CN104411366A - 紫外线辐射吸收性聚合物 - Google Patents
紫外线辐射吸收性聚合物 Download PDFInfo
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- CN104411366A CN104411366A CN201380034690.6A CN201380034690A CN104411366A CN 104411366 A CN104411366 A CN 104411366A CN 201380034690 A CN201380034690 A CN 201380034690A CN 104411366 A CN104411366 A CN 104411366A
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- Prior art keywords
- acid
- base
- ultraviolet radiation
- polymer composition
- alkane esters
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- 229920000642 polymer Polymers 0.000 title claims abstract description 89
- 230000005855 radiation Effects 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 239000000178 monomer Substances 0.000 claims abstract description 65
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 18
- -1 alkane esters Chemical class 0.000 claims description 59
- ARIWANIATODDMH-UHFFFAOYSA-N rac-1-monolauroylglycerol Chemical compound CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 47
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 38
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 229940068939 glyceryl monolaurate Drugs 0.000 claims description 21
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 19
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 19
- 150000007519 polyprotic acids Chemical class 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
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- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 claims description 6
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
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- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 6
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- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 6
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 6
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- 230000003252 repetitive effect Effects 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000001261 hydroxy acids Chemical class 0.000 claims description 5
- 150000003852 triazoles Chemical class 0.000 claims description 5
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- GHBFNMLVSPCDGN-UHFFFAOYSA-N rac-1-monooctanoylglycerol Chemical compound CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 claims description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 3
- GVSPXQVUXHMUMA-MDWZMJQESA-N (e)-3-(3,5-ditert-butyl-4-hydroxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GVSPXQVUXHMUMA-MDWZMJQESA-N 0.000 claims description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 229940025250 camphora Drugs 0.000 claims description 3
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- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 235000001671 coumarin Nutrition 0.000 claims description 3
- 229960000956 coumarin Drugs 0.000 claims description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 229930005346 hydroxycinnamic acid Natural products 0.000 claims description 3
- 235000010359 hydroxycinnamic acids Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 230000000699 topical effect Effects 0.000 claims description 3
- NGSWKAQJJWESNS-ZZXKWVIFSA-N trans-4-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C=C1 NGSWKAQJJWESNS-ZZXKWVIFSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- ISDGWTZFJKFKMO-UHFFFAOYSA-N 2-phenyl-1,3-dioxane-4,6-dione Chemical compound O1C(=O)CC(=O)OC1C1=CC=CC=C1 ISDGWTZFJKFKMO-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
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- 235000011090 malic acid Nutrition 0.000 claims description 2
- 150000004682 monohydrates Chemical class 0.000 claims description 2
- 150000002772 monosaccharides Chemical class 0.000 claims description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
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- 229940043375 1,5-pentanediol Drugs 0.000 claims 1
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- 238000007306 functionalization reaction Methods 0.000 claims 1
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- 239000007795 chemical reaction product Substances 0.000 abstract 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/85—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
本发明包括紫外线辐射吸收性聚合物组合物，所述组合物包括如在说明书中所描述和要求保护的含有UV发色团的聚合物，甘油单酯和含有UV发色团的多元酸单体的反应产物。
Description
本申请要求2012年6月28日提交的美国临时申请61/665430的权益，其整个公开内容据此以引用方式并入本文以用于所有目的。
技术领域
本发明涉及带有适于吸收紫外线辐射的发色团的聚合物。
背景技术
皮肤癌是显著的公共健康问题，其在美国占确诊癌症病例的50％。紫外线辐射(UV)可以造成分子和细胞水平损坏，并且被认为是引起皮肤癌的主要环境因素。长时间暴露于UV辐射，如来自太阳的UV辐射，可以导致轻度皮肤病和红斑的形成，以及增加皮肤癌(诸如黑素瘤)的风险，并加速皮肤老化过程，诸如皮肤失去弹性和起皱纹。
通过局部施用防晒剂可以抑制紫外线暴露的损坏效应，所述防晒剂含有吸收、反射或散射通常在光谱的UVA(波长约320-400nm)或UVB(波长大约290-320nm)范围内的UV的化合物。许多防晒剂化合物是可商购可得的，它们具有不同的为身体屏蔽紫外线的能力。
已经提出使用具有高分子量的防晒剂分子，以降低防晒剂分子渗透穿过表皮。然而，本发明人已经认识到，期望具有全新的聚合物型防晒剂配混物(紫外线辐射吸收性聚合物)，以提供多种益处中的任一种(诸如改善的防UV)。
发明内容
本发明包括紫外线辐射吸收性聚合物，其包括如下所示的重复单元：
其中X包含UV吸收性发发色团，并且R1是具有介于4和30之间的碳原子数的饱和或不饱和的烃部分；包括甘油单酯和含有UV发色团的多元酸单体的反应产物的、紫外线辐射吸收性聚合物，以及包括本发明的紫外线辐射吸收性聚合物和美容上可接受的载体的组合物。
具体实施方式
据信，本领域技术人员基于本文中的描述可以在最完全程度上使用本发明。下述的具体实施例应当解释为仅是示例性的，无论如何不以任何方式限制本公开内容的其它部分。除非另外定义，否则本文使用的所有技术和科学术语具有本发明所属领域的普通技术人员所通常理解的相同含义。并且，在本文中提及的所有出版物、专利申请、专利和其它参考文献通过引用并入。
UV吸收性聚合物
本发明的实施例涉及包括紫外线辐射吸收性聚合物(即，“UV吸收性聚合物”)的聚合物组合物。所谓“UV吸收性聚合物”是指吸收紫外光谱(在290-400nm之间的波长)的某些部分中的辐射的聚合物。UV吸收性聚合物组合物具有这样的分子量(Mw)：其可能适合于减少或阻止UV发色团穿过皮肤的吸收。根据一个实施例，UV吸收性聚合物的合适分子量是Mw大于500。在一个实施例中，Mw是在约500至约50,000的范围内。在另一个实施例中，所述UV吸收性聚合物组合物具有约4000至约12,000的Mw。
根据本发明的一个方面，所述聚合物组合物包括具有如下面式1A中所示的重复单元的UV吸收性聚合物：
如本文中定义的和本领域已知的，“重复单元”是构成大分子、寡聚体、段或链的基本结构的一部分的最小原子或原子基团(具有侧链原子或基团，如果有的话)，其重复构成规则的大分子、规则的寡聚体分子、规则的段或规则的链。
在式IA中，X包含UV吸收性部分，或具有侧链UV吸收性的部分(UV发色团)(诸如UVA吸收性部分)的结构。R1是具有介于4和30之间的碳原子数的饱和或不饱和的烃部分；在一个实施例中，碳原子的数在12和18之间。此外，下标“n”指示聚合物链中的重复单元数。
UV发色团可以是聚合物主链的一部分，或者可以是聚合物主链的侧基。本领域技术人员应当认识到，“主链”通常是指具有最大数目的连续的和共价地键合的原子的聚合物分子的部分。共价地键合的原子的其它更小的基团被视作从主链分支的侧基。
根据一个实施例，UV吸收性聚合物组合物包括具有如下面式I中所示的结构的聚合物。
根据另一个实施例，UV吸收性聚合物组合物包括下面式II中所示的支化聚合物。
一些UV发色团具有单个适合于共价连接至聚合物的官能团。这些官能团的例子包括但不限于：羧酸、胺、醇、硫醇和异氰酸酯。使用不同的方案，可以将这些UV发色团作为侧基共价地连接至聚合物如在式I和式II中所示的那些。本文描述了两个实施例：UV发色团与聚合物主链的共价连接，和单体与侧链UV发色团的聚合。
根据另一个实施例，UV吸收性聚合物组合物是甘油单酯和含有UV发色团的多元酸单体的反应产物。在一个实施例中，所述UV发色团含有单个与聚合物上的补充官能团共价地连接的官能团。在一个实施例中，通过甘油单酯与含有额外官能团的多元酸单体(即，具有至少两个羧酸基团)的缩聚作用而合成聚合物。所述额外官能团并入聚合物中，并提供UV发色团与聚合物的共价连接部位。作为UV发色团的共价连接部位的官能团的例子包括但不限于：缀合的烯烃、胺、醇和羧酸。
甘油单酯在本文中被定义为含有单个长链(例如，4至30(包括30)个碳原子，诸如12至18(包括18)个碳原子)烷基酯的甘油衍生物。合适的甘油单酯包括但不限于：单硬脂酸甘油酯、单棕榈酸甘油酯、单肉豆蔻酸甘油酯、单癸酸甘油酯(glycerol monocaprate)、单癸酸甘油酯(glycerol monodecanoate)、单月桂酸甘油酯、单亚油酸甘油酯、单油酸甘油酯以及它们的组合。在一个实施例中，所述甘油单酯是单月桂酸甘油酯。
具有缀合的烯烃官能团的多元酸单体的例子包括马来酸、富马酸、衣康酸和柠康酸。用胺或硫醇官能化的UV发色团例如可以通过共轭加成反应与聚合物中的这些烯烃基共价地键合。通过甘油单酯与含有胺或羟基官能团的多元酸单体的缩聚作用，合成含有胺或羟基基团的聚合物。使用本领域技术人员已知的保护基遮蔽胺或羟基基团，以防止干扰所述聚合反应。在聚合后除去保护基。在含有游离羟基或胺基的聚合物的情况下，使用本领域技术人员熟知的多种方法，可以将含有羧酸酯基的UV发色团与所述聚合物共价地连接。可以使用缩合试剂在UV发色团与聚合物上的羧酸和胺基或羟基之间形成共价键，分别产生酰胺键和酯键；在一个实施例中，所述缩合试剂是N-(3-二甲基氨基丙基)-N'-乙基碳二亚胺盐酸盐。使用过渡金属催化剂，也可以将UV发色团的羧酸通过酯键与聚合物上的羟基基团连接。在一个实施例中，所述催化剂是乙基己酸锡(II)。通过将UV发色团羧酸转化成对应的酰基氯，也可以将UV发色团与聚合物连接。酰基氯与功能聚合物上的胺基或羟基反应，分别形成酰胺键或酯键。在一个实施例中，使用亚硫酰氯进行这种向酰基氯的转化。通过中间体酰基叠氮化物的Curtius重排，也可以将UV发色团羧酸转化成异氰酸酯。UV发色团异氰酸酯与功能聚合物上的胺基或羟基基团反应，分别形成脲键或氨基甲酸酯键。
在第二实施例中，含有单个官能团的UV发色团是化学改性的。改性的产物含有两个或更多个羧酸官能团，并且可以参加与甘油单酯的缩聚聚合。可以用于化学改性UV发色团以产生具有多个羧酸基团的结构的分子包括但不限于：亚氨基二乙酸、氨基异酞酸、谷氨酸和氨基丙二酸。在一个实施例中，可以用于产生具有多个羧酸基团的结构的分子是亚氨基二乙酸。式III中的结构“A”示出了含有羧酸和亚氨基二乙酸的UV发色团的反应产物。本领域技术人员会认识到，使用多种方式，包括缩合试剂和使用氯化剂(诸如亚硫酰氯)的活化，通过活化UV发色团上的羧酸，可以合成由结构“A”表示的分子。可替换地，通过中间体酰基叠氮化物的Curtius重排，可以将UV发色团上的羧酸转化成异氰酸酯。该异氰酸酯与亚氨基二乙酸的胺的反应将产生由式III中的结构“B”表示的产物。
合适的UV发色团包括具有UVA辐射的吸收的那些；其它合适的UV发色团是具有在UVB区域中的吸收的那些。在一个实施例中，所述UV发色团在UVA和UVB区域中吸收。在一个实施例中，当将UV吸收性聚醚浇铸成膜时，可能产生针对在该波长范围内的至少一种波长测量的以下摩尔消光系数：至少约1000mol-1cm-1，优选至少约2000mol-1cm-1，更优选至少约4000mol-1cm-1。在一个实施例中，至少40％的在该光谱部分中的波长的摩尔消光系数是至少约1000mol-1cm-1。吸收UVA的UV发色团的例子包括：三唑诸如苯并三唑；樟脑诸如亚苄基樟脑及其衍生物(诸如对苯二亚甲基二樟脑磺酸)；二苯甲酰甲烷和它们的衍生物。三唑是指含有5元杂环的部分，所述5元杂环具有两个碳原子和3个氮原子。
在一个实施例中，所述UV发色团是苯并三唑，诸如具有在式IV中表示的结构的苯并三唑，其提供光稳定性和强UV-A吸收：
其中R14独立地选自氢、C1-C20烷基、烷氧基、酰基、烷氧基、烷基氨基和卤素；R15独立地选自氢、C1-C20烷基、烷氧基、酰基、烷氧基和烷基氨基；并且R21选自C1-C20烷基、烷氧基、酰基、烷氧基和烷基氨基。R15或R21基团中的任一个可以包括这样的官能团：其允许连接至聚合物，或允许参加缩合聚合反应。式IV的单体化合物描述在美国专利号5,869,030中，并且包括但不限于亚甲基双苯并三唑基四甲基丁基苯酚(由BASFCorporation,Wyandotte,Michigan以商品名TINSORB M出售的化合物)。在一个实施例中，所述UV吸收性三唑是3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酸与聚乙二醇300的酯交换产物，也可以商品名TINUVIN 213下商购得自BASF。在另一个实施例中，所述UV发色团是三嗪部分。所谓三嗪是指含有3个氮原子和3个碳原子的6元杂环。一种示例性三嗪是6-辛基-2-(4-(4,6-二([1,1’-联苯]-4-基)-1,3,5-三嗪-2-基)-3-羟基苯氧基)丙酸酯(由BASF Corporation,Wyandotte,Michigan以商品名TINUVIN479出售的化合物)。
在另一个实施例中，所述UV发色团上吸收UVB的部分。“UV吸收性的”是指UV发色团具有在紫外光谱的UVB部分(290-320nm)中的可察觉的吸收。在一个实施例中，视作吸收UVB的发色团的标准类似于上面关于吸收UVA的发色团描述的那些，但是波长范围是290nm至320nm。
合适的吸收UVB的发色团的例子包括：4-氨基苯甲酸及其烷烃酯；邻氨基苯甲酸及其烷烃酯；水杨酸及其烷烃酯；羟基肉桂酸及其烷烃酯；二羟基-、二羧基-和羟基羧基二苯甲酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-、和羟基羧基查耳酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-、和羟基羧基香豆素以及它们的烷烃酯或酰卤衍生物；丙二酸苯亚甲酯(丙二酸亚苄酯)；苯并咪唑衍生物(诸如苯基benzilimazole磺酸，PBSA)、苯并唑衍生物、和能够在聚合物链内共聚的其它适当地官能化的物质。
在某些情况下，UV发色团可以具有两个或更多个适合于与甘油单酯聚合的羧酸官能团。在这些情况下，UV发色团将掺入聚合物的主链中。在聚合时，预期含有3个或更多个羧酸的UV发色团会产生如在式II中所示的支化结构。在一个实施例中，所述UV发色团是碱促进的2,2',2″-(((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4,1-二基))三(氧基))三丙酸三辛酯(由BASFCorporation,Wyandotte,Michigan以商品名TINUVIN 477出售的UV发色团)的水解的产物。
为了优化材料性能，除了甘油单酯以外，UV吸收性聚合物可以任选地进一步包含其它多元醇，即具有至少两个羟基的部分。合适的多元醇包括但不限于：乙二醇、1,2-丙二醇、1,3-丙二醇、双-2-羟乙基醚、1,4-丁二醇、1,5-戊二醇、1、6-己二醇、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇、其它二元醇、直链聚(乙二醇)、支化聚(乙二醇)、直链聚丙二醇、支化聚丙二醇、直链乙烯-丙二醇共聚物和支化乙烯-丙二醇共聚物二醇类、聚甘油、聚甘油酯、甘油、单糖、二糖和多糖。合适的多元醇也包括用甲醇基团官能化的直链聚硅氧烷末端，在聚合物主链中的硅氧烷连接(—Si—O—)的数目在1至约100的范围内。在一个实施例中，硅氧烷连接的数目在5和50之间。
为了优化材料性能，除了含有UV发色团的多元酸单体以外，UV吸收性聚合物可以任选地进一步包括其它多元酸。合适的多元酸包括但不限于：天然的多官能羧酸，诸如琥珀酸、戊二酸、己二酸、庚二酸、辛二酸和癸二酸；羟基酸，诸如二羟乙酸、苹果酸、酒石酸和柠檬酸；和不饱和酸，诸如富马酸和马来酸。多元酸衍生物包括酸酐，诸如琥珀酸酐、二羟乙酸酐、戊二酸酐和马来酸酐、混合酸酐、酯、活化的酯和酰卤。在一个实施例中，所述多元酸是琥珀酸。在另一个实施例中，所述多元酸是癸二酸。
在式V中显示了UV吸收性聚合物的替代实施例：
其中X和R1如上面关于式I和式II所定义；n、m和o是指示在上面式V中所示的每个重复单元的数目的实数，其中(n-m)、(n-o)、(m)和(o)表示例如不同组分的摩尔进料比；含有结构Y的单体表示来自额外多元酸(诸如上面定义的那些)的结构；含有结构Z的单体表示由如上定义的额外多元醇的使用产生的结构。
在一个实施例中，UV吸收性聚合物组合物通过熔化聚合，通过甘油单酯与含有UV发色团的多元酸的缩聚作用来制备。在有机金属催化剂存在下在升高的温度下进行甘油单酯、含有UV发色团的多元酸和在某些情况下与其它多元醇和多元酸的聚合。在一个实施例中，所述催化剂是基于锡的催化剂，例如乙基己酸锡(II)。在一个实施例中，含有UV发色团的多元酸、甘油单酯、其它多元酸和其它多元醇的摩尔进料比使得，n等于1，并且m和o(式V)等于0和0.9或在0和0.9之间。在另一个实施例中，n等于1，并且m和o都等于0。所述催化剂将如下存在于混合物中：多元醇和多羧酸与催化剂的摩尔比在约100/1-100,000/1的范围内。在一个实施例中，所述催化剂以1000/1-10,000/1的范围存在。在120℃至240℃之间的温度下进行熔化聚合反应。在一个实施例中，在约180℃下进行所述聚合。使聚合反应在该温度下进行约15分钟至约72小时。在一个实施例中，所述反应进行约4小时。
在另一个实施例中，使用缩合试剂，通过溶液聚合，进行甘油单酯、含有UV发色团的多元酸和在某些情况下其它多元醇和多元酸的聚合。缩合试剂包括但不限于：1-乙基-3-(3'-二甲基氨基丙基)碳二亚胺、二环己基碳二亚胺、二异丙基碳二亚胺、苯并三唑-1-基-氧基-三-(二甲基氨基)-六氟磷酸盐、O-(7-氮杂苯并三唑-1-基)-N,N,N',N'-四甲基脲六氟磷酸盐、1,1'-羰基二咪唑、1-[(1-(氰基-2-乙氧基-2-氧代亚乙基氨基氧基)二甲基氨基吗啉代)]脲六氟磷酸盐、3-(二乙氧基-磷酰氧基)-1,2,3-苯并[d]三嗪-4(3H)-酮、N,N’-二琥珀酰亚胺基碳酸盐、2-(1H-苯并三唑-1-基)-1,1,3,3-四甲基脲六氟磷酸盐、O-(1H-6-氯苯并三唑-1-基)-1,1,3,3-四甲基脲六氟磷酸盐、6-氯-苯并三唑-1-基氧基-三-吡咯烷基六氟磷酸盐和2-(1H-苯并三唑-1-基)-1,1,3,3-四甲基铵(aminium)四氟硼酸盐。在一个实施例中，所述缩合试剂是二异丙基碳二亚胺。
使用有机亲核催化剂在溶液中进行缩合聚合。在一个实施例中，所述催化剂是二甲基氨基吡啶。在另一个实施例中，所述催化剂是二甲基氨基吡啶和对甲苯磺酸的1:1盐。
在-20℃至100℃的范围内进行反应。在一个实施例中，所述反应在25℃和50℃之间进行。所述反应的合适溶剂包括但不限于：丙酮、乙腈、苯、二氯甲烷、二甘醇二甲醚乙酸乙酯、乙二醇二甲醚、吡啶、四氢呋喃和三甘醇二甲醚。在一个实施例中，所述反应溶剂是二氯甲烷和吡啶的混合物。在另一个实施例中，所述反应溶剂是丙酮。本文描述的UV吸收性聚合物可用于其中期望UV吸收的应用中。例如，所述聚合物可用于与合适的美容上可接受的用于化妆品用途的载体组合。美容上可接受的局部用载体适合于局部施用至人皮肤，并且可以包括例如载体，诸如水、乙醇、异丙醇、软化剂、保湿剂中的一种或多种，和/或表面活性剂/乳化剂、香料、防腐剂、防水聚合物和在化妆品制剂中常用的类似成分中的一种或多种。这样，使用本领域已知的成分，可以将UV吸收性聚合物配制成喷雾剂、洗剂、凝胶、棒或其它产品形式。类似地，根据某些实施例，通过局部地施用包含UV吸收性聚合物的组合物，可以保护人皮肤免于紫外线辐射。
此外，可以将UV吸收性聚合物与其它材料(例如，塑料、橡胶或其它固体材料)组合以减少这些材料的UV降解(例如，将所述材料与UV吸收性聚合物熔融共混，或用UV吸收性聚合物涂布所述材料)。本发明的聚合物在这样的组合物中的掺入可以提供增强的SPF(主要是UVB吸收)、增强的PFA(主要是UVA吸收)或二者的增强。
以下实例是本发明的原理和实践的示例，尽管不限于此。本领域技术人员在获知本公开内容的益处之后，将会明白在本发明的范围和实质内的许多其它实施例。
实例
实例1：含有UV发色团的二酸单体的合成
如式VI中所示，进行含有UV发色团的二酸单体4(2-{3-[3-(2H-1,2,3-苯并三唑-2-基)-5-叔丁基-4-羟基苯基]-N-(羧甲基)丙烷酰氨基}乙酸)的合成。在烘干的玻璃器皿中进行反应。溶剂和试剂购自商业来源并以接收状态使用，除非另外指出。在Varian Unity Inova 400MHz波谱仪(1H)波谱仪上在30℃下进行NMR分析；在δ量表上以百万份数(ppm)为单位报告化学位移，并参考残余质子化溶剂峰或四甲基硅烷。在DMSO-d6中得到的波谱参考在在δH2.50处的(CHD2)(CD3)SO。
亚氨基二乙酸二乙酯1购自Aldrich或使用从文献改进的规程制备(Kuehn,T.；Schwalbe,H.J.Am.Chem.Soc.2000,122,6169)。含有磁力搅拌棒的烘干的2-颈圆底烧瓶配有均压加料漏斗和具有氮入口接头的回流冷凝器。将无水乙醇(EtOH，750mL)加入烧瓶中；将烧瓶浸入冰水浴中。向加料漏斗中装入亚硫酰氯(SOCl2，110mL，1503mmol)；在搅拌下将SOCl2滴加到EtOH中。SOCl2添加结束后，将亚氨基二乙酸(50g，376mmol)加入反应混合物中。将烧瓶转移到加热的油浴中；将悬浮液加热至回流；白色悬浮液逐渐变成更半透明，最终变成澄清和无色。将反应混合物回流过夜。从油浴中移出烧瓶，并将混合物冷却至室温。在剧烈搅拌下将2.5％碳酸氢钠水溶液(NaHCO3，200mL)小心地加入反应混合物中。然后将小份的无水NaHCO3加入搅拌混合物中，直到气体形成停止。将混合物通过纸真空过滤，并通过旋转蒸发进行浓缩，得到漂浮在澄清水溶液上的油状物。将两相混合物与转移到含有1:1的NaCl(盐水)/H2O饱和水溶液(200mL)的分液漏斗中。将水层用二氯甲烷(CH2Cl2，1×100mL，然后2×50mL)萃取。将CH2Cl2层合并，用盐水洗涤，用无水Na2SO4干燥，通过纸过滤，并通过旋转蒸发而浓缩成淡褐色油状物。将该油状物在减压下蒸馏(约95℃馏出液，在0.65托)，得到澄清油状物亚氨基二乙酸二乙酯(1，44.7g)。1H NMR(400MHz,CDCl3)δppm 4.20(q,J＝7.2Hz,4H),3.46(s,4H),2.04(br.s.,1H),1.28(t,J＝7.1Hz,6H)。
将3-[3-(2H-1,2,3-苯并三唑-2-基)-5-叔丁基-4-羟基苯基]丙酸酯(由BASF Corporation,Wyandotte,Michigan以商品名TINUVIN 213出售的UV发色团)的聚乙二醇酯(81.0g)加入含有磁力搅拌棒的2L圆底烧瓶中。通过漏斗将EtOH(600mL)加入烧瓶中，并将混合物搅拌至均匀。将氢氧化钠(NaOH，30.8g)溶解在H2O(400mL)中；将碱溶液转移到2L烧瓶上方的加料漏斗中。将NaOH溶液缓慢地加入搅拌混合物中；淡琥珀色混浊溶液立即变成澄清和深橙色。当加入结束时，将混合物在室温下搅拌过夜。通过旋转蒸发浓缩溶液，以除去大部分EtOH。将所得的橙色油状物用H2O稀释至1400mL。将混合物机械地搅拌，并通过加入1M的HCl水溶液(约700mL)酸化至约pH 1。将所得的白色沉淀物过滤，并压缩以除去水，然后从EtOH中重结晶。第一批晶体是长形薄无色针状物。除去上清液并通过旋转蒸发进行浓缩；将第二批材料分离为白色无定形固体。将两批合并和在真空干燥箱中干燥过夜，得到白色固体状3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酸(2，37.2g)。1H NMR(400MHz,DMSO-d6)δppm 11.25(br.s,1H),8.00-8.20(m,2H),7.95(d,J＝2.1Hz,1H),7.50-7.67(m,2H),7.28(d,J＝2.1Hz,1H),2.87(t,J＝7.5Hz,2H),2.56(t,J＝7.5Hz,2H),1.45(s,9H)。
向含有磁力搅拌棒的烘干的1000mL圆底烧瓶中装入2(35.00g，103.1mmol)和1(23.42g，123.8mmol)。在氮气压力下，通过插管将无水二甲基甲酰胺(DMF，344mL)加入烧瓶中；将所得的悬浮液剧烈搅拌至均匀。将N-(3-二甲基氨基丙基)-N'-乙基碳二亚胺盐酸盐(EDC·HCl，23.72g，123.8mmol)和羟基苯并三唑一水合物(HOBt·H2O，3.16g，20.6mmol)加入悬浮液中。在加入偶联剂后，悬浮液开始变澄清。用注射器将二异丙基乙胺(DIPEA，18.0mL，103mmol)缓慢地加入反应混合物中。用橡胶塞密封烧瓶，并将混合物搅拌3小时。除去磁力搅拌棒后，将混合物通过旋转蒸发进行浓缩，从50℃水浴温度开始，并增加至90℃。将所得的油状物与乙酸乙酯(EtOAc，550mL)和2.5％的NaHCO3水溶液(350mL)一起转移至分液漏斗。摇晃烧瓶，并使层分离。将NaHCO3层用EtOAc(1×100mL)反萃取。将合并的EtOAc层用1M的HCl水溶液(2×200mL)和盐水(2×200mL)洗涤。将EtOAc层用无水Na2SO4干燥，通过纸过滤，并通过旋转蒸发进行浓缩，得到黄色油状2,2'-((3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酰基)氮烷二基)二乙酸二乙酯(3，52.23g)，其不经进一步纯化地使用。静置后，油固化成星状灰白色晶体。1H NMR(400MHz,CDCl3)δppm 11.78(s,1H),8.13(d,J＝2.1Hz,1H),7.89-7.96(m,2H),7.43-7.51(m,2H),7.22(d,J＝2.1Hz,1H),4.14-4.27(m,8H),2.98-3.07(m,2H),2.62-2.73(m,2H),1.50(s,9H),1.17-1.33(m,6H)。
将四氢呋喃(THF，800mL)转移到含有3(52.23g，103.1mmol，来自前一反应的理论值)和磁力搅拌棒的1000mL圆底烧瓶中。搅拌混合物，直到3完全溶解。然后将水(200mL)加入烧瓶中。将氢氧化锂(12.34g，515.7mmol)缓慢地加入搅拌的反应混合物中；澄清的淡黄色反应混合物立即变成橙色。搅拌混合物过夜后，通过旋转蒸发将溶液浓缩至约300mL的体积，以除去大部分THF。将所得的深橙色溶液转移至含有额外1300mLH2O的2L分液漏斗。将水溶液用二异丙基醚(1×250mL)萃取；将醚层用水(1×200mL)反萃取。将合并的水层转移到4L锥形瓶中。在剧烈机械搅拌下，用1M的HCl水溶液(约750mL)将溶液酸化至约pH 1；这产生白色沉淀物。将EtOAc加入搅拌悬浮液中，直到所有沉淀物已经溶解(加入的EtOAc的终体积为750mL)。分离有机层和水层；将水层用另一部分EtOAc(1×200mL)萃取。将EtOAc层合并，用无水Na2SO4干燥，通过纸过滤，并通过旋转蒸发进行浓缩，得到白色糊状物。将糊状物与2:3EtOAc/己烷类(500mL)一起研磨。将沉淀物过滤，然后在真空干燥箱中干燥，得到细微白色固体状2,2'-((3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酰基)氮烷二基)二乙酸(4，32.04g)。1HNMR(400MHz,DMSO-d6)δppm 11.91-13.25(br s,1H),11.24(s,1H),8.03-8.12(m,2H),7.96(d,J＝2.1Hz,1H),7.55-7.63(m,2H),7.28(d,J＝2.0Hz,1H),4.21(s,2H),3.99(s,2H),2.85(t,J＝6.8Hz,2H),2.63(t,J＝7.5Hz,2H),1.46(s,9H)。
实例2：含有油增溶部分的二酸单体的合成
如在式VII中所示，制备含有油增溶部分的二酸单体的合成。用注射器将亚氨基二乙酸二乙酯(1，13.42g，70.93mmol)加入烘干的500mL圆底烧瓶中，所述烧瓶配有橡胶隔片并含有磁力搅拌棒。在氮气压力下，通过插管将无水CH2Cl2(200mL)加入烧瓶中。用注射器将三乙胺(TEA，8.2mL，59mmol)加入烧瓶中。然后用注射器将2-乙基己酰氯缓慢地加入搅拌的反应混合物中。将混合物搅拌20小时，在这期间形成白色沉淀物。将反应混合物通过旋转蒸发进行浓缩；将所得的油状物用EtOAc(250mL)稀释并转移至分液漏斗。将EtOAc溶液用1M的HCl水溶液(2×100mL)、然后用盐水(1×250mL)洗涤。将EtOAc层用无水Na2SO4干燥，通过纸过滤，并通过旋转蒸发进行浓缩，得到无色油状2,2'-((2-乙基己酰基)氮烷二基)二乙酸二乙酯(5，19.45g)，其不经进一步纯化用在后续反应中。1H NMR(400MHz,CDCl3)δppm 4.08-4.29(m,8H),2.44(tt,J＝8.1,5.4Hz,1H),1.56-1.75(m,2H),1.36-1.55(m,2H),1.14-1.35(m,10H),0.79-0.94(m,6H)。
在氮气压力下，通过插管将THF(500mL)转移到1L圆底烧瓶中，所述烧瓶含有粗制的5(19.5g，59.1mmol；从前一反应的理论收率)和磁力搅拌棒。搅拌混合物，直到5完全溶解。将水(100mL)加入混合物中，随后加入氢氧化锂(7.1g，296mmol)；溶液变成混浊和淡绿色。将混合物在室温下搅拌过夜。将反应混合物通过旋转蒸发浓缩为淡黄色糖浆。将其用水(500mL)稀释，转移至分液漏斗，并用二异丙基醚(1×150mL)洗涤。将醚层用水(1×100mL)反萃取，然后用1M的HCl水溶液酸化至约pH 1。然后将酸化的水层用EtOAc(3×100mL)萃取。将有机层合并，用无水Na2SO4干燥，通过纸过滤，并通过旋转蒸发而浓缩成澄清油状物。将该油状物在己烷类中研磨以除去残余的EtOAc。倾析己烷，剩下半固体，将其在真空干燥箱中在80℃下加热过夜。这得到白色结晶固体状期望产物2,2'-((2-乙基己酰基)氮烷二基)二乙酸(6，11.01g)。1H NMR(400MHz,DMSO-d6)δppm 11.31-13.50(m,1H),4.19(dd,J＝31.4,18.6Hz,2H),3.97(dd,J＝33.5,17.9Hz,2H),2.41-2.48(m,1H),1.40-1.55(m,2H),1.33-1.40(m,1H),1.25-1.33(m,1H),1.07-1.25(m,4H),0.68-0.93(m,6H)。
实例3：单体4与单硬脂酸甘油酯的聚合
向含有磁力搅拌棒的圆底烧瓶中装入单体4(3.80g，8.37mmol)和单硬脂酸甘油酯(由Kerrygroup plc,Kerry,Ireland以商品名MYVEROL 18-06出售的甘油单酯；通过重结晶从EtOAc纯化；3.00g，8.37mmol)。所述烧瓶配有真空蒸馏头；在真空(0.2-1托)下将烧瓶中的空气排空1小时。然后用氮气回填烧瓶。取下蒸馏头，并用注射器将酯化催化剂2-乙基己酸锡(II)(27μL，0.08mmol)加入烧瓶中。将设备重装，并进行3个真空净化循环，随后进行氮气回填。在最终的氮气填充后，将反应烧瓶浸入预热至180℃的油浴中。将混合物在氮气下搅拌4小时，然后在氮气氛下将其冷却至室温。如下从反应容器中移出聚合物：在液氮中冷冻烧瓶，然后将聚合物破碎成较小的块；然后将所述材料转移到贮存容器中。使所述容器在真空下温热至室温。这得到淡黄色固体状聚合物(4.73g)。1H NMR(400MHz,CDCl3)δppm 11.51-11.90(1H),7.97-8.25(1H),7.67-7.97(2H),7.31-7.60(2H),7.06-7.25(1H),4.95-5.56(1H),4.15(8H),2.80-3.14(2H),2.47-2.80(2H),2.17(2H),1.48(11H),1.24(28H),0.87(3H)。由于聚合物1H波谱的质子共振的广阔性，将积分结果四舍五入至最接近的整数值。
以0.5mL/min THF(用0.025％BHT稳定化)的流速，在WatersAlliance 2695 Separations模块(Waters,Milford,MA)上在35℃下进行用于分子量确定的凝胶渗透色谱法。2695配有两个串联的GPC柱(Waters CorpHR 0.5和HR3，具有7.8×300mm的尺寸，5μm粒度)和Waters 410型折射率检测器。通过与聚苯乙烯标准品进行对比，确定样品的分子量。如下制备标准品：将1-2mg每种聚苯乙烯(PS)聚合物称量到含有THF溶剂的2mL小瓶中(每个小瓶2种标准品)；在分析之前将样品过滤(0.22μm)。聚苯乙烯标准品跨70,000-600道尔顿的范围，由3个供应商(Polymer Standards Service-USA、Phenomenex和Shodex)制备。所得的校正曲线提供了r2＝0.9999。以3-5mg/mL的浓度，将实验样品溶解在THF中，并在分析之前过滤(0.22μm)。报告每种材料的数均分子量(Mn)和重均分子量(Mw)。实例3的聚合物的GPC(THF)分析：Mn5078,Mw10202。
使用HPLC分析来确定聚合后带有UV发色团的残余单体(例如，4)；将结果报告为残余单体的重量百分比。该技术使用适当单体的外标准品。通过将1-2mg(±0.1mg)单体称量到10mL容量瓶中，制备标准溶液。将材料溶解在甲醇(MeOH)中，并稀释至刻度。将8-10mg聚合物样品溶解在4mL瓶内的1.0mL THF中，然后通过声处理进行溶解。溶解后，在搅拌下加入2.0mL MeOH。然后将混浊溶液穿过0.2um注射器式滤器过滤进HPLC小瓶中。在具有Discovery C18柱(150×4.6mm，3μm粒度)和302nm的光电二极管阵列检测器(Agilent Technologies,Santa Clara,CA)的Agilent 1100HPLC上在50℃下进行HPLC分析。梯度为：40:60至10:90A/B历时5.5分钟，其中A＝含有0.1％三氟乙酸的水，B＝乙腈，总运行时间为6.5分钟。实例3的聚合物的HPLC分析：0.16重量％的残余物4。
使用下述体外防日光测试方法，进行UV吸收性聚合物的防日光系数(SPF)测量。将聚合物样品测量进8mL玻璃管形瓶中。将混合的苯甲酸C12-C15烷酯(由Innospec,Newark,NJ以商品名FINSOLV TN出售的化妆油溶剂)加入瓶中，以得到期望重量百分比的聚合物溶液。将磁力搅拌棒加入瓶中，然后将瓶用特氟隆衬里的螺旋帽密封。将聚合物/油溶液在100℃铝反应块中搅拌至均匀。冷却后，将32mg聚合物溶液施加于聚甲基丙烯酸甲酯(PMMA)板(由Helioscience,Marseille,France以商品名HELIOPLATE HD6出售的测试衬底)。使用胶乳套，使用一个手指，将溶液均匀地铺展在板上面，直到板上的样品重量已经下降至26mg。使用从生产商接收状态的HD6板，测量基线传播。使用校准的Labsphere UV-1000S UV传播分析仪(Labsphere,North Sutton,N.H.,USA)测量吸收。使用吸收测量来计算SPF指数。使用本领域已知的方法来计算SPF。方程式1描述了用于计算SPF的方程式。
SPF体外＝[∫E(λ)I(λ)dλ]/[∫E(λ)I(λ)10-A 0 (λ)(dλ)] (1)
其中：
E(λ)＝红斑作用光谱
I(λ)＝从UV源接收的光谱辐照度
A0(λ)＝在紫外线暴露之前测试产物层的平均单色吸收
dλ＝波长步骤(1nm)
并且在290nm至400nm的波长范围上进行每个积分。
将体外SPF测试的结果报告为[在FINSOLV TN中的重量百分比，平均SPF值]。实例3的聚合物的分析数据如下：SPF测试：[50％,17.5],[40％,12.7],[30％,11.3],[20％,10.7],[10％,6.0]。所有聚合物的体外SPF结果的总结提供在实例26的表1中。
实例4：单体4与单月桂酸甘油酯的聚合
如在实例3中所述，使单体4(3.00g，6.60mmol)、单月桂酸甘油酯(由Cognis Corporation,Monheim,germany以商品名MONOMULS 90-L 12出售的甘油单酯；1.81g，6.60mmol)和2-乙基己酸锡(II)(21μL，0.07mmol)反应，得到黄色固体(3.85g)。HPLC分析：0.03重量％的残余物4。GPC(THF):Mn3500,Mw9600。1H NMR(400MHz,CDCl3)δppm11.47-12.05(1H),7.97-8.24(1H),7.61-7.97(2H),7.28-7.61(2H),7.21(1H),5.27(1H),3.70-4.74(8H),2.80-3.16(2H),2.46-2.80(2H),1.87-2.45(2H),1.35-1.77(11H),1.24(18H),0.87(3H)。SPF测试：[29％,19.3],[40％,29.0]。
实例5：单体4与单油酸甘油酯的聚合
如在实例3中所述，使单体4(3.00g，6.60mmol)、单油酸甘油酯(由Cognis Corporation,Monheim,germany以商品名MONOMULS 90-O 18出售的甘油单酯；2.35g，6.60mmol)和2-乙基己酸锡(II)(21μL，0.07mmol)反应，得到深黄色硬胶质(4.55g)。HPLC分析：0.05重量％的残余物4。GPC(THF):Mn3115,Mw4148。1H NMR(400MHz,CDCl3)δppm 11.80(1H),7.99-8.31(1H),7.68-7.97(2H),7.31-7.59(2H),7.03-7.24(1H),4.84-5.62(4H),3.55-4.77(8H),2.83-3.11(2H),2.49-2.83(4H),2.11-2.48(2H),2.03(4H),1.39-1.70(11H),0.99-1.38(18H),0.72-0.99(3H)。SPF测试：[19％,16.0],[38％,22.7]。
实例6：单体4和癸二酸与单硬脂酸甘油酯的聚合
如在实例3中所述，使单体4(1.90g，4.28mmol)、癸二酸(0.85g，4.18mmol)、单硬脂酸甘油酯(MYVEROL 18-06；3.00g，8.37mmol)、和2-乙基己酸锡(II)(27μL，0.08mmol)反应，得到蜡状淡黄色固体(4.55g)。HPLC分析：0.02重量％的残余物4。GPC(THF):Mn3300,Mw9500。1H NMR(400MHz,CDCl3)δppm 11.03-12.14(1H),7.99-8.26(1H),7.69-7.97(2H),7.32-7.62(2H),7.02-7.25(1H),4.80-5.50(2H),3.75-4.74(12H),2.83-3.26(2H),2.47-2.83(2H),1.93-2.43(8H),1.40-1.77(17H),1.25(64H),0.69-0.95(6H)。SPF测试：[20％,10.4]。
实例7：单体4和琥珀酸与单硬脂酸甘油酯的聚合
如在实例3中所述，使单体4(1.90g，4.18mmol)、琥珀酸(0.49g，4.18mmol)、单硬脂酸甘油酯(MYVEROL 18-06；3.00g，8.37mmol)和2-乙基己酸锡(II)(21μL，0.07mmol)反应，得到淡黄色固体(4.51g)。HPLC分析：0.02重量％的残余物4。GPC(THF):Mn3,300,Mw9,100。1HNMR(400MHz,CDCl3)δppm 11.46-11.99(1H),8.01-8.27(1H),7.72-7.99(2H),7.30-7.63(2H),7.08-7.25(1H),4.82-5.66(2H),3.50-4.73(12H),2.84-3.40(2H),2.45-2.83(5H),2.03-2.43(5H),1.40-1.87(m,13H),1.27(56H),0.74-0.97(6H)。SPF测试：[20％,10.6],[40％,15.0]。
实例8：单体4和6与单硬脂酸甘油酯的聚合
如在实例3中所述，使单体4(3.00g，6.60mmol)、亚氨基二乙酸乙基己基酯6(1.71g，6.60mmol)、单硬脂酸甘油酯(MYVEROL 18-06；4.73g，13.2mmol)和2-乙基己酸锡(II)(21μL，0.07mmol)反应，得到淡黄色不透明的固体(8.15g)。HPLC分析:0.01重量％的残余物4。GPC(THF):Mn4200,Mw11800。1H NMR(400MHz,CDCl3)δppm 11.43-12.03(1H),8.01-8.32(1H),7.70-7.99(2H),7.31-7.58(2H),7.05-7.26(1H),4.95-5.52(2H),3.38-4.69(15H),2.84-3.23(2H),2.52-2.81(2H),1.96-2.52(5H),1.36-1.78(17H),1.26(60H),0.61-0.96(9H)。SPF测试：[10％,5],[21％,11],[29％,14],[40％,17]。
实例9：单体4和马来酸与单油酸甘油酯的聚合
如在实例3中所述，使单体4(2.00g，4.40mmol)、马来酸(0.51g，4.40mmol)、单油酸甘油酯(MONOMULS 90-O 18；3.14g，8.80mmol)和2-乙基己酸锡(II)(14μL，0.04mmol)反应，得到澄清的橙黄色固体(4.01g)。HPLC分析：<0.01重量％的残余物4。GPC(THF):Mn3044,Mw8628。1H NMR(400MHz,CDCl3)δppm 11.49-11.95,8.00-8.24,7.70-7.96,7.46,7.22,5.27,3.71-4.72,2.45-3.16,2.11-2.42,2.04,1.37-1.69,1.24,0.71-0.93。SPF测试：[20％,13.7],[29％,11.7],[34％,14.7]。
实例10：单体4和马来酸与单硬脂酸甘油酯的聚合
如在实例3中所述，使单体4(2.00g，4.40mmol)、马来酸(510mg，4.40mmol)、单硬脂酸甘油酯(MYVEROL 18-06；3.16g，8.80mmol)和2-乙基己酸锡(II)(29μL，0.09mmol)反应，然后在减压下在180℃下反应另外1小时，得到不透明的黄橙色固体(4.59g)。HPLC分析：<0.01重量％的残余物4。GPC(THF):Mn3205,Mw8605.1H NMR(400MHz,CDCl3)δppm 11.47-11.99(1H),7.97-8.26(1H),7.70-7.97(2H),7.33-7.62(2H),7.10-7.24(1H),6.56-6.94(1H),4.84-5.50(1H),3.87-4.67(12H),2.83-3.15(2H),2.48-2.83(2H),2.32(4H),1.37-1.70(15H),1.26(57H),0.70-0.95(6H)。SPF测试：[25％,15],[35％,20],[40％,44]。
实例11：单体4和衣康酸与单硬脂酸甘油酯的聚合
如在实例3中所述，使单体4(2.50g，5.50mmol)、衣康酸(715mg，5.50mmol)、单硬脂酸甘油酯(MYVEROL 18-06；3.94g，11.00mmol)和2-乙基己酸锡(II)(38μL，0.11mmol)反应，得到淡橙色不透明的固体(5.92g)。HPLC分析:0.01重量％的残余物4。GPC(THF):Mn2498,Mw4543。1H NMR(400MHz,CDCl3)δppm 11.54-12.06(1H),7.99-8.23(1H),7.68-7.97(2H),7.32-7.58(2H),7.06-7.25(1H),6.00-6.49(1H),5.55-5.87(1H),4.80-5.46(1H),3.97-4.70(11H),3.53-3.87(1H),3.14-3.49(1H),2.82-3.11(2H),2.55-2.82(2H),2.09-2.45(5H),1.39-1.75(14H),1.26(58H),0.76-0.96(6H)。SPF测试：[10％,6],[20％,9],[40％,22]。
实例12：单体4与单月桂酸甘油酯和1k有机硅的聚合
如在实例3中所述，使单体4(2.02g，4.44mmol)、单月桂酸甘油酯(MONOMULS 90-L 12；974mg，3.55mmol)、单二甲醇(monodicarbinol)聚二甲基硅氧烷(甲醇改性的聚二甲基硅氧烷，得自Gelest,Morrisville,PA；目录号MCR-C61，约1000分子量，903mg，约0.88mmol)和2-乙基己酸锡(II)(7μL，0.02mmol)反应，其中反应时间为5小时(而不是4小时)，得到淡黄色的、澄清的、易碎固体(3.10g)。HPLC分析：0.16重量％的残余物4。GPC(THF):Mn4100,Mw11,900.1HNMR(400MHz,CDCl3)δppm 11.52-11.91(1H),7.97-8.22(1H),7.93(2H),7.48(2H),7.04-7.26(1H),4.96-5.49(1H),3.81-4.70(12H),3.11-3.44(1H),2.81-3.10(3H),2.48-2.81(3H),2.07-2.45(3H),1.49(18H),0.98-1.37(21H),0.66-0.98(5H),0.28-0.61(1H),0.00-0.15(22H)。SPF测试：[40％,22],[75％,155]。
实例13：单体4与单月桂酸甘油酯和5k有机硅的聚合
如在实例3中所述，使单体4(6.00g，13.2mmol)、单月桂酸甘油酯(MONOMULS 90-L 12；3.53g，12.89mmol)、羟基封端的聚二甲基硅氧烷(甲醇改性的聚二甲基硅氧烷，得自Gelest,Morrisville,PA；目录DMS-C21，约5000分子量，1.65g，约0.33mmol)和乙基己酸锡(II)(21μL，0.07mmol)反应，其中反应时间为7小时(而不是4小时)，得到不透明的黄色固体(10.10g)。HPLC分析：0.04重量％的残余物4。GPC(THF):Mn3600,Mw11700。1H NMR(400MHz,CDCl3)δppm 11.31-11.97,7.98-8.21,7.87,7.43,6.88-7.25,5.02-5.53,3.82-4.71,3.63-3.78,3.50-3.59,3.35-3.49,2.99,2.49-2.82,1.97-2.44,1.71-1.92,1.37-1.68,1.25,0.87,0.03-0.15。SPF测试：[63％,76]。
实例14：单体4与单月桂酸甘油酯和<1k有机硅的聚合
如在实例3中所述，使单体4(6.00g，13.2mmol)、单月桂酸甘油酯(MONOMULS 90-L 12；3.26g，11.9mmol)、羟基封端的聚二甲基硅氧烷(甲醇改性的聚二甲基硅氧烷，得自Gelest,Morrisville,PAgelest DMS-C16，约725分子量，0.96g，约1.32mmol)和乙基己酸锡(II)(21μL，0.07mmol)反应，得到淡黄色、半透明的固体(8.43g)。HPLC分析：0.21重量％的残余物4。GPC(THF):Mn3300,Mw9200.1H NMR(400MHz,CDCl3)δppm 11.14-12.07(1H),7.99-8.29(1H),7.63-7.96(2H),7.31-7.57(2H),7.06-7.25(1H),4.96-5.43(1H),3.67-4.71(12H),2.83-3.13(3H),2.45-2.83(3H),2.00-2.43(3H),1.35-1.85(20H),1.24(23H),0.74-1.01(4H),0.40-0.67(1H),-0.01-0.18(33H)。SPF测试：[58％,118]；[40％,16]。
实例15：单体4与单月桂酸甘油酯和十二烷二醇的聚合
如在实例3中所述，使单体4(6.00g，13.2mmol)、单月桂酸甘油酯(MONOMULS 90-L 12，3.26g，11.9mmol)、1,12-十二烷二醇(267mg，1.32mmol)和乙基己酸锡(II)(21μL，0.07mmol)反应，其中反应时间为6小时(而不是4小时)，得到透明的黄色固体(8.39g)。HPLC分析：0.02重量％的残余物4。GPC(THF):Mn3600,Mw9800。1H NMR(400MHz,CDCl3)δppm 11.53-11.90(1H),7.97-8.26(1H),7.59-7.97(2H),7.46(2H),7.22(1H),5.27(1H),3.70-4.73(7H),2.83-3.16(2H),2.43-2.81(2H),2.11-2.40(3H),2.04(1H),1.79(1H),1.36-1.66(14H),1.24(20H),0.66-0.98(4H)。
实例16：单体4与单月桂酸甘油酯和单硬脂酸三甘油酯的聚合
如在实例3中所述反应，使单体4(6.00g，13.2mmol)、单月桂酸甘油酯(MONOMULS 90-L 12；3.26g，11.9mmol)、单硬脂酸三甘油酯(由Lonza,Allendale,NJ以商品称TGMS-KFG出售的聚甘油衍生物；0.335g，0.66mmol)和乙基己酸锡(II)(21μL，0.07mmol)反应，其中反应时间为6小时(而不是4小时)，得到透明的黄色固体(7.53g)。HPLC分析：0.08重量％的残余物4。GPC(THF)Mn3500,Mw11600。1H NMR(400MHz,CDCl3)δppm 11.48-11.99(2H),7.98-8.22(2H),7.68-7.98(4H),7.29-7.54(4H),7.22(2H),5.28(2H),3.79-4.81(17H),2.81-3.16(5H),2.50-2.81(4H),1.99-2.45(4H),1.36-1.74(23H),1.25(34H),0.88(6H)。
实例17：含有UV发色团的三元酸单体的合成
在式VIII中示出了三元酸单体7的合成。将2,2’,2”-(((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4,1-二基))三(氧基))三丙酸三辛酯(由BASFCorporation,Wyandotte,Michigan以商品名TINUVIN 477出出售的UV发色团；材料编号55430622,42.4g)转移到含有磁力搅拌棒的500mL圆底烧瓶中。将MeOH(300mL)加入烧瓶中；搅拌混合物，产生黄色悬浮液。将水(50mL)加入烧瓶中，悬浮液从黄色变成白色。将氢氧化钾小片(33.1g)缓慢地加入搅拌悬浮液中，导致颜色立即变成黄色；进一步加入KOH，产生深橙色颜色。将反应混合物在室温下搅拌20小时，然后通过旋转蒸发进行浓缩以除去大部分MeOH。将所得的深橙色溶液用水稀释至600mL，并转移到分液漏斗中。将水溶液用二异丙基醚(2×125mL)洗涤，然后通过加入6M的HCl水溶液酸化至约pH 1，导致沉淀物的形成。将水层用EtOAc(1×300mL，1×100mL，然后1×50mL)萃取。将EtOAc层合并，用盐水洗涤，用Na2SO4干燥，并通过有凹槽的纸锥体过滤。将溶液通过旋转蒸发进行浓缩，得到黄色糊状物；将糊状物与己烷类(约400mL)一起研磨，并将所得的悬浮液过滤。将过滤的固体在真空下在约80℃下干燥，得到黄色固体状期望产物(22.4g)。1H NMR(400MHz,DMSO-d6)δppm 13.27(s,1H),13.10(br.s.,3H),12.79(br.s.,2H),7.98-8.48(3H),6.26-6.81(6H),4.84-5.20(3H),1.46-1.67(9H)。
实例18：单体7与单硬脂酸甘油酯(1:1.5比率)的聚合
使用文献规程的变体(Moore,J.S.；Stupp,S.I.Macromolecules 1990,23,65-70)，进行化合物7的溶液聚合。将单体7(1.00g，1.61mmol)、单硬脂酸甘油酯(MYVEROL 18-06，865mg，2.41mmol)和催化剂4-二甲基氨基吡啶/对甲苯磺酸1:1盐(DPTS；284mg，0.97mmol)加入烘干的含有磁力搅拌棒的100mL圆底烧瓶中。将烧瓶用橡胶隔片密封，并用氮气清扫。用注射器将无水CH2Cl2(40mL)引入烧瓶中；在50℃油浴中加热的同时，搅拌所得的悬浮液。然后在搅拌下将吡啶(3mL)加入烧瓶中，使大多数悬浮的固体溶解在溶液中。然后将烧瓶从油浴中移出，并将其冷却至室温。用注射器将二异丙基碳二亚胺(1.24mL，8.04mmol)加入搅拌的溶液中。溶液不久变澄清，然后形成沉淀物。将反应混合物搅拌26小时，然后倒入MeOH中，产生微黄色沉淀物。将沉淀物从悬浮液中过滤出，并在真空干燥箱中在约50℃下干燥，得到具有少量黄色色调的白色粉末状聚合物(1.57g)。GPC(THF):Mn11,200,Mw21,700。1H NMR(400MHz,CDCl3)δppm 11.83-13.82(3H),7.32-9.02(4H),5.68-7.15(9H),5.12-5.68(2H),3.45-5.12(17H),2.00-2.71(6H),1.42-2.00(26H),0.95-1.42(92H),0.87(10H)。SPF测试：[20％,23]。
实例19：单体7与单月桂酸甘油酯(1:1比率)的聚合
将单体7(1.00g，1.61mmol)、单月桂酸甘油酯(MONOMULS 90-L12；441mg，1.61mmol)和DPTS催化剂(284mg，0.97mmol)加入烘干的含有磁力搅拌棒的100mL圆底烧瓶中。将烧瓶用橡胶隔片密封，并用氮气清扫。用注射器将吡啶(6mL)加入烧瓶中，随后加入CH2Cl2(30mL)。在搅拌下，反应混合物变成稍微混浊的溶液。在室温下搅拌混合物的同时，将二异丙基碳二亚胺(1.25mL，8.04mmol)加入反应混合物中。将烧瓶浸入50℃的油浴中，将所述油浴逐渐冷却至35℃。将混合物在氮气下在35℃下搅拌26小时，然后倒入300mL剧烈搅拌的MeOH中。用额外的MeOH，将悬浮液的体积调至500mL；通过真空过滤来分离固体，然后在真空干燥箱中在约50℃下干燥过夜。所得的聚合物为淡黄色固体(1.20g)。GPC(THF):Mn19,100,Mw45,233。1H NMR(400MHz,CDCl3)δppm 12.05-13.64(m,1H),7.46-8.95(3H),5.83-7.20(6H),2.94-5.83(12H),1.98-2.69(5H),1.54(21H),0.95-1.41(37H),0.85(7H)。
实例20：单体7与单月桂酸甘油酯(1:1.5比率)的聚合
将单体7(1.00g，1.61mmol)、单月桂酸甘油酯(MONOMULS 90-L12,662mg，2.41mmol)和DPTS催化剂(284mg，0.97mmol)加入烘干的含有磁力搅拌棒的100mL圆底烧瓶中。将烧瓶用橡胶隔片密封，用氮气清扫，并浸入50℃油浴中。用注射器将吡啶(6mL)和无水CH2Cl2(40mL)加入烧瓶中。然后将烧瓶从油浴中移出，并将其冷却至室温。然后用注射器将二异丙基碳二亚胺(1.25mL，8.04mmol)加入搅拌的反应混合物中。将混合物搅拌21小时，然后倒入剧烈搅拌的MeOH(300mL)中。用MeOH将悬浮液的体积调至500mL；通过真空过滤来分离沉淀物，并在真空干燥箱中在约50℃下干燥过夜。所得的聚合物为淡黄色固体(1.19g)。GPC(THF):Mn9,957,Mw18,661。1H NMR(400MHz,CDCl3)δppm 12.08-13.78(2H),7.33-9.29(3H),5.83-6.95(2H),3.16-5.74(6H),1.99-2.68(2H),1.54(9H),1.24(13H),0.71-0.98(3H)。SPF测[39％,>500]。
实例21：单体7与单硬脂酸甘油酯(1:1比率)的聚合
将单体7(1.00g，1.61mmol)、单硬脂酸甘油酯(MYVEROL 18-06；577mg，1.61mmol)和DPTS催化剂(284mg)加入烘干的含有磁力搅拌棒的100mL圆底烧瓶中。所述烧瓶配有橡胶隔片，用氮气清扫，并浸入50℃油浴中。用注射器加入无水CH2Cl2(40mL)，随后加入吡啶(6mL)；在搅拌下，大多数固体溶解在溶剂中，形成澄清溶液。将烧瓶从油浴中移除，并将混合物冷却至室温。用注射器将二异丙基碳二亚胺加入搅拌的反应混合物中。将混合物搅拌25小时，然后倒入剧烈搅拌的MeOH(500mL)中。将所得的沉淀物通过真空过滤进行收集，并在真空干燥箱中在约50℃下干燥过夜。所得的聚合物为奶油色固体(1.34g)。HPLC分析：0.01重量％的残余单体7。GPC(THF):Mn13,036,Mw24,948。1H NMR(400MHz,CDCl3)δppm 11.53-13.89(3H),7.40-9.02(4H),5.71-7.23(9H),3.54-5.58(7H),2.06-2.58(5H),1.00-2.03(108H),0.88(10H)。
实例22：在熔化条件下单体7与单月桂酸甘油酯的聚合
将三元酸单体7(3.51g)、己二酸(1.15g)、单月桂酸甘油酯(MONOMULS 90-L 12；3.48g)和硬脂醇(2.86g)称量到100mL 2-颈圆底烧瓶中。所述烧瓶在侧颈上配有氮气入口，并在中央颈上配有蒸馏接头，做成冰冷却的接收烧瓶。将磁力搅拌棒加入圆底烧瓶中，然后将其浸入磁力搅拌板上面的油浴中。开始混合，并将混合物在氮气掩盖下加热至161℃的内部温度。最初，反应混合物显现为三元酸7在其它熔化组分中的糊状黄色悬浮液。50分钟后，三元酸单体7溶解，并且反应混合物变成澄清的黄色溶液。将4.97％的乙基己酸锡(II)在THF(0.217g)中的溶液加入该溶液中。将反应混合物在氮气下搅拌190分钟，得到粘稠的黄色液体，其在冷却至室温后变成粘性的固体。HPLC分析:<0.2重量％的残余单体7。GPC(THF):Mn2,500,Mw26,000。1H NMR(400MHz,CDCl3)δppm 12.10-13.72(1H),7.29-8.69(3H),5.72-6.98(5H),3.50-5.57(14H),2.02-2.65(8H),1.46-1.91(18H),1.27(65H),0.65-0.96(9H)。
实例23：用胺官能化的苯并三唑UV发色团后聚合改性聚(单硬脂酸甘
油酯/衣康酸酐)
在该实例中，描述了含有可官能化的乙烯基团的基于甘油单酯的聚酯的合成，和UV发色团与聚酯主链的共价连接。在式IX中示出了该方案。
已经描述了3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)-N-(2-氨基乙基)丙酰胺盐酸盐(化合物8)的合成(US 5166234)。将8的盐酸盐(5.0g，12.0mmol)加入具有约75mL氯仿(CHCl3)的250mL分液漏斗中。将NaOH水溶液(1M，50mL)加入漏斗中。摇动混合物后，除去水层，并将CHCl3层用2份另外的NaOH溶液洗涤。将CHCl3层用几份盐水洗涤；使用通用指示剂条监测所得水层的pH。重复盐水洗涤，直到水溶液的pH为约7。CHCl3溶液用MgSO4干燥，通过纸过滤，并通过旋转蒸发进行浓缩；将残余溶剂在真空下除去溶剂，得到游离碱(化合物9)。1HNMR(400MHz,DMSO-d6)δppm 8.03-8.11(m,1H),7.94(d,1H),7.81(t,1H),7.53-7.63(m,2H),7.24(d,1H),4.73(br.s.,3H),3.04(q,2H),2.87(t,2H),2.52(t,2H),2.42(t,2H),1.37-1.49(m,9H)。
将单硬脂酸甘油酯(由Kerrygroup plc,Kerry,Ireland以商品名MYVEROL 18-06出售的甘油单酯；通过重结晶由EtOAc纯化；14.34g，40.0mmol)、衣康酸酐(4.48g，40.0mmol)和2-乙基己酸锡(II)(3.6μL在甲苯中的0.33摩尔溶液)加入含有磁力搅拌棒的250mL单颈圆底烧瓶中。所述烧瓶配有蒸馏接头，所述蒸馏接头具有100mL圆底收集容器并且连接至真空/氮气管线。将烧瓶放在真空下并用氮气回填。将反应烧瓶浸入预热至185℃的油浴中；将混合物搅拌24小时。将所述材料冷却，并通过冷冻破碎从反应烧瓶除去，然后在氮气下温热至室温。所得聚合物(10)为具有淡棕色-橙色和蜡状稠度的不透明固体。GPC(THF):Mn3400,Mw15700。1H NMR(400MHz,CDCl3)δppm 6.70-6.86,6.25-6.47,5.66-6.02,5.01-5.52,3.94-4.68,3.59-3.87,3.21-3.47,2.32,2.18-2.23,1.97-2.16,1.49-1.71,1.26,0.77-0.98。
将聚合物10(5.00g，11.0mmol)、胺衍生化的UV发色团9(2.11g，5.5mmol)和2,2'-偶氮双(2-甲基丙腈)(AIBN；82mg，0.5mmol)加入含有磁力搅拌棒的250mL圆底烧瓶中。将THF(150mL)加入烧瓶中。所述烧瓶配有回流冷凝器，然后浸入预热至50℃的油浴中；将反应混合物搅拌72小时。然后将混合物滴加至搅拌的冰冷甲醇(400mL)中；将悬浮液在-20℃冰柜中放置30分钟。然后将甲醇从烧瓶中倾析出，并用200mL新鲜甲醇替代；将烧瓶在冰柜中放置15分钟。将悬浮液通过纸真空过滤；将沉淀物用另外一份甲醇洗涤；将残余溶剂在室温下减压除去，得到固体状缀合物11。GPC(THF):Mn900,Mw5100。1H NMR(400MHz,CDCl3)δppm 11.45-11.98(1H),7.99-8.22(1H),7.74-7.99(2H),7.37-7.56(2H),7.08-7.25(1H),6.68-6.92(1H),5.63-6.49(2H),4.91-5.51(3H),4.18(22H),3.11-3.88(16H),2.86-3.10(5H),2.42-2.84(10H),2.19-2.42(15H),1.70-2.19(6H),0.96-1.70(193H),0.89(19H)。
实例24：苯并三唑羧酸酯至酰基氯12(3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酰氯)的转化
在式X中示出了苯并三唑羧酸2至对应的酰基氯12的转化。将化合物2(50g，147mmol，如实例1中所述合成)加入含有磁力搅拌棒的1000mL3颈烧瓶中；所述烧瓶配备有回流冷凝器、氮气入口和橡胶隔片。通过穿过隔片的插管，将无水甲苯(约500mL)转移到烧瓶中。用注射器将亚硫酰氯(16.1mL，221mmol)转移到烧瓶中；然后用注射器将DMF(2.7mL)加入烧瓶中。将烧瓶浸入设定在80℃的油浴中；搅拌悬浮液；固体开始分散，最终产生澄清溶液。约4小时后，使反应混合物冷却，转移至圆底烧瓶，并通过旋转蒸发进行浓缩。将所得油状物与己烷类一起研磨，得到米色固体。通过加入额外的己烷类并温热至回流，将材料的悬浮液重结晶，通过纸过滤，并在搅拌下缓慢地冷却至室温。将所得的米色晶体过滤，并在真空下在50℃干燥。将滤液浓缩，并进行第二次重结晶，得到第二批晶体；合并批次的化合物12的质量为44.7克。1H NMR(400MHz,CDCl3)δ11.88(s,1H),8.16(d,J＝2.2Hz,1H),7.91-7.98(m,2H),7.47-7.54(m,2H),7.21(d,J＝2.2Hz,1H),3.29(t,J＝7.5Hz,2H),3.07(t,J＝7.5Hz,2H),1.50-1.53(s,9H)。
实例25：苯并三唑酰氯12至异氰酸酯13(2-(2H-苯并[d][1,2,3]三唑-2-
基)-6-(叔丁基)-4-(2-异氰酰乙基)苯酚)的转化
将叠氮化钠(NaN3，2.5g，38mmol：警告！NaN3为剧毒)小心地转移至含有磁力搅拌棒的500mL单颈圆底烧瓶中。将去离子水(20mL)加入烧瓶中；在搅拌下NaN3溶解，得到澄清溶液。将烧瓶浸入冰浴中。将酰基氯12(7.0g，20mmol)和无水丙酮(45mL)转移至正压N2气氛手套箱中的均压加料漏斗中。在轻柔涡旋下将酰基氯溶解在丙酮中，得到澄清黄色溶液。将含有12的加料漏斗装配到含有NaN3水溶液的烧瓶中；加料漏斗的顶部配有与Schlenk管线连接的N2接头。将12的溶液滴加至NaN3溶液中。加入数滴之后，白色沉淀物开始出现，悬浮于水溶液中。12的完全加入在30分钟内完成；混合在冰浴中持续20分钟。将水(30mL)加入所得白色浆液中；通过在真空下穿过烧结玻璃过滤来收集固体。将白色固体转移至分液漏斗，随后转移CHCl3(185mL)。摇晃所述烧瓶，并使层分离。将下层有机相从少的水层中移出，并用Na2SO4干燥。将溶液过滤；滤液放在含有磁力搅拌棒的500mL单颈圆底烧瓶中；所述烧瓶配具有氮气入口接头的回流冷凝器，并浸入油浴中。在搅拌下，在30分钟内将溶液缓慢加热至回流。最终油浴温度为65℃。当油浴温度超过55℃时，在溶液中出现鼓泡。使反应回流共计90min。然后通过旋转蒸发除去CHCl3；将所得的油状物在静置下结晶过夜，得到略微灰色固体状产物12(5.8g)。1H NMR(400MHz,CDCl3)δ11.91(s,1H),8.18(d,J＝1.9Hz,1H),7.92-7.98(m,2H),7.47-7.53(m,2H),7.23(d,J＝2.1Hz,1H),3.59(t,J＝6.9Hz,2H),2.96(t,J＝6.9Hz,2H),1.52(s,9H)。
实例26：SPF结果的总结
在表1中总结了在前面的实例中描述的选择聚合物的体外SPF测量结果。在实例3中描述了用于测量聚合物样品的体外测试方法。
表1：选择实例的体外SPF测试结果的总结
Claims (12)
1.一种紫外线辐射吸收性聚合物组合物，包含甘油单酯和含有UV发色团的多元酸单体的反应产物。
2.根据权利要求1所述的组合物，其中所述甘油单酯选自单硬脂酸甘油酯、单棕榈酸甘油酯、单肉豆蔻酸甘油酯、单癸酸甘油酯、单癸酸甘油酯、单月桂酸甘油酯、单亚油酸甘油酯和单油酸甘油酯。
3.根据权利要求1所述的组合物，其中所述UV发色团选自：三唑、樟脑、二苯甲酰甲烷、4-氨基苯甲酸以及它们的烷烃酯；邻氨基苯甲酸及其烷烃酯；水杨酸及其烷烃酯；羟基肉桂酸及其烷烃酯；二羟基-、二羧基-和羟基羧基二苯甲酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-和羟基羧基查耳酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-和羟基羧基香豆素以及它们的烷烃酯或酰卤衍生物；苯亚甲基丙二酸酯；苯并咪唑衍生物、苯并唑衍生物、3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)、6-辛基-2-(4-(4,6-二([1,1’-联苯]-4-基)-1,3,5-三嗪-2-基)-3-羟基苯氧基)丙酸酯；和2,2',2″-(((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4,1-二基))三(氧基))三丙酸三辛酯。
4.根据权利要求1所述的组合物，包含所述甘油单酯、所述含有UV发色团的多元酸单体和多元醇的反应产物，所述多元醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、双-2-羟乙基醚、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇、直链聚(乙二醇)、支化聚(乙二醇)、直链聚(丙二醇)、支化聚(丙二醇)、直链乙烯-丙二醇共聚物和支化乙烯-丙二醇共聚物二醇、聚甘油、聚甘油酯、甘油、单糖、二糖、多糖和用甲醇基团末端官能化的直链聚硅氧烷。
5.根据权利要求1所述的组合物，其中所述聚合物组合物是所述甘油单酯、所述含有UV发色团的多元酸单体和多元酸的反应产物，所述多元酸选自：天然的多官能羧酸，其选自琥珀酸、戊二酸、己二酸、庚二酸、辛二酸和癸二酸；羟基酸，其选自二羟乙酸、苹果酸、酒石酸和柠檬酸；和不饱和酸，其选自富马酸和马来酸。
6.根据权利要求1所述的组合物，其中所述紫外线辐射吸收性聚合物组合物具有约500至约50,000的重均分子量。
7.一种紫外线辐射吸收性聚合物组合物，包含含有以下重复单元的聚合物
其中X包含UV发色团，并且R1是具有介于4和30之间的碳原子数的饱和或不饱和的烃部分。
8.根据权利要求7所述的紫外线辐射吸收性聚合物组合物，包含具有以下结构的聚合物
9.根据权利要求7所述的紫外线辐射吸收性聚合物组合物，其中n是使得所述紫外线辐射吸收性聚合物组合物具有约500至约50,000的重均分子量的数。
10.根据权利要求7所述的紫外线辐射吸收性聚合物组合物，其中所述UV发色团选自：三唑、樟脑、二苯甲酰甲烷、4-氨基苯甲酸以及它们的烷烃酯；邻氨基苯甲酸及其烷烃酯；水杨酸及其烷烃酯；羟基肉桂酸及其烷烃酯；二羟基-、二羧基-和羟基羧基二苯甲酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-和羟基羧基查耳酮以及它们的烷烃酯或酰卤衍生物；二羟基-、二羧基-和羟基羧基香豆素以及它们的烷烃酯或酰卤衍生物；丙二酸苯亚甲酯；苯并咪唑衍生物、苯并唑衍生物、3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)、6-辛基-2-(4-(4,6-二([1,1’-联苯]-4-基)-1,3,5-三嗪-2-基)-3-羟基苯氧基)丙酸酯和2,2',2″-(((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4,1-二基))三(氧基))三丙酸三辛酯。
11.一种组合物，包含美容上可接受的局部用载体和紫外线辐射吸收性聚合物组合物，所述组合物包含甘油单酯和含有UV发色团的多元酸单体的反应产物。
12.一种组合物，包含美容上可接受的局部用载体和紫外线辐射吸收性聚合物组合物，所述组合物包含含有以下重复单元的聚合物：
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| CN108703892B (zh) * | 2018-07-27 | 2021-05-11 | 广州汇朗生物科技有限公司 | 1,5-戊二醇的新应用 |
| CN115403734A (zh) * | 2022-10-08 | 2022-11-29 | 安徽泓泽新材料科技有限公司 | 一种呔哔克基聚酯固化剂及其制备方法 |
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| CA2877476A1 (en) | 2014-01-03 |
| BR112014032814A2 (pt) | 2017-06-27 |
| CN104411366B (zh) | 2017-09-08 |
| KR20150027241A (ko) | 2015-03-11 |
| AU2013280915B2 (en) | 2017-09-07 |
| IN2014DN11009A (zh) | 2015-09-25 |
| CA2877476C (en) | 2021-01-26 |
| TW201410732A (zh) | 2014-03-16 |
| KR102057876B1 (ko) | 2020-02-07 |
| RU2015102541A (ru) | 2016-08-20 |
| EP2866898B1 (en) | 2018-04-04 |
| TWI598375B (zh) | 2017-09-11 |
| ES2668478T3 (es) | 2018-05-18 |
| WO2014004176A1 (en) | 2014-01-03 |
| EP2866898A1 (en) | 2015-05-06 |
| US9469725B2 (en) | 2016-10-18 |
| AU2013280915A1 (en) | 2015-01-22 |
| BR112014032814A8 (pt) | 2022-08-16 |
| RU2642974C2 (ru) | 2018-01-29 |
| US20140004060A1 (en) | 2014-01-02 |
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