Sulfhydrylated phosphorylcholine for hair humectant as well as preparation method and application of sulfhydrylated phosphorylcholine

Abstract

The invention belongs to the technical field of humectant preparation, and discloses sulfhydrylated phosphorylcholine for a hair humectant as well as a preparation method and application of the sulfhydrylated phosphorylcholine. According to the present invention, the moisture absorption capacity and the moisture retention capacity of the prepared sulfhydrylated phosphorylcholine as the hair moisturizing agent are both stronger than the moisture retention capacity of the commonly used moisturizing agent on the market, the sulfydryl group in the sulfhydrylated phosphorylcholine and the sulfydryl group of the hair can form the disulfide bond, the chemical bonding is firm, and the hair moisturizing effect is good; a good use effect can still be kept at a relatively high temperature, and the hydrogel has good biocompatibility. The preparation method is simple, green and environment-friendly, and the thiolated phosphorylcholine can be applied to the field of preparation of hair moisturizers.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of moisturizers, and particularly relates to a mercapto-phosphorylcholine for hair moisturizers, a preparation method thereof, and an application thereof. Background Art

[0002] Generally, moisturizers can be classified into inorganic, organic, and metal-organic moisturizers. Among them, the inorganic moisturizer is mainly calcium chloride; the organic moisturizers include polyols, amino acids, and polysaccharides; the metal-organic moisturizers include lactate and gluconate. Moisturizers are often incorporated into topical agents, cosmetics, and quasi-drugs to adjust the moisture on the hair surface, impart a moist feeling to the hair, and extend the moisturizing effect. For example, Luo Lingling synthesized N-mercaptoacetylserine from N-chloroacetylserine and sodium hydrosulfide, which is a mercapto-containing moisturizer that can graft onto hair and has good moisture absorption performance. However, this moisturizer is easily inactivated at high temperatures and is easily oxidized (Research on mercapto-active ingredients in hair cosmetics [D]. Master's thesis of Jiangnan University, 2006: 30-39). Yamanashi Minokuma et al. designed cationic vesicles encapsulating cholesterol using cholesterol as a raw material, which can achieve the introduction of cholesterol into hair and effectively improve the moisture absorption and retention ability of hair. However, the preparation process is complex and the practical application is difficult, which limits its use (Yamanashi Minokuma, Sagara Keisuke, Konno Yoshikazu, et al. Cholesterol introduction system hair moisturizer [C] / / China Flavor and Fragrance Cosmetics Industry Association. Proceedings of the 9th China Cosmetics Symposium (Part 1). Institute of Kose Co., Ltd.;, 2012: 231-237.).

[0003] Monomers with phospholipid groups have excellent moisture absorption and retention capabilities and are highly favored by researchers in the field of biomaterials. When these monomers with phospholipid groups modify the surface of a material to mimic the outer structure of the cell membrane, the material will have good biocompatibility and exhibit ideal interactions with biological tissues. Therefore, monomers with phospholipid groups have great application potential in the field of moisturizers. Chinese Patent CN 107652392 B, "Preparation Method of a Polymer Containing Mercapto Phosphorylcholine," polymerizes a vinyl monomer containing a phosphorylcholine hydrophilic group and styrene by free radical polymerization to obtain a phosphorylcholine polymer containing a benzene ring, then conducts a chloromethylation reaction on it, and finally reacts with sodium hydrosulfide to prepare a polymer containing mercapto phosphorylcholine. Arunee Sangsuwan et al. used MPC, 1,6-hexanedithiol, and diisopropylamine as raw materials to react at room temperature to obtain a mercapto-functionalized phosphorylcholine monomer (Arunee Sangsuwan, Thiolated-2-methacryloyloxyethyl phosphorylcholine protected silver nanoparticles as novel photo-induced cell-killing agents, Colloids and Surfaces B: Biointerfaces, 2015). However, the above-obtained mercapto phosphorylcholine does not belong to the field of moisturizer preparation. Therefore, it is of great significance to prepare a moisturizer with excellent moisture absorption and retention capabilities, good biocompatibility, stability at high temperatures, and stable binding to hair by a simple and environmentally friendly method. Summary of the Invention

[0004] To solve the above-mentioned deficiencies and drawbacks of the prior art, the primary object of the present invention is to provide a mercapto phosphorylcholine for use in hair moisturizers. This mercapto phosphorylcholine simultaneously contains a mercapto group, a phosphorylcholine group, and a hydroxyl group, and has good moisture absorption and retention capabilities, biocompatibility, binding stability, and adjustable overall hydrophilicity.

[0005] Another object of the present invention is to provide a preparation method for the above-mentioned mercapto phosphorylcholine. Under an alkaline catalyst and a suitable solvent, by controlling the appropriate dosage ratio of reactants, epichlorohydrin undergoes a ring-opening reaction with glycerophosphorylcholine to carry out an etherification reaction, then reacts with a sodium hydrosulfide solution under suitable conditions, and finally adjusts the pH to obtain mercapto phosphorylcholine.

[0006] Another object of the present invention is to provide the application of the above-mentioned mercapto phosphorylcholine in the field of preparing hair moisturizers.

[0007] The objects of the present invention are achieved through the following technical solutions:

[0008] The molecular formula of thiolated phosphorylcholine for hair moisturizer is shown as follows:

[0009]

[0010] The preparation method of the thiolated phosphorylcholine for hair moisturizer includes two steps:

[0011] S1. Add the alkaline catalyst solution to glycerophosphorylcholine dried under vacuum at 40 - 50 °C. After stirring evenly at 50 - 60 °C for 10 - 15 min, add epichlorohydrin dropwise and continue stirring and reacting for 3 - 3.5 h to obtain an etherification product;

[0012] S2. Add hydrochloric acid dropwise to an aqueous solution of sodium sulfide to prepare a NaSH solution;

[0013] S3. At 70 - 80 °C, add the NaSH solution dropwise to the etherification product obtained in step S1. After the addition is complete, carry out condensation reflux and stirring reaction for 2 - 2.5 h. After the reaction ends and cools down, stir and add dilute hydrochloric acid until a white precipitate is precipitated. After centrifuging to remove the precipitate, dry the supernatant to obtain thiolated phosphorylcholine.

[0014] Preferably, in step S1, the molar ratio of glycerophosphorylcholine to epichlorohydrin is 1:(1.5 - 1.8); the alkaline catalyst is sodium hydroxide or / and potassium hydroxide, and the molar ratio of glycerophosphorylcholine to the alkaline catalyst in the alkaline catalyst solution is 2:(1 - 3); the volume of deionized water and the mass of the alkaline catalyst in the alkaline catalyst solution are (5 - 10) mL:0.1 g; the stirring rate is 400 - 600 r / min.

[0015] Preferably, in step S2, the molar ratio of sodium sulfide nonahydrate in the aqueous solution of sodium sulfide to glycerophosphorylcholine in step S1 is 2:(1 - 1.2); the molar ratio of hydrochloric acid to sodium sulfide nonahydrate in the aqueous solution of sodium sulfide is 1:(1 - 1.2); the concentration of hydrochloric acid is 1 - 3 mol / L.

[0016] Preferably, in step S3, the molar concentration of the dilute hydrochloric acid is 6 - 12 mol / L; the concentration of the NaSH solution is 0.1 - 0.5 g / mL; the stirring rate is 400 - 600 r / min.

[0017] The application of the thiolated phosphorylcholine in the field of preparing hair moisturizer.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The hydroxyl groups contained in the mercapto phosphoryl choline of the present invention can better regulate the overall moisture absorption and retention properties. By introducing mercapto groups, it can bind to hair in the form of disulfide chemical bonds, and the firm binding can prolong the moisturizing effect. The hair moisturizer prepared based on mercapto phosphoryl choline has phosphoryl choline groups on its surface, has a stronger moisture absorption ability than common moisturizers on the market, and at the same time has good biocompatibility.

[0020] 2. The preparation method of the present invention is simple, highly practical, green and environmentally friendly. The raw materials used have low costs, are rich in sources and easy to obtain, and are easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the synthesis chemical formula of mercapto phosphoryl choline of the present invention;

[0022] Figure 2 It is the infrared spectrum of mercapto phosphoryl choline in Example 1;

[0023] Figure 3 It is the 1H NMR spectrum of mercapto phosphoryl choline in Example 2;

[0024] Figure 4 It is the hygroscopicity test chart of mercapto phosphoryl choline in Example 3:

[0025] Figure 5 It is the high-definition industrial camera picture and TG test chart of hair with mercapto phosphoryl choline in Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0026] The content of the present invention will be further described below in conjunction with specific examples, but it should not be construed as a limitation to the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well-known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

[0027] Example 1

[0028] 1. Glycerophosphoryl choline (GPC) ( Figure 1 as shown in (a) below) was dried overnight in vacuo at 40 °C. In a three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, 0.2 g of sodium hydroxide was added to 20 mL of deionized water to prepare an aqueous sodium hydroxide solution, and glycerophosphoryl choline (5 mmol, 1.3 g) was added. The mixture was stirred at 50 °C for 10 min, and then epichlorohydrin (7.5 mmol, 0.7 g) was slowly titrated within 30 min. The reaction was continued at 50 °C for 3 h to obtain an etherification product, the structure of which is as shown in Figure 1 shown in (b) below.

[0029] 2. Weigh sodium sulfide nonahydrate (10 mmol, 2.4 g), add it to 10 mL of deionized water and dissolve it to obtain a sodium sulfide solution with a concentration of 1 mol / L; take 12 mol / L HCl (10 mmol, 0.83 mL), add it to 20 mL of deionized water to obtain dilute HCl with a concentration of 0.5 mol / L, and slowly drip the dilute HCl into the sodium sulfide solution to prepare a NaSH solution;

[0030] 3. Dissolve the etherification product dried in step S1 in 10 mL of deionized water, heat it to 70 °C, drip the NaSH solution, continue stirring for 3 h after dripping, after the reaction ends and cools down, add dilute HCl to the reactant ( Figure 1 as shown in (c)) to adjust the pH value to 2, precipitate a flocculent precipitate, centrifuge for 10 min to remove the precipitate, dry the clear liquid to remove the solvent, and obtain thiolated phosphorylcholine ( Figure 1 as shown in (d)), and its synthesis process is as Figure 1 shown.

[0031] Figure 2 are the infrared spectra of glycerophosphorylcholine and thiolated phosphorylcholine in Example 1. From Figure 2 it can be seen that an infrared absorption peak of -OH appears at 3300 cm -1 for thiolated glycerophosphorylcholine, and an infrared absorption peak of -SH appears at 2400 cm -1 ; it shows that only one hydroxyl group reacted during the etherification reaction of glycerophosphorylcholine, and one hydroxyl group was retained, and the subsequent thiolation successfully grafted the mercapto group, and thiolated phosphorylcholine was successfully prepared.

[0032] Example 2

[0033] 1. Glycerophosphorylcholine (GPC) is dried overnight in vacuo at 40 °C. In a three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, take 0.2 g of sodium hydroxide, add it to 20 mL of deionized water to prepare an aqueous sodium hydroxide solution, add glycerophosphorylcholine (5 mmol, 1.3 g), stir at 50 °C for 10 min, and then slowly titrate epichlorohydrin (7.5 mmol, 0.7 g) within 30 min. Continue the reaction at 50 °C for 3 h to obtain an etherification product, and its structure is as Figure 1 shown in (b).

[0034] 2. Weigh sodium sulfide nonahydrate (10 mmol, 2.4 g), add it to 10 mL of deionized water and dissolve it to obtain a sodium sulfide solution with a concentration of 1 mol / L; take 12 mol / L HCl (10 mmol, 0.83 mL), dilute it in 20 mL of deionized water to obtain dilute HCl with a concentration of 0.5 mol / L, and slowly drip the dilute HCl into the sodium sulfide solution to prepare a NaSH solution.

[0035] 3. Dissolve the dried etherification reaction product in 10 mL of deionized water, heat to 70 °C, and dropwise add the NaSH solution. After the addition is complete, continue stirring for 3 h. After the reaction ends and cools, add dilute HCl to the reactant to adjust the pH value to 2, precipitate flocculent precipitate, centrifuge for 10 min to remove the precipitate, obtain the clear liquid, dry to remove the solvent, and obtain mercapto-phosphorylcholine.

[0036] Figure 3 1H NMR spectra of glycerophosphorylcholine and mercapto-glycerophosphorylcholine in Example 2. It can be seen from Figure 3 that mercapto-phosphorylcholine was successfully prepared.

[0037] Example 3

[0038] 1. Glycerophosphorylcholine (GPC) was dried overnight under vacuum at 40 °C. In a three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, add 0.2 g of sodium hydroxide to 20 mL of deionized water to prepare an aqueous sodium hydroxide solution, add glycerophosphorylcholine (5 mmol, 1.3 g), stir at 50 °C for 10 min, and then slowly titrate epichlorohydrin (7.5 mmol, 0.7 g) within 30 min. Continue the reaction at 50 °C for 3 h to obtain the etherification product, the structure of which is shown in Figure 1 (b) in.

[0039] 2. Weigh sodium sulfide nonahydrate (10 mmol, 2.4 g) and dissolve it in 10 mL of deionized water to obtain a sodium sulfide solution with a concentration of 1 mol / L; take 12 mol / L HCl (10 mmol, 0.83 mL) and dilute it in 20 mL of deionized water to obtain dilute HCl with a concentration of 0.5 mol / L; slowly add the dilute HCl to the sodium sulfide solution to prepare the NaSH solution.

[0040] 3. Dissolve the dried etherification product in 10 mL of deionized water, heat to 70 °C, and dropwise add the NaSH solution. After the addition is complete, continue stirring for 3 h. After the reaction ends and cools, add dilute HCl to the reactant to adjust the pH value to 2, precipitate flocculent precipitate, centrifuge for 10 min to remove the precipitate, obtain the clear liquid, dry to remove the solvent, and obtain mercapto-phosphorylcholine.

[0041] Take the mercapto-phosphorylcholine in Example 3 and commercially available xylitol and dry them under vacuum overnight. Weigh 0.1 g of mercapto-glycerophosphorylcholine and xylitol respectively and place them evenly on a clean glass slide. Let them stand at room temperature for h, 4 h, 5 h, 6 h, 7 h, 8 h, 24 h, and measure the sample weights. By measuring their weight changes, the weight changes reflect their water absorption. Figure 4 1H NMR spectra of glycerophosphorylcholine and mercapto-glycerophosphorylcholine in Example 3. It can be seen from Figure 4It can be seen that the short-term hygroscopicity (3 - 8 h) of mercapto phosphoryl choline is better than that of xylitol, and the short-term hygroscopic capacity is 2 - 3 times that of xylitol; the long-term hygroscopicity (24 h) of mercapto phosphoryl choline is also better than that of xylitol, and the long-term hygroscopic capacity is about 3 times that of xylitol.

[0042] Example 4

[0043] 1. Glycerophosphoryl choline (GPC) was dried overnight under vacuum at 40 °C. In a three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, 0.2 g of sodium hydroxide was added to 20 mL of deionized water to prepare an aqueous sodium hydroxide solution. Glycerophosphoryl choline (5 mmol, 1.3 g) was added. After stirring at 50 °C for 10 min, epichlorohydrin (7.5 mmol, 0.7 g) was slowly titrated within 30 min, and the reaction continued at 50 °C for 3 h to obtain an etherification product, the structure of which is as Figure 1 shown in (b) below.

[0044] 2. Sodium sulfide nonahydrate (10 mmol, 2.4 g) was weighed and dissolved in 10 mL of deionized water to obtain a sodium sulfide solution with a concentration of 1 mol / L; 12 mol / L HCl (10 mmol, 0.83 mL) was added to 20 mL of deionized water to obtain dilute HCl with a concentration of 0.5 mol / L; the dilute HCl was slowly added dropwise to the sodium sulfide solution to prepare a NaSH solution.

[0045] 3. The dried etherification reaction product was dissolved in 10 mL of deionized water, and the NaSH solution was added dropwise while heating to 70 °C. After the addition was completed, stirring continued for 3 h. After the reaction ended and cooled, dilute HCl was added to the reactant to adjust the pH value to 2, and a flocculent precipitate was precipitated. The precipitate was removed by centrifugation for 10 min, and the clear liquid was dried to remove the solvent to obtain mercapto phosphoryl choline.

[0046] The mercapto phosphoryl choline in Example 4 and the purchased xylitol were dried under vacuum overnight. 0.5 g of mercapto phosphoryl choline and 0.5 g of xylitol were weighed and added to 10 mL of deionized water respectively and dissolved evenly to obtain a mercapto phosphoryl choline solution and a xylitol solution; then 4 hairs of the same person were taken, the roots and tips were cut off, and cut into appropriate lengths. The hairs were washed with water, then dried, dried at 50 °C for 10 min. Two of the dried hairs were taken and placed in the above-mentioned humectant solutions respectively. The hairs were wrapped with plastic wrap and heated at 50 °C for 1 h. Finally, the hairs were taken out and soaked in 10 mL of deionized water for 5 min, dried under vacuum at room temperature for 12 h, and the hairs were taken out and placed at room temperature for 24 h, photographed with a high-definition industrial camera (×100) and subjected to TG testing. Figure 5 The high-definition industrial camera pictures and TG test pictures of the hair with mercapto phosphoryl choline in Example 4 as a hair humectant. From Figure 5It can be seen that after being placed for 24 hours, for the hair treated with xylitol (A) and thiolated glycerophosphorylcholine (B) respectively, water droplets gather on the surface of the hair treated with thiolated glycerophosphorylcholine (B), while there are no such water droplets on the hair treated with xylitol (A); it can be learned from the TG test spectrum (C) that the hair treated with thiolated glycerophosphorylcholine (B) has a lower weight loss and better moisturizing ability, indicating that thiolated glycerophosphorylcholine has been successfully grafted onto the hair and the combination is stable, and it has better moisture absorption and moisturizing ability.

[0047] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A thiolated phosphorylcholine for a hair moisturizer, characterized in that, The molecular formula of the thiolated phosphorylcholine is as follows:

2. The preparation method of thiolated phosphorylcholine for a hair moisturizer according to claim 1, characterized in that, It includes two steps: S1. Add the alkaline catalyst solution to glycerophosphorylcholine that has been vacuum-dried at 40-50°C. After stirring evenly at 50-60°C for 10-15 minutes, add epichlorohydrin dropwise and continue stirring and reacting for 3-3.5 hours to obtain an etherification product; S2. Add hydrochloric acid to an aqueous sodium sulfide solution to prepare a NaSH solution; S3. At 70-80°C, add the NaSH solution dropwise to the etherification product obtained in step S1. After the addition is complete, carry out reflux condensation and stirring reaction for 2-2.5 hours. After the reaction ends and cools, stir and add dilute hydrochloric acid until a white precipitate appears. After centrifuging to remove the precipitate, dry the supernatant to obtain thiolated phosphorylcholine.

3. The preparation method of thiolated phosphorylcholine for a hair moisturizer according to claim 2, characterized in that, In step S1, the molar ratio of the glycerophosphorylcholine to epichlorohydrin is 1:(1.5-1.8); the alkaline catalyst is sodium hydroxide or / and potassium hydroxide, and the molar ratio of the glycerophosphorylcholine to the alkaline catalyst in the alkaline catalyst solution is 2:(1-3); the volume of deionized water and the mass of the alkaline catalyst in the alkaline catalyst solution are (5-10) mL:0.1 g; the stirring rate is 400-600 r / min.

4. The preparation method of thiolated phosphorylcholine for a hair moisturizer according to claim 2, wherein In step S2, the molar ratio of sodium sulfide nonahydrate in the aqueous sodium sulfide solution to the glycerophosphorylcholine in step S1 is 2:(1-1.2); the molar ratio of hydrochloric acid to sodium sulfide nonahydrate in the aqueous sodium sulfide solution is 1:(1-1.2); the concentration of the hydrochloric acid is 1-3 mol / L.

5. The preparation method of thiolated phosphorylcholine for a hair moisturizer according to claim 2, characterized in that, In step S3, the molar concentration of the dilute hydrochloric acid is 6-12 mol / L; the concentration of the NaSH solution is 0.1-0.5 g / mL; the stirring rate is 400-600 r / min.

6. The application of the thiolated phosphorylcholine according to claim 1 in the field of preparing hair moisturizers.

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