CN114085373B - Hyaluronic acid polyether polyol and preparation method and application thereof - Google Patents
Hyaluronic acid polyether polyol and preparation method and application thereof Download PDFInfo
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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Abstract
The invention discloses hyaluronic acid polyether polyol, a preparation method and application thereof, wherein the hyaluronic acid polyether polyol has a structure shown in a formula 1:
Description
Technical Field
The invention relates to hyaluronic acid polyether polyol, a preparation method and application thereof, and belongs to the technical field of polyether polyol preparation.
Background
The surfactant is an indispensable chemical product in daily life, and is called industrial monosodium glutamate. The functions of the surfactant are various, and the surfactant has the body and shadow in the fields of textile, coating, medical, metal processing and daily chemical industry, and along with the development of the age and the improvement of the living standard of people, people not only pursue daily surface activities with high cleaning power, but also pursue high-quality, multifunctional, green and environment-friendly degradable surfactants. In addition, part of the high molecular weight polyether surfactant has the characteristic of quenching liquid, but the preparation of the high molecular weight polyether by starting with small molecules has a certain difficulty, and a reaction kettle of a manufacturer is required to have a large growth ratio, and meanwhile, when the molecular weight is more than 5000, the phenomenon of chain breakage easily occurs, and the molecular weight is difficult to grow.
Hyaluronic acid is an acidic mucopolysaccharide, which also has a well-known alias: hyaluronic acid. Hyaluronic acid shows various important physiological functions in the body by virtue of unique molecular structure and physicochemical properties, such as lubricating joints, regulating permeability of vascular walls, regulating protein, water electrolyte diffusion and operation, promoting wound healing and the like. It is particularly important that hyaluronic acid has a specific water-retaining effect, and is a substance which is found in nature to be the best in its heat retaining property at present, and is called an ideal natural moisturizing factor, in which skin also contains a large amount of hyaluronic acid. The maturation and aging process of human skin also changes along with the content and metabolism of hyaluronic acid, and the hyaluronic acid can improve the nutrition metabolism of the skin, make the skin tender, smooth, remove wrinkles, increase elasticity, prevent aging, and is a good percutaneous absorption promoter while keeping moisture. However, conventional hyaluronic acid is solid and has poor compatibility, which limits its application.
At present, some of the research on hyaluronic acid at home and abroad is related to the preparation and purification, and the other part is directly used as an additive in cosmetics, and no precedent of adding evolved cosmetics after being modified by ethylene oxide and propylene oxide exists yet, for example, patent application CN104069019A of the Lizhou Anhua bioengineering Co., ltd. Discloses a shampoo containing hyaluronic acid, the main emphasis is that the yield of hyaluronic acid is high, the protein content is low, the glucuronic acid content is high, and the hyaluronic acid is directly used as an additive to prepare the shampoo, so that the compatibility of the formulation of the shampoo is difficult to practice.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a hyaluronic acid polyether polyol and a preparation method thereof, wherein hyaluronic acid and derivatives thereof are used as an initiator, and the hyaluronic acid and derivatives thereof are combined with epoxide (EO, PO) to prepare the polyether polyol, which is a nonionic surfactant with excellent performance.
The method can change the hyaluronic acid and the derivatives thereof from solid into liquid, so that the hyaluronic acid and the derivatives thereof have good biocompatibility, meanwhile, the hyaluronic acid polyether polyol is colorless and transparent, does not affect the color of any other formula when in use, has degradability, cleanliness and skin beautifying, moisturizing and moisturizing effects, and has great application prospects in the fields of paint, textile and daily washing by adjusting the EO/PO ratio and the number of the hyaluronic acid and the derivatives thereof.
In addition, based on the characteristics of hyaluronic acid macromolecules, the high-molecular-weight polyether is particularly suitable for preparing high-molecular-weight polyether, and the high-molecular-weight polyether has excellent thermal stability and cooling stability and is also suitable for being used as quenching liquid.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a hyaluronic acid polyether polyol, which has a structure shown in a formula 1:
wherein m, n, p, q, x, y is an integer of 0-50, at least 1 of m, n, p, q, x, y is not 0, and the m, n, p, q, x, y values may be the same or different; z is an integer from 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 m, n, p, q, x, y value is 1-30;
preferably, the z takes a value of 20-30.
The average molecular weight of the hyaluronic acid polyether polyol according to the invention is 11000-673000, preferably 23000-410000.
The chroma of the hyaluronic acid surfactant is less than or equal to 30Hazen, preferably less than or equal to 20Hazen, measured by a national standard GB/T9282 method.
The transmittance of the hyaluronic acid surfactant measured by the GBT2566-2010 method is more than or equal to 85%, and the transmittance is preferably more than or equal to 90%.
The viscosity of the hyaluronic acid surfactant is 300-6000Pa.s, and the acid value is less than or equal to 0.5mgKOH/g.
The invention also provides a preparation method of the hyaluronic acid polyether polyol shown in the formula 1, which comprises the steps of reacting hyaluronic acid and derivatives thereof serving as an initiator 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 invention, the hyaluronic acid and the derivatives thereof 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 derivatives thereof is 4000-200000g/mol, preferably 10000-100000g/mol;
preferably, the water content of the hyaluronic acid and the derivative raw materials is lower than 1000ppm, preferably lower than 400ppm; preferably, the said acid or derivative thereof is dehydrated in vacuo before reaction at a temperature of 80-130 ℃, preferably 100-120 ℃, for a period of 0.5-3 hours, preferably 0.5-1.5 hours, to a moisture content of at least less than 1000ppm.
In the method of the invention, the mass ratio of the hyaluronic acid and the derivatives thereof to the ethylene oxide and the propylene oxide is 1:0-29:0-38, ethylene oxide, propylene oxide not both 0, preferably 1:0.3-18:0.4-23.
In the method of the present invention, the alkaline 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, alkali metal ethoxide, preferably any one 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 derivatives thereof, and the ethylene oxide and the propylene oxide.
In the process of the invention, the reaction is carried out at a temperature of from 100 to 180 ℃, preferably from 120 to 140 ℃;
in the reaction process, ethylene oxide and propylene oxide are continuously fed, and the control pressure of the feeding process is 0.1-0.6MPaG, preferably 0.1-0.3MpaG; the aging reaction is carried out for 0.5 to 3 hours, preferably 0.5 to 1.5 hours after the completion of the feeding, and the reaction reaches the end.
In the method, the reaction can be carried out in any reactor such as a tubular reactor, a stirred tank, a loop reactor and the like, and the method also comprises the step of removing unreacted ethylene oxide, propylene oxide and other gas impurities in vacuum after the reaction is finished;
preferably, the reaction further comprises adding acid to the reaction solution for neutralization treatment, wherein the acid is selected from organic acids such as acetic acid, lactic acid, neodecanoic acid and the like, and preferably acetic acid; preferably, the reaction solution is neutralized to a pH of 5 to 7, preferably 6 to 7;
preferably, the reaction system may be further added with an inorganic acid and treated with an adsorbent, for example, in some specific examples, a certain amount of phosphoric acid is added first to adjust to PH 4-5, then magnesium silicate is added to be stirred for adsorption, then diatomite is added to be stirred for adsorption, then pressure filtration is performed, and the adsorbed product has PH 6-7, which is a conventional operation in the art, and the present invention has no special requirement.
The invention further provides application of the hyaluronic acid polyether polyol in the fields of washing, pharmacy, textile, cosmetics and metal processing, and is preferably used as a surfactant and a quenching liquid.
Preferably, the hyaluronic acid polyether polyol is used as a surfactant in cosmetics, and the shower gel composition comprises the following components in parts by weight:
wherein, preferably, the humectant is sorbitol, hexaglycerin, vaseline; the essence is water-oil essence with rose or gardenia taste; the bactericide is polyhexamethylene guanidine or hydantoin; the pH regulator is citric acid or lactic acid.
The preparation method of the bath lotion composition comprises the steps of weighing the components according to a proportion, stirring and mixing for 0.5-4h, preferably 1-2h at 30-60 ℃ until the components are fully and uniformly mixed.
The pH value of the bath lotion composition is 6.0-7.0, the viscosity of the bath lotion composition is 500-6000mpa.s at 25 ℃, the light transmittance is more than or equal to 70%, and the chromaticity 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 once the liquid temperature around the workpiece rises above the cloud point of the solution in the quenching process of the workpiece, the polymer in the quenching liquid is stripped from the solution and suspended in the quenching liquid in the form of tiny liquid beads. As soon as the suspended polymer liquid beads contact the red hot workpiece, the suspended polymer liquid beads adhere to the surface of the workpiece by virtue of the very good wettability of the suspended polymer liquid beads, and the workpiece is wrapped by a water-rich coating, so that the cooling speed of water is regulated, and the quenching cracking of the workpiece is avoided. When the workpiece is cooled down, the polymer adhered to the workpiece is dissolved back into the quenching liquid, so that the polymer capable of being used for the quenching liquid must have high-temperature stability.
The hyaluronic acid polyether polyol is a high molecular polymer, and meanwhile, the characteristic of multiple branched chains is easier to structure 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 interact through hydrogen bonds, the hydrogen bonds are broken when the liquid temperature is increased, water molecules combined on the ether group are separated, high molecular weight polyether can be separated out from the water and adhered to the surface of a workpiece, and a layer of polymer film is formed, so that the cooling speed of the workpiece is reduced, and the workpiece is protected to reduce cracks. After stirring, cooling circulation and water vapor escape to take out a part of heat, the temperature of the quenching liquid is gradually reduced, the high molecular weight polyether and water form stable aqueous solution again under the action of hydrogen bonds, the aqueous solution is removed from the surface of the workpiece, and few high molecular weight polyether are attached when the workpiece is taken out of the water, so that the concentration stability 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, ensures that the concentration of quenching liquid is more stable, and reduces the times of replacement and supplementation.
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 changes solid hyaluronic acid and derivatives thereof into liquid at normal temperature, has the advantage of good fluidity, has good solubility in a formula, is colorless and transparent, and does not have any adverse effect on the color of the formula.
2) The hyaluronic acid polyether polyol disclosed by the invention has the characteristics of good degradability, good biocompatibility, small cytotoxicity and the like of hyaluronic acid after being subjected to EO/PO modification, and can have the characteristics of water retention and moisturizing effect and surfactant by introducing EO/PO chain segments and controlling molecular weight, so that the formula emulsifying, cleaning, foaming and wetting capabilities are improved, and excellent flowability, formula compatibility, cleaning performance and foam performance are shown.
3) The hyaluronic acid polyether polyol provided by the invention has the characteristics of high molecular weight, high stability, good water locking effect and the like, shows excellent heat stability and cooling stability, is especially 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 will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.
The main raw material source information adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
hyaluronic acid: the purity of Qingdao Wanshenshan biotechnology limited company is more than or equal to 99 percent;
sodium methoxide: the purity of the Ara Ding Shiji is more than or equal to 30 percent, and the Ara Ding Shiji is sodium methoxide methanol solution;
potassium methoxide: the purity of the Ara Ding Shiji is more than or equal to 99.5 percent, and the Ara Ding Shiji is in powder form;
phosphazene: the purity of the product is more than or equal to 40 percent and the product is phosphazene ethanol solution;
EO, PO: wanhua chemistry, moisture content < 100ppm;
phosphoric acid: ara Ding Shiji with purity not less than 85% and phosphoric acid water solution;
KOH, national medicine reagent, the purity is 50%, is aqueous solution;
sodium sulfate of natural fatty alcohol ether (AESS 70%): in Zanyu science and technology, the purity is 70%, and 30% of water is contained;
natural fatty alcohol ammonium sulfate (K12 99%): the purity of Hunan is more than or equal to 99 percent;
cocamidopropyl betaine: the purity of the Jinan Zhongsheng chemical industry is more than or equal to 99 percent;
cocamide DEA: the purity of the Wuhan Xin chemical industry is more than or equal to 99 percent;
humectant (sorbitol): the purity of Fule materials in Hubei Kochia Kogyo is more than or equal to 99%;
essence (rose flavor): the purity of Jinan poly Yili chemical industry Co., ltd is more than or equal to 99 percent;
bactericide (polyhexamethylene guanidine): the purity of Jinan Zheng chemical industry Co., ltd is more than or equal to 95 percent;
PH adjuster (citric acid): cheng Longhua, the purity is more than or equal to 99 percent.
Sodium benzoate: the purity of Zhejiang Yang biotechnology Co., ltd is more than or equal to 99 percent.
2. 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 method of GB/T16886;
average molecular weight: measured by GPC;
chromaticity: the method is measured by a national standard GB/T9282 method;
foam volume, defoaming time: measured by a GB/T12579 method;
stain removal rate: the stain removal rate was calculated as a comparison of whiteness before and after cleaning.
Viscosity: measured by GBT 10247-2008;
acid value: measured by GBT12008.5 method;
transmittance: measured by GBT 2566-2010;
wetting: measured by a method of GB 11983-2008;
pH: the pH of a 1% aqueous solution thereof was measured with a conventional pH meter;
product characterization: the measurement IS carried out by using a Thermo Fisher IS50 FTIR infrared spectrometer, and the set parameters are as follows: the scanning times are 16 times, and the scanning range is 4000-400cm < -1 >.
The method for evaluating the moisturizing and water retention effects of the shower gel comprises the following steps:
selecting 800 volunteers with the age of 18-30 years old, randomly dividing into 8 groups, respectively testing one of the body wash samples, 100 cases of each group, respectively selecting a place with basically no difference in initial skin state and initial water content of about 30% at 3cm x 3cm on double forearms, testing the initial water content by using an intelligent water white detector (Shenzhen Mei-well technology Co., ltd.), cleaning the test area by using the body wash sample to be tested after 5 minutes, measuring the water content of the test area just washed without using any skin care product, measuring the water content of the test area after 1 hour, and taking an average value 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 one week of testing, the initial concentration is 10+/-0.2%, and the concentration is measured by taking a circulating sample after 1 week of use.
Example 1
Preparation of hyaluronic acid polyether polyol:
200g of hyaluronic acid (z=26, average molecular weight 10000 g/mol) and 75.2g of KOH catalyst were added to the reaction vessel, the temperature was raised to 120℃and the dehydration was carried out under vacuum for 3 hours until the water content was 430ppm; the reaction temperature is controlled to 120 ℃, 3158g of ethylene oxide and 4162g of propylene oxide are added into a reaction vessel, the feeding time is 10 hours, the pressure is controlled to be 0.1-0.3MPaG, aging reaction is carried out for 3 hours after the ethylene oxide and the propylene oxide are fed, then vacuum pumping is carried out for 30 minutes at 80 ℃ to remove unreacted monomers, 79g of 85% phosphoric acid is added into the reaction solution to neutralize to pH 4-5, 76g of magnesium silicate adsorbent is added into the reaction solution to stir for 1 hour, then 8g of diatomite is added to stir for 20 minutes, and pressure filtration is carried out, so that the hyaluronic acid polyether polyol is obtained, and the pH of the hyaluronic acid polyether polyol is 6.9.
The infrared spectrometer is adopted to test, and the raw materials are 3310 cm to 3340cm -1 Has single stretching vibration peak of-NH-and the characteristic absorption peak of the wave band of the product disappears after the reaction, 1101cm -1 The C-O-C telescopic vibration absorption peak is enhanced. The raw material is 3350cm -1 The region exhibits a strong absorption peak, mainly a hydroxyl group stretching vibration, while the crude product (without aftertreatment) is 3350cm -1 The nearby absorption peak is obviously weakened, and the hydroxyl value absorption peak is obviously enhanced at the position after neutralization, so that the product is proved to be the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The hyaluronic acid polyether polyol pure product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The bath foam composition is prepared from the hyaluronic acid polyether polyol, and comprises the following components in formula:
68g of deionized water, 14g of natural fatty alcohol ether sodium sulfate (AESS 70%), 4g of natural fatty alcohol ammonium sulfate (K12%) 4g of cocamidopropyl betaine 3g, 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, thereby obtaining the bath foam composition.
The pH, viscosity at 25℃and light transmittance, water replenishing and water retaining properties of the body wash composition were measured according to the above-mentioned methods, 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 this example was prepared into aqueous solutions with mass concentrations of 3%, 5%, 10% and 20%, and 0.2% sodium benzoate was added as an anti-corrosion additive, and the cooling performance test was performed according to the petrochemical standard SH/T0220, and compared with the commercial PAG quenching liquid, and the results are shown in table 3.
The stability of the quenching liquid was tested by the method described above, and the test results are shown in table 4.
Example 2
Preparation of hyaluronic acid polyether polyol:
200g of hyaluronic acid (z=10, average molecular weight 4000 g/mol) and 54.4g of sodium methoxide catalyst were added to the reaction vessel, the temperature was raised to 110 ℃, and vacuum dehydration was carried out for 2 hours to a water content of 260ppm; controlling the reaction temperature to 160 ℃, adding 2037 ethylene oxide and 2685g propylene oxide into a reaction container, feeding for 7 hours, controlling the pressure to be 0.1-0.3MPaG during the feeding period, aging for 1.5 hours after the ethylene oxide and the propylene oxide are fed, vacuumizing for 30 minutes at 80 ℃ to remove unreacted monomers, adding 18.5g acetic acid into the reaction solution, and neutralizing until the PH is 6.5, thus obtaining the hyaluronic acid polyether polyol.
The results of the infrared spectrometer test prove that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The hyaluronic acid polyether polyol pure product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The bath foam composition prepared by adopting the hyaluronic acid polyether polyol of the embodiment has the formula composition and the preparation method referring to the embodiment 1, and the only difference is that the hyaluronic acid polyether polyol of the embodiment is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, light transmittance, water replenishing and water retaining properties of the body wash composition 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 process is described with reference to example 1, except that the hyaluronic acid polyether polyol of this example is replaced, and the other operations are unchanged. The results of the performance test are shown in tables 3 and 4.
Example 3
Preparation of hyaluronic acid polyether polyol:
1000g of hyaluronic acid (z=30, average molecular weight 11600 g/mol) and 3.2g of phosphazene catalyst are added into a reaction vessel, the temperature is raised to 80 ℃, and vacuum dehydration is carried out for 0.5h until the water content is 300ppm; the reaction temperature is controlled to be 100 ℃, 680g of ethylene oxide and 897g of propylene oxide are added into a reaction vessel, the feeding time is 1h, the pressure is controlled to be 0.1-0.3MPaG, the aging reaction is carried out for 1h after the ethylene oxide and the propylene oxide are fed, then the vacuum pumping is carried out for 30min at 80 ℃ to remove unreacted monomers, 0.4g of acetic acid is added into the reaction solution to neutralize until the PH is 6.6, and the hyaluronic acid polyether polyol is obtained.
The results of the infrared spectrometer test prove that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The hyaluronic acid polyether polyol pure product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The bath foam composition prepared by adopting the hyaluronic acid polyether polyol of the embodiment has the formula composition and the preparation method referring to the embodiment 1, and the only difference is that the hyaluronic acid polyether polyol of the embodiment is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, light transmittance, water replenishing and water retaining properties of the body wash composition 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 process is described with reference to example 1, except that the hyaluronic acid polyether polyol of this example is replaced, and the other operations are unchanged. The results of the performance test are shown in tables 3 and 4.
Example 4
Preparation of hyaluronic acid polyether polyol:
300g of hyaluronic acid (z=27, average molecular weight 10500 g/mol) and 18.8g of sodium hydroxide catalyst were added to the reaction vessel, the temperature was raised to 130 ℃, and vacuum dehydration was performed for 1h to a water content of 400ppm; the reaction temperature is controlled to 140 ℃, 1531g of ethylene oxide and 2018g of propylene oxide are added into a reaction vessel, the feeding time is5 hours, the pressure is controlled to be 0.2-0.3MPaG, after the ethylene oxide and the propylene oxide are fed, the aging reaction is carried out for 1 hour, then the reaction vessel is vacuumized for 30 minutes at 80 ℃ to remove unreacted monomers, 29g of acetic acid is added into the reaction vessel to neutralize until the PH is 6.7, and the hyaluronic acid polyether polyol is obtained.
The results of the infrared spectrometer test prove that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The hyaluronic acid polyether polyol pure product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The bath foam composition prepared by adopting the hyaluronic acid polyether polyol of the embodiment has the formula composition and the preparation method referring to the embodiment 1, and the only difference is that the hyaluronic acid polyether polyol of the embodiment is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, light transmittance, water replenishing and water retaining properties of the body wash composition 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 process is described with reference to example 1, except that the hyaluronic acid polyether polyol of this example is replaced, and the other operations are unchanged. The results of the performance test are shown in tables 3 and 4.
Example 5
Preparation of hyaluronic acid polyether polyol:
1000g of hyaluronic acid (z=50, average molecular weight 19400 g/mol) and 4.4g of potassium methoxide catalyst were added to the reaction vessel, the temperature was raised to 100 ℃, and vacuum dehydration was performed for 1.5h to a water content of 200ppm; the reaction temperature is controlled to be 130 ℃, 680g of ethylene oxide and 1345g of propylene oxide are added into a reaction vessel, the feeding time is 2 hours, the pressure is controlled to be 0.1-0.3MPaG, the aging reaction is carried out for 1 hour after the ethylene oxide and the propylene oxide are fed, then the vacuum is pumped at 80 ℃ for 30 minutes to remove unreacted monomers, 3.9g of acetic acid is added into the reaction solution to neutralize until the PH is 6.8, and the hyaluronic acid polyether polyol is obtained.
The results of the infrared spectrometer test prove that the product is the hyaluronic acid polyether polyol with the structure shown in the formula 1.
The hyaluronic acid polyether polyol pure product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The bath foam composition prepared by adopting the hyaluronic acid polyether polyol of the embodiment has the formula composition and the preparation method referring to the embodiment 1, and the only difference is that the hyaluronic acid polyether polyol of the embodiment is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, light transmittance, water replenishing and water retaining properties of the body wash composition 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 process is described with reference to example 1, except that the hyaluronic acid polyether polyol of this example is replaced, and the other operations are unchanged. 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: 1531g of ethylene oxide and 2018g of propylene oxide were replaced with butylene oxide, the sum of the molar amounts of which, the hyaluronic acid butane polyether was prepared.
The performance indicators were tested 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 comparative example was replaced with butane polyether hyaluronate, and other operations were unchanged. The performance indicators were tested 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: the hyaluronic acid polyether polyol (m, n, p, q, x, y values were 60) was prepared by substituting 2574g of ethylene oxide and 3393g of propylene oxide with 10296g of ethylene oxide and 13572g of propylene oxide.
The performance indicators were tested 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 comparative example was replaced with hyaluronic acid polyether, and other operations were unchanged. The performance indicators were tested according to the method of example 4 and the results are shown in table 2.
Comparative example 3
The shower gel formulation of reference example 4 differs only in that: the hyaluronic acid polyether polyol is replaced by the hyaluronic acid with equal quality, and other operations are unchanged. The performance indicators were tested according to the method of example 4 and the results are shown in table 2.
Referring to example 4, the quenching liquid formulation was replaced with hyaluronic acid polyether polyol of equal quality, 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=27, average molecular weight 10500 g/mol) is replaced by the ultra-high molecular weight hyaluronic acid (z=60, average molecular weight 23300 g/mol), and the activity is poor, the feeding time is as long as 25 hours, the aging time is as long as 5 hours, and the product has turbid appearance, high viscosity and low light transmittance. It is stated that when z > 50, the activity of the starting materials decreases and is unsuitable for the preparation of polyethers.
The performance indicators were tested 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 comparative example was replaced with hyaluronic acid polyether, and other operations were unchanged. The performance indicators were tested according to the method of example 4 and the results are shown in table 2.
TABLE 1 pure performance parameters of hyaluronic acid polyether polyols
Table 2 performance parameters of body wash compositions
Table 3 test of cooling ability of quench liquid composition
Table 4 stability test of quench liquid composition
| Sample name | Initial concentration% | Concentration after 1 week |
| Example 1 | 10 | 9.9 |
| Example 2 | 10.1 | 9.8 |
| Example 3 | 10 | 9.8 |
| Example 4 | 10 | 9.7 |
| Example 5 | 10 | 9.9 |
| Comparative example 1 | 10.1 | 6.2 |
| Comparative example 2 | 10 | 7.8 |
| Comparative example 3 | 10 | 6 |
| Commercial PAG | 10.1 | 8.2 |
From the data in table 1, it can be seen that the hyaluronic acid polyether polyol within the scope of the invention has excellent light transmittance, biocompatibility and degradability, and meanwhile, the foam is more abundant and the decontamination performance is better. Comparative example 2 shows that foam and stain removal performance is poor when m, n, p, q, x, y is > 50. As can be seen from comparative example 4, when z > 50, the reactivity becomes poor, the polyether is not suitably prepared in an amount, and the appearance of the product is cloudy after the reaction is completed, and the viscosity is very high. From the data of table 2, it can be seen that the hyaluronic acid polyether polyol body wash within the range of the present invention has excellent moisturizing and moisturizing properties.
As can be seen from Table 3, the cooling capacity of 10% of the hyaluronic acid high molecular weight polyether of the invention can basically reach 20% of the commercial PAG level, the hyaluronic acid high molecular weight polyether is used as quenching liquid, the consumption is less, and the metal with good cooling stability is not easy to crack.
The comparison of the table 4 shows that the concentration of the cooling liquid prepared by the hyaluronic acid high molecular weight polyether is higher than that of the comparative example and the commercial quenching liquid, the service time is long, frequent replacement is not needed, and the cooling liquid is more convenient.
The foregoing description is directed to 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 or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (36)
1. A hyaluronic acid polyether polyol having a structure represented by formula 1:
wherein m, n, p, q, x, y is an integer of 1 to 30, and z is an integer of 10 to 50.
2. The hyaluronic acid polyether polyol according to claim 1, characterized in that said z has a value of 20-30.
3. The hyaluronic acid polyether polyol according to claim 1, characterized in that it has an average molecular weight of 11000-673000, a chromaticity of not more than 30Hazen, a light transmittance of not less than 85%, a viscosity of 300-600mpa.s and an acid value of not more than 0.5mgKOH/g.
4. The hyaluronic acid polyether polyol according to claim 3, characterized in that it has an average molecular weight of 23000-410000.
5. The hyaluronic acid polyether polyol according to claim 3, characterized in that the colour is less than or equal to 20Hazen.
6. The hyaluronic acid polyether polyol according to claim 3, characterized in that the light transmittance is not less than 90%.
7. A process for producing a hyaluronic acid polyether polyol according to any of claims 1-6, characterized in that hyaluronic acid and its derivatives are reacted with ethylene oxide and/or propylene oxide in the presence of an alkaline catalyst to give a hyaluronic acid polyether polyol;
the mass ratio of the hyaluronic acid and the derivatives thereof to the ethylene oxide and the propylene oxide is 1:0.3-18:0.4-23.
8. The method according to claim 7, wherein the hyaluronic acid and the derivative thereof 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.
9. The method according to claim 7, wherein the molecular weight of the hyaluronic acid and its derivatives is 4000-200000g/mol.
10. The method of claim 9, wherein the hyaluronic acid and derivatives thereof have a molecular weight of 10000-100000g/mol.
11. The method according to claim 7, wherein the water content of the hyaluronic acid and its derivative raw materials is less than 1000ppm.
12. The method according to claim 11, wherein the water content of the hyaluronic acid and its derivative raw materials is less than 400ppm.
13. The method according to claim 11, wherein the hyaluronic acid or the derivative thereof is dehydrated in vacuum before the reaction at a dehydration temperature of 80 to 130 ℃ for a period of 0.5 to 3 hours to a water content of at least 1000ppm.
14. The method according to claim 13, wherein the vacuum dehydration is performed at a dehydration temperature of 100 to 120 ℃ for a dehydration time of 0.5 to 1.5 hours.
15. The method according to claim 7, wherein the basic catalyst is selected from any one or a combination of at least two of an alkali metal hydroxide, an alkaline earth metal oxide, a phosphazene catalyst, an alkali metal methoxide, and an alkali metal ethoxide.
16. The method according to claim 15, wherein the basic catalyst is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, and phosphazene.
17. The preparation method according to claim 7, wherein the amount of the basic catalyst is 0.01-0.5% of the total mass of the hyaluronic acid and its derivatives, and ethylene oxide and propylene oxide.
18. The preparation method according to claim 17, wherein the amount of the basic catalyst is 0.05-0.2% of the total mass of the hyaluronic acid and its derivatives, and ethylene oxide and propylene oxide.
19. The method of claim 7, wherein the reaction is at a temperature of 100-180 ℃;
in the reaction process, ethylene oxide and propylene oxide are fed continuously, and the pressure is controlled to be 0.1-0.6MPaG in the feeding process; and after the feeding is finished, the aging reaction is carried out for 0.5 to 3 hours, and the reaction reaches the end point.
20. The method of claim 19, wherein the reaction is at a temperature of 120-140 ℃.
21. The method of claim 19, wherein the feed process control pressure is 0.1-0.3mpa g.
22. The method of claim 19, wherein the aging reaction is 0.5 to 1.5 hours after completion of the feeding.
23. The method of claim 7, further comprising removing gaseous impurities in vacuo after the reaction is completed.
24. The method according to claim 7, wherein the reaction further comprises neutralizing the reaction mixture with an acid selected from the group consisting of acetic acid, lactic acid, and neodecanoic acid.
25. The method according to claim 24, wherein the neutralization treatment neutralizes the reaction solution to a pH of 5 to 7.
26. The process of claim 25 wherein the reaction solution is neutralized to a PH of 6 to 7.
27. The method according to claim 24, wherein the system after the reaction is further treated with an inorganic acid and an adsorbent.
28. The preparation method according to claim 27, wherein the specific method is as follows: firstly adding phosphoric acid to adjust the pH to 4-5, then adding magnesium silicate to adsorb and stir, then adding diatomite to adsorb and stir, and then carrying out pressure filtration to adsorb to the pH of 6-7.
29. Use of the hyaluronic acid polyether polyol of any of claims 1-6 or prepared by the method of any of claims 7-28 in the fields of washing, pharmaceutical, textile, cosmetic, metalworking.
30. The use according to claim 29, characterized in that it is used as a surfactant or quenching liquid.
31. A body wash composition comprising the hyaluronic acid polyether polyol of any of claims 1-6 or prepared by the method of any of claims 7-28, the composition comprising in parts by weight:
32. the body wash composition of claim 31, wherein the composition comprises in parts by weight:
33. the body wash composition of claim 31, wherein the humectant is sorbitol, hexaglycerin, petrolatum; the essence is water-oil essence with rose or gardenia taste; the bactericide is polyhexamethylene guanidine or hydantoin; the pH regulator is citric acid or lactic acid.
34. A quench liquid composition comprising the hyaluronic acid polyether polyol of any of claims 1-6 or prepared by the method of any of claims 7-28, the composition comprising hyaluronic acid polyether polyol, sodium benzoate, water.
35. The quench liquid composition of claim 34, wherein the hyaluronic acid polyether polyol is present in an amount of 1-20% and the sodium benzoate is present in an amount of 0.05% -1% based on 100% total mass of quench liquid.
36. The quench liquid composition of claim 35, wherein the hyaluronic acid polyether polyol is present in an amount of 3-10% and the sodium benzoate is present in an amount of 0.1-0.5% based on 100% total mass of quench liquid.
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