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:
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:
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
TABLE 2 shower gel composition Performance parameters
Table 3 quench liquid composition coolability test
Table 4 quench bath composition stability testing
| 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 |
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.