2018g of propylene oxide alkane with the sum of the molar amounts of butylene oxide.
The performance indexes were measured according to the method of example 4, and the results are shown in Table 1.
The shower gel composition and the preparation method refer to example 4, except that hyaluronic acid butane polyether of the comparative example is replaced, and other operations are not changed. The performance indexes were measured according to the method of example 4, and the results are shown in Table 2.
Comparative example 2
The hyaluronic acid polyether polyol was prepared according to the method of example 4, except that: 2574g of ethylene oxide and 3393g of propylene oxide were replaced by 10296g of ethylene oxide and 13572g of propylene oxide, giving the hyaluronic acid polyether polyol (m, n, p, q, x and y all having values of 60).
The performance indexes were measured according to the method of example 4, and the results are shown in Table 1.
The shower gel composition and the preparation method refer to example 4, except that the hyaluronic acid polyether is replaced by the hyaluronic acid polyether of the comparative example, and other operations are not changed. The performance indexes were measured according to the method of example 4, and the results are shown in Table 2.
Comparative example 3
Reference example 4 shower gel formulation, except that: the hyaluronic acid polyether polyol is replaced by hyaluronic acid with equal mass, and other operations are unchanged. The performance indexes were measured according to the method of example 4, and the results are shown in Table 2.
Referring to example 4, the hyaluronic acid polyether polyol was replaced with hyaluronic acid of equal mass in the quenching liquid formulation, and the performance test results are shown in tables 3 and 4.
Comparative example 4
The hyaluronic acid polyether polyol was prepared according to the method of example 4, except that: the raw material hyaluronic acid (z is 27, the average molecular weight is 10500g/mol) is replaced by the ultra-high molecular weight hyaluronic acid (z is 60, the average molecular weight is 23300g/mol), and the activity is found to be poor through experiments, the feeding time is as long as 25h, the aging time is as long as 5h, the product has turbid appearance, high viscosity and low light transmittance. It is shown that when z > 50, the activity of the raw material is lowered and it is not suitable for preparing polyether.
The performance indexes were measured according to the method of example 4, and the results are shown in Table 1.
The shower gel composition and the preparation method refer to example 4, except that the hyaluronic acid polyether is replaced by the hyaluronic acid polyether of the comparative example, and other operations are not changed. The performance indexes were measured according to the method of example 4, and the results are shown in Table 2.
TABLE 1 hyaluronic acid polyether polyol neat Property parameters
Figure BDA0003402276370000161
TABLE 2 shower gel composition Performance parameters
Figure BDA0003402276370000162
Table 3 quench liquid composition coolability test
Figure BDA0003402276370000171
Table 4 quench bath composition stability testing
Sample nameInitial concentration%Concentration after 1 week
Example 1109.9
Example 210.19.8
Example 3109.8
Example 4109.7
Example 5109.9
Comparative example 110.16.2
Comparative example 2107.8
Comparative example 3106
Commercial PAG10.18.2
The data in table 1 show that the hyaluronic acid polyether polyol in the range of the invention has excellent light transmittance, biocompatibility and degradability, and meanwhile, the hyaluronic acid polyether polyol has richer foam and better decontamination performance. Comparative example 2 shows that the foam and soil release properties deteriorate when m, n, p, q, x, y are all > 50. As can be seen from comparative example 4, when z > 50, the reactivity becomes poor, it is not suitable for preparing polyether in a quantity, and the product is cloudy in appearance and very high in viscosity after the reaction is completed. It can be seen from the data in table 2 that the hyaluronic acid polyether polyol shower gel within the range of the present invention has excellent moisturizing and moisturizing properties.
Table 3 shows that the cooling capacity of 10% of the hyaluronic acid high molecular weight polyether can basically reach the level of 20% of commercial PAG, the hyaluronic acid high molecular weight polyether is used as quenching liquid, the required dosage is less, and the cooling stability of the hyaluronic acid high molecular weight polyether is good, and metal is not easy to crack.
The comparison in Table 4 shows that the cooling liquid prepared from the hyaluronic acid high molecular weight polyether has higher concentration ratio and higher stability than the cooling liquid prepared from the hyaluronic acid high molecular weight polyether and the commercially available quenching liquid, has long service time, does not need frequent replacement and is more convenient.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the present invention.

Claims (10)

1. A hyaluronic acid polyether polyol having a structure represented by formula 1:
Figure FDA0003402276360000011
in the formula, m, n, p, q, x and y are all integers from 0 to 50, at least 1 of m, n, p, q, x and y is not 0, and the values of m, n, p, q, x and y can be the same or different; z is an integer of 10 to 50;
preferably, m and n are not 0 at the same time, p and q are not 0 at the same time, and x and y are not 0 at the same time;
preferably, the values of m, n, p, q, x and y are 1-30;
preferably, the value of z is 20-30.
2. The hyaluronic acid polyether polyol of claim 1, characterized in that the average molecular weight is 11000-673000, preferably 23000-410000; the chroma is less than or equal to 30Hazen, and preferably the chroma is less than or equal to 20 Hazen; the light transmittance is more than or equal to 85 percent, and preferably more than or equal to 90 percent; the viscosity is 300-6000mPa.s, and the acid value is less than or equal to 0.5 mgKOH/g.
3. The method for producing the hyaluronic acid polyether polyol according to claim 1 or 2, wherein the hyaluronic acid polyether polyol is obtained by reacting hyaluronic acid and a derivative thereof with ethylene oxide and/or propylene oxide in the presence of an alkaline catalyst as an initiator.
4. The preparation method according to claim 3, wherein the hyaluronic acid and its derivatives are selected from any one or a combination of at least two of hyaluronic acid, sodium hyaluronate, potassium hyaluronate, magnesium hyaluronate, calcium hyaluronate, zinc hyaluronate, preferably hyaluronic acid and/or sodium hyaluronate;
preferably, the molecular weight of the hyaluronic acid and the derivatives thereof is 4000-200000g/mol, preferably 10000-100000 g/mol;
preferably, the water content of the raw material of hyaluronic acid and its derivatives is lower than 1000ppm, preferably lower than 400 ppm; preferably, the hyaluronic acid or the derivative thereof is dehydrated in vacuum before reaction, the dehydration temperature is 80-130 ℃, preferably 100-120 ℃, the dehydration time is 0.5-3h, preferably 0.5-1.5h, and the water content is at least lower than 1000 ppm;
the mass ratio of the hyaluronic acid and the derivatives thereof to the ethylene oxide and the propylene oxide is 1: 0-29: 0 to 38, ethylene oxide and propylene oxide are not both 0, preferably 1: 0.3-18: 0.4-23.
5. The method according to claim 3 or 4, wherein the basic catalyst is selected from any one of or a combination of at least two of alkali metal hydroxide, alkaline earth metal oxide, phosphazene catalyst, alkali metal methoxide, alkali metal ethoxide, preferably any one of or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, phosphazene;
preferably, the amount of the alkaline catalyst is 0.01-0.5%, preferably 0.05-0.2% of the total mass of the hyaluronic acid and the derivatives thereof, ethylene oxide and propylene oxide.
6. The process according to any one of claims 3 to 5, wherein the reaction is carried out at a temperature of 100-180 ℃, preferably at a temperature of 120-140 ℃;
in the reaction process, ethylene oxide and propylene oxide adopt a continuous feeding mode, and the pressure in the feeding process is controlled to be 0.1-0.6MPaG, preferably 0.1-0.3 MpaG; after the feeding is finished, the aging reaction is carried out for 0.5 to 3 hours, preferably 0.5 to 1.5 hours, and the reaction reaches the end point;
preferably, after the reaction is finished, the method further comprises removing gas impurities in vacuum.
7. The process according to any one of claims 3 to 6, further comprising neutralizing the reaction mixture by adding an acid selected from the group consisting of acetic acid, lactic acid, and neodecanoic acid, preferably acetic acid; preferably, the reaction solution is neutralized to a pH of 5 to 7, preferably 6 to 7;
preferably, the system after the reaction can be further added with inorganic acid and treated by adding an adsorbent, and more preferably, the specific method is as follows: firstly, adding phosphoric acid to adjust the pH value to 4-5, then adding magnesium silicate to adsorb and stir, then adding diatomite to adsorb and stir, then pressurizing and filtering to adsorb until the pH value is 6-7.
8. Use of the hyaluronic acid polyether polyol according to claim 1 or 2 or the hyaluronic acid polyether polyol prepared by the method according to any of claims 3-7 in the fields of washing, pharmaceutical, textile, cosmetic, metal processing, preferably as a surfactant, quench liquid.
9. A body wash composition comprising the hyaluronic acid polyether polyol of claim 1 or 2 or the hyaluronic acid polyether polyol prepared by the method of any one of claims 3 to 7, wherein the composition in parts by weight comprises:
Figure FDA0003402276360000031
Figure FDA0003402276360000041
preferably, the humectant is sorbitol, hexaglycerol, petrolatum; the essence is rose or gardenia flavor water-oil essence; the bactericide is polyhexamethylene guanidine or hydantoin; the pH regulator is citric acid or lactic acid.
10. A quench liquid composition comprising the hyaluronic acid polyether polyol of claim 1 or 2 or the hyaluronic acid polyether polyol prepared by the method of any one of claims 3 to 7, wherein the composition comprises hyaluronic acid polyether polyol, sodium benzoate, and water;
preferably, the content of the hyaluronic acid polyether polyol is 1-20%, preferably 3-10%, and the content of sodium benzoate is 0.05% -1%, preferably 0.1-0.5%, based on 100% of the total mass of the quenching liquid.
CN202111499793.2A2021-12-092021-12-09Hyaluronic acid polyether polyol and preparation method and application thereofActiveCN114085373B (en)

Priority Applications (1)

Application NumberPriority DateFiling DateTitle
CN202111499793.2ACN114085373B (en)2021-12-092021-12-09Hyaluronic acid polyether polyol and preparation method and application thereof

Applications Claiming Priority (1)

Application NumberPriority DateFiling DateTitle
CN202111499793.2ACN114085373B (en)2021-12-092021-12-09Hyaluronic acid polyether polyol and preparation method and application thereof

Publications (2)

Publication NumberPublication Date
CN114085373Atrue CN114085373A (en)2022-02-25
CN114085373B CN114085373B (en)2023-07-14

Family

ID=80307119

Family Applications (1)

Application NumberTitlePriority DateFiling Date
CN202111499793.2AActiveCN114085373B (en)2021-12-092021-12-09Hyaluronic acid polyether polyol and preparation method and application thereof

Country Status (1)

CountryLink
CN (1)CN114085373B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN87106919A (en)*1986-10-131988-08-24菲迪亚公司Cross-linked esters of hyaluronic acid
CN104558467A (en)*2014-12-312015-04-29江苏奥斯佳材料科技有限公司Polyurethane catalyst and application thereof
CN109251924A (en)*2018-09-302019-01-22江南大学A kind of preparation method of dynamic key polymer and its application in terms of improving enzyme heat stability
CN110054767A (en)*2018-01-192019-07-26辽宁奥克化学股份有限公司Polyether polyol and preparation method thereof and polyurethane foam
CN112029086A (en)*2020-08-312020-12-04荆晓东Preparation method of autocatalytic soft foam polyether polyol for sponge
EP3854377A1 (en)*2020-01-222021-07-28Laboratoires Genevrier SasComposition comprising hyaluronic acid and a polyol or carboxymethylcellulose

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN87106919A (en)*1986-10-131988-08-24菲迪亚公司Cross-linked esters of hyaluronic acid
CN104558467A (en)*2014-12-312015-04-29江苏奥斯佳材料科技有限公司Polyurethane catalyst and application thereof
CN110054767A (en)*2018-01-192019-07-26辽宁奥克化学股份有限公司Polyether polyol and preparation method thereof and polyurethane foam
CN109251924A (en)*2018-09-302019-01-22江南大学A kind of preparation method of dynamic key polymer and its application in terms of improving enzyme heat stability
EP3854377A1 (en)*2020-01-222021-07-28Laboratoires Genevrier SasComposition comprising hyaluronic acid and a polyol or carboxymethylcellulose
CN112029086A (en)*2020-08-312020-12-04荆晓东Preparation method of autocatalytic soft foam polyether polyol for sponge

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
阎世翔,瞿康华,刘宇红,张富强,李钧,郭立萍: "固体山梨醇在化妆品中的应用", 日用化学工业, no. 06*

Also Published As

Publication numberPublication date
CN114085373B (en)2023-07-14

Similar Documents

PublicationPublication DateTitle
JP3634988B2 (en) Anionic surfactant and detergent composition
Olofsson et al.Interactions between surfactants and uncharged polymers in aqueous solution studied by microcalorimetry
CN104144673A (en)Use of powdered cellulose in cosmetic applications
CN110267996B (en)Polymers containing certain levels of biobased carbon
JP2001131578A (en)Anionic surfactant and detergent composition
JP2007217348A (en)Thickener and cosmetic and cleaner containing the same
EP2163603A1 (en)Surfactant composition
JPS5910720B2 (en) Hypoallergenic cleaning composition
CN116370349B (en)Amino acid facial cleanser, and preparation method and application thereof
CN112472630B (en)Self-thickening compositions of amino acid surfactants
CN114259416A (en)Surfactant composition, and preparation method and application thereof
CN117384018A (en)Synthesis method of polidocanol
US5490950A (en)Liquid concentrated aqueous solutions of salts of alkyl ether carboxylic acid, and a process for preparing such solutions
KR20100032864A (en)Surfactant composition
CN114085373A (en)Hyaluronic acid polyether polyol and preparation method and application thereof
KR20160093730A (en)Cosmetic composition
EP3932988A1 (en)Viscous composition
KR0142321B1 (en) Toothpaste composition
JP5432504B2 (en) External preparation for skin and method for producing the same
US20040059150A1 (en)Reduced odor esters and process for producing same
JP2013199498A (en)Skin care preparation and manufacturing method of the same
JP3525848B2 (en) Anionic surfactant and detergent composition
JPH0680704A (en)Hydroxyalkylchitosan salt, its production and cosmetic composition
CN113979934B (en)Nicotinamide surfactant and preparation method and application thereof
KR102013254B1 (en)Method for Manufacturing Silicon Free Conditioner for Shampoo

Legal Events

DateCodeTitleDescription
PB01Publication
PB01Publication
SE01Entry into force of request for substantive examination
SE01Entry into force of request for substantive examination
GR01Patent grant
GR01Patent grant

[8]ページ先頭

©2009-2025 Movatter.jp