Photo-crosslinkable polymer with anti-ultraviolet effect as well as preparation method and application of photo-crosslinkable polymer

Abstract

The invention relates to a photo-crosslinkable polymer with an anti-ultraviolet effect and a preparation method and application of the photo-crosslinkable polymer with the anti-ultraviolet effect, a small molecule compound with the anti-ultraviolet effect is connected to a hydrophilic natural polymer skeleton in a chemical bonding mode, and meanwhile photo-crosslinkable (methyl) acryloyl is introduced to prepare the photo-crosslinkable polymer with the anti-ultraviolet effect. A photocrosslinkable polymer with an anti-ultraviolet effect is prepared by using a photoinitiator as a crosslinking agent, and after a solution of the photocrosslinkable polymer is irradiated by light with a specific wavelength, a crosslinking polymerization reaction of (methyl) acryloyl is initiated under the action of the photoinitiator to form a non-flowing hydrogel, and a physical barrier is formed at a contact part to block external ultraviolet irradiation or pollution. The anti-ultraviolet small molecules are connected to the cross-linked network through chemical bonds, so that the sunscreen effect is exerted, and meanwhile, the mechanical strength of the gel network can resist the impact of flowing water and the permeation of sweat, so that the sunscreen hydrogel prolongs the residence time of the sunscreen molecules, and has a good sunscreen effect. And the safety risk caused by penetration of the small molecular sun-screening agent into the skin is also reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of cosmetics, and particularly relates to a photocrosslinkable polymer with anti-ultraviolet efficacy, a preparation method thereof, and an application thereof. Background Art

[0002] Ultraviolet rays (UV) are divided into three categories according to wavelength: UVA (320 - 400 nm), UVB (280 - 320 nm), and UVC (100 - 280 nm). Among them, UVC is basically blocked by the ozone layer, while UVA and UVB can reach the earth's surface. Short-term exposure to these lights will cause skin erythema, edema, pigment deposition, etc., and long-term exposure will cause skin photoaging, skin cancer, pigment abnormalities, eye damage and other hazards. Therefore, it is particularly important to develop ultraviolet protection products.

[0003] Sunscreen is a protective cosmetic applied on the human body surface and is the last barrier against ultraviolet rays. Sunscreen mainly relies on various sunscreen agents to play a role. Sunscreen agents can be divided into physical sunscreen agents and chemical sunscreen agents. Physical sunscreen agents (such as zinc oxide, titanium dioxide, etc.) achieve the sunscreen effect by reflecting ultraviolet rays, while chemical sunscreen agents are a class of organic compounds that absorb ultraviolet rays and convert them into heat energy for release, used to protect the skin from UVA and UVB damage. Different from physical sunscreen, chemical sunscreen agents have a thinner texture, are easier to apply, and are more suitable for daily use.

[0004] However, current chemical sunscreen agents will undergo phenomena such as photodegradation and skin penetration, which will cause potential safety problems such as biological toxicity and endocrine disruption. In addition, sunscreen stays on the human skin surface through physical coating, and there is a problem of loss when encountering water or sweating, resulting in the loss of the function of resisting ultraviolet rays. Therefore, it is particularly necessary to develop long-lasting, water-resistant, and sweat-proof ultraviolet protection products. Summary of the Invention

[0005] Aiming at the technical problems existing in the above-mentioned prior art, the present invention provides a photocrosslinkable polymer with anti-ultraviolet efficacy, a preparation method thereof, and an application thereof, aiming to achieve long-lasting, water-resistant, and sweat-proof ultraviolet protection functions.

[0006] In the first aspect of the present invention, there is provided a photocrosslinkable polymer with anti-ultraviolet efficacy, having the structure shown in Formula I:

[0007] In Formula I, the curve represents a natural polymer backbone, which is selected from any one of hyaluronic acid, alginic acid, gelatin, collagen, chitosan, cellulose, and chondroitin sulfate; R is any one of a hydroxyl group, a carboxyl group, and an amino group, and R1 is the decarboxylation residue of a small molecule sunscreen agent with a carboxyl group-containing structure; R2 is an (meth)acryloyl group; X and Y are each independently selected from an ester bond, an amide bond, and a coupling agent with ester bonds or amide bonds at both ends.

[0008] In some embodiments of the present invention, the coupling agent is selected from any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, pimelic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, and aminated PEG; In some embodiments of the present invention, the small molecule sunscreen agent is selected from any one of cinnamic acid, cinnamic acid derivatives, salicylic acid, salicylic acid derivatives, o-hydroxybenzoic acid, 4-diethylamino ketonic acid, 4-dimethylaminobenzoic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-dihydroxy-3-carboxyanthraquinone.

[0009] In some embodiments of the present invention, the R1 modification rate of the polymer backbone is between 5% and 50%; In some embodiments of the present invention, the R2 modification rate of the polymer backbone is between 10% and 50%.

[0010] In some embodiments of the present invention, the molecular weight of the polymer is 1000 Da to 5000000 Da.

[0011] In a second aspect of the present invention, a sunscreen hydrogel is provided, which includes the above-mentioned photocrosslinkable polymer with ultraviolet resistance, a photoinitiator, and water.

[0012] In some embodiments of the present invention, the concentration of the photocrosslinkable polymer is 2 to 10 wt%, the concentration of the photoinitiator is 0.05 - 0.5 wt%, and the balance is water.

[0013] In some embodiments of the present invention, the photoinitiator is selected from any one or more of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate (LAP), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, α-ketoglutaric acid, eosin Y, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 1-hydroxycyclohexylbenzophenone.

[0014] In a third aspect of the present invention, a method for preparing the above-mentioned sunscreen hydrogel is provided, which comprises dissolving the photocrosslinkable polymer with ultraviolet resistance and the photoinitiator in water, and carrying out a crosslinking reaction for 2 to 180 s under irradiation with light of 200 nm - 800 nm to obtain the product.

[0015] In the fourth aspect of the present invention, a preparation method of the above-mentioned photocrosslinkable polymer with ultraviolet resistance is provided, and any one of the following preparation methods a and b is selected: a. Dissolve the natural polymer containing hydroxyl and / or amino groups, add (meth)acrylic anhydride, and after the reaction, sediment, filter, and dry to obtain a (meth)acrylic acid-modified polymer; Add the activated small molecule sunscreen and catalyst to the (meth)acrylic acid-modified polymer solution, and after the reaction, sediment, filter, and dry to obtain the product; b. Dissolve the natural polymer containing carboxyl groups, add an excessive amount of coupling agent, and after the reaction, sediment, filter, and dry to obtain a polymer modified with amino or hydrazide at the carboxyl site; Add (meth)acrylic anhydride to the polymer solution modified with amino or hydrazide at the carboxyl site, and after the reaction, sediment, filter, and dry to obtain a (meth)acrylic acid-modified polymer; Add the activated small molecule sunscreen and catalyst to the (meth)acrylic acid-modified polymer solution, and after the reaction, sediment, filter, and dry to obtain the product.

[0016] Preferably, the coupling agent in the preparation method b is selected from any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, pimelic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, and amino-terminated PEG.

[0017] Preferably, the specific implementation process of the preparation method a includes: dissolving the polymer raw material containing hydroxyl and / or amino groups in water, adjusting the pH to 7-10, adding an appropriate amount of (meth)acrylic anhydride at 1-60 °C, continuously stirring for 10-24 h, and after the reaction, removing small molecule impurities by ethanol precipitation, deionized water dialysis or ultrafiltration, etc., and freeze-drying to obtain a (meth)acrylic acid-modified polymer; after dissolving the (meth)acrylic acid-modified polymer, adding activated cinnamic acid or cinnamic acid derivative and an appropriate amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, continuously stirring for 5-24 h, and after the product is sedimented with tetrahydrofuran, dialyzed with deionized water or ultrafiltered to remove small molecule impurities, and then freeze-dried to obtain the final product.

[0018] Preferably, the specific implementation process of preparation method b includes: dissolving the polymer raw material containing carboxyl groups in water, adding an excessive amount of adipic dihydrazide, adjusting the pH to 3-6, continuously stirring for 10-24 h. After the reaction, remove small molecule impurities by ethanol precipitation, deionized water dialysis or ultrafiltration, etc., and obtain the polymer modified with amino groups at the carboxyl sites after freeze-drying; dissolve the above polymer in water, adjust the pH to 7-10, add an appropriate amount of (meth)acrylic anhydride at 1-60 °C, continuously stir for 10-24 h. After the reaction, remove small molecule impurities by ethanol precipitation, deionized water dialysis or ultrafiltration, etc., and obtain the (meth)acrylic acid-modified polymer after freeze-drying; dissolve the (meth)acrylic acid-modified polymer again, add cinnamic acid or cinnamic acid derivatives activated by NHS and an appropriate amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, continuously stir for 5-24 h. After the product is subjected to tetrahydrofuran sedimentation, deionized water dialysis or ultrafiltration, etc. to remove small molecule impurities, and then freeze-dried, the final product is obtained.

[0019] In the fifth aspect of the present invention, an application of the above-mentioned photocrosslinkable polymer is provided, selected from the following applications: The application of the photocrosslinkable polymer in ultraviolet protection products; When R1 is selected from cinnamic acid or its derivatives, the photocrosslinkable polymer has functions such as scavenging free radicals and inhibiting lipid peroxidation, and has application value in antioxidant products; When R1 is selected from cinnamic acid or its derivatives, the photocrosslinkable polymer can damage cell membranes, inhibit enzyme activity, and interfere with DNA / RNA synthesis, so it has application value in antiseptic and bactericidal products.

[0020] The photocrosslinkable polymer with anti-ultraviolet effect, its preparation method and application disclosed in the embodiments of the present invention connect small molecule compounds with anti-ultraviolet effect to the hydrophilic natural polymer backbone by chemical bonding, and at the same time introduce photocrosslinkable (meth)acryloyl groups to prepare a photocrosslinkable polymer with anti-ultraviolet effect. After its solution is irradiated with light of a specific wavelength, under the action of a photoinitiator, a cross-linking polymerization reaction of (meth)acryloyl groups is initiated to form a non-flowing hydrogel, forming a physical barrier at the contact site to block external ultraviolet irradiation or pollution. The anti-ultraviolet small molecules are connected to the cross-linking network by chemical bonds, exerting the sunscreen effect. At the same time, the mechanical strength of the gel network can resist the impact of running water and the penetration of sweat, so that the sunscreen hydrogel of the present invention not only prolongs the retention time of the sunscreen molecules, but also reduces the safety risk brought by the penetration of small molecule sunscreen agents into the skin.

[0021] In summary, the photocrosslinkable polymer with UV resistance of the present invention contains multiple active modification sites such as hydroxyl groups, amino groups or carboxyl groups, which are respectively connected with (meth)acryloyl groups and functional groups with strong UV absorption such as small molecule sunscreen agents. Such polymers can not only crosslink under light conditions to form a network structure, which can resist water flow impact or sweat erosion, but also achieve a sunscreen enhancement effect, effectively avoiding the safety risks brought by the penetration of small molecule sunscreen agents into the skin. The hydrophilic polymer is modified with (meth)acryloyl groups and sunscreen functional groups at the same time, has the characteristics of photocrosslinking and film-forming and UV resistance, and can achieve triple effects of waterproofing, sweatproofing and sunscreen.

[0022] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings herein are incorporated into the specification and constitute a part of this specification, showing embodiments consistent with the present invention, and are used together with the specification to explain the principles of the present invention; Figure 1 It is a test effect diagram of the gel-forming performance of the sunscreen hydrogel of the embodiment of the present invention; Figure 2 It is a test effect diagram of the UV absorption performance of the sunscreen hydrogel of the embodiment; Figure 3 It is a comparative test effect diagram of the UV absorption performance of the sunscreen hydrogel of the embodiment. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] The following will clearly and completely describe the concept of the present invention and the technical effects produced in combination with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.

[0025] For the experimental methods without specific conditions in the embodiments, they are usually carried out according to the conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets.

[0026] Example 1. Preparation of photocrosslinkable polymer A1; Step 1: Weigh 2 g of sodium hyaluronate (Mw = 200 - 400 kDa) powder, dissolve it in 400 mL of deionized water, add an excessive amount of adipic dihydrazide coupling agent and 2.05 g of EDC, adjust the pH of the reaction system to 4 - 5, continuously stir overnight. After the reaction is completed, dialyze it in a large amount of deionized water using a dialysis bag with MWCO = 20 kDa for 3 days, and after freeze-drying, obtain sodium hyaluronate with side-chain modified amino groups, and the yield is about 85%.

[0027] Step 2: At 40 °C, dissolve 5 g of p-nitrocinnamic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the generated by-product dicyclohexylurea, pour the filtrate into water for precipitation, and the obtained solid is vacuum dried and recrystallized with DMF / ethanol to obtain N-succinimidyl p-nitrocinnamate, and the yield is about 90%.

[0028] Step 3: Take 0.4 g of the above-mentioned sodium hyaluronate with modified amino groups, dissolve it in 50 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature. Dissolve a certain amount of N-succinimidyl cinnamate in 10 mL of DMF, and drop it into the above solution, then add an excessive amount of methacrylic anhydride, and react in the dark at room temperature for 72 h, during which NaOH solution is used to maintain the pH at 8 - 9. After the reaction is completed, precipitate and filter in excessive tetrahydrofuran, wash the solid with THF and then vacuum dry to obtain sodium hyaluronate A1 modified with p-nitrocinnamic acid and methacryloyl groups, and the yield is about 80%.

[0029] Example 2: Preparation of photocrosslinkable polymer A2; The difference between the preparation method of Example 2 and that of Example 1 is only that: replace sodium hyaluronate in Example 1 with an equimolar amount of sodium alginate, and finally obtain sodium alginate A2 modified with p-nitrocinnamic acid and methacryloyl groups, and the yield is about 77%.

[0030] Example 3: Preparation of photocrosslinkable polymer A3; Step 1: At 40 °C, dissolve 5 g of salicylic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the generated by-product dicyclohexylurea, pour the filtrate into water for precipitation, and the obtained solid is vacuum dried and recrystallized with DMF / ethanol to obtain N-succinimidyl salicylate.

[0031] Step 2: Take 5 g of gelatin and dissolve it in 50 mL of NaHCO3 solution with a pH of 8.3 at 50 °C. Dropwise add 40 mL of DMF at room temperature. Dissolve a certain amount of N-succinimidyl salicylate in 10 mL of DMF and drop it into the above solution. Then add an appropriate amount of methacrylic anhydride and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8 - 9. After the reaction is completed, precipitate in excess tetrahydrofuran, filter, wash the solid with THF, and then dry it under vacuum to obtain gelatin A3 modified with salicylic acid and methacryloyl group, with a yield of about 80%.

[0032] Example 4: Preparation of photocrosslinkable polymer A4; The difference between the preparation method of Example 4 and that of Example 3 is only that: replace the gelatin in Example 3 with an equimolar amount of collagen, and finally obtain collagen A4 modified with salicylic acid and methacryloyl group, with a yield of about 83%.

[0033] Example 5: Preparation of photocrosslinkable polymer A5; Step 1: At 40 °C, dissolve 5 g of o-hydroxybenzoic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the by-product dicyclohexylurea generated. Pour the filtrate into water for precipitation. The obtained solid is dried under vacuum and then recrystallized with DMF / ethanol to obtain N-succinimidyl o-hydroxybenzoate.

[0034] Step 2: Take 2 g of hydroxyethyl chitosan and dissolve it in 200 mL of NaHCO3 solution with a pH of 8.3. Dropwise add 40 mL of DMF at room temperature. Dissolve a certain amount of N-succinimidyl o-hydroxybenzoate in 10 mL of DMF and drop it into the above solution. Then add an appropriate amount of methacrylic anhydride and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8 - 9. After the reaction is completed, precipitate in excess tetrahydrofuran, filter, wash the solid with THF, and then dry it under vacuum to obtain chitosan A5 modified with o-hydroxybenzoic acid and methacryloyl group.

[0035] Example 6: Preparation of photocrosslinkable polymer A6; Step 1: At 40 °C, dissolve 5 g of 4-diethylamino ketonic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the by-product dicyclohexylurea generated. Pour the filtrate into water for precipitation. The obtained solid is dried under vacuum and then recrystallized with DMF / ethanol to obtain N-succinimidyl 4-diethylamino ketonate.

[0036] Step 2: Take 2 g of carboxymethyl chitosan, dissolve it in 200 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature. Dissolve a certain amount of N-succinimidyl 4-diethylamino ketone acid ester in 10 mL of DMF, add it dropwise to the above solution, then add an appropriate amount of methacrylic anhydride, and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8 - 9. After the reaction is completed, precipitate with excess tetrahydrofuran, filter, wash the solid with THF, and then dry it under vacuum to obtain carboxymethyl chitosan A6 modified with 4-diethylamino ketone acid and methacryloyl group.

[0037] Example 7: Preparation of photocrosslinkable polymer A7; Step 1: Weigh 2 g of carboxymethyl cellulose powder, dissolve it in 400 mL of deionized water, add an excessive amount of hexamethylenediamine and 2.05 g of EDC, adjust the pH of the reaction system to 4 - 5, stir continuously overnight. After the reaction is completed, dialyze with a dialysis bag with MWCO = 10 kDa in a large amount of deionized water for 3 days, and then obtain carboxymethyl cellulose with modified amino groups on the side chain after freeze-drying.

[0038] Step 2: At 40 °C, dissolve 5 g of 4-dimethylaminobenzoic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the by-product dicyclohexylurea generated, pour the filtrate into water to precipitate, and recrystallize the obtained solid with DMF / ethanol after vacuum drying to obtain N-succinimidyl 4-dimethylaminobenzoate.

[0039] Step 3: Take 0.4 g of the above-mentioned carboxymethyl cellulose with modified amino groups, dissolve it in 50 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature. Dissolve a certain amount of N-succinimidyl 4-dimethylaminobenzoate in 10 mL of DMF, add it dropwise to the above solution, then add an excessive amount of methacrylic anhydride, and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8 - 9. After the reaction is completed, precipitate with excess tetrahydrofuran, filter, wash the solid with THF, and then dry it under vacuum to obtain carboxymethyl cellulose A7 modified with 4-dimethylaminobenzoic acid and methacryloyl group.

[0040] Example 8: Preparation of photocrosslinkable polymer A8; Step 1: Weigh 2 g of chondroitin sulfate, dissolve it in 400 mL of deionized water, add an excessive amount of butanediamine coupling agent and 2.05 g of EDC, adjust the pH of the reaction system to 4 - 5, stir continuously overnight. After the reaction is completed, dialyze with a dialysis bag with MWCO = 10 kDa in a large amount of deionized water for 3 days, and then obtain chondroitin sulfate with modified amino groups on the side chain after freeze-drying.

[0041] Step 2: Dissolve 5 g of 2,6-naphthalenedicarboxylic acid in 50 mL of N,N'-dimethylformamide (DMF) at 40 °C, then add equimolar amounts of NHS and EDC, and react under dark for 24 h. After the reaction is completed, filter to remove the by-product dicyclohexylurea formed. Pour the filtrate into water for precipitation. The obtained solid is dried in vacuum and recrystallized with DMF / ethanol to obtain N-succinimidyl 2,6-naphthalenedicarboxylate.

[0042] Step 3: Take 0.4 g of the above-mentioned chondroitin sulfate modified with amino group, dissolve it in 50 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature. Dissolve a certain amount of N-succinimidyl 2,6-naphthalenedicarboxylate in 10 mL of DMF, and drop it into the above solution. Then add an excessive amount of methacrylic anhydride, and react under dark at room temperature for 72 h. During this period, use NaOH solution to maintain the pH at 8 - 9. After the reaction is completed, precipitate and filter in excessive tetrahydrofuran. The solid is washed with THF and then dried in vacuum to obtain chondroitin sulfate A8 modified with 2,6-naphthalenedicarboxylic acid and methacryloyl.

[0043] Example 9: Preparation of photocrosslinkable polymer A9; Step 1: Weigh 2 g of sodium hyaluronate (Mw = 200 - 400 kDa) powder, dissolve it in 400 mL of deionized water, add an excessive amount of glutaric dihydrazide coupling agent and 2.05 g of EDC, adjust the pH of the reaction system to 4 - 5, stir continuously overnight. After the reaction is completed, dialyze with a dialysis bag with MWCO = 20 kDa in a large amount of deionized water for 3 days, and obtain sodium hyaluronate with side-chain modified hydrazide after freeze-drying.

[0044] Step 2: Dissolve 5 g of 1,8-dihydroxy-3-carboxyanthraquinone in 50 mL of N,N'-dimethylformamide (DMF) at 40 °C, then add equimolar amounts of NHS and EDC, and react under dark for 24 h. After the reaction is completed, filter to remove the by-product dicyclohexylurea formed. Pour the filtrate into water for precipitation. The obtained solid is dried in vacuum and recrystallized with DMF / ethanol to obtain N-succinimidyl 1,8-dihydroxy-3-carboxyanthraquinone ester.

[0045] Step 3: Take 0.4 g of the above-mentioned hyaluronic acid sodium modified with hydrazide, dissolve it in 50 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature, dissolve a certain amount of N-succinimidyl 1,8-dihydroxy-3-carboxy anthraquinone ester in 10 mL of DMF, drop it into the above solution, then add an excessive amount of methacrylic anhydride, and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8-9. After the reaction is completed, precipitate and filter in excessive tetrahydrofuran. The solid is washed with THF and then dried in vacuo to obtain 1,8-dihydroxy-3-carboxy anthraquinone and methacryloyl-modified hyaluronic acid sodium A9.

[0046] Example 10. Preparation of photocrosslinkable polymer A10; Step 1: Weigh 2 g of hyaluronic acid sodium (Mw = 200 - 400 kDa) powder, dissolve it in 400 mL of deionized water, add an excessive amount of azelaic acid dihydrazide coupling agent and 2.05 g of EDC, adjust the pH of the reaction system to 4 - 5, stir continuously overnight. After the reaction is completed, dialyze with a dialysis bag with MWCO = 20 kDa in a large amount of deionized water for 3 days, and then obtain hyaluronic acid sodium with side-chain modified amino groups after freeze-drying.

[0047] Step 2: At 40 °C, dissolve 5 g of p-methoxycinnamic acid in 50 mL of N, N'-dimethylformamide (DMF), then add an equimolar amount of NHS and EDC, and react in the dark for 24 h. After the reaction is completed, filter to remove the generated by-product dicyclohexylurea, pour the filtrate into water for precipitation, and the obtained solid is dried in vacuo and then recrystallized with DMF / ethanol to obtain N-succinimidyl p-methoxycinnamate.

[0048] Step 3: Take 0.4 g of the above-mentioned hyaluronic acid sodium modified with amino groups, dissolve it in 50 mL of NaHCO3 solution with pH 8.3, add 40 mL of DMF dropwise at room temperature, dissolve a certain amount of N-succinimidyl p-methoxycinnamate in 10 mL of DMF, drop it into the above solution, then add an excessive amount of methacrylic anhydride, and react at room temperature in the dark for 72 h. During this period, use NaOH solution to maintain the pH at 8-9. After the reaction is completed, precipitate and filter in excessive tetrahydrofuran. The solid is washed with THF and then dried in vacuo to obtain p-methoxycinnamic acid and methacryloyl-modified hyaluronic acid sodium.

[0049] The coupling agents used in each example can be selected from any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and terminal amino-functionalized PEG.

[0050] Example 11: Preparation of a sunscreen hydrogel; Polymers A1 - A10 were separately dissolved in water at a concentration range of 2 wt% - 10 wt%, and 0.05 wt% - 0.5 wt% of a photoinitiator was added to obtain a sunscreen hydrogel. The initiator was equally selected from any one of lithium phenyl(2,4,6 - trimethylbenzoyl)phosphate (LAP), 2 - hydroxy - 2 - methyl - 1 - [4 - (2 - hydroxyethoxy)phenyl] - 1 - propanone, α - ketoglutaric acid, eosin Y, 2,4,6 - trimethylbenzoyldiphenylphosphine oxide, and 1 - hydroxycyclohexylbenzophenone.

[0051] Comparative Example 1: p - Nitrocinnamic acid was dissolved in DMSO at a concentration of 2 wt%.

[0052] Comparative Example 2: Salicylic acid was dissolved in DMSO at a concentration of 2%.

[0053] Test Example 1: Performance test on the ultraviolet resistance of photocrosslinkable polymers A1 - A10 with ultraviolet resistance efficacy A1 - A10 were separately prepared into 0.1% aqueous solutions, and Comparative Example 1 and Comparative Example 2 were separately diluted to 0.1% with DMSO. Scanning was carried out in the range of 200 nm - 800 nm using an ultraviolet spectrophotometer. The ranges where the obtained ultraviolet absorption peaks are located are shown in Table 1 as follows: Table 1 Polymer Ultraviolet absorption range (nm) A1 260~380 A2 260~380 A3 250~360 A4 250~360 A5 210~250 A6 310~390 A7 230~320 A8 310~365 A9 240~320 A10 270~350 Comparative Example 1 250~360 Comparative Example 2 250~360 As shown in Table 1, it shows that the photocrosslinkable polymer has the function of absorbing ultraviolet rays and has ultraviolet resistance efficacy. It shows that small - molecule compounds with ultraviolet resistance efficacy are connected to the hydrophilic natural polymer backbone through chemical bonding, and at the same time, photocrosslinkable (meth)acrylic double bonds are introduced. Compared with the single small - molecule compounds with ultraviolet resistance efficacy in Comparative Example 1 and Comparative Example 2 (ultraviolet absorption range 250 - 360 nm), the present invention can prepare a photocrosslinkable polymer with better ultraviolet resistance efficacy (ultraviolet absorption range 210 - 390 nm).

[0054] Test Example 2: Compressive modulus and ultraviolet transmittance test of the sunscreen hydrogel The sunscreen hydrogels with different concentration components were irradiated with 405 nm ultraviolet light, and the sunscreen hydrogels were all cured to form sunscreen hydrogels in about 30 s.

[0055] The compressive modulus test was carried out using a WDF - 20 digital inference force gauge. The compression test sample was a cylindrical specimen with a diameter of 10 mm and a height of 3 mm, and the test speed was 1 mm / min. The compressive modulus of the sunscreen hydrogel is shown in Table 2.

[0056] Uniformly coat 2 ml of the polymerized aqueous solution of A1 - A10 on a 5 cm × 5 cm transparent PMMA plate. Place the PMMA plate 2 cm above the TM - 223 (TENMARS) ultraviolet light meter. Use a 365 nm ultraviolet lamp to irradiate directly above the PMMA plate, and record the ultraviolet light intensity detected by the ultraviolet light meter. Take the blank PMMA plate as 100% as a reference, and record the data in Table 2. It can be seen from the data in Table 2 that the polymerized aqueous solutions of A1 - A10 all have good ultraviolet resistance effects.

[0057] Table 2 Sun protection hydrogel (component concentration) Compressive modulus (kPa) Ultraviolet transmittance A1: 2 wt%; Initiator: 0.5 wt% 42 9.7% A2: 2 wt%; Initiator: 0.5 wt% 45 10.1% A3: 10 wt%; Initiator: 0.5 wt% 62 14.3% A4: 10 wt%; Initiator: 0.5 wt% 54 14.7% A5: 2 wt%; Initiator: 0.5 wt% 39 17.2% A6: 2 wt%; Initiator: 0.5 wt% 35 13.5% A7: 2 wt%; Initiator: 0.5 wt% 39 15.4% A8: 2 wt%; Initiator: 0.5 wt% 45 13.2% A9: 2 wt%; Initiator: 0.5 wt% 43 16.1% A10: 2 wt%; Initiator: 0.5 wt% 40 17.3% A1: 2 wt%; Initiator: 0.05 wt% 20 9.6% A1: 2 wt%; Initiator: 0.2 wt% 31 9.7% A1: 3 wt%; Initiator: 0.5 wt% 50 9.7% The values of the compression modulus in Table 2 indicate that under the action of the photoinitiator, the cross - linking polymerization reaction of the (meth) acrylene double bonds in the photocrosslinkable polymer will be initiated, forming a non - flowing hydrogel. The mechanical strength of the gel network can resist the impact of running water and the penetration of sweat, prolong the residence time of the sunscreen molecules on the skin surface, and also reduce the safety risks brought by the penetration of small - molecule sunscreen agents into the skin. Test Example 2: Gel - forming property test of the sunscreen hydrogel According to the method of Example 11, prepare sunscreen hydrogels with different concentration components. Select any one of the components and irradiate it with light of 405 nm wavelength. The flowing sunscreen hydrogel solidifies to form a non - flowing sunscreen hydrogel in about 10 s, as Figure 1 shown (the components of the sunscreen hydrogel shown in the figure: A1: 2 wt%; photoinitiator: 0.5 wt%).

[0058] Test Example 3: Ultraviolet absorption property test of the sunscreen hydrogel According to the method of Example 11, prepare sunscreen hydrogels with different concentration components. Select any one group of sunscreen hydrogels: A1: 2 wt%; photoinitiator: 0.5 wt%, and drop it on the induction area of the ultraviolet sunscreen card. Irradiate it with ultraviolet light, as Figure 2 shown (the components of the sunscreen hydrogel shown in the figure: A1: 2 wt%; photoinitiator: 0.5 wt%). When performing ultraviolet light irradiation, the induction area absorbs ultraviolet light, and the color of the area other than the sunscreen hydrogel becomes significantly darker. After removing the sunscreen hydrogel, it can be clearly seen that the area coated with the sunscreen hydrogel has basically not changed color, proving that the hydrogel has absorbed ultraviolet light. This shows that the sunscreen hydrogel has a significant ultraviolet shielding effect on the ultraviolet induction card.

[0059] Test Example 4: Comparative test of the ultraviolet absorption properties of the sunscreen hydrogel According to the method of Example 11, prepare sunscreen hydrogels with different concentration components. Select any one group of sunscreen hydrogels and drop it on the right side of the induction area of the ultraviolet sunscreen card. Select Comparative Example 1 and drop it on the left side of the induction area of the ultraviolet sunscreen card. Irradiate it with ultraviolet light, and the polymer solution on the right side cross - links to form a non - flowing gel. AsFigure 3 As shown (in the figure, the components of the sunscreen hydrogel are: A1: 2 wt%; initiator: 0.5 wt%), when ultraviolet light irradiation is carried out, except for the areas other than the solution of Comparative Example 1 and the sunscreen hydrogel, the induction area changes color due to the absorption of ultraviolet light. After the ultraviolet sunscreen card is immersed in water for 10 minutes and then taken out, the solution of Comparative Example 1 is washed away by water, while the gel remains intact. When ultraviolet light irradiation is carried out again, the area coated with the gel on the ultraviolet sunscreen card does not change color. After removing the sunscreen hydrogel, the color contrast change can be clearly seen. It further shows that the sunscreen hydrogel has significant waterproof effect and long-lasting ultraviolet protection effect.

[0060] Example 12: Application of the photocrosslinkable polymer in ultraviolet protection products For the photocrosslinkable polymers prepared in Examples 1 - 10, through Ultraviolet Absorption Test 1, it can be seen that the photocrosslinkable polymers have the function of absorbing ultraviolet light in the range of 210 - 390 nm. The polymers A1 - A10 are respectively dissolved in water with a concentration range of 2 wt% - 10 wt%, and 0.05 wt% - 0.5 wt% of photoinitiator is added to obtain the sunscreen hydrogel, which can be used in ultraviolet protection products. Through Elastic Modulus and Ultraviolet Penetration Rate Test Example 2, Gel Formation Performance Test Example 3, and Ultraviolet Absorption Performance Test Example 4 of the sunscreen hydrogel, the effects of the ultraviolet protection products are evaluated.

[0061] Example 13: Application of the photocrosslinkable polymer in antioxidant products For the photocrosslinkable polymers obtained in Examples 1 and 2, small molecule compounds with anti-ultraviolet efficacy are connected to the hydrophilic natural polymer backbone by chemical bonding, and at the same time, photocrosslinkable (meth)acryloyl groups are introduced, which have the effects of scavenging free radicals and inhibiting lipid peroxidation, and have application value in antioxidant products.

[0062] Example 14: Application of the photocrosslinkable polymer in anti-corrosion and bactericidal products For the photocrosslinkable polymers obtained in Examples 1 and 2, small molecule compounds with anti-ultraviolet efficacy are connected to the hydrophilic natural polymer backbone by chemical bonding, and at the same time, photocrosslinkable (meth)acryloyl groups are introduced, which can damage cell membranes, inhibit enzyme activity, and interfere with DNA / RNA synthesis, so it has application value in anti-corrosion and bactericidal products.

[0063] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0064] The above-described embodiments merely represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several variations and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A photocrosslinkable polymer with anti-ultraviolet efficacy, characterized in that, It includes the structure shown in Formula I: ， In Formula I, the curve is a natural polymer backbone, which is selected from any one of hyaluronic acid, alginic acid, gelatin, collagen, chitosan, cellulose, and chondroitin sulfate; R is selected from at least one of a hydroxyl group, a carboxyl group, and an amino group, and R1 is the decarboxylation residue of a small molecule sunscreen containing a carboxyl group structure; R2 is an (meth)acryloyl group; X and Y are each independently selected from an ester bond, an amide bond, and a coupling agent with ester bonds or amide bonds at both ends.

2. The photocrosslinkable polymer having an anti-ultraviolet effect according to claim 1, wherein, The small molecule sunscreen includes at least one of cinnamic acid, cinnamic acid derivatives, salicylic acid, salicylic acid derivatives, o-hydroxybenzoic acid, 4-diethylamino ketonic acid, 4-dimethylaminobenzoic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-dihydroxy-3-carboxyanthraquinone.

3. The photocrosslinkable polymer with anti-ultraviolet efficacy according to claim 1, wherein The coupling agent is selected from any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, pimelic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, and amino-functionalized PEG.

4. The photocrosslinkable polymer with ultraviolet resistance according to claim 1, wherein, The modification rate of R1 on the natural polymer backbone is between 5% and 50%, and / or the modification rate of R2 on the natural polymer backbone is between 10% and 50%.

5. The photocrosslinkable polymer with anti-ultraviolet efficacy according to claim 1, characterized in that, The molecular weight of the natural polymer is 1000 Da to 5000000 Da.

6. A sunscreen hydrogel, characterized in that, It includes the photocrosslinkable polymer with anti-ultraviolet efficacy described in Claim 1, a photoinitiator, and water; Among them, the concentration of the photocrosslinkable polymer is 2 to 10 wt%, the concentration of the photoinitiator is 0.05 - 0.5 wt%, and the balance is water.

7. The sunscreen hydrogel according to claim 6, wherein The photoinitiator is selected from any one or more of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate (LAP), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, α-ketoglutaric acid, eosin Y, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.

8. The preparation method of the sunscreen hydrogel according to claim 6, wherein, Dissolve the photocrosslinkable polymer with anti-ultraviolet efficacy and the photoinitiator in water, and carry out a crosslinking reaction for 2 to 180 s under irradiation with light of 200 nm - 800 nm to obtain it.

9. A method for preparing a photocrosslinkable polymer having an anti-ultraviolet effect as described in claim 1, characterized in that, Select any one of the following preparation methods a and b: a. Dissolve the natural polymer containing a hydroxyl group and / or an amino group, add (meth)acrylic anhydride, carry out a reaction, then sediment, filter, and dry to obtain a (meth)acrylic acid-modified polymer; Add the activated small molecule sunscreen and a catalyst to the (meth)acrylic acid-modified polymer solution, carry out a reaction, then sediment, filter, and dry to obtain it. b. Dissolve the natural polymer containing a carboxyl group, add an excessive amount of coupling agent, carry out a reaction, then sediment, filter, and dry to obtain a polymer modified with an amino group or hydrazide at the carboxyl site; Add (meth)acrylic anhydride to the polymer solution modified with an amino group or hydrazide at the carboxyl site, carry out a reaction, then sediment, filter, and dry to obtain a (meth)acrylic acid-modified polymer; Add the activated small molecule sunscreen and a catalyst to the (meth)acrylic acid-modified polymer solution, carry out a reaction, then sediment, filter, and dry to obtain it.

10. Use of the photocrosslinkable polymer according to any one of claims 1 to 5, characterized in that, It is selected from the following applications: The application of the photocrosslinkable polymer in ultraviolet protection products; Application of the photocrosslinkable polymer in antioxidant products; Application of the photocrosslinkable polymer in antiseptic and bactericidal products.

Images