CN101305041B - 光潜体系 - Google Patents
光潜体系 Download PDFInfo
- Publication number
- CN101305041B CN101305041B CN2006800417598A CN200680041759A CN101305041B CN 101305041 B CN101305041 B CN 101305041B CN 2006800417598 A CN2006800417598 A CN 2006800417598A CN 200680041759 A CN200680041759 A CN 200680041759A CN 101305041 B CN101305041 B CN 101305041B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- phenyl
- compound
- group
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 6
- -1 sulphinyl Chemical group 0.000 claims description 198
- 239000000203 mixture Substances 0.000 claims description 80
- 239000000126 substance Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 37
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 28
- 235000013599 spices Nutrition 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 19
- 230000009189 diving Effects 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 17
- 239000003973 paint Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 9
- 239000000123 paper Substances 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002304 perfume Substances 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000005243 carbonyl alkyl group Chemical group 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 125000000081 (C5-C8) cycloalkenyl group Chemical group 0.000 claims description 4
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005356 cycloalkylalkenyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002781 deodorant agent Substances 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- 229910052740 iodine Chemical group 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000002453 shampoo Substances 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- 239000004599 antimicrobial Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 66
- 239000002585 base Substances 0.000 description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 55
- 229910052757 nitrogen Inorganic materials 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 37
- 239000000049 pigment Substances 0.000 description 37
- 238000002360 preparation method Methods 0.000 description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 33
- 238000003756 stirring Methods 0.000 description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 27
- 150000002148 esters Chemical class 0.000 description 27
- 150000001412 amines Chemical class 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 24
- 238000001704 evaporation Methods 0.000 description 22
- 230000008020 evaporation Effects 0.000 description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 229960003742 phenol Drugs 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- 235000009499 Vanilla fragrans Nutrition 0.000 description 16
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 16
- 244000263375 Vanilla tahitensis Species 0.000 description 16
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 16
- 150000001408 amides Chemical class 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 13
- 239000005864 Sulphur Substances 0.000 description 13
- 239000012043 crude product Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229920000877 Melamine resin Polymers 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 235000009518 sodium iodide Nutrition 0.000 description 8
- WFOVEDJTASPCIR-UHFFFAOYSA-N 3-[(4-methyl-5-pyridin-4-yl-1,2,4-triazol-3-yl)methylamino]-n-[[2-(trifluoromethyl)phenyl]methyl]benzamide Chemical compound N=1N=C(C=2C=CN=CC=2)N(C)C=1CNC(C=1)=CC=CC=1C(=O)NCC1=CC=CC=C1C(F)(F)F WFOVEDJTASPCIR-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- XUQNLOIVFHUMTR-UHFFFAOYSA-N 2-[[2-hydroxy-5-nonyl-3-(1-phenylethyl)phenyl]methyl]-4-nonyl-6-(1-phenylethyl)phenol Chemical compound OC=1C(C(C)C=2C=CC=CC=2)=CC(CCCCCCCCC)=CC=1CC(C=1O)=CC(CCCCCCCCC)=CC=1C(C)C1=CC=CC=C1 XUQNLOIVFHUMTR-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 229940035422 diphenylamine Drugs 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
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- 235000012141 vanillin Nutrition 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
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- 239000003513 alkali Substances 0.000 description 5
- 229920000180 alkyd Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
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- 239000000839 emulsion Substances 0.000 description 5
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- 239000000835 fiber Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229940038384 octadecane Drugs 0.000 description 5
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- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- PMNGNPRHPYYVNM-UHFFFAOYSA-N 1-hydroxyundecane-3-sulfonic acid Chemical compound CCCCCCCCC(CCO)S(O)(=O)=O PMNGNPRHPYYVNM-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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Abstract
Description
本发明涉及到效应分子例如香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的新颖的光潜(photolatent)4-羟基-苯甲酰甲基衍生物,涉及到组合物,该组合物包含技术材料(technical material)(该技术材料优选是溶剂、蜡、成膜基料、油漆、涂料、天然或者合成的聚合物、织物、纸、清洁剂、上光剂、织物护理剂、香波、护发素、发胶、肥皂、洗浴凝胶或者身体除臭剂)和效应分子的新颖的光潜4-羟基-苯甲酰甲基衍生物;以及涉及到新颖的光潜4-羟基-苯甲酰甲基衍生物作为用光释放例如香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的前体的用途。
光潜体系的现有技术是具有或者不具有另外的取代基的2-硝基苄基衍生物作为保护中间体,如例如由Peter Wan等人,J.Am.Chem.Soc.1999,121,5625 5632中所公开。但是,2-硝基苄基保护基团具有几个缺点。硝基芳族化合物是热不稳定的并且不能在高温例如当在热塑性聚合物例如诸如聚丙烯中挤出时加工。此外,通过光脱保护,形成作为副产物的有毒和有色的2-亚硝基-苯甲醛,给基底增加了某些不期望的性能例如变色和毒性。2-硝基苄基保护基团另一个缺点是光产物与保护中间体具有相同的光谱区域的吸收,因此妨碍了有效的通过内在的滤波效应的脱保护。
目前已经发现新的4-羟基-苯甲酰甲基衍生物基本上避免了全部这些缺点。4-羟基-苯甲酰甲基衍生物在高到220-260℃是热稳定的。光产物是4-羟基苯基乙酸衍生物,其是很少有色和很少有毒的。此外,与所述的保护中间体相比,该光产物在更短的波长吸收,其产生小得多的不期望的滤波效应。
本发明因此提供一种式I的光潜化合物
其中
R1和R2彼此独立地是C1-C10烷基或者C3-C8环烷基,
R3是氢或C1-C4烷基,和
其中光化学裂解基团R4OH选自香料、UV吸收剂、抗菌剂、防雾剂和澄清剂;条件是:当R1和R2是叔丁基并且R3是氢时,R4不是甲基或苯基。
令人感兴趣是下述式I的光潜化合物,其中
R1和R2彼此独立地是C1-C10烷基或者C3-C8环烷基,
R3是氢或C1-C4烷基,
R4是未被取代的C1-C25烷基,C3-C25链烯基,C3-C25链炔基,C6-C10芳基,C3-C12环烷基或C3-C12环链烯基;或者被C1-C18烷基,C2-C18链烯基,C3-C18链炔基,C3-C12环烷基,C1-C18烷氧基,羟基,C2-C18烷氧基羰基,甲酰基,C1-C18烷硫基,C1-C18烷基亚磺酰基,C1-C18烷基磺酰基,卤素,羧基,C2-C18羧基烷基,C2-C18羧基烷氧基,C3-C18烷氧基羰基烷基,C3-C18烷氧基羰基烷氧基,C7-C9苯基烷基,苯氧基,卤素取代的苯氧基,山梨醇基(sorbityl)或取代的C1-C25烷基,C3-C25链烯基,C3-C25链炔基,C6-C10芳基,C3-C12环烷基和C3-C12环链烯基,;
R5是氢,C1-C4烷基或者卤素,和
R6和R7彼此独立地是苯基或者C1-C4烷基取代的苯基;条件是:当R1和R2是叔丁基并且R3是氢时,R4不是甲基或苯基。
具有高到25个碳原子的烷基是支化的或者未支化的基团,例如甲基,乙基,丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,2-乙基丁基,正戊基,异戊基,1-甲基戊基,1,3-二甲基丁基,正己基,1-甲基己基,正庚基,异庚基,1,1,3,3-四甲基丁基,1-甲基庚基,3-甲基庚基,正辛基,2-乙基己基,1,1,3-三甲基己基,1,1,3,3-四甲基戊基,壬基,癸基,十一烷基,1-甲基十一烷基,十二烷基,十八烷基,二十烷基或者二十二烷基。
C3-C12环烷基是例如环丙基,环丁基,环戊基,环己基,环庚基,环辛基,环壬基,环癸基,环十一烷基或者环十二烷基。优选给出的是环己基。
具有2-25个碳原子的链烯基是支化的或者未支化的基团例如诸如乙烯基,丙烯基,2-丁烯基,3-丁烯基,异丁烯基,正2,4-戊二烯基,3-甲基-2-丁烯基,正2-辛烯基,正2-十二碳烯基,异十二碳烯基,油基,正2-十八碳烯基或者正4-十八碳烯基。
具有3-25个碳原子的链炔基是支化的或者未支化的基团例如诸如丙炔基,2-丁炔基,3-丁炔基,正2,4-戊二炔基,3-甲基-2-丁炔基,正2-辛炔基,正2-十二碳炔基,异十二碳炔基,正2-十八碳炔基或者正4-十八碳炔基。
C6-C10芳基是例如苯基或者萘基。
C3-C12环链烯基是例如环丙烯基,环丁烯基,环戊烯基,环己烯基,环庚烯基,环辛烯基,环壬烯基,环癸烯基,环十一碳烯基或者环十二碳烯基。优选给出的是环己烯基。
具有高到18个碳原子的烷氧基支化的或者未支化的基团,例如甲氧基,乙氧基,丙氧基,异丙氧基,正丁氧基,异丁氧基,戊氧基,异戊氧基,己氧基,庚氧基,辛氧基,癸氧基,十四烷氧基,十六烷氧基或者十八烷氧基。
C2-C18烷氧基羰基是支化的或者未支化的基团,例如甲氧基羰基,乙氧基羰基,丙氧基羰基,异丙氧基羰基,正丁氧基羰基,异丁氧基羰基,戊氧基羰基,异戊氧基羰基,己氧基羰基,庚氧基羰基,辛氧基羰基,癸氧基羰基,十四烷氧基羰基,十六烷氧基羰基或者十八烷氧基羰基。
具有高到18个碳原子的烷硫基是支化的或者未支化的基团,例如甲基硫,乙基硫,丙基硫,异丙基硫,正丁基硫,异丁基硫,戊基硫,异戊基硫,己基硫,庚基硫,辛基硫,癸基硫,十四烷硫基,十六烷硫基或者十八烷硫基。
具有高到18个碳原子的烷基亚磺酰是支化的或者未支化的基团,例如甲基亚磺酰,乙基亚磺酰,丙基亚磺酰,异丙基亚磺酰,正丁基亚磺酰,异丁基亚磺酰,戊基亚磺酰,异戊基亚磺酰,己基亚磺酰,庚基亚磺酰,辛基亚磺酰,癸基亚磺酰,十四烷基亚磺酰,十六烷基亚磺酰或者十八烷基亚磺酰。
具有高到18个碳原子的烷基亚磺酰基是支化的或者未支化的基团,例如甲基磺酰基,乙基磺酰基,丙基磺酰基,异丙基磺酰基,正丁基磺酰基,异丁基磺酰基,戊基磺酰基,异戊基磺酰基,己基磺酰基,庚基磺酰基,辛基磺酰基,癸基磺酰基,十四烷基磺酰基,十六烷基磺酰基或者十八烷基磺酰基。
卤素取代基有利的是氯、溴或者碘。
C2-C18羧基烷基是支化的或者未支化的基团,例如羧甲基,羧乙基,羧丙基,羧丁基,羧戊基,羧己基,羧庚基,羧辛基,羧壬基,羧癸基,羧基十一烷基,羧基十二烷基,羧基十四烷基,羧基十六烷基或者羧基十八烷基。
C2-C18羧基烷氧基是支化的或者未支化的基团,例如羧基甲氧基,羧基乙氧基,羧基丙氧基,羧基丁氧基,羧基戊氧基,羧基己氧基,羧基庚氧基,羧基辛氧基,羧基壬氧基,羧基癸氧基,羧基十一烷氧基,羧基十二烷氧基,羧基十四烷氧基,羧基十六烷氧基或者羧基十八烷氧基。
C3-C18烷氧基羰基烷基是支化的或者未支化的基团,例如甲氧基羰甲基,甲氧基羰乙基,乙氧基羰甲基,丙氧基羰乙基,乙氧基羰乙基,乙氧基羰丙基,乙氧基羰丁基,乙氧基羰戊基,丁氧基羰己基或者丁氧基羰基十二烷基。
C3-C18烷氧基羰基烷氧基是支化的或者未支化的基团,例如甲氧基羰基甲氧基,甲氧基羰基乙氧基,乙氧基羰基甲氧基,丙氧基羰基乙氧基,乙氧基羰基乙氧基,乙氧基羰基丙氧基,乙氧基羰基丁氧基,乙氧基羰基戊氧基,丁氧基羰基己氧基或者丁氧基羰基十二烷氧基。
C7-C9苯基烷基是例如苄基,α-甲基苄基,α,α-二甲基苄基或者2-苯基乙基。
卤素取代的苯氧基,其优选包含1-3个特别是1或者2个卤素,是例如邻、间或者对氯苯氧基,或者2,4-二氯苯氧基。
特别令人感兴趣的是下述式I的光潜化合物,其中
R1和R2彼此独立地是C3-C8烷基或者C5-C8环烷基,
R3是氢或甲基,
R4是未被取代的C1-C18烷基,C3-C18链烯基,C3-C18链炔基,C6-C10芳基,C5-C8环烷基或者C5-C8环链烯基;或者被C1-C12烷基,C2-C12链烯基,C3-C12链炔基,C5-C8环烷基,C1-C12烷氧基,羟基,C2-C12烷氧基羰基,甲酰基,C1-C12烷硫基,C1-C12烷基亚磺酰基,C1-C12烷基磺酰基,卤素,羧基,C2-C12羧基烷基,C2-C12羧基烷氧基,C3-C12烷氧基羰基烷基,C3-C12烷氧基羰基烷氧基,C7-C9苯基烷基,苯氧基,卤素取代的苯氧基,山梨醇基或取代的C1-C18烷基,C3-C18链烯基,C3-C18链炔基,C6-C10芳基,C5-C8环烷基和C5-C8环链烯基;
R5是氢或卤素,和
R6和R7是苯基。
非常令人感兴趣的是下述式I的光潜化合物,其中R3是氢。
还令人感兴趣的是下述式I的光潜化合物,其中R1和R2彼此独立地是C3-C5烷基或者环己基。
优选的是下述式I的光潜化合物,其中
R4是未被取代的C2-C12烷基,C3-C12链烯基,C3-C12链炔基,苯基,环己基或者环己烯基;或者被C1-C4烷基,C2-C8链烯基,C3-C8链炔基,环己基,C1-C8烷氧基,甲酰基,氯,羧基,C7-C9苯基烷基,苯氧基,氯取代的苯氧基,山梨醇基或取代的C2-C12烷基,C3-C12链烯基,C3-C12链炔基,苯基,环己基和环己烯基;
R5是氢或氯,和
R6和R7是苯基。
还优选的是式I的光潜化合物,其中R1和R2是异丙基,叔丁基,枯基或者环己基。
非常特别令人感兴趣兴趣的是下述式I的光潜化合物,
其中
R1是C3-C5烷基或者环己基,
R2是C3-C5烷基或者环己基,
R3是氢,
R4是未被取代的C2-C12烷基,C3-C12链烯基,C3-C12链炔基,苯基,环己基或者环己烯基;或者被C1-C4烷基,C2-C8链烯基,C3-C8链炔基,环己基,C1-C8烷氧基,甲酰基,氯,羧基,C7-C9苯基烷基,苯氧基,氯取代的苯氧基,山梨醇基或取代的C2-C12烷基,C3-C12链烯基,C3-C12链炔基,苯基,环己基和环己烯基;
R5是氢或氯,和
R6和R7是苯基。
式I的光潜化合物可以以本身已知的方式来制备。在一种典型的制备反应过程中,在溶剂和碱的存在下,式Ia的化合物与醇R4-OH进行反应,
其中R1,R2和R3含义同上,X是离去基团例如卤素,
其中R4含义同上。
特别令人感兴趣的碱是例如碳酸盐例如碳酸钾;氢氧化物例如氢氧化钠或者氢氧化钾;或者胺例如叔胺如三乙基胺;或者吡啶。
优选的溶剂是例如质子或者非质子溶剂例如羧酸酯例如乙酸乙酯;醚例如二乙基醚或者四氢呋喃;醇例如甲醇或者乙醇;和偶极非质子溶剂,例如二甲基甲酰胺、N-甲基吡咯烷酮或者乙腈。
式I的光潜化合物适于作为用光释放的香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的前体。在本发明的上下文中,香料包括日用香料和食用香味(所述香料人和动物通过嗅觉和味觉能够有意识地和下意识地察觉,包括用于昆虫、啮齿动物和其他害物的信息素、引诱剂和驱避剂)和气味诱饵以及它们的混合物。
式I的光潜化合物因此可以被混入或者加入到任何种类的技术材料中。
本发明因此还涉及组合物,其包含a)技术材料,和b)至少一种式I的光潜化合物。
优选的,技术材料是例如溶剂、蜡、成膜基料、油漆、涂料、天然或者合成的聚合物、织物、纸、清洁剂、上光剂、织物护理剂、香波、护发素、发胶、肥皂、洗浴凝胶或者身体除臭剂
天然或者合成的聚合物示例性的例子是:
1.单烯烃和二烯烃的聚合物例如聚丙烯,聚异丁烯,聚丁-1-烯,聚-4-甲基戊-1-烯,聚乙烯基环己烷,聚异戊二烯或者聚丁二烯,以及环烯烃的聚合物例如环戊烯或者降冰片烯者,聚乙烯(其任选可以是交联的)例如高密度聚乙烯(HDPE),高密度和高分子量聚乙烯(HDPE-HMW),高密度和超高分子量聚乙烯(HDPE-UHMW),中密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),(VLDPE)和(ULDPE)。
聚烯烃,即上一段示例性的单烯烃的聚合物,优选聚乙烯和聚丙烯,其可以通过不同的方法,特别是下面的方法来制备:
a)自由基聚合(通常在高压和高温下)。
b)使用催化剂的催化聚合,催化剂通常包括一种或者大于一种的元素周期表的IVb、Vb、VIb或者VIII族金属。这些金属通常具有一个或者大于一个的配位体,典型的是氧化物、卤化物、醇化物、酯、醚、胺、烷基、链烯基和/或芳基,其可以是π-或者σ-配位的。这些金属配合物可以是游离态的或者固定在基质上,典型的是在活化的氯化镁、氯化钛(lll)、氧化铝或者二氧化硅上。这些催化剂在聚合基质中可以是可溶的或者不溶的。催化剂可以以其自身用于聚合中或者可以使用另外的活化剂,典型的是烷基金属,金属氢化物,金属烷基卤,金属烷基化氧或者金属烷基噁烷(alkyloxane),所述的金属是元素周期表的Ia、IIa和/或IIIa族的元素。活化剂可以用另外的酯、醚、胺或者甲硅烷基醚类进行方便改性。这些催化剂体系通常被称为Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(DuPont),金属茂或者单中心催化剂(SSC)。
2.在1)中提及的聚合物混合物,例如聚丙烯和聚异丁烯的混合物,聚丙烯和聚乙烯的混合物(例如PP/HDPE,PP/LDPE)和不同类型的聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃彼此或者和其他乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)及其和低密度聚乙烯(LDPE)的混合物,丙烯/丁-1-烯共聚物,丙烯/异丁烯共聚物,乙烯/丁-1-烯共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,乙烯/乙烯基环己烷共聚物,乙烯/环烯烃共聚物(例如乙烯/降冰片烯诸如COC),乙烯/1-烯烃共聚物,这里所述的1-烯烃是原位产生的;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烯共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯基酯共聚物或者乙烯/丙烯酸共聚物和它们的盐(离聚物)以及乙烯与丙烯和二烯例如己二烯、二环戊二烯或者亚乙基-降冰片烯的三元共聚物;和这样的共聚物彼此的混合物以及这样的共聚物和上面的1)中提到的聚合物的混合物,例如聚丙烯/乙烯丙烯共聚物,LDPE/乙烯-乙酸乙烯基酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或者无规聚亚烷基/一氧化碳共聚物以及它们和其他聚合物例如聚酰胺的混合物。
4.烃树脂(例如C5-C9),包括其的氢化改性物(例如增粘剂),以及聚亚烷基和淀粉的混合物。
1.)-4.)的均聚物和共聚物可以具有任何的立体结构,包括间规立构的,全同立构的,半全同立构的或者无规立构的;这里无规立构的聚合物是优选的。还包括立构嵌段的聚合物。
5.聚苯乙烯,聚(对甲基苯乙烯),聚(α-甲基苯乙烯)。
6.衍生自乙烯基芳族单体的芳族均聚物和共聚物,所述的乙烯基芳族单体包括苯乙烯,α-甲基苯乙烯,全部的乙烯基甲苯的异构体,特别是对乙烯基甲苯,全部的乙基苯乙烯的异构体,丙基苯乙烯,乙烯基联苯,乙烯基萘和乙烯基蒽以及它们的混合物。均聚物和共聚物可以具有任何的立体结构,包括间规立构的,全同立构的,半全同立构的或者无规立构的;这里无规立构的聚合物是优选的。还包括立构嵌段的聚合物。
6a.包括前述的乙烯基芳族单体和共聚单体的共聚物,共聚单体选自乙烯,丙烯,二烯烃,腈类,酸类,马来酸酐类,马来酰亚胺类,乙酸乙烯基酯和氯乙烯或者丙烯酸衍生物以及它们的混合物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/乙烯(在三元共聚物中),苯乙烯/甲基丙烯酸烷基酯,苯乙烯/丁二烯/丙烯酸烷基酯,苯乙烯/丁二烯/甲基丙烯酸烷基酯,苯乙烯/马来酸酐,苯乙烯/丙烯腈/丙烯酸甲基酯;高冲击强度的苯乙烯共聚物和另一种聚合物的混合物,例如聚丙烯酸酯,二烯烃聚合物或者乙烯/丙烯/二烯烃三元共聚物;和苯乙烯的嵌段共聚物例如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或者苯乙烯/乙烯/丙烯/苯乙烯。
6b.衍生自在6.)中提到的聚合物的氢化的氢化芳族聚合物,特别包括通过氢化无规立构的聚苯乙烯制备的聚环己基乙烯(PCHE),其经常被称为聚乙烯基环己烷(PVCH)。
6c.衍生自在6a.)中提到的聚合物的氢化的氢化芳族聚合物。
均聚物和共聚物可以具有任何的立体结构,包括间规立构的,全同立构的,半全同立构的或者无规立构的;这里无规立构的聚合物是优选的。还包括立构嵌段的聚合物。
7.乙烯基芳族单体例如苯乙烯或者α-甲基苯乙烯的接枝共聚物,例如苯乙烯在聚丁二烯上的接枝,苯乙烯在聚丁二烯-苯乙烯或者聚丁二烯-丙烯腈共聚物上的接枝;苯乙烯和丙烯腈(或甲基丙烯腈)在聚丁二烯上的接枝;苯乙烯,丙烯腈和甲基丙烯酸甲基酯在聚丁二烯上的接枝;苯乙烯和马来酸酐在聚丁二烯上的接枝;苯乙烯,丙烯腈和马来酸酐或者马来酰亚胺在聚丁二烯上的接枝;苯乙烯和马来酰亚胺在聚丁二烯上的接枝;苯乙烯和丙烯酸烷基酯或者甲基丙烯酸烷基酯在聚丁二烯上的接枝;苯乙烯和丙烯腈在乙烯/丙烯/二烯烃三元共聚物上的接枝;苯乙烯和丙烯腈在聚丙烯酸烷基酯或者聚甲基丙烯酸烷基酯上的接枝,苯乙烯和丙烯腈在丙烯酸酯/丁二烯共聚物上的接枝,以及它们和6)中所列的共聚物的混合物,例如称为ABS,MBS,ASA或者AES聚合物的共聚物混合物。
8.含卤素的聚合物例如聚氯丁二烯,氯化橡胶,氯化和溴化异丁烯-异戊二烯的共聚物(卤代丁基橡胶),氯化或者磺氯化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均聚物和共聚物,特别是含卤素的乙烯基化合物的聚合物,例如聚氯乙烯,聚二氯乙烯,聚氟乙烯,聚二氟乙烯,以及它们的共聚物例如氯乙烯/二氯乙烯,氯乙烯/乙酸乙烯基酯或者二氯乙烯/乙酸乙烯基酯共聚物。
9.衍生自α,β-不饱和酸以及它们的衍生物的聚合物例如聚丙烯酸酯和聚甲基丙烯酸酯;聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈,用丙烯酸丁酯进行冲击改性者。
10.在9)中提到的单体彼此或者和其他不饱和单体的共聚物,例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或者丙烯腈/乙烯基卤共聚物或者丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和的醇和胺或者其的酰基衍生物或者缩醛的聚合物,例如聚乙烯醇,聚乙酸乙烯酯,聚硬脂酸乙烯酯,聚安息香酸乙烯酯,聚马来酸乙烯酯,聚乙烯醇缩丁醛,聚邻苯二甲酸烯丙基酯或者聚烯丙基蜜胺;以及它们和上面1)中提到的烯烃的共聚物。
12.环醚的均聚物和共聚物例如聚亚烷基二醇,聚环氧乙烷,聚环氧丙烷或者它们和二缩水甘油醚的共聚物。
13.聚缩醛例如聚甲醛和那些包含环氧乙烷作为共聚单体的聚甲醛;用热塑性聚氨酯、丙烯酸酯或者MBS改性的聚缩醛。
14.聚苯醚和聚亚苯硫醚,和聚苯醚和苯乙烯聚合物或者聚酰胺的混合物。
15.一方面衍生自羟基封端的聚醚、聚酯或者聚丁二烯和另一方面衍生自脂肪族或者芳族聚异氰酸酯、以及衍生自它们的前体的聚氨酯。
16.衍生自二胺和二羧酸和/或衍生自氨基羧酸或者相应的内酰胺的聚酰胺和共聚酰胺,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,由间二甲苯二胺和己二酸制备的芳族聚酰胺;由六亚甲基二胺和间苯二酸或/和对苯二酸制备的聚酰胺,并具有或者不具有作为改性剂的弹性体,例如聚对苯二甲酰2,4,4-三甲基六亚甲基二胺或者聚间苯二甲酰间苯二胺;以及还有前述的聚酰胺和聚烯烃,烯烃共聚物,离聚物或者化学键合的或者接枝的弹性体的嵌段共聚物;或者和聚醚例如和聚乙二醇,聚丙二醇或者聚四亚甲基二醇的嵌段共聚物;以及用EPDM或者ABS改性的聚酰胺或者共聚酰胺;和在加工过程中缩合(condensed)的聚酰胺(反应注射成型(RIM)聚酰胺体系)。
17.聚脲,聚酰亚胺,聚酰胺-酰亚胺,聚醚酰亚胺,聚酯酰亚胺,聚乙内酰脲和聚苯并咪唑。
18.衍生自二羧酸和二醇和/或衍生自羟基羧酸或者相应的内酯的聚酯,例如聚对苯二酸乙二醇酯,聚对苯二酸丁二醇酯,聚对苯二酸1,4-二羟甲基环己烷酯,聚萘二甲酸亚烷基酯(PAN)和聚羟基安息香酸酯,以及衍生自羟基封端的聚醚的嵌段的共聚醚酯;还有用聚碳酸酯或者MBS改性的聚酯。
19.聚碳酸酯和聚酯碳酸盐。
20.聚砜,聚醚砜和聚醚酮。
21.一方面衍生自醛,另一方面衍生自酚、脲和蜜胺的交联聚合物,例如酚/甲醛树脂,脲/甲醛树脂和蜜胺/甲醛树脂。
22.干性和非干性醇酸树脂。
23.衍生自饱和和不饱和的二羧酸和多羟基醇以及作为交联剂的乙烯基化合物的共聚酯的不饱和聚酯树脂,还有其的低可燃性的含卤改性物。
24.衍生自取代的丙烯酸酯的可交联的丙烯酸树脂,例如环氧丙烯酸酯,氨基甲酸酯丙烯酸酯或者聚酯丙烯酸酯。
25.和蜜胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、聚异氰酸酯或者环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
26.衍生自脂肪族,脂环族,杂环或者芳族缩水甘油基化合物的交联的环氧树脂,例如双酚A和双酚F的二缩水甘油基醚产物,其是和常规的固化剂例如酸酐或者胺交联的,具有或者不具有促进剂。
27.天然聚合物例如纤维素,橡胶,明胶和它们的化学改性的相应的衍生物,例如乙酸纤维素,丙酸纤维素和丁酸纤维素,或者纤维素醚例如甲基纤维素;以及松香和它们的衍生物。
28.前述的聚合物的共混物和合金(高聚物共混体),例如PP/EPDM,聚酰胺/EPDM或者ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PC/聚酯,PBTP/ABS,PC/ASA,PC/PBT,PVC/CPE,PVC/丙烯酸酯,POM/热塑性PUR,PC/热塑性PUR,POM/丙烯酸酯,POM/MBS,PPO/HIPS,PPO/PA6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或者PBT/PET/PC。
29.天然存在和合成的有机材料,其是纯的单体化合物或者这样的化合物的混合物,例如矿物油,动植物脂肪、油和蜡,或者基于合成的酯(例如邻苯二甲酸酯,己二酸酯,磷酸酯或者偏苯三酸酯)的油、脂肪和蜡,还有合成的酯和矿物油以任何重量比例的混合物,这些典型的用作纺纱组合物(spinning composition),以及这样的材料的水乳液。
30.天然或者合成的橡胶的水乳液,例如天然乳胶或者羧化苯乙烯/丁二烯共聚物的胶乳。
特别优选的技术材料是合成的聚合物,最优选热塑性聚合物和用于油漆和涂料的成膜基料。特别优选的技术材料同样是橡胶和硫化胶。
在另外一种实施方案中,技术材料是涂料,油墨或者黏合剂。特定的基料的例子是:
用在涂料中的树脂典型地是交联的聚合物,例如,一方面衍生自醛,另一方面衍生自酚、脲和蜜胺的交联聚合物,例如酚/甲醛树脂,脲/甲醛和蜜胺/甲醛树脂。
再者有用的是不饱和的聚酯树脂,衍生自饱和和不饱和的二羧酸和多羟基醇以及作为交联剂的乙烯基化合物的共聚酯,还有其的低可燃性的含卤改性物。
优选使用的是可交联的丙烯酸树脂,其衍生自取代的丙烯酸酯,例如环氧丙烯酸酯,氨基甲酸酯丙烯酸酯或者聚酯丙烯酸酯。
还可能的是和蜜胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、聚异氰酸酯或者环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
衍生自脂肪族,脂环族,杂环或者芳族缩水甘油基化合物的交联的环氧树脂,例如双酚A和双酚F的二缩水甘油基醚产物,其是和常规的固化剂例如酸酐或者胺交联的,具有或者不具有促进剂。
涂覆材料还可以是可辐射固化组合物,含有烯属不饱和单体或者低聚物和聚不饱和的脂族低聚物。
醇酸树脂漆是常规的烘干漆,其特别用于涂覆汽车(汽车挥发性面漆),例如基于醇酸/蜜胺树脂和醇酸/丙烯酸/蜜胺树脂的漆(参见H.Wagner和H.F.Sarx,“Lack-kunstharze”(1977),第99-123页)。其他的交联剂包括甘脲(glycouril)树脂,封闭型异氰酸酯或者环氧树脂。
还要注意的是本发明的化合物适于用在无酸催化的热固性树脂中例如环氧树脂,环氧-聚酯树脂,乙烯基树脂,醇酸树脂,丙烯酸树脂和聚酯树脂,任选地用硅,异氰酸酯或者异氰脲酸酯进行改性。环氧和环氧-聚酯树脂是用常规的交联剂例如酸,酸酐,胺等进行交联的。相应的,环氧化物可以用作不同的丙烯酸或者聚酯树脂体系(该体系其已经通过在主链结构上存在的反应性基团进行改性)的交联剂。
当期望得到水可溶的、水混溶的或者水可分散涂料时,则形成存在于树脂中的酸基团的铵盐。粉末涂料组合物可以通过将甲基丙烯酸缩水甘油基酯和所选择的醇组份反应来制备。
水性涂覆材料可以基于水可溶的,水可稀释的聚合物或者聚合物分散体。高极性有机成膜剂,例如聚乙烯醇,聚丙烯酰胺,聚乙二醇,纤维素衍生物,丙烯酸酯和具有非常高的酸值的聚酯是水可溶的聚合物的例子。水可稀释的成膜剂由具有引入其侧链的能够成盐的酸或者碱基团的相对短链聚合物组成。它们用合适的碱或者酸进行中和,所述的合适的碱或者酸在成膜过程中蒸发,导致不溶的聚合物。其例子是短油度羧酸醇酸树脂和中油度羧酸醇酸树脂,水可稀释的蜜胺树脂,可乳化的环氧树脂或者有机硅基乳液。几种类型聚合物被用作水可稀释成膜剂。这些类型中最重要的是马来酸二丁酯和乙酸乙烯基酯的共聚物,叔羧酸的乙烯基酯,丙烯酸酯酸或者乙烯和氯乙烯、丙酸乙烯酯的三元共聚物,由聚丙烯酸酯和聚甲基丙烯酸酯组成的纯丙烯酸酯,丙烯酸酯和苯乙烯的共聚物和苯乙烯-丁二烯共聚物。另外的水性基料体系是聚氨酯的分散体或者乳液,包括物理干燥体系和带有另外的可交联基团的体系。涂覆材料还可以是可光聚合化合物的水性辐射固化配方。
黏合剂优选选自聚氨酯,聚丙烯酸类,环氧类,酚类,聚酰亚胺类,聚乙烯醇缩丁醛,聚氰基丙烯酸酯,聚丙烯酸酯,乙烯/丙烯酸共聚物和它们的盐(离聚物),硅聚合物,聚(乙烯/乙酸乙烯基酯),无规立构聚丙烯,苯乙烯-二烯烃共聚物,聚酰胺,羟基封端的聚丁二烯,聚氯丁二烯,聚乙酸乙烯基酯,羧化苯乙烯/丁二烯共聚物和聚乙烯醇。
天然或者合成的橡胶的水性乳液是例如天然乳胶或者羧化苯乙烯/丁二烯共聚物的胶乳。
式I的光潜化合物优选以0.001-10%,优选0.01-10%,典型的为0.1-5%浓度加入到待处理的技术材料中,基于技术材料的重量。
除了包含式I的光潜化合物,本发明的组合物可以包含另外的添加剂,典型的为下面的添加剂:
1.抗氧化剂
1.1.烷基化一元酚,例如2,6-二叔丁基-4-甲基酚,2-叔丁基-4,6-二甲基酚,2,6-二叔丁基-4-乙基酚,2,6-二叔丁基-4-正丁基酚,2,6-二叔丁基-4-异丁基酚,2,6-二环戊基-4-甲基酚,2-(α-甲基环己基)-4,6-二甲基酚,2,6-二(十八烷基)-4-甲基酚,2,4,6-三环己基酚,2,6-二叔丁基-4-甲氧基甲基酚,侧链上是线性或者支化的壬基酚,例如,2,6-二壬基-4-甲基酚,2,4-二甲基-6-(1′-甲基十一烷-1′-基)酚,2,4-二甲基-6-(1′-甲基十七烷-1′-基)酚,2,4-二甲基-6-(1′-甲基十三烷-1′-基)酚和它们的混合物。
1.2.烷硫基甲基酚,例如2,4-二辛基硫甲基-6-叔丁基酚,2,4-二辛基硫甲基-6-甲基酚,2,4-二辛基硫甲基-6-乙基酚,2,6-二-十二烷硫基甲基-4-壬基酚。
1.3.对苯二酚和烷基化对苯二酚,例如2,6-二叔丁基-4-甲氧基-酚,2,5-二叔丁基对苯二酚,2,5-二叔戊基对苯二酚,2,6-二苯基-4-十八烷氧基酚,2,6-二叔丁基对苯二酚,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,硬脂酸3,5-二叔丁基-4-羟基苯基酯,己二酸双(3,5-二叔丁基-4-羟基苯基)酯。
1.4.生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和它们的混合物(维生素E)。
1.5.羟基化硫二苯基醚,例如2,2′-硫双(6-叔丁基-4-甲基酚),2,2′-硫双(4-辛基酚),4,4′-硫双(6-叔丁基-3-甲基酚),4,4′-硫双(6-叔丁基-2-甲基酚),4,4′-硫双(3,6-二仲戊基酚),4,4′-双(2,6-二甲基-4-羟基苯基)二硫。
1.6.亚烷基双酚,例如2,2′-亚甲基双(6-叔丁基-4-甲基酚),2,2′-亚甲基双(6-叔丁基-4-乙基酚),2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)-酚],2,2′-亚甲基双(4-甲基-6-环己基酚),2,2′-亚甲基双(6-壬基-4-甲基酚),2,2′-亚甲基双(4,6-二叔丁基酚),2,2′-亚乙基双(4,6-二叔丁基-酚),2,2′-亚乙基双(6-叔丁基-4-异丁基酚),2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基酚],2,2′-亚甲基双[6-(α,α-二甲基苄基)-4-壬基酚],4,4′-亚甲基双(2,6-二叔丁基酚),4,4′-亚甲基双(6-叔丁基-2-甲基酚),1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-双(5-叔丁基-4-羟基-2-甲基-苯基)-3-正十二烷基巯基丁烷,乙二醇双[3,3-双(3′-叔丁基-4′-羟基苯基)丁酸酯],双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯,双[2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二酸酯,1,1-双-(3,5-二甲基-2-羟基苯基)丁烷,2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双(5-叔丁基-4-羟基2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-,N-和S-苄基化合物,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯,十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯,三(3,5-二叔丁基-4-羟基苄基)胺,双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫对苯二酸酯,双(3,5-二叔丁基-4-羟基-苄基)硫,异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8.羟基苄基化丙二酸酯,例如二(十八烷基)-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯,二(十八烷基)-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯,二-十二烷基巯基乙基-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯,双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟基苄基化合物,例如1,3,5-三(3,5-二叔丁基-4-羟基-苄基)-2,4,6-三甲基苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)酚。
1.10.三嗪化合物,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基-苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三-嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三-(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯,2,4,6-三-(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基-苯基丙酰)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯,二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯,二(十八烷基)3,5-二叔丁基-4-羟基苄基膦酸酯,二(十八烷基)-5-叔丁基-4-羟基-3-甲基苄基膦酸酯,3,5-二叔丁基-4-羟基苄基膦酸的单乙基酯的钙盐。
1.12.酰基氨基酚,例如4-羟基月桂酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛基酯。
1.13.β-(3,5-二叔丁基-4-羟基苯基)丙酸和单-或者多羟基醇的酯,所述的醇是例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三乙二醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟基乙基)乙二酰二胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸和单-或者多羟基醇的 酯,所述的醇是例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三乙二醇,季戊四醇,三(羟基乙基)异氰脲酸酯,N,N′-双(羟基乙基)乙二酰二胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷;3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]-十一烷。
1.15.β-(3,5-二环己基-4-羟苯基)丙酸和单-或者多羟基醇的酯,所述的醇是例如甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三乙二醇,季戊四醇,三(羟基乙基)异氰脲酸酯,N,N′-双(羟基乙基)乙二酰二胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.16.3,5-二叔丁基-4-羟基苯基乙酸和单-或者多羟基醇的酯,所述的醇是例如甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫二甘醇,二甘醇,三乙二醇,季戊四醇,三(羟基乙基)异氰脲酸酯,N,N′-双(羟基乙基)乙二酰二胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰)六亚甲基二酰胺,N,N′-双(3,5-二叔丁基-4-羟基-苯基丙酰)三亚甲基二酰胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰)酰肼,N,N′-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]乙二酰二胺(NaugardXL-1,由Uniroyal提供)。
1.18.抗坏血酸(维生素C)。
1.19.胺抗氧化剂,例如N,N′-二异丙基-对亚苯基二胺,N,N′-二-仲丁基-对亚苯基二胺,N,N′-双(1,4-二甲基戊基)-对亚苯基二胺,N,N′-双(1-乙基-3-甲基戊基)-对亚苯基二胺,N,N′-双(1-甲基庚基)-对亚苯基二胺,N,N′-二环己基-对亚苯基二胺,N,N′-二苯基-对亚苯基二胺,N,N′-双(2-萘基)-对亚苯基二胺,N-异丙基-N′-苯基-对亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-对亚苯基二胺,N-(1-甲基庚基)-N′-苯基-对亚苯基二胺,N-环己基-N′-苯基-对亚苯基二胺,4-(p-甲苯氨磺酰基)二苯基胺,N,N′-二甲基-N,N′-二-仲丁基-对亚苯基二胺,二苯基胺,N-烯丙基二苯基胺,4-异丙氧基二苯基胺,N-苯基-1-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化二苯基胺,例如p,p′-二叔辛基二苯基胺,4-正丁基-氨基酚,4-丁酰基氨基酚,4-壬酰基氨基酚,4-十二碳酰氨基酚,4-十八碳酰氨基酚,双(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲基氨基-甲基酚,2,4′-二氨基二苯基甲烷,4,4′-二氨基二苯基甲烷,N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷,1,2-双[(2-甲基苯基)氨基]乙烷,1,2-双(苯基氨基)丙烷,(邻甲苯基)双胍,双[4-(1′,3′-二甲基丁基)苯基]胺,叔辛基化N-苯基-1-萘基胺,单-和二烷基化叔丁基/叔辛基二苯基胺的混合物,单-和二烷基化壬基二苯基胺的混合物,单-和二烷基化十二烷基二苯基胺的混合物,单-和二烷基化异丙基/异己基二苯基胺的混合物,单-和二烷基化叔丁基二苯基胺的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单-和二烷基化叔丁基/叔辛基吩噻嗪的混合物,单-和二烷基化叔辛基-吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯。
2.UV吸收剂和光稳定剂。
2.1.2-(2′-羟基苯基)苯并三唑,例如2-(2′-羟基-5′-甲基苯基)-苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)苯并三唑,2-(5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑,2-(3′-仲丁基-5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-4′-辛氧基苯基)苯并三唑,2-(3′,5′-二叔戊基-2′-羟基苯基)苯并三唑,2-(3′,5′-双-(α,α-二甲基苄基)-2′-羟基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基-乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基-苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2′-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基酚];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基]-2H-苯并三唑和聚乙二醇300的酯交换产物;[R-CH2CH2-COO-CH2CH2-]2-,这里R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基,2-[2′-羟基-3′-(α,α-二甲基苄基)-5′-(1,1,3,3-四甲基丁基)-苯基]-苯并三唑;2-[2′-羟基-3′-(1,1,3,3-四甲基丁基)-5′-(α,α-二甲基苄基)-苯基]苯并三唑。
2.2.2-羟基二苯甲酮类,例如4-羟基,4-甲氧基,4-辛氧基,4-癸氧基,4-十二烷氧基,4-苄氧基,4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3.取代的和未被取代的苯甲酸的酯,例如水杨酸4-叔丁基-苯基酯,水杨酸苯基酯,水杨酸辛基苯基酯,二苯甲酰间苯二酚,双(4-叔丁基苯甲酰)间苯二酚,苯甲酰间苯二酚,3,5-二叔丁基-4-羟基安息香酸2,4-二叔丁基苯基酯,3,5-二叔丁基-4-羟基安息香酸十六烷基酯,3,5-二叔丁基-4-羟基安息香酸十八烷基酯,3,5-二叔丁基-4-羟基安息香酸2-甲基-4,6-二叔丁基苯基酯。
2.4.丙烯酸酯,例如α-氰基-β,β-二苯基丙烯酸乙基酯,α-氰基-β,β-二苯基丙烯酸异辛基酯,α-甲氧甲酰基肉桂酸甲基酯,α-氰基-β-甲基-对甲氧基肉桂酸甲基酯,α-氰基-β-甲基-对甲氧基-肉桂酸丁基酯,α-甲氧甲酰基-对甲氧基肉桂酸甲基酯,N-(β-甲氧甲酰基-β-氰基乙烯基)-2-甲基二氢吲哚,四(α-氰基-β,β-二苯基丙烯酸新戊基酯。
2.5.镍化合物,例如2,2′-硫-双[4-(1,1,3,3-四甲基-丁基)酚]的镍络合物,例如1∶1或者1∶2络合物,具有或者不具有另外的配位体例如正丁基胺,三乙醇胺或者N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯例如甲基或乙基酯的镍盐,酮肟例如2-羟基-4-甲基苯基十一烷基酮肟的镍络合物,1-苯基-4-月桂酰-5-羟基吡唑的镍络合物,具有或者不具有另外的配位体。
2.6.空间位阻胺,例如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯,双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯,双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯,双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯,双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯,1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或者环状缩合物,三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯,四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯,1,1′-(1,2-乙烷二基)-双(3,3,5,5-四甲基哌嗪酮),4-苯甲酰-2,2,6,6-四甲基哌啶,4-十八烷酰氧-2,2,6,6-四甲基-哌啶,双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯,双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基-二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或者环状缩合物,2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)-乙烷的缩合物,2-氯-4,6-二-(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-双(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS Reg.No.[136504-96-6]);1,6-己烷二胺和2,4,6-三氯-1,3,5-三嗪以及N,N-二丁基胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS Reg.No.[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺-[4,5]癸烷,7,7,9,9-四甲基-4-环十一烷基-1-氧杂-3,5-二氮杂-4-氧代-螺-[4,5]癸烷和表氯醇的反应产物,1,1-双(1,2,2,6,6-五甲基-4-哌啶氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N′-双-甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺,4-甲氧基亚甲基丙二酸和1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐-α-烯烃共聚物和2,2,6,6-四甲基-4-氨基哌啶或者1,2,2,6,6-五甲基-4-氨基哌啶的反应产物,2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟基乙基)氨基-1,3,5-三嗪,1-(2-羟基-2-甲基丙氧基)-4-十八酰氧-2,2,6,6-四甲基哌啶,5-(2-乙基-己酰)氧甲基-3,3,5-三甲基-2-吗啉,Sanduvor(Clariant;CAS Reg.No.106917-31-1),5-(2-乙基己酰)氧甲基-3,3,5-三甲基-2-吗啉,2,4-双[(1-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪和N,N′-双(3-氨基丙基)乙二胺)的反应产物,1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪,1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.7.乙二酰二胺,例如4,4′-二辛氧基草酰替苯胺,2,2′-二乙氧基草酰替苯胺,2,2′-二辛氧基-5,5′-二叔丁基草酰替苯胺,2,2′-二(十二烷氧基)-5,5′-二叔丁基草酰替苯胺,2-乙氧基-2′-乙基草酰替苯胺,N,N′-双(3-二甲基氨基丙基)乙二酰二胺,2-乙氧基-5-叔丁基-2′-乙基草酰替苯胺和其与2-乙氧基-2′-乙基-5,4′-二叔丁基草酰替苯胺的混合物,邻和对甲氧基-二取代的草酰替苯胺的混合物和邻和对乙氧基-二取代的草酰替苯胺的混合物。
2.8.2-(2-羟基苯基)-1,3,5-三嗪,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-双(2,4-二甲基-苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2-{2-羟基-4-[3-(2-乙基己基-1-氧)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(4-[2-乙基己氧基]-2-羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪。
3.金属减活化剂,例如N,N′-二苯基乙二酰二胺,N-水杨醛-N′-水杨酰肼,N,N′-双(水杨酰)肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰)肼,3-水杨酰氨基-1,2,4-三唑,双(亚苄基)乙二酰二酰肼,草酰替苯胺,间苯二甲酰二酰肼,癸二酰二苯基酰肼,N,N′-二乙酰基己二酰二酰肼,N,N′-双(水杨酰)乙二酰二酰肼,N,N′-双(水杨酰)硫代丙酰二酰肼。
4.亚磷酸酯和亚膦酸酯,例如三苯基亚磷酸酯,二苯基烷基亚磷酸酯,苯基二烷基亚磷酸酯,三(壬基苯基)亚磷酸酯,三月桂基亚磷酸酯,三(十八烷基)亚磷酸酯,二(十八烷基)季戊四醇二亚磷酸酯,三(2,4-二叔丁基苯基)亚磷酸酯,二异癸基季戊四醇二亚磷酸酯,双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,双(2,4-二-枯基苯基)季戊四醇二亚磷酸酯,双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯,二异癸氧基季戊四醇二亚磷酸酯,双(2,4-二叔丁基-6-甲基苯基)-季戊四醇二亚磷酸酯,双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯,三(十八烷基)山梨糖醇三亚磷酸酯,四(2,4-二叔丁基苯基)4,4′-二亚苯基二亚膦酸酯,6-异辛氧基-2,4,8,10-四-叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷杂环辛烯,双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯,双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯,6-氟-2,4,8,10-四-叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂磷杂环辛烯,2,2′,2″-次氮基-[三乙基三(3,3′,5,5′-四-叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯],2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯,5-丁基-5-乙基-2-(2,4,6-三-叔丁基苯氧基)-1,3,2-二氧磷杂环丙烷。
5.羟基胺,例如N,N-二苄基羟基胺,N,N-二乙基羟基胺,N,N-二辛基羟基胺,N,N-二月桂基羟基胺,N,N-二(十四烷基)羟基胺,N,N-二(十六烷基)羟基胺,N,N-二(十八烷基)羟基胺,N-十六烷基-N-十八烷基羟基胺,N-十七烷基-N-十八烷基羟基胺,衍生自氢化牛脂胺的N,N-二烷基羟基胺。
6.硝酮,例如,N-苄基-α-苯基硝酮,N-乙基-α-甲基硝酮,N-辛基-α-庚基硝酮,N-月桂基-α-十一烷基硝酮,N-十四烷基-α-十三烷基硝酮,N-十六烷基-α-十五烷基硝酮,N-十八烷基-α-十七烷基硝酮,N-十六烷基-α-十七烷基硝酮,N-十八烷基-α-十五烷基硝酮,N-十七烷基-α-十七烷基硝酮,N-十八烷基-α-十六烷基硝酮,衍生自衍生自氢化牛脂胺的N,N-二烷基羟基胺的硝酮。
7.硫增效剂,例如硫二丙酸二月桂基酯,硫二丙酸dimistryl酯,硫二丙酸二(十八烷基)酯或二(十八烷基)二硫。
8.过氧化物猝灭剂,例如β-硫代二丙酸的酯例如月桂基,十八烷基,十四烷基或者十三烷基酯,巯基苯并咪唑或者2-巯基-苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二(十八烷基)二硫,季戊四醇四(β-十二烷基巯基)丙酸酯。
9.聚酰胺稳定剂,例如和碘化物和/或磷化合物结合的铜盐和二价锰的盐。
10.碱性共稳定剂,例如蜜胺,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰脲酸酯,脲衍生物,肼衍生物,胺,聚酰胺,聚氨酯,高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙,硬脂酸锌,山嵛酸镁,硬脂酸镁,蓖麻油酸钠和棕榈酸钾,邻苯二酚锑或者邻苯二酚锌。
11.成核剂,例如无机物,例如滑石,金属氧化物,例如二氧化钛或者氧化镁,优选碱土金属的磷酸盐、碳酸盐或者硫酸盐;有机化合物,例如单-或者多元羧酸和其盐,例如4-叔丁基苯甲酸,己二酸,二苯基乙酸,琥珀酸钠或者安息香酸钠;聚合物化合物,例如离子共聚物(离聚物)。特别优选的是1,3:2,4-双(3′,4′-二甲基亚苄基)山梨糖醇,1,3:2,4-二(对甲基-二亚苄基)山梨糖醇,和1,3:2,4-二(亚苄基)山梨糖醇。
12.填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃珠,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,炭黑,石墨,木粉和面粉或者其他天然产物的纤维,合成纤维。
13.取决于应用的类型的颜料和着色剂,有机以及无机颜料被用作着色剂。颜料的例子是无机颜料,例如诸如二氧化钛如金红石型和锐钛矿型,氧化锌例如锌白,硫化锌,硫酸钡,硅酸铝,硅酸钙,炭黑,氧化铁例如氧化铁黄,氧化铁红,氧化铁黑,铁蓝,亚铬酸铜黑,氧化铬绿,铅铬绿、紫(例如锰紫,磷酸钴,CoLiPO4),铬黄,铬绿,铬酸铅,钼酸铅,钛酸镉以及珠光和金属颜料,镍钛黄,群青蓝,钴蓝,钒酸铋,镉黄或者镉红;以及有机颜料,例如单偶氮颜料,重氮颜料,重氮缩合颜料,以及其的金属络合物,多环颜料,例如苝系颜料,蒽醌颜料,硫靛颜料,或者三苯基甲烷颜料,以及二酮基吡咯并吡咯颜料,异吲哚啉酮颜料,例如四氯异吲哚啉酮颜料,异二氢吲哚颜料,二噁嗪颜料,苯并咪唑酮颜料和喹诺酞酮颜料,喹吖啶酮颜料,二噁嗪紫,瓮颜料和酞菁颜料。合适的颜料的例子包括用于黑色涂料的炭黑,用于白色涂料的二氧化钛,用于黄色涂料的联苯胺黄或者重氮基颜料,用于蓝色涂料的酞菁蓝和其他酞菁,用于红色涂料的蒽醌红,萘酚红,单偶氮基颜料,喹吖啶酮颜料,蒽醌和苝系,用于绿色涂料的酞菁绿和亚硝基颜料,用于橙色涂料单偶氮和重氮颜料,喹吖啶酮颜料,蒽醌和苝系的,和用于紫色涂料的喹吖啶酮紫,碱性染料性颜料和咔唑二噁嗪基颜料。本领域技术人员公知如果需要更多的着色的涂料例如水绿色,褐色,灰色,粉红色等等,则可以配制和结合合适的另外的颜料。有机颜料另外的例子可以在专论:W.Herbst,K.Hunger“Industrielle Organische Pigmente”2.sup.nd Edition,1995,VCHVerlagsgesellschaft,ISBN:3-527-28744-2中找到。
14.其他添加剂,例如增塑剂,润滑剂,乳化剂,颜料,流变添加剂,催化剂,流动控制剂,荧光增白剂,防火剂,抗静电剂和发泡剂。
15.苯并呋喃酮和吲哚啉酮,例如在U.S.4325863;U.S.4338244;U.S.5175312;U.S.5216052;U.S.5252643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839,EP-A-0591102;EP-A-1291384中公开的那些,或者3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基苯并呋喃-2-酮,5,7-二叔丁基-3-[4-(2-十八烷酰氧-乙氧基)苯基]苯并呋喃-2-酮,3,3′-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮],5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮,3-(4-乙酰氧基-3,5-二-甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮,3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮,3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮,3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮,3-(2-乙酰基-5-异辛基苯基)-5-异辛基-苯并呋喃-2-酮。
16.光引发剂,光催化剂和光敏剂,例如α-羟基酮(AHK),α-烷氧基酮(苯偶酰二甲基缩酮DBK)和α-氨基酮(AAK),二苯酮类,单-和双酰氧化膦(BAPO),苯基-乙醛酸酯,异丙基-噻吨酮(ITX),肟-酯,氨基安息香酸酯,潜在酸和潜在碱以及它们的混合物。其他可以用于这种方法的光引发剂已经描述在K.Dietliker,Photoinitiators for FreeRadical,Cationic And Anionic PhotoPolymerization,Volume III in theseries Chemistry And Technology of UV And EB Fomulation for Coating,Inks And Paints,第2版;John Wiley And Sons/SITA TechnologyLimited,纽约/伦敦1998。
如果填料和着色剂是0.01-60%,则所述的另外的添加剂典型的以0.01-10%的浓度使用,基于待处理的材料的总重量。
式I的新颖的光潜化合物特别可以和酚抗氧化剂,光稳定剂和/或加工稳定剂一起使用。
如果需要,将组份(b)和另外的添加剂混入到所述的合成的聚合物中是以已知的方法来进行,例如在配料,挤出,混合挤出之前或者之中混入其中,否则如果具有适当的溶剂随后缓慢的蒸发,则通过施用溶解的或者分散的化合物到所述的合成的聚合物。
本发明还涉及到母料或者浓缩形式的组合物,其包含5-90%的组份(a)和5-80%组份(b),按重量计。
如果需要,将组份(b)和另外的添加剂还可以在聚合之前或聚合过程中或者在交联之前加入到技术材料中例如通过将该材料直接溶解到技术材料中或者合适的溶剂中。
组份(b),具有或者不具有另外的添加剂,可以以纯的形式或者在蜡,油或者聚合物中的胶囊化的形式加入到所述的合成的聚合物中。
组份(b),具有或者不具有另外的添加剂,还可以喷涂到所述的合成的聚合物上。可以稀释其他添加剂(例如上述常规的添加剂)或者它们的熔融物,目的是它们也可以和这些添加剂一起喷涂到聚合物上。在聚合催化剂钝化期间通过喷涂加入是特别有利的,可以使用例如用于钝化的蒸汽来进行喷涂。
例如,在球状聚合的聚烯烃的情况中,通过喷涂施用组份(b),具有或者不具有另外的添加剂,是有利的。
以这种方式制备的合成的聚合物可以以广泛的多种形式使用,例如作为泡沫,薄膜,纤维,带,模塑组合物,作为型材或者用于涂料特别是粉末涂料的基料,黏合剂,油灰或者特别是作为其长期与抽取介质接触的厚层聚烯烃模制品,例如诸如用于液体或者气体的管道,薄膜,纤维,土工膜,带,型材或者槽。
优选的厚层聚烯烃模制品具有1-50mm,特别是1-30mm,例如2-10mm的层厚。
根据本发明的组合物可以有利的用于制备不同形状的制品。例子是:
1-1)漂浮装置,海洋应用,浮桥,浮标,甲板等船用塑料材(plasticlumber),码头,小船,皮船、桨和湖海摊加固件。
1-2)汽车应用,特别是缓冲器,仪表盘,电池,后面和前面的内衬,防护罩下的模塑零件,顶板架,后备箱衬套,内部衬套,气囊盖,电子成型配件(灯),仪表板格,前灯玻璃,仪表盘,外部衬套,内饰,汽车灯,前灯,停车灯,后灯,停止灯,内外装饰品;门框架;油箱;前侧玻璃窗;后窗玻璃;座位靠背,外窗格,绝缘线,密封挤出型材,覆层,杆套,底盘零件,排气系统,燃料过滤器/填料,燃油泵,燃料槽,车侧身模件,可折叠蓬顶,外置镜,外饰品,紧固件/嵌装件,车外前端总成,玻璃,铰链,锁体系,行李架/车顶架,压制/冲压零件,密封件,防侧冲梁,消音器隔音器和遮阳蓬。
1-3)公路交通装置,特别是设置标志牌,路标柱,汽车附件,警告三角,医用箱,头盔,轮胎。
1-4)用于飞机、火车、机动车(汽车,摩托车)的装置,包括内饰。
1-5)用于空间应用的装置,特别是火箭和卫星,例如重返大气层的屏蔽。
1-6)用于建筑设计,采矿应用,净音体系,街道庇护所和掩体的装置。
11-1)通常的器具,包装和覆盖物和电气/电子装置(个人电脑,电话,便携电话,打印机,电视机,音频和视频装置),花盆,卫星电视锅和面板盘。
II-2)用于其他材料例如钢或者纺织品的护套。
II-3)电子工业装置,特别是插头绝缘,特别是计算机插头,电气和电子零件包装,印刷板,和用于电子数据存储的材料例如芯片,支票保证(check)卡或者信用卡。
II-4)电器,特别是洗衣机,滚光机,炉子(微波炉),洗碗机,混合器和熨斗。
II-5)光罩(例如路灯,灯罩)。
II-6)电线和电缆应用(半导体,绝缘和电缆套)。
II-7)用于电容器,冰箱,加热设备,空调,电子器件胶囊,半导体,咖啡机和真空吸尘器的箔片。
111-1)技术制品例如嵌齿轮(齿轮),滑扣,垫片,螺杆,螺钉,把手和旋钮。
III-2)动叶片,空调和风车叶片,日光装置,游泳池,游泳池盖,池衬垫,池塘衬垫,壁橱,衣橱,分隔墙,条板隔墙,可折叠墙,屋顶,百叶窗(例如辊轴百叶窗),配件,管道连接件,套管和传送带。
III-3)洁具制品,特别是淋浴室,坐便器,盖子和水槽。
III-4)卫生制品,特别是尿布(婴儿,成人失禁),妇女卫生制品,浴帘,刷子,垫子,浴盆,流动厕所,牙刷和便盆。
III-5)用于水,废水和化学品的管道(横向连接的或者不是横向连接的),电线和电缆保护管道,气体,油和和下水道的管道,排水沟槽,下水管和排水体系。
III-6)任何几何形状(窗格)和板壁的型材。
III-7)玻璃替代品,特别是挤出或者混合挤出板,建筑窗玻璃(整体的,双壁或者多壁),航空器,学校,挤出片材,用于建筑窗玻璃、火车、交通工具、卫生制品和温室的窗膜。
111-8)板(墙壁,切隔板),挤出涂料(照相纸,利乐包和管子涂料),筒仓,木材替代品,塑料材,木材复合物,墙壁,表面,家具,装饰片,楼面料(内部和外部使用),地板,沟槽板道和瓷砖。
III-9)上集气管和下集气管。
111-10)水泥-、混凝土-、复合材料应用和盖子,壁板和覆层,扶手,栏杆支柱,厨房机件面板,屋顶,屋面板材,瓷砖和防水油布。
IV-1)板(墙壁和切隔板),盘子,人工草,绿色人造草皮(astroturf),露天大型运动场圆形场地(运动)的人造覆盖物,露天大型运动场圆形场地(运动)的人造地板和磁带。
IV-2)机织织物,连续和定长的纤维(地毯/卫生制品/土工布/单丝;过滤器;擦拭品/窗帘(遮光物)/医学应用),散纤维(应用例如长袍/防护服),网状物,绳子,粗索,细绳,灯芯绒,线,坐椅安全带,织物,内衣,手套;靴子;橡胶靴子,贴身内衣,衣服,游泳衣,运动服,伞(阳伞,天棚伞),降落伞,滑翔降落伞,帆,“气球绸”,野营制品,帐篷,充气床垫,日光浴床,吨袋(bulk bag)和包。
IV-3)隔膜,绝缘,覆盖物和密封,用于屋顶,隧道,堆存处,池塘,堆存处,墙屋顶隔膜,土工膜,游泳池,窗帘(遮光帘)/遮阳板,遮阳篷,遮篷,壁纸,食品包装和包装纸(柔软的和硬的),医学包装(柔软的和硬的),气囊/安全带,扶手和头托,地毯,中心控制台,仪表板,驾驶员座舱,门,车顶盒模块,门框贴脸,船首缆,车内灯,车内后视镜,行李架,后行李箱,坐椅,驾驶杆,方向盘,纺织品和舱室饰板。
V)薄膜(包装,堆存,层压,农业和园艺,温室,覆盖物,隧道,青储),打包带,游泳池,废物袋,壁纸,拉伸膜,酒椰叶纤维,脱盐膜,电池和连接器。
VI-1)食品包装和包装纸(柔软的和硬的),瓶子。
VI-2)储存体系例如盒子(板条箱),行李,箱子,家用盒子,货盘,架子,轨道,螺丝盒,包裹和罐头。
VI-3)筒,注射器,医学应用,用于任何运输的容器,废物篮和废物箱,废物袋,箱子,垃圾箱,箱衬垫,滑轮箱,常规容器,用于水/用过的水/化学/气体/油/汽油/柴油的槽子;槽垫,盒子,板条箱,电池盒,水槽,医学设备例如活塞,眼科应用,诊断设备,和药品泡罩包装。
VII-1)挤出涂料(照相纸,利乐包和管子涂料),任何种类的家用制品(例如器具,热水瓶/衣架),扣紧体系例如插头,电线和电缆夹,拉链,关闭物,锁子和锁扣。
VII-2)支撑装置,休闲制品例如运动和健身设备,体操垫子,滑雪靴,溜冰鞋,雪橇,big foot,运动地面(例如网球场);螺旋盖,瓶盖和瓶塞和罐头。
VII-3)常规家具,泡沫制品(垫子,冲击吸收器),泡沫,海绵,盘套,垫子,花园椅子,露天大型运动场座位,桌子,长沙发椅,玩具,建筑工具(板/轮廓/球),剧场,滑板和游戏运载工具。
VII-4)光和磁数据存储材料。
VII-5)厨房器皿(吃、喝、烹、储)。
VII-6)CD,磁带和录像带的盒子;DVD电子制品,任何种类的办公用品(圆珠笔,印章和印泥,鼠标,架子,轨道),任何体积和内容突然的瓶子(饮料,清洁剂,包括香水的化妆品)和胶带。
VII-7)鞋类(鞋子/鞋底),鞋垫,鞋罩,黏合剂,结构黏合剂,食品盒子(水果,蔬菜,肉,鱼),合成的纸,瓶子标签,长沙发椅,人造关节(人),印刷版(柔性树脂版),印刷线路板和显示技术。
VII-8)填充聚合物的装置(滑石,粉笔,陶土(高岭土),硅灰石,颜料,炭黑,TiO2,云母,纳米复合材料,白云石,硅酸盐,玻璃,石棉)。
因此,本发明另外一种实施方案涉及到含如上所述的组合物的成型制品,特别是薄膜、管、型材、瓶子、槽或者容器。
本发明另外一种实施方案涉及到含如上所述的组合物模塑制品。模塑特别是通过注射、吹塑、压模、滚塑或者搪塑或者挤出进行。
本发明还涉及包含成膜基料和式I化合物的组合物。这样的组合物包含涂料,油漆,油墨和黏合剂。涂料,油漆和油墨可以用作全部种类的基质的涂覆材料,所述基质是例如木头,纺织品,纸张,陶瓷,玻璃,塑料例如聚酯,聚对苯二酸乙二酯,聚烯烃或者乙酸纤维素,特别是以薄膜的形式,以及还有有打算施用保护层到其上的或者通过在其上成像曝光来产生图像的金属例如Al,Cu,Ni,Fe,Zn,Mg或者Co和GaAs,Si或者SiO2。
基质的涂覆可以通过将液体组合物,溶液或者悬浮液施涂到基质上来进行。溶剂和浓度的选择主要取决于组合物的类型和涂覆技术。溶剂应当是惰性的,即它不和组份发生化学反应并应当在涂覆之后,在干燥过程中能够重新除去。合适的溶剂的例子是酮,醚和酯,例如甲基乙基酮,异丁基甲基酮,环戊酮,环己酮,N-甲基吡咯烷酮,二噁烷,四氢呋喃,2-甲氧基乙醇,2-乙氧基乙醇,1-甲氧基-2-丙醇,1,2-二甲氧基乙烷,乙酸乙基酯,乙酸正丁基酯和3-乙氧基丙酸乙基酯。所述的溶液通过已知的涂覆技术均匀的施涂到基质上,例如通过旋涂、浸涂、刮涂、帘流涂布、刷涂、喷涂(特别是通过静电喷涂)和逆辊涂覆,以及通过电泳沉积。还可能将光敏层施涂到临时的、柔性载体上,然后涂覆最终的基质,例如通过经由迭片结构的转印的覆铜线路板。施涂量(涂层厚度)和基质(层载体)的性质依据期望的应用领域而定。
本发明还涉及一种释放香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的方法,包括用光辐射式I的光潜化合物。
优选的,所述的光具有200-700nm,更特别是250-400nm的波长。
在用光释放香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的方法中,优选的式I的光潜化合物和任选的另外的添加剂和所述的关于新颖的式I化合物和组合物的那些是相同的。在本发明的上下文中,香料包括日用香料和食用香料(所述香料人和动物通过嗅觉和味觉能够有意识地和下意识地察觉的,包括用于昆虫、啮齿动物和其他害物的信息素,引诱剂和驱避剂)和气味诱饵以及它们的混合物。
本发明一种优选的实施方案还是式I的光潜化合物作为用光释放香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的前体的用途。用于香料释放的光潜化合物特定的应用是摹仿天然的产物诸如合成的木头或者皮革,其是由具有木头或者皮革的外观和触觉性能的合成的和天然的产物制成的材料。此外本发明涉及一种方法,其中释放香料的目的是掩盖由一种产物所散发的难闻的气味。
一些用于制备式I的光潜化合物的起始材料是新颖的。
因此本发明还涉及新颖的式Ia的化合物
其中
R1和R2彼此独立地是C1-C10烷基或者C3-C8环烷基,
R3是氢或C1-C4烷基,和
X是氯、溴或者碘;条件是:当X是氯时,R1异丙基、仲丁基或环己基和R2是环己基;和条件是:当X是溴时,R1和R2是环己基。
下面的实施例进一步说明本发明。份数或者百分比指的是重量。
实施例1:1-(4-羟基-3,5-二异丙基苯基)-2-碘代-乙酮的制备(化合物201)。
在室温下将30.94g(206mmol)的碘化钠在250ml的1,2-二甲氧基乙烷中的溶液逐滴加入到50.95g(200mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在250ml的1,2-二甲氧基乙烷的溶液中。加入之后,连续室温搅拌16小时。然后加入100ml己烷,在搅拌另外15分钟之后,通过过滤除去沉淀的盐。将得到溶液蒸发,并将形成的剩余物通过从己烷/二氯甲烷再结晶而净化,得到48.5g(70%)的化合物201,熔点127-128℃。
实施例2:1-(4-羟基-3,5-二叔丁基苯基)-2-碘代-乙酮的制备(化合物202)。
在室温下将3.14g(21mmol)的碘化钠在25ml的1,2-二甲氧基乙烷中的溶液逐滴加入到6.54g(20mmol)的2-溴-1-(4-羟基-3,5-二叔丁基苯基)-乙酮在25ml的1,2-二甲氧基乙烷的溶液中。加入之后,连续室温搅拌16小时。然后加入10ml己烷,在搅拌另外15分钟之后,通过过滤除去沉淀的盐。将得到溶液蒸发,并将形成的剩余物通过从己烷中再结晶而净化,得到5.21g(70%)的化合物202,熔点88-89℃。
实施例3:1-(4-羟基-3,5-二-环己基苯基)-2-碘代-乙酮的制备(化合物203)。
在室温下将7.87g(50mmol)的碘化钠在75ml的1,2-二甲氧基乙烷中的溶液逐滴加入到19.47g(50mmol)的2-溴-1-(4-羟基-3,5-二-环己基苯基)-乙酮在75ml的1,2-二甲氧基乙烷的溶液中。加入之后,连续室温搅拌16小时。然后加入25ml己烷,在搅拌另外15分钟之后,通过过滤除去沉淀的盐。将得到溶液蒸发,并将形成的剩余物通过从己烷中再结晶而净化,得到12.1g(57%)的化合物203,熔点183-185℃。
实施例4:1-(3,5-双(1,1-二甲基丙基)-4-羟基苯基)-2-碘代-乙酮的制备(化合物204)。
在室温下将1.65g(11mmol)的碘化钠在10ml的1,2-二甲氧基乙烷中的溶液逐滴加入到3.56g(10mmol)的1-(3,5-双(1,1-二甲基丙基)-4-羟基苯基)-2-溴-乙酮在15ml的1,2-二甲氧基乙烷的溶液中。加入之后,连续室温搅拌16小时。然后加入5ml己烷,在搅拌另外15分钟之后,通过过滤除去沉淀的盐。将得到溶液蒸发,并将形成的剩余物通过从己烷中再结晶而净化,得到2.15g(53%)的化合物204,熔点76-77℃。
实施例5:1-(4-羟基-3,5-叔丁基苯基)-2-碘代-丙烷-1-酮的制备(化合物205)。
将1.58g(10.5mmol)的碘化钠和3.41g(10.0mmol)的2-溴-1-(4-羟基-3,5-二叔丁苯基)-丙烷-1-酮溶解在25ml的1,2-二甲氧基乙烷中并在室温搅拌一整夜。然后将反应混合物浓缩成它体积的三分之二,将无机沉淀物滤出,并用乙酸乙基酯清洗。将收集的有机滤液用水清洗三次并浓缩。将形成的剩余物通过从己烷中结晶而净化,得到2.91g(75%)的化合物205,熔点141℃。
实施例6:4-[2-(3,5-二叔丁基-4-羟基苯基)-2-氧代-乙氧基]-3-甲氧基-苯甲醛的制备(化合物101)。
将19.4g(125mmol)的4-羟基-3-甲氧基-苯甲醛,1.88g(12.5mmol)的碘化钠和34.5g(250mmol)的碳酸钾在1000ml的乙酸乙基酯中的混合物搅拌30分钟。然后加入43.6g(125mmol)的2-溴-1-(4-羟基-3,5-二叔丁基苯基)-乙酮并在室温连续搅拌16小时。然后将该混合物用2NHCl酸化并用乙酸乙基酯萃取。将合并的萃取液用水清洗,干燥和蒸发。粗产物从二氯甲烷/己烷中结晶产生36.85g的化合物101,熔点99-100℃。
实施例7:4-[2-(3,5-二异丙基-4-羟基苯基)-2-氧代-乙氧基]-3-甲氧基-苯甲醛的制备(化合物102)。
将5.00g(36.7mmol)碳酸钾加入到6.00g(18.3mmol)的2-溴-1-(4-羟基-3,5-二异丙基苯基)-乙酮和2.78g(18.3mmol)的4-羟基-3-甲氧基-苯甲醛在20ml的乙酸乙基酯中的溶液,并将混合物室温搅拌18小时。在加入水并通过加入32%HCl调整pH为5-6之后,将混合物用乙酸乙基酯萃取。将合并的萃取液用水清洗,干燥和蒸发来得到化合物102。1H-NMR(300MHz,CDCl3),δ(ppm):7.79(s,2H),7.46-7.45(d,1H),7.41-7.38(dd,1H),6.90-6.87(d,1H),5.43(s,2H),3.97(s,3H),3.24-3.15(sept,2H),1.32-1.29(d,12H)。
实施例8:4-[2-(3,5-二-环己基-4-羟基苯基)-2-氧代-乙氧基]-3-甲氧基-苯甲醛的制备(化合物103)。
将1.52g(10mmol)的4-羟基-3-甲氧基-苯甲醛,0.3g(2.0mmol)的碘化钠和3.05g(22mmol)的碳酸钾在80ml的乙酸乙基酯中的混合物搅拌30分钟。然后加入3.8g(10mmol)的2-溴-1-(4-羟基-3,5-二-环己基苯基)-乙酮并在室温连续搅拌16小时。然后将该混合物用2N HCl酸化并用乙酸乙基酯萃取。将合并的萃取液用水清洗,干燥和蒸发。粗产物从二氯甲烷/二异丙醚中结晶产生1.35g的化合物103,熔点163-164℃。
实施例9:2-[4-氯-2-(2,4-二氯-苯氧基)-苯氧基]-1-(3,5-二叔丁基-4-羟基苯基)-乙酮的制备(化合物104)。
将6.3g(45.7mmol)碳酸钾加入到10.0g(30.5mmol)的2-溴-1-(4-羟基-3,5-二叔丁基苯基)-乙酮和8.8g(30.5mmol)的5-氯-2-(2,4-二-氯-苯氧基)-酚在50ml四氢呋喃的溶液中,将混合物室温搅拌4天。在加入水并通过加入32%HCl调整pH为5-6之后,将混合物用乙酸乙基酯萃取。将合并的萃取液用水清洗,干燥和蒸发。粗产物从甲醇中结晶产生15.4g的化合物104,熔点111-114℃。
实施例10:1-(4-羟基-3,5-二异丙基苯基)-2-对甲苯氧基-乙酮的制备(化合物105)。
在室温下将3.90g(15.3mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在70ml的二甲基甲酰胺中的溶液在100分钟内加入到4.47g(30.6mmol)的4-甲基酚钾在150ml的二甲基甲酰胺的溶液中。在另外的室温2小时搅拌之后,用1N HCl调整pH为6-7,将混合物用乙酸乙基酯萃取。将收集的有机相用水清洗,干燥和蒸发。粗产物从乙酸乙基酯/己烷中结晶产生1.8g的化合物105,熔点124-125℃。
实施例11:2-(2-苯并三唑-2-基-4-甲基-苯氧基)-1-(3,5-二叔丁基4-羟基-苯基)-乙酮的制备(化合物106)。
将6.54g(20mmol)的2-溴-1-(4-羟基-3,5-二叔丁基苯基)-乙酮和1.98g(30mmol)的氢氧化钾溶解在150ml的乙腈中并在室温和惰性气氛中搅拌30分钟。然后将5.27g(20mmol)的2-苯并三唑-2-基-4-甲基-酚盐分份加入。在室温连续搅拌另外3小时。在调整pH为6-7之后,将混合物用乙酸乙基酯萃取。将收集的有机相用水清洗,干燥和蒸发。粗产物从甲醇中结晶产生6.85g的化合物106,熔点155-157℃。
实施例12:4-{2-[3,5-双(1,1-二甲基-丙基)-4-羟基-苯基]-2-氧代-乙氧基}-3-甲氧基-苯甲醛的制备(化合物107)。
将1.55g(10mmol)的4-羟基-3-甲氧基-苯甲醛,0.30g(2.0mmol)的碘化钠和3.05g(22mmol)的碳酸钾在100ml的乙酸乙基酯中的混合物搅拌30分钟。然后加入3.56g(10mmol)的1-[3,5-双(1,1-二甲基-丙基)-4-羟基-苯基]-2-溴-乙酮并在室温连续搅拌16小时。然后用2N HCl将混合物酸化,并用乙酸乙基酯萃取。将合并的萃取液用水清洗,干燥和蒸发。粗产物从己烷中结晶产生2.95g(69%)的化合物107,熔点106-107℃。
实施例13:2-[(E)-3,7-二甲基-辛-2,6-二烯基氧基]-1-(4-羟基-3,5-二异丙基-苯基)-乙酮的制备(化合物108)。
在室温和惰性气氛下将58.59g(230mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在100ml的N-甲基吡咯烷酮中的溶液逐滴加入到86.4g(560mmol)的(E)-3,7-二甲基-辛-2,6-二烯-1-醇和64.5g(1150mmol)的氢氧化钾在150ml的N-甲基吡咯烷酮的溶液中。加入完成后,连续搅拌另外的16小时。然后用1N HCl将反应混合物酸化,并乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从己烷中结晶产生45.3g的化合物108,熔点70-71℃。
实施例14:2-(3,7-二甲基-辛-6-烯基氧基)-1-(4-羟基-3,5-二异丙基-苯基)-乙酮的制备(化合物109)。
在室温和惰性气氛下将3.82g(15mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在75ml的N-甲基吡咯烷酮中的溶液逐滴加入到4.69g(30mmol)的3,7-二甲基-辛-6-二烯-1-醇和4.21g(75mmol)的氢氧化钾在150ml的N-甲基吡咯烷酮的溶液中。加入完成后,连续搅拌另外的16小时。然后用1N HCl将反应混合物酸化,并用乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从己烷中结晶产生2.58g的化合物109,熔点37-39℃。
实施例15:1-(4-羟基-3,5-二异丙基苯基)-2-[(1R,2S,5R)-2-异丙基-5-甲基-环己氧基]-乙酮的制备(化合物110)。
在室温和惰性气氛下将12.73g(50mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在400ml的N-甲基吡咯烷酮中的溶液逐滴加入到15.63g(100mmol)的(1R,2S,5R)-2-异丙基-5-甲基-环己醇和16.5g(250mmol)的氢氧化钾在100ml的N-甲基吡咯烷酮中的溶液中。加入完成后,连续搅拌另外的16小时。然后用1N HCl将反应混合物酸化,并用乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从己烷中结晶产生6.37g的化合物110,熔点83-84℃。
实施例16:2-(1,5-二甲基-1-乙烯基-己-4-烯基氧基)-1-(4-羟基-3,5-二异丙基苯基)-乙酮的制备(化合物111)。
在室温和惰性气氛下将10.0g(39mmol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮在120ml的N-甲基吡咯烷酮的溶液逐滴加入到12.7g(79mmol)的3,7-二甲基-辛-1,6-二烯-3-醇和10.9g(195mmol)的氢氧化钾在80ml的N-甲基吡咯烷酮的溶液中。加入完成后,连续搅拌另外的16小时。然后用1N HCl将反应混合物酸化,并用乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从己烷中结晶产生0.32g的化合物111,熔点71-72℃。
实施例17:2-乙氧基-1-(4-羟基-3,5-二异丙基-苯基)-乙酮的制备(化合物112)。
在惰性气氛下将187g(3.33mol)的氢氧化钾溶解在1000ml乙醇中。在室温分份加入254.8g(1.00mol)的2-氯-1-(4-羟基-3,5-二异丙基苯基)-乙酮之后,连续搅拌另外的16小时。然后用10%HCl将反应混合物酸化,并用乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从甲苯/己烷和异丙醇/水中结晶产生243g的化合物112,熔点97-98℃。
实施例18:2-乙氧基-1-(4-羟基-3,5-二叔丁基苯基)-乙酮的制备(化合物113)。
在惰性气氛下将8.4g(150mmol)的氢氧化钾溶解在150ml乙醇中。在室温分份加入10.0g(31mmol)的2-溴-1-(4-羟基-3,5-二叔丁基苯基)-乙酮之后,连续搅拌另外的16小时。然后用10%HCl将反应混合物酸化,并用乙酸乙基酯萃取。将收集的有机相用水和盐水清洗,干燥和蒸发。粗产物从己烷中结晶产生3.8g的化合物113,熔点73-75℃。
实施例19:2-[2-(4-羟基-3,5-二异丙基苯基)-2-氧代-乙氧基]-异吲哚-1,3-二酮的制备(化合物114)。
将3.03g(15mmol)的1,3-二氧代-1,3-二氢-异吲哚-2-醇钾[制备根据P.Consonni,D Favara,A.Omodei-Salé,G.Bartolini,A.Ricci,J.Chem.Soc,Perkin Trans.2,1983,967-973],3.82g(15mmol)的2-氯-1-(4-羟基-3,5-二异丙基-苯基)-乙酮,2.3ml三乙基胺和100ml二甲基甲酰胺的混合物在室温和氮气氛中搅拌1.5小时。然后将混合物倾倒入500ml的含9ml的2N HCl的水中并用乙酸乙基酯萃取。将收集的有机相用水清洗,干燥和蒸发。所形成的粗产物从乙酸乙基酯和己烷中再结晶产生2.52g的化合物114,熔点136-139℃。
实施例20:1-(3,5-二叔丁基-4-羟基苯基)-2-乙氧基-丙烷-1-酮的制备(化合物115)。
将6.6g(117mmol)的氢氧化钾溶解在130ml乙醇中并搅拌1小时。然后室温和搅拌下加入在溶解在20mlN-甲基吡咯烷酮中的10.0g(29.3mmol)的2-溴-1-(3,5-二叔丁基-4-羟基苯基)-丙烷-1-酮。搅拌20小时之后,将反应混合物用冰浴冷却并加入5ml浓盐酸和150ml水。然后蒸发乙醇,加入200ml乙酸乙基酯,分离水相。将有机相用100ml盐水清洗,通过硫酸钠干燥并蒸发浓缩。将剩余物通柱色谱法净化,从己烷中结晶纯的级分来产生4.1g(45%)的化合物115;熔点64℃。
实施例21:1-(3,5-二叔丁基-4-羟基苯基)-2-[(E)-3,7-二甲基-辛-2,6-二烯基氧基]-乙酮的制备(化合物116)。
将9.6g(62mmol)的(E)-3,7-二甲基-辛-2,6-二烯-1-醇,8.4g(150mmol)的氢氧化钾和20ml的N-甲基吡咯烷酮的混合物室温搅拌1小时。然后分份加入10.0g(33mmol)的2-溴-1-(3,5-二叔丁基-4-羟基苯基)-乙酮,室温连续搅拌20小时。加入30ml水后,将混合物用6N盐酸中和,同时冰浴冷却,然后用乙酸乙基酯萃取。将有机相用盐水清洗两次,通过硫酸钠干燥并蒸发浓缩。将剩余物通柱色谱法净化,从己烷中结晶纯的级分来产生6.1g(50%)的化合物116;熔点50℃。
实施例22:2-(2-苯并三唑-2-基-4-甲基-苯氧基)-1-(3,5-二叔丁基-4-羟基-苯基)-丙烷-1-酮的制备(化合物117)。
将5.5g(24mmol)的2-苯并三唑-2-基-4-甲基-酚,4.7g(72mmol)的氢氧化钾和100mlN-甲基吡咯烷酮的混合物室温搅拌2小时。然后加入溶解在40mlN-甲基吡咯烷酮中的8.0g(24mmol)的2-溴-1-(3,5-二叔丁基-4-羟基苯基)-丙烷-1-酮并室温连续搅拌20小时。加入50ml水和15ml的2N盐酸之后,滤出沉淀固体,从乙醇中再结晶产生8.9g(76%)的化合物117;熔点161℃。
实施例23:在聚丙烯中的香草精的光化学释放。
将0.50g IrganoxB215[Ciba Specialty Chemicals Inc.,一种1份Irganox1010(3-(3,5-二叔丁基-4-羟基苯基)丙酸的季戊四醇酯)和2份的lrgafos168(三(2,4-二叔丁基苯基)亚磷酸酯)的混合物]和30g的化合物(101)[根据实施例6制备]在汽轮混合器中和来自Basell的969.5g的聚丙烯粉末Profax PH350一起混合。将该混合物在双螺杆挤出机中160-170℃挤出,产生20mm宽、1mm厚的带子。将该带子切成大约50mm长度的块,并在PPG UV固化设备上使用80W/cm的2个汞弧光灯泡和20m/min的线速度进行照射。重复该照射直至达到在表1所示的灯下的通过(passage)数。从试样的香草释放通过闻表面的气味来确定,并将香草气味的强度划分如下:
没有香草气味-
非常轻微的香草气味(+)
弱香草气味+
明显的香草气味++
强烈的香草气味+++
结果汇总在表1中。
表1:
实施例 | 灯下的通过数 | 香草气味 |
23a | 0 | (+) |
23b | 2 | (+) |
23c | 5 | + |
23d | 10 | +++ |
实施例24:从涂料的光化学香味释放。
份数和百分比按重量计,除非另有指示。
使用下面的光潜香料:化合物101[光潜香草醛];化合物108[光潜香叶醇];化合物109[光潜香茅醇]和化合物110[光潜薄荷醇]。
气味通过至少2个人来嗅觉评价。将对强度的感觉分为3种:
无气味-
弱气味+
强烈的气味++
实施例24.1:从常规的透明涂层的香料光化学释放
根据下面的表2的配方制备一种透明的溶剂型热固涂料:
表2:
产物 | 说明 | 供应者 | 份数(%)Millibase | 份数(%)Let-Down |
1-丁醇 | 溶剂 | 4.00 | 5.14 | |
Baysilone MA(100%) | 防沉降和流动添加剂 | Borchers GmbH | 0.035 | 0.045 |
乙酸丁二醇酯 | 溶剂 | 4.00 | 2.57 | |
Setal 84xx-70(70%) | 短油度醇酸树脂 | Nuplex Resins | 42.93 | 55.06 |
Setamine | 丁基化蜜胺甲醛树脂 | Nuplex Resins | 16.66 | 21.39 |
Solvesso 100 | 溶剂 | 32.36 | 15.79 |
最终的配料是通过混合以Millbase∶Let-Down=30∶70的比例的Millbase和Let-Down来制备的。制备下面的试样(表3):
表3:
实施例 | 光潜香料 | 重量[g/100g配料] |
24a | 无 | 无 |
24b | 化合物101 | 1.40 |
24c | 化合物108 | 1.40 |
24d | 化合物109 | 1.40 |
24e | 化合物110 | 1.40 |
将光潜香料以7.5mmol/100g固体的浓度溶解在所述的配料中。通过在室温搅拌将光潜香料溶解在配料中来制备20g液体配料试样。将试样使用绕线刮板以200μm的湿膜厚度施用到白色预涂的铝面板上,并在120℃的对流炉中固化30min。然后在由AETEC国际的UV固化设备GEO UV Processor上使用80W/cm的2个中压水银灯和10m/min的线速度于照射之前和之后,评价试样的香味。固化前后的嗅觉评价汇总在表4中。
表4:
实施例 | 照射前的香味 | 照射后的香味 | 香味说明 |
24a | 无 | 无 | 无香味 |
24b | 无 | ++ | 类似香草 |
24c | 无 | + | 果味,花似的,新鲜的 |
24d | 无 | ++ | 新鲜的,类似柑桔 |
24e | 无 | ++ | 新鲜的,薄荷味 |
实施例24.2:从水性透明涂层的香料光化学释放。
根据下面的表5的配方制备水可稀释的透明涂料:
表5:
产物 | 说明 | 供应者 | 份数(%) |
软化水 | 溶剂 | 47.0 | |
Maprenal MF900W/95 | 蜜胺甲醛树脂 | Cytec Surface Specalties | 0.54 |
Surfynol 104E | 非离子润湿和消泡添加剂 | Air Products | 0.8 |
Surfynol MD20 | 消泡和润湿添加剂 | Air Products | 0.3 |
EnviroGem AE02 | 润湿剂 | Air Products | 0.4 |
丁二醇 | 溶剂 | 5.51 | |
正丁醇 | 溶剂 | 2.0 | |
Dow Coming57 | 滑爽添加剂 | Dow Corning | 0.2 |
Viscalex HV30 | 增稠剂和流变控制添加剂 | Ciba Specialty Chemicals | 3,5 |
DMEA(10%,在水中) | 二甲氨基乙醇 | Fluka | 2.5 |
APU 1012 | 水性丙烯酸聚氨酯分散液 | Alberdingk Boley | 37.25 |
制备下面的试样(表6):
表6:
实施例 | 光潜香料 | 重量[g/100g配料] |
24f | 无 | 无 |
24g | 化合物101 | 0.534 |
24h | 化合物108 | 0.534 |
24i | 化合物109 | 0.534 |
24j | 化合物110 | 0.534 |
光潜香料的量等于3%固体量。试样通过在40℃搅拌60分钟来制备。全部的光潜香料在水性配方中是可溶的。将涂料使用绕线刮板以150μm的湿膜厚度施用到白色预涂的铝面板上。然后将试样在对流炉中130℃干燥30min。将面板切成两块。一组试样如实施例24.1所述在UV固化设备中照射。评价照射前后的香味。香味强度的嗅觉评价结果表示在下面的表7中。
表7:
实施例 | 照射前的香味 | 在UV固化设备照射 | 香味说明 |
24f | 无 | 无 | 无香味 |
24g | 无 | 2 | 类似香草 |
24h | 无 | + | 果味,花似的,新鲜的 |
24i | 无 | ++ | 新鲜的,类似柑桔 |
24j | 无 | ++ | 新鲜的,薄荷味 |
实施例24.3:在着色常规的涂料中的香草光化学释放。
制备基于醇酸/蜜胺体系的具有下面的成分的白色热固性屏蔽配料:
1.millbase:(表8)
表8:
产物 | 说明 | 供应者 | 份数 |
Alkydal F 310(60%) | 基于饱和脂肪酸的短油度醇酸树脂 | Bayer Material Science | 27.58 |
Disperbyk 161 | 用于溶剂基涂料的高分子量润湿分散添加剂 | BYK Chemie | 5.5 |
硅油(1%,在二甲苯中) | 1.0 | ||
1-甲氧基-2-丙醇 | 溶剂 | 1.56 | |
丁醇 | 溶剂 | 1.56 | |
二甲苯 | 溶剂 | 7.3 | |
Aerosil 200 | 亲水热解法二氧化硅 | Degussa | 0.5 |
Tiona 696 | 金红石颜料 | Millennium Chemicals | 55.0 |
总和 | 100.0 |
2.Let-Down:(表9)
表9:
产物 | 说明 | 供应者 | 份数 |
Millbase | 参见表1 | 45.45 | |
Alkydal F310(60%) | 基于饱和脂肪酸的短油度醇酸树脂 | Bayer Material Science | 35.08 |
Maprenal MF650 | 蜜胺树脂 | Cytec Surface Specialties | 17.59 |
1-甲氧基-2-丙醇 | 溶剂 | 0.22 | |
丁醇 | 溶剂 | 0.22 | |
二甲苯 | 溶剂 | 1.04 | |
Tinuvinl23 | 光稳定剂 | Ciba Specialty Chemicals | 0.40 |
总和 | 100.0 |
颜料负载量是25%。
试样制备[实施例24I]:在100g屏蔽配料中称重加入1.147g的化合物101[参见实施例6],产生3%固体的光潜物质含量。将该试样在磁搅拌装置中50℃搅拌大约60分钟。
使用绕线式涂布器将试样施涂到具有白色卷涂底漆的铝面板上(WFT100μm)上并在130℃的炉子固化40分钟。为了参照,将纯的屏蔽配料试样如前所述进行施涂[实施例24k]。
照射和香草的释放
1.用UV固化设备照射:
将固化试样如实施例24.1所述在PPG UV固化设备中进行照射,在UV-照射之后立即使用80W/cm的2个汞弧光灯泡和10m/min的线速度。从试样的香草的释放通过闻涂料表面的气味来确定。结果汇总在表10中。
表10:
实施例 | 光潜化合物 | 香草气味 |
24ka) | 无 | 无 |
24lb) | 3%的化合物101 | ++ |
a)对照实施例。
b)根据本发明的实施例。
2.用人造日光照射
将试样放置在根据DIN6173的人造日光灯下并照射4个工作周(5天/周),具有每周之间2天中断,这里试样被储存在黑暗的地方。在时间间隔时,通过闻涂层表面的气味来确定从试样的香草释放。香草气味的强度评价如前所述。结果汇总如下:
实施例24.4:在常规的透明涂层中的结合有光敏剂的香料光化学释放
用于这个实施例的涂料配方等同于实施例24.1中所述者。制备下面的试样(表11):
表11:
实施例 | 光潜香料 | 光敏剂 |
24m | 化合物108 | 2-异丙基噻吨酮和4-异丙基噻吨酮的混合物(Darocur ITX) |
24n | 化合物108 | 1-氯-4-丙氧基-9H-噻吨-9-酮(Aldrich) |
24o | 化合物108 | 苯甲酮(Darocur BP) |
24p | 化合物110 | 2-异丙基噻吨酮和4-异丙基噻吨酮的混合物(Darocur ITX) |
24q | 化合物110 | 1-氯-4-丙氧基-9H-噻吨-9-酮(Aldrich) |
24r | 化合物110 | 苯甲酮(Darocur BP) |
该试样在100g配料中包含1.5g(3%固体)的光潜香料和1.0g(2%固体)的光敏剂。将这两种添加剂加入到涂料中并通过在40℃搅拌来溶解。将试样使用绕线刮板以120μm的湿膜厚度施用到白色预涂的铝面板上,并在100℃的对流炉中固化30min。将该涂覆的面板切成小块,在UV荧光灯TL K40W/05(Philips,发射峰在365nm)下照射大约30分钟和用天然的白昼光,夏季,午后,南向,密集云层照射大约60分钟。香味强度的结果表示在下面的表12中。
表12:
实施例 | 照射前的香味 | 用UV荧光灯照射的香味 | 用自然日光照射的香味 |
24m | 无 | + | + |
24n | 无 | + | + |
24o | 无 | + | + |
24p | 无 | + | + |
24q | 无 | + | + |
24r | 无 | + | + |
Claims (16)
1.一种式I的光潜化合物,
其中
R1和R2彼此独立地是C1-C10烷基或者C3-C8环烷基,
R3是氢或C1-C4烷基,
R4是未被取代的C1-C25烷基,C3-C25链烯基,C3-C25链炔基,C6-C10芳基,C3-C12环烷基或C3-C12环链烯基;或者被C1-C18烷基,C2-C18链烯基,C3-C18链炔基,C3-C12环烷基,C1-C18烷氧基,羟基,C2-C18烷氧基羰基,甲酰基,C1-C18烷硫基,C1-C18烷基亚磺酰基,C1-C18烷基磺酰基,卤素,羧基,C2-C18羧基烷基,C2-C18羧基烷氧基,C3-C18烷氧基羰基烷基,C3-C18烷氧基羰基烷氧基,C7-C9苯基烷基,苯氧基,卤素取代的苯氧基,山梨醇基或取代的C1-C25烷基,C3-C25链烯基,C3-C25链炔基,C6-C10芳基,C3-C12环烷基或C3-C12环链烯基,
R5是氢、C1-C4烷基或者卤素,和
R6和R7彼此独立地是苯基或者C1-C4烷基取代的苯基;
其中式I的光潜化合物的光化学裂解产物R4OH选自香料、UV吸收剂、抗菌剂、防雾剂和澄清剂;条件是:当R1和R2是叔丁基并且R3是氢时,R4不是甲基或苯基。
2.根据权利要求1的光潜化合物,其中
R1和R2彼此独立地是C3-C8烷基或者C5-C8环烷基,
R3是氢或甲基,
R4是未被取代的C1-C18烷基,C3-C18链烯基,C3-C18链炔基,C6-C10芳基,C5-C8环烷基或者C5-C8环链烯基;或者被C1-C12烷基,C2-C12链烯基,C3-C12链炔基,C5-C8环烷基,C1-C12烷氧基,羟基,C2-C12烷氧基羰基,甲酰基,C1-C12烷硫基,C1-C12烷基亚磺酰基,C1-C12烷基磺酰基,卤素,羧基,C2-C12羧基烷基,C2-C12羧基烷氧基,C3-C12烷氧基羰基烷基,C3-C12烷氧基羰基烷氧基,C7-C9苯基烷基,苯氧基,卤素取代的苯氧基,山梨醇基或取代的C1-C18烷基,C3-C18链烯基,C3-C18链炔基,C6-C10芳基,C5-C8环烷基或C5-C8环链烯基,
R5是氢或卤素,和
R6和R7是苯基。
3.根据权利要求1的光潜化合物,其中R3是氢。
4.根据权利要求1的光潜化合物,其中R1和R2彼此独立地是C3-C5烷基或者环己基。
6.根据权利要求1的光潜化合物,其中R1和R2是异丙基、叔丁基或者环己基。
8.一种组合物,其包含
a)选自溶剂、蜡、成膜基料、涂料、天然或者合成的聚合物、织物、纸、清洁剂、上光剂、织物护理剂、护发素、发胶或者身体除臭剂的技术材料,和
b)至少一种根据权利要求1的式I的光潜化合物。
9.根据权利要求8的组合物,其中组份(b)以0.001-10%的量存在,基于组份(a)的重量。
10.根据权利要求8的组合物,其中所述涂料是油漆,所述清洁剂是香波、肥皂或者洗浴凝胶。
11.根据权利要求8的组合物,除了组份(a)和(b),其包含另外的添加剂。
12.根据权利要求11的组合物,其包含作为另外的添加剂的酚抗氧化剂、光稳定剂和/或加工稳定剂。
13.一种释放香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的方法,其包括用光照射根据权利要求1的式I的光潜化合物。
14.根据权利要求13的方法,其中所述的光具有250-400nm的波长。
15.根据权利要求1的式I的光潜化合物作为前体用光释放香料、UV吸收剂、抗菌剂、防雾剂和澄清剂的用途。
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PCT/EP2006/067912 WO2007054446A1 (en) | 2005-11-09 | 2006-10-30 | Photolatent systems |
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US20110083245A1 (en) * | 2009-10-13 | 2011-04-14 | Simon Lee | Textile Structure with Pheromone Particles |
US8663873B2 (en) | 2012-01-13 | 2014-03-04 | Sabic Innovative Plastics Ip B.V. | Holographic recording medium and method of recording a hologram |
DE102014226196A1 (de) * | 2014-12-17 | 2016-06-23 | Henkel Ag & Co. Kgaa | Photolabile Duftstoffvorläuferverbindung |
GB2549061B (en) * | 2015-09-03 | 2020-04-01 | Si Group Switzerland Chaa Gmbh | Stabilising Compositions |
JP7393205B2 (ja) * | 2017-10-05 | 2023-12-06 | 株式会社Adeka | 化合物、潜在性紫外線吸収剤、組成物、硬化物及び硬化物の製造方法 |
US11417857B2 (en) * | 2018-01-24 | 2022-08-16 | Samsung Display Co., Ltd. | Heterocyclic compound and electronic apparatus |
CN113226468A (zh) | 2018-06-27 | 2021-08-06 | 康奈尔大学 | 作为hcn1拮抗剂的经取代的烷基苯酚 |
CN111635704A (zh) * | 2020-06-19 | 2020-09-08 | 常州驰科光电科技有限公司 | 一种双约束层阻尼材料 |
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Title |
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Kai Zhang,et. al..Mechanism of Photosolvolytic Rearrangement of p-Hydroxyphenacyl Esters: Evidence for Excited-State Intramolecular Proton Transfer as the Primary Photochemical Step.《Journal of the American Chemical Society》.1999,第121卷(第24期),5625-5632. * |
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US20090162307A1 (en) | 2009-06-25 |
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JP5138599B2 (ja) | 2013-02-06 |
US7820865B2 (en) | 2010-10-26 |
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