CN115636934A - Macromolecular sun-screening agent and preparation method thereof - Google Patents
Macromolecular sun-screening agent and preparation method thereof Download PDFInfo
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- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 230000000475 sunscreen effect Effects 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 108010000222 polyserine Proteins 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- WVYADZUPLLSGPU-UHFFFAOYSA-N salsalate Chemical compound OC(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1O WVYADZUPLLSGPU-UHFFFAOYSA-N 0.000 claims description 10
- FCDLCPWAQCPTKC-UHFFFAOYSA-N Rhein Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)O)=CC(O)=C3C(=O)C2=C1O FCDLCPWAQCPTKC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 5
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 claims description 5
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- HJBWJAPEBGSQPR-GQCTYLIASA-N 3,4-dimethoxycinnamic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1OC HJBWJAPEBGSQPR-GQCTYLIASA-N 0.000 claims description 5
- NJESAXZANHETJV-UHFFFAOYSA-N 4-methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- HJBWJAPEBGSQPR-UHFFFAOYSA-N DMCA Natural products COC1=CC=C(C=CC(O)=O)C=C1OC HJBWJAPEBGSQPR-UHFFFAOYSA-N 0.000 claims description 5
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000000385 dialysis solution Substances 0.000 claims description 5
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims description 5
- 235000001785 ferulic acid Nutrition 0.000 claims description 5
- 229940114124 ferulic acid Drugs 0.000 claims description 5
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002674 hyaluronan Polymers 0.000 claims description 5
- 229960003160 hyaluronic acid Drugs 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 5
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229960000953 salsalate Drugs 0.000 claims description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims description 5
- 229920002307 Dextran Polymers 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000936 Agarose Polymers 0.000 claims description 3
- 108010033949 polytyrosine Proteins 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims 1
- 240000007472 Leucaena leucocephala Species 0.000 claims 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims 1
- 241000209140 Triticum Species 0.000 claims 1
- 235000021307 Triticum Nutrition 0.000 claims 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000035515 penetration Effects 0.000 abstract description 4
- 231100000683 possible toxicity Toxicity 0.000 abstract description 4
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229920000084 Gum arabic Polymers 0.000 description 3
- 229930182555 Penicillin Natural products 0.000 description 3
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 3
- 241000978776 Senegalia senegal Species 0.000 description 3
- 239000000205 acacia gum Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 229940049954 penicillin Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 1
- 229960005193 avobenzone Drugs 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 229960004881 homosalate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical group C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 229960000601 octocrylene Drugs 0.000 description 1
- 230000008789 oxidative DNA damage Effects 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Cosmetics (AREA)
Abstract
The invention discloses a macromolecular sun-screening agent and a preparation method thereof, the sun-screening agent is a series of macromolecular sun-screening agents which are obtained by using macromolecular polymers and various micromolecular ultraviolet absorbers to carry out structural modification on the macromolecular polymers through esterification reaction under the action of condensing agents, additives or catalysts and the like to obtain compounds which take the macromolecular polymers as framework structures and contain ultraviolet absorption functional groups on the framework structures, and the compounds are subjected to impurity removal. The sunscreen agent can not be absorbed by skin penetration, overcomes the defect that the micromolecule sunscreen agent commonly used in the current market is easy to absorb through skin to cause potential toxicity, improves the safety of sunscreen products, is an excellent substitute of the existing micromolecule sunscreen agent, and is suitable for the field of sunscreen cosmetics.
Description
Technical Field
The invention belongs to the technical field of sunscreen cosmetics, and particularly relates to a macromolecular sunscreen agent and a preparation method thereof.
Background
Prolonged exposure to the sun and ultraviolet radiation can cause many adverse effects on the skin, such as sunburn, tanning, aging, and even skin cancer. Sunscreens are often used to help the skin reduce or temporarily prevent the effects of sunlight and ultraviolet radiation. The existing commercial sunscreens mainly comprise two types of physical sunscreens and chemical sunscreens, wherein the physical sunscreens mainly comprise zinc oxide, titanium dioxide and the like, and the chemical sunscreens mainly comprise avobenzone, tianshi M, octocrylene, maifanitum SX, homosalate and the like. These sunscreens have been widely used in ultraviolet protection, having strong and broad absorption/scattering in the short-wavelength ultraviolet (280-315 nm) region and long-wavelength ultraviolet (315-400 nm) region.
While the problem of broad spectral coverage has been well developed, physical sunscreens have been shown to enhance the production of reactive oxygen species, which can lead to oxidative stress or deoxyribonucleic acid damage to tissues, while chemical sunscreens also suffer from potential toxicity and endocrine disruption due to photodegradation, skin penetration, and the like. New sunscreen products based on bioadhesive or gel systems, plant sunscreens or bioengineered sunscreens also present more or less problems. Therefore, it is necessary to develop a safe and reliable macromolecule sunscreen agent with the advantages of micromolecule sunscreen agents.
Disclosure of Invention
The invention aims to provide a macromolecular sunscreen agent and a preparation method thereof, wherein the macromolecular sunscreen agent is obtained by esterification reaction of a macromolecular polymer and various micromolecular ultraviolet absorbers under the action of a condensing agent, an additive or a catalyst and the like.
The structural formula of the macromolecular sun-screening agent is shown as the following formula:
wherein R represents a large moiety having a hydroxyl group structureThe dehydroxylated or partially dehydroxylated residue of the subpolymer is specifically as follows: dehydroxylated or partially dehydroxylated residues of hydroxyalkyl cellulose, hydroxyethyl cellulose (HEC), polyethylene glycol, sodium alginate, soluble starch, gum arabic, cyclodextrin, hyaluronic acid, chitosan, dextran, polyserine, and polytyrosine; r is 1 The decarboxylated residue of the small molecule sunscreen with a carboxyl structure is shown as follows: ferulic acid, 4-methoxy cinnamic acid, 3, 4-dimethoxy cinnamic acid, 4-dimethylamino benzoic acid, o-hydroxybenzoic acid, 4-diethylamino keto acid, disalicylic acid, 4-methyl salicylic acid, 2, 6-naphthalene dicarboxylic acid, 1, 8-dihydroxy-3-carboxy anthraquinone, and decarboxylated residue of Maillard color filter SX.
The preparation method of the macromolecular sun-screening agent comprises the following steps:
(1) Dissolving a micromolecular ultraviolet absorbent with a carboxyl structure in a solvent A, adding a condensing agent and an additive or a catalyst at the temperature of 0-10 ℃, naturally heating to room temperature, and stirring for activating reaction;
(2) Adding the macromolecular polymer with the hydroxyl structure into the solvent B, and stirring until the macromolecular polymer is completely dissolved;
(3) Dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature to perform an esterification reaction;
(4) And (4) removing impurities and purifying the reaction liquid obtained in the step (3), and freeze-drying to obtain the macromolecular sunscreen agent.
In the step (1), the small molecular ultraviolet absorbent with a carboxyl structure is preferably any one of ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, 4-dimethylaminobenzoic acid, o-hydroxybenzoic acid, 4-diethylamino-keto acid, disalicylic acid, 4-methyl salicylic acid, 2, 6-naphthalene dicarboxylic acid, 1, 8-dihydroxy-3-carboxyl anthraquinone and Maifanitum filtration SX.
In the step (2), the macromolecular polymer having a hydroxyl structure is preferably any one of hydroxyalkyl cellulose, hydroxyethyl cellulose (HEC), polyethylene glycol, sodium alginate, soluble starch, gum arabic, cyclodextrin, hyaluronic acid, chitosan, dextran, agarose, polyserine, and polytyrosine.
When the condensation reaction is an anhydrous system, the solvent A and the solvent B are respectively one or more than two mixed liquids of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, and the solvent A and the solvent B can be the same or different; the condensing agent is any one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is any one of 1-hydroxybenzotriazole, N-hydroxysuccinimide and 2-oxime ethyl cyanoacetate, and the catalyst is 4-dimethylaminopyridine.
When the condensation reaction is a water-containing system, the solvent A and the solvent B are respectively a mixed solution of at least one of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran and deionized water in a volume ratio of 0-1, the condensing agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is N-hydroxysuccinimide, and the catalyst is 4-dimethylaminopyridine.
In the step (1), the molar ratio of the small-molecule ultraviolet absorber having a carboxyl structure to the condensing agent to the additive is preferably 1 to 3.
In the step (3), the molar ratio of the macromolecular polymer with a hydroxyl structure to the micromolecular ultraviolet absorbent calculated by the monomer is preferably 1.1-2, and the condensation reaction time is preferably 17-22 h.
In the step (4), the method for removing impurities and purifying comprises the following steps: transferring the reaction solution into a dialysis bag with the molecular weight cutoff of 1 kD-5 kD, and dialyzing for 2-3 days, wherein the used dialysis solution is one or a mixed solution of ethanol and deionized water.
The invention has the following beneficial effects:
under the action of a condensing agent, an additive or a catalyst and the like, various micromolecular ultraviolet absorbers with carboxyl structures carry out structural modification on macromolecular polymers with hydroxyl structures through esterification reaction to obtain compounds which take the macromolecular polymers as skeleton structures and contain ultraviolet absorption functional groups on the skeleton structures, and a series of macromolecular sun-screening agents are obtained after the compounds are subjected to impurity removal. The sunscreen agent can not be absorbed by skin penetration, overcomes the defect that the micromolecule sunscreen agent commonly used in the current market is easy to absorb through skin to cause potential toxicity, improves the safety of sunscreen products, is an excellent substitute of the existing micromolecule sunscreen agent, and is suitable for the field of sunscreen cosmetics.
Detailed Description
The technical solutions of the present invention are further described in detail by the following examples, which are only for further illustration of the present invention and do not limit the scope of the present invention.
Example 1
1. Adding 1mmol 4-dimethylaminobenzoic acid into 10mL N, N-dimethylformamide, stirring and dissolving, then adding 1.5mmol N, N' -diisopropylcarbodiimide and 1.5mmol 2-oxime cyanoacetic acid ethyl ester at the temperature of 0-10 ℃, naturally heating to room temperature, and stirring and activating for reaction for 6 hours;
2. adding 0.9mmol (calculated by monomer) of polyserine (with the molecular weight of 5000-10000) into 10mL of dimethyl sulfoxide, and stirring until the polyserine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours after dropwise adding;
4. transferring the reaction solution in the step 3 into a dialysis bag with the molecular weight cut-off of 5KD, dialyzing for four times by using a dialysis solution with the volume ratio of ethanol to deionized water of 1; transferring the dialyzed solution into a penicillin bottle, freeze-drying to obtain the polyserine-4-dimethylaminobenzoic acid (PSA-BJS) macromolecular sunscreen with the structural formula as shown in the specification, wherein the yield is 70 percent, the binding rate is 100 percent,
wherein n =58 to 115.
The PSA-BJS sample is characterized by nuclear magnetism, hydrogen of side chain hydroxyl of polyserine at 4.94ppm disappears, hydrogen at each position on a benzene ring of 4-dimethylaminobenzoic acid appears at 7.84ppm and 6.76ppm, and hydrogen at all other positions corresponds to hydrogen at the position in polyserine and 4-dimethylaminobenzoic acid one by one; the successful connection of 4-dimethylaminobenzoic acid to polyserine is shown, and the PSA-BJS structure is correct.
Example 2
In step 1 of this example, N' -diisopropylcarbodiimide in step 1 of example 1 was replaced with equimolar 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, ethyl 2-oxime cyanoacetate in step 1 of example 1 was replaced with equimolar N-hydroxysuccinimide, dimethyl sulfoxide in step 2 of example 1 was replaced with an equal volume of deionized water, and other steps were the same as in example 1 to obtain a PSA-BJS macromolecular sunscreen with a yield of 76% and a binding rate of 100%.
Example 3
1. Adding 1mmol 4-dimethylaminobenzoic acid into 10mL N, N-dimethylformamide, stirring and dissolving, then adding 1.5mmol 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.05mmol 4-dimethylaminopyridine at the temperature of 0-10 ℃, naturally heating to room temperature, and stirring and activating for reaction for 6 hours;
2. adding 0.9mmol (calculated by monomer) of polyserine (with molecular weight of about 5000-10000) into 10mL of deionized water, and stirring until the polyserine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18 hours;
4. transferring the reaction solution in the step 3 into a dialysis bag with the molecular weight cut-off of 5KD, dialyzing for four times by using a dialysis solution with the volume ratio of ethanol to deionized water of 1; transferring the dialyzed solution into a penicillin bottle, and freeze-drying to obtain the PSA-BJS macromolecular sunscreen agent with the yield of 61% and the binding rate of 100%.
Example 4
1. Adding 0.2mmol of 4-dimethylaminobenzoic acid into 10mL of N, N-dimethylformamide, stirring for dissolving, adding 1.5mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.05mmol of 4-dimethylaminopyridine at the temperature of 0-10 ℃, naturally heating to room temperature, and stirring for activation reaction for 6 hours;
2. 1.0mmol (calculated by monomer) of polyserine (with molecular weight of 5000-10000) is added into 10mL of deionized water and stirred until the polyserine is completely dissolved;
3. dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature for reacting for 18h;
4. transferring the reaction solution in the step 3 into a dialysis bag with the molecular weight cut-off of 5KD, dialyzing for four times by using a dialysis solution with the volume ratio of ethanol to deionized water of 1; transferring the dialyzed solution into a penicillin bottle, and freeze-drying to obtain the polyserine-4-dimethylaminobenzoic acid (PSA-BJS-20) macromolecular sunscreen with the binding rate of 20%, wherein the yield is 75%.
Wherein x/n =0.2, n =58 to 115.
The PSA-BJS-20 sample is characterized by nuclear magnetism, hydrogen of side chain hydroxyl of polyserine still exists at 4.94ppm, hydrogen at each position on a benzene ring of 4-dimethylaminobenzoic acid appears at 7.84ppm and 6.76ppm, and hydrogen at all other positions corresponds to hydrogen at the position in polyserine and 4-dimethylaminobenzoic acid one by one; the successful connection of the 4-dimethylaminobenzoic acid to the polyserine is shown, and the PSA-BJS-20 structure is correct as part of the connection.
Example 5
In step 1 of this example, the 4-dimethylaminobenzoic acid was increased to 0.5mmol and 0.8mmol, the solvent used was increased in the same proportion, and the other steps were the same as in example 4, to obtain PSA-BJS sunscreens with binding ratios of 50% and 80%, respectively.
In step 1 of examples 1 to 5, ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, o-hydroxybenzoic acid, 4-diethylaminoketonic acid, disalicylic acid, 4-methylsalicylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-dihydroxy-3-carboxyanthraquinone, maillard SX, etc. were used in place of 4-dimethylaminobenzoic acid, or in step 2 of examples 1 to 5, polyhydroxyalkylcellulose, hydroxyethylcellulose, polyethylene glycol, sodium alginate, soluble starch, gum arabic, cyclodextrin, hyaluronic acid, chitosan, dextran, agarose, polyserine, etc. were used in place of polyserine, and other steps were the same as in the corresponding examples, whereby other macromolecular sunscreen agents were obtained.
To demonstrate the beneficial effects of the present invention, the molecular weight and UV absorption of the PSA-BJS macromolecular sunscreen agent prepared in example 1, the PSA-BJS-20 macromolecular sunscreen agent prepared in example 4, and 4-dimethylaminobenzoic acid were compared, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, the molecular weight of the small molecule sunscreen agent is 137.1, while the molecular weights of the macromolecular sunscreen agents prepared in the embodiments 1 and 4 of the present invention are both greater than 5000, which does not cause skin penetration, overcomes the defect of potential toxicity caused by easy transdermal absorption of the small molecule sunscreen agent, and improves the safety of the sunscreen product; compared with the ultraviolet absorption range, the ultraviolet absorption ranges of the macromolecular sunscreen agent and the micromolecular sunscreen agent are basically the same, which shows that the macromolecular sunscreen agent still has excellent sunscreen performance.
Claims (8)
1. A macromolecular sun-screening agent is characterized in that the structural formula is as follows:
wherein R represents a dehydroxylated residue or a partially dehydroxylated residue of a macromolecular polymer having a hydroxyl structure 1 Representing the decarboxylated residue of a small molecule sunscreen having a carboxyl structure.
2. A macromolecular sunscreen according to claim 1 characterized in that R represents any of hydroxyalkyl cellulose, hydroxyethyl cellulose, polyethylene glycol, sodium alginate, soluble starch, acacia, cyclodextrin, hyaluronic acid, chitosan, dextran, polyserine, and polytyrosineA dehydroxylated or partially dehydroxylated residue; the R is 1 The compound is decarboxylated residue of any one of ferulic acid, 4-methoxy cinnamic acid, 3, 4-dimethoxy cinnamic acid, 4-dimethylamino benzoic acid, o-hydroxybenzoic acid, 4-diethylamino keto acid, disalicylic acid, 4-methyl salicylic acid, 2, 6-naphthalene dicarboxylic acid, 1, 8-dihydroxy-3-carboxyl anthraquinone and Maifanitum filtration SX.
3. A method of preparing a macromolecular sunscreen according to claim 1 comprising the steps of:
(1) Dissolving a micromolecular ultraviolet absorbent with a carboxyl structure in a solvent A, adding a condensing agent and an additive or a catalyst at the temperature of 0-10 ℃, naturally heating to room temperature, and stirring for activating reaction;
(2) Adding the macromolecular polymer with the hydroxyl structure into the solvent B, and stirring until the macromolecular polymer is completely dissolved;
(3) Dropwise adding the activated solution obtained in the step (1) into the solution obtained in the step (2), and stirring at room temperature to perform an esterification reaction;
(4) And (4) removing impurities and purifying the reaction liquid obtained in the step (3), and freeze-drying to obtain the macromolecular sunscreen agent.
4. The method for preparing a macromolecular sunscreen agent according to claim 3, wherein the small molecular ultraviolet absorber having a carboxyl structure is any one of ferulic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, 4-dimethylaminobenzoic acid, o-hydroxybenzoic acid, 4-diethylamino-keto acid, disalicylic acid, 4-methylsalicylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-dihydroxy-3-carboxyanthraquinone, and wheat filter SX; the macromolecular polymer with a hydroxyl structure is any one of hydroxyalkyl cellulose, hydroxyethyl cellulose, polyethylene glycol, sodium alginate, soluble starch, arabic gum, cyclodextrin, hyaluronic acid, chitosan, glucan, agarose, polyserine and polytyrosine.
5. The method for preparing a macromolecular sunscreen agent according to claim 3, wherein the solvent A and the solvent B are each one or a mixture of two or more of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, the condensing agent is any one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is any one of 1-hydroxybenzotriazole, N-hydroxysuccinimide and ethyl 2-oxime cyanoacetate, and the catalyst is 4-dimethylaminopyridine.
6. The method for preparing a macromolecular sunscreen agent according to claim 3, wherein the solvent A and the solvent B are mixed solutions of at least one of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran and deionized water in a volume ratio of 0-1, the condensing agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, the additive is N-hydroxysuccinimide, and the catalyst is 4-dimethylaminopyridine.
7. A method for preparing a macromolecular sunscreen according to any of claims 3 to 6, characterized in that in step (1), the molar ratio of the small molecular ultraviolet absorber with carboxyl structure to the condensing agent and the additive is 1 to 3; the mol ratio of the micromolecule ultraviolet absorbent with the carboxyl structure to the condensing agent and the catalyst is 1; in the step (3), the molar ratio of the macromolecular polymer with the hydroxyl structure to the micromolecular ultraviolet absorbent with the carboxyl structure calculated by the monomer is 1.1-2, and the esterification reaction time is 17-22 h.
8. A method for preparing a macromolecular sunscreen agent according to claim 3, characterized in that in step (4), the method for removing impurities and purifying comprises the following steps: transferring the reaction solution into a dialysis bag with the molecular weight cutoff of 1 kD-5 kD, dialyzing for 2-3 days, wherein the used dialysis solution is one or a mixed solution of ethanol and deionized water, and freeze-drying a sample in the dialysis bag in a freeze-drying machine to obtain the macromolecular sunscreen agent.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4699779A (en) * | 1986-02-18 | 1987-10-13 | Victor Palinczar | Waterproof sunscreen compositions |
| US5869099A (en) * | 1996-08-26 | 1999-02-09 | Basf Aktiengesellschaft | Cosmetic composition with polymer-bound benzophenone chromophores |
| US20020172646A1 (en) * | 2001-03-15 | 2002-11-21 | Weipert Paul David | Polyesters based on hydroxy fatty acids and lower hydroxy alkyl acids and uses thereof |
| US20140227212A1 (en) * | 2011-09-09 | 2014-08-14 | University Of Florida Research Foundation, Inc. | Polymerized sunscreen absorbers |
| US20190016850A1 (en) * | 2017-07-12 | 2019-01-17 | Everlight Chemical Industrial Corporation | Use of polymerizable ultraviolet absorber in polyurethane and composition for preparing polyurethane comprising the same |
| US20210228684A1 (en) * | 2018-06-04 | 2021-07-29 | Cocoon Biotech Inc. | Silk-based product formulations and methods of use |
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2022
- 2022-11-11 CN CN202211413582.7A patent/CN115636934A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4699779A (en) * | 1986-02-18 | 1987-10-13 | Victor Palinczar | Waterproof sunscreen compositions |
| US5869099A (en) * | 1996-08-26 | 1999-02-09 | Basf Aktiengesellschaft | Cosmetic composition with polymer-bound benzophenone chromophores |
| US20020172646A1 (en) * | 2001-03-15 | 2002-11-21 | Weipert Paul David | Polyesters based on hydroxy fatty acids and lower hydroxy alkyl acids and uses thereof |
| US20140227212A1 (en) * | 2011-09-09 | 2014-08-14 | University Of Florida Research Foundation, Inc. | Polymerized sunscreen absorbers |
| US20190016850A1 (en) * | 2017-07-12 | 2019-01-17 | Everlight Chemical Industrial Corporation | Use of polymerizable ultraviolet absorber in polyurethane and composition for preparing polyurethane comprising the same |
| US20210228684A1 (en) * | 2018-06-04 | 2021-07-29 | Cocoon Biotech Inc. | Silk-based product formulations and methods of use |
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