CN1727338A - Benzotriazole compound with alkenyl ester structure and preparation method thereof - Google Patents
Benzotriazole compound with alkenyl ester structure and preparation method thereof Download PDFInfo
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- CN1727338A CN1727338A CN 200410065921 CN200410065921A CN1727338A CN 1727338 A CN1727338 A CN 1727338A CN 200410065921 CN200410065921 CN 200410065921 CN 200410065921 A CN200410065921 A CN 200410065921A CN 1727338 A CN1727338 A CN 1727338A
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- hydroxyl
- benzotriazole
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- -1 Benzotriazole compound Chemical class 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012964 benzotriazole Substances 0.000 title claims description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000002148 esters Chemical group 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000004611 light stabiliser Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 64
- 150000001565 benzotriazoles Chemical class 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000002585 base Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 11
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- 239000006096 absorbing agent Substances 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VXMQKONTARQGPP-UHFFFAOYSA-N (ethoxyamino)oxyethane Chemical compound CCONOCC VXMQKONTARQGPP-UHFFFAOYSA-N 0.000 description 2
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012675 alcoholic extract Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005905 mesyloxy group Chemical group 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- PLAWCFOMHQCJBK-UHFFFAOYSA-N 1-(2,2-dimethylpropylperoxy)pentane Chemical compound CCCCCOOCC(C)(C)C PLAWCFOMHQCJBK-UHFFFAOYSA-N 0.000 description 1
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 description 1
- CSDKGXVAOFGEAM-UHFFFAOYSA-N 2-propanoyloxybutanoic acid Chemical compound CCC(C(O)=O)OC(=O)CC CSDKGXVAOFGEAM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010934 O-alkylation reaction Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JFOZKMSJYSPYLN-QHCPKHFHSA-N lifitegrast Chemical compound CS(=O)(=O)C1=CC=CC(C[C@H](NC(=O)C=2C(=C3CCN(CC3=CC=2Cl)C(=O)C=2C=C3OC=CC3=CC=2)Cl)C(O)=O)=C1 JFOZKMSJYSPYLN-QHCPKHFHSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [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])O* 0.000 description 1
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a compound of a general formula and a preparation method thereof, wherein the compound of the general formula (II) is subjected to esterification reaction or ester exchange reaction in a first technical scheme, and the compound of the general formula (III) is subjected to condensation reaction with alkenyl acid alkali metal salt in a second technical scheme. Hydrogen, halogen, alkyl or alkoxy substituted in the 3, 4, 5, 6 positions of X in the above formulae , (II), (III); r ═ alkyl, cycloalkyl, carboxylic acid, aryl, or substituted aryl; r1、R2And R3Independently hydrogen, alkyl or alkenyl; m is an alkylene group. Y is halogen and sulfonyloxy. The invention also relates to the application characteristics of the compound in the general formula I as a light stabilizer on the aging resistance of polymers; and to certain novel compounds of the general formula I and other novel 2-substituted phenylbenzotriazoles.
Description
Technical field: the present invention relates to effectively to absorb structural modification and preparation method that the alkenyl ester type structure unit of 2-(2-hydroxy phenyl) benzotriazole compound of uviolizing is introduced.2-(2-hydroxy phenyl) benzotriazole compound that the present invention relates to new introducing alkenyl ester type structure on the other hand with and as the purposes of UV light absorber.
Background technology: in polymkeric substance anti-aging technology, 2-(2-hydroxy phenyl) benzotriazole cpd is the important UV light absorber of a class.In order to adapt to complicated and harsh polymer processing and working conditions, benzotriazole compound is carried out chemical structure modify to reach the purpose of improving its high thermal resistance, weathering resistance, long-lasting, volatility and consistency.
In order to reach the requirement of above-mentioned application characteristic, described 3 of phenyl ring among the open EP0738718A of European patent and carried out the modifying method that α-cumyl replaces; 5 introduction-CF that United States Patent (USP) 6166218 discloses at the benzo ring
3Modify; United States Patent (USP) 6268505 and 6407254 discloses 3 introducings 2 at phenyl ring, 4-imidazolinedione-5, the two structures that replace of 5-.Mostly related all kinds of 2-(2-hydroxy phenyl) benzotriazole compound of above-mentioned public technology is structural simple extension and group replacement, does not relate to the group of thiazolinyl structure.
United States Patent (USP) 6489486 discloses at 3 of phenyl ring and has carried out alkylating method, but the mode of resetting again by the O-alkylation can obtainable certain alkenyl segments because factors such as steric effect often are difficult to have response characteristic.
Summary of the invention: in order to solve conventional 2-(2-hydroxy phenyl) benzotriazole compound in the limitation aspect the characteristics such as high thermal resistance, weathering resistance, long-lasting, volatility and consistency, the invention discloses a kind of benzotriazole that has alkenyl ester type structure with general formula (I) with as the new ultra-violet light absorbers, and preparation method about this general formula (I) is provided, have reaction conditions gentleness, highly selective, advantage cheaply.
Because phenyl ring 3 bit strips of this 2-(2-hydroxy phenyl) benzotriazole have alkenyl ester type structure, when its be applied to polymer materials processing as UV light absorber and the process used in the time, can be so that there be the grafting assembly effect between light stabilizing active fragment and the polymeric substrate; Simultaneously because polymerisable response characteristic makes its volatility extremely low.Simultaneously because general formula (I) response characteristic that structure had makes the anti-aging feature of polymkeric substance have better weather resistance and long-lasting.Also be based on the structural modification of alkenyl ester type group in addition, general formula (I) compound can have better consistency with various polymeric substrate, comprises coating and plastics etc.
Wherein, X=3, hydrogen, halogen, alkyl or the alkoxyl group of 4,5,6 replacements; R=alkyl, cycloalkyl, carboxylic acid group, aryl or substituted aryl; R
1, R
2And R
3Be hydrogen, alkyl or alkenyl independently; M is an alkylene.
We provide three kinds of alternative economical and efficient process programs to synthesize general formula (I) compound in the present invention, and its technological design is as follows.
Process program one: by general formula (II) compound of 3-hydroxyalkyl replacement
And general formula (IV) thiazolinyl formic acid
Carrying out alcoholic acid esterification reacts and prepares general formula (I) compound.
Among above-mentioned formula II, the IV, X, R, R
1, R
2, R
3, the definition of M is with the definition in the general formula I.
Process program two: by general formula (II) compound and logical formula V thiazolinyl formic acid lower alkyl ester
Carry out the transesterify reaction and prepare general formula (I) compound.
Among above-mentioned formula II, the V, X, R, R
1, R
2, R
3, the definition of M is with the definition in the general formula I; R
4It is C1～C4 alkyl.
Process program three: by general formula (III) compound that the 3-alkylhalide group replaces or the sulphonyl oxyalkyl replaces
And general formula (IV) thiazolinyl formic acid or its an alkali metal salt react and prepare general formula (I) compound.
Among above-mentioned formula III, the IV, X, R, R
1, R
2, R
3, the definition of M is with the definition in the general formula I; Y is halogen and sulfonyloxy.
In above-mentioned compound of Formula I, those are X, R, R wherein
1, R
2, R
3, M the definition compound identical with its definition in claim 1 be new compound, the 3-bit strip that its characteristic is at phenyl ring has the alkenyl ester type structure unit.Work as R
1, R
2, R
3In one or more groups can be to be alkenyl, then the alkenyl ester type structure characteristic can be understood as the ester type structure of polyene-based feature.Thereby it also is a purpose of the present invention.
New compound specific examples as general formula (I) is:
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen methyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen propyl group)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen propyl group)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen methyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-tertiary butyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-tertiary butyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryl oxygen propyl group)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen propyl group)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen methyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen methyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen methyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen methyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(2-butylene acyl group oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(alpha-methyl-2-crotonoyl oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(1,3-pentadiene acyl group oxygen ethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
On the other hand, the 2-hydroxy-phenyl-benzotriazole compound that the present invention relates to contain above-mentioned general formula (I) separately or and at least a other UV-A and/or UV-B hush up the new UV light absorber of agent, be also referred to as photostabilizer.At last, the present invention relates to the purposes of the new 2-hydroxy-phenyl-benzotriazole compound of general formula defined above (I) as photostabilizer.
Particularly preferred compound as UV light absorber is:
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(acryl oxygen ethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryl oxygen ethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl)) benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-tertiary butyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji)-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-(1-methyl isophthalic acid-phenylethyl))-5-trifluoromethyl benzo triazole
Most preferred general formula (I) compound is as follows:
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-tertiary butyl)-5-chlorinated benzotriazole
2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji)-5-chlorinated benzotriazole
The term alkyl that the present invention uses represents to contain 1-21 carbon atom, the saturated straight chain or the branched-chain alkyl that preferably contain 1-8 carbon atom, for example, methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, amyl group, neo-pentyl, hexyl, 2-ethyl-hexyl, Te Xinji.Similarly, the term alkoxyl group is represented 1-21 the carbon atom that contain by the Sauerstoffatom bonding, the saturated straight chain or the branched-chain alkyl that preferably contain 1-8 carbon atom, for example, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, sec-butoxy, tert.-butoxy, pentyloxy, neopentyl oxygen, hexyloxy, 2-ethyl-hexyloxy, special octyloxy.The term cycloalkyl is represented cycloalkyl and 2-21 carbon atom substituted cycloalkyl of C5～C7.The term carboxylic acid group represents C2-21 carbon atom carboxylic acid and carboxylic acid C1～C18 alkyl ester, for example formyloxy, acetoxyl, propionyloxy, butyric acid base, valeric acid base, methyl-formiate base, ethyl propionate base.Aryl is represented phenyl, heterocyclic radical, for example pyridine-2-base, furyl, thienyl.Substituted aryl is represented the aryl that abovementioned alkyl, alkoxyl group replace, the defining as above-mentioned definition of alkyl and alkoxyl group.The term alkenyl represents to contain at least one two keys and 2-21 carbon atom, preferably contains the straight or branched alkyl of 2-8 atom, and described non-limiting examples of alkenyls is propylene-2-base, propylene-3-base, butylene-4-base, amylene-4-base and amylene-5-base.Term halogen is represented fluorine, chlorine, bromine and iodine.The term sulfonyloxy is represented tosyloxy, mesyloxy.The term alkylene is represented C1～C18 alkylene base, the saturated straight chain and the side chain alkylene base that preferably contain 1-8 carbon atom, for example methylene, ethylene, trimethylene, different trimethylene, fourth support, Zhong Ding support, the support of uncle's fourth, pentamethylene, new pentamethylene, hexamethylene, 2-ethyl-hexamethylene, special octamethylene.
R in one group of preferred general formula (I) benzotriazole compound
1Be hydrogen, methyl, ethyl, most preferably hydrogen and methyl.And preferred R
2, R
3Be hydrogen, be no more than the alkyl of 5 carbon atoms and be no more than the alkenyl of 5 carbon atoms, more preferably hydrogen and be no more than the alkyl and the alkenyl of 3 carbon atoms.Preferred X is hydrogen, chlorine, the trifluoromethyl of 5 replacements of benzo ring, and difluoro one chloromethyl, a fluorine dichloromethyl more are chosen as hydrogen, chlorine.The cumyl that straight chain that preferred R is C1-C8 and branched-chain alkyl and C1-C8 replace, more selecting is methyl, the tertiary butyl, Te Xinji, α-cumyl.Preferred M is the C1-C4 alkylene, and more preferably methylene and ethylene most preferably are methylenes.
According to novel method of the present invention, general formula (I) compound can be selected to be prepared shown in following chemical equation 1-3, and it is corresponding above-mentioned process program 1-3 respectively.
Chemical equation one:
In this process program one, utilize alcoholic extract hydroxyl group and thiazolinyl acid on 3 of the phenyl ring to carry out esterification.The mol ratio of general formula I I benzotriazole cpd and the acid of general formula I V thiazolinyl selects 1: 0.1～10, be preferably 1: 0.8～and 1.2, most preferably be 1: 0.9～1.1.Catalyst for reaction can be selected sulfuric acid, phosphoric acid, alkansulfonic acid, aryl sulfonic acid and multi-element, inorganic acid, is preferably sulfuric acid and tosic acid, most preferably is tosic acid.Catalyst concn in the reaction mixture is generally 0.5 to 10wt%, is preferably 1 to 5wt%, most preferably is 2 to 3wt% (by total mixtures).
For polymerization retarder, select (for example) thiodiphenylamine, quinhydrones, Hydroquinone monomethylether or its compound and possible air, more preferably thiodiphenylamine, Hydroquinone monomethylether or its compound.The polymerization retarder consumption is chosen as 100 to 5000ppm, more preferably 2000ppm to 3000ppm (by reaction mixture).
As entrainment agent, can select to use stable hydrocarbon (as hexanaphthene) or aromatic hydrocarbons (as toluene) in the present invention; Preferred entrainment agent is benzene and toluene among the present invention.
Preferred 70 to 160 ℃ of temperature of reaction in the reactor, more preferably 90 to 130 ℃.Reaction times is preferably 1 to 10 hour, more preferably 1 to 6 hour.
Reaction can be at normal atmosphere, be lower than normal atmosphere or be higher than under the normal atmosphere continuously or carry out in the gap, wherein more is chosen as under the normal pressure situation gap and carries out.
Chemical equation two:
In this process program two, utilize alcoholic extract hydroxyl group and thiazolinyl acid lower alkyl ester on 3 of the phenyl ring to carry out transesterification reaction.R
4Be C1～C4 alkyl, be preferably methyl, ethyl, most preferably be methyl.The mol ratio of general formula I I benzotriazole cpd and general formula V thiazolinyl acid lower alkyl ester selects 1: 1～20, be preferably 1: 1～and 15, most preferably be 1: 1.2～10.Reaction mixture comprises at least one polymerization retarder, the polymerization retarder that is fit to comprises the diethyl oxyamine, to methoxyl group phenol, quinhydrones, thiodiphenylamine, 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl free radical (4-hydroxyl-TEMPO), 4-first acryloxy-2,2,6,6-tetramethyl-piperidyl free radical and their mixture.Based on the weight of general formula I I benzotriazole compound, the polymerization retarder consumption is chosen as 10 to 10000ppm, and preferred 100 to 5000ppm, most preferably is 200ppm to 3000ppm.
Suitable transesterification catalyst comprises that C1-C3 hangs down sodium alkyl alcohol, dibutyltin oxide, dibutyl tin methylate, C4-C8 zinc alkyl(s), Quilonum Retard, thiazolinyl acid C1-C4 alkyl quaternary ammonium salts, lithium hydroxide, magnesium methylate methide, preferred dibutyltin oxide and lithium hydroxide among the present invention.Transesterification catalyst concentration is generally 0.1 to 10 mole of %, is preferably 0.5 to 7 mole of %, most preferably is 1 to 5 mole of %.
Process program two of the present invention utilizes the Oldershaw distillation tower, and the stage number of suitable Oldershaw distillation tower is 5 to 40, and more preferably 10 to 20.Reflux ratio selects 10～30.
As entrainment agent, can select to use stable hydrocarbon (as hexanaphthene, normal hexane) or aromatic hydrocarbons (as toluene) in the present invention, the preferred entrainment agent normal hexane that adds among the present invention.
Preferred 70 to 160 ℃ of temperature of reaction in the reactor, more preferably 90 to 130 ℃.Reaction times is preferably 1 to 20 hour, more preferably 1 to 10 hour.
Reaction can be at normal atmosphere, be lower than normal atmosphere or be higher than under the normal atmosphere continuously or carry out in the gap, wherein more is chosen as slightly under the decompression situation gap and carries out.
Chemical equation three:
In this process program three, utilize in the general formula III phenyl ring 3 bit substituents groups easy leavings group Y and with carboxylic acid group or carboxylate salt condensation prepared compound of Formula I under alkaline condition of general formula I V structure.Y preferably can be chlorine, mesyloxy.Compound as alkaline substance can be selected NaOH, KOH, LiOH, more preferably NaOH.This optimal process step was two steps, and the first step is to prepare the pairing carboxylate compounds of exsiccant general formula I V by acid-base neutralisation; Second step continued and general formula III condensation prepared target compound I.
The mol ratio of general formula I V and alkaline hydrated oxide selects 1: 0.8～4, be preferably 1: 0.9～and 1.1.Alkaline hydrated oxide can be a solids, also can be the water solution system more than 10%.The temperature of neutralization reaction is selected 0～100 ℃, is chosen as 25～60 ℃.The gained carboxylate salt need pass through processed, and dewatering commonly used can be selected, and preferred method is a spray-drying process.
In step 2, need to select phase-transfer catalyst to improve speed of reaction, appropriate catalyst can be a quaternary ammonium salt, most preferably be tetramethyl ammonium chloride, the carboxylate salt of the relative general formula I V of its consumption is 0.1 mole of %～3 mole %, is preferably 0.3～1 mole of %.Reaction mixture comprises at least one polymerization retarder, the polymerization retarder that is fit to comprises the diethyl oxyamine, to methoxyl group phenol, quinhydrones, thiodiphenylamine, 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl free radical (4-hydroxyl-TEMPO), 4-first acryloxy-2,2,6,6-tetramethyl-piperidyl free radical and their mixture are preferably thiodiphenylamine.The carboxylate salt of the relative general formula I V of polymerization retarder consumption is chosen as 0.05～1 mole of %, preferred 0.1 to 0.5 mole of %.The mol ratio of general formula III benzotriazole cpd and general formula I V carboxylic acid selects 1: 1～10, be preferably 1: 1～and 5, most preferably be 1: 1～2.
Preferred 70 to 160 ℃ of the temperature of reaction of step 2 condensation reaction, more preferably 90 to 120 ℃.Reaction times is preferably 1 to 20 hour, more preferably 1 to 10 hour.Reaction can be carried out having under solvent or the solvent-free condition, and the solvent that can select comprises DMF, DMSO, NMP or the like.
Following example will describe the present invention in detail, but in no case limit the scope of the invention.
According to existing synthetic report, 3 hydroxyalkyl substituted benzenes of phenyl ring benzotriazole compound of general formula I I can pass through corresponding diazonium salt and 2,6-5 two (hydroxyalkyl)-alkylphenol is carried out coupling because a hydroxyalkyl breaks away from, can obtain the compound as general formula I I when coupling.
When 3 of 2-(2-hydroxy phenyl) benzotriazole phenyl ring are H, on 3 C atom of phenyl ring, can carry out electrophilic substitution, the compound that haloalkylation or the sulphonyl alkylation by routine can obtain general formula III.
Embodiment:
Preparation embodiment one: (process program one)
[preparation of 2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole]
(target compound 1)
255.3g 2-(2 '-hydroxyl-3 '-methylol-5 '-methyl) benzotriazole and 1000ml benzene are joined in the reaction vessel of 2000ml, and heating makes its dissolving evenly.Add 0.8g thiodiphenylamine, 75g vinylformic acid in said mixture, be warmed up to slow reflux state, the 10g tosic acid keeps reflux state in batches.After the stirring reaction 4 hours, note observing the water yield of collecting in the water-and-oil separator.
By oily-water seperating equipment, when isolated water near the 18ml time, get final product stopped reaction.Can analyze by high performance liquid chromatography (HPLC) near ending phase in reaction simultaneously.Be confirmed as the disappearance of 2-(2 '-hydroxyl-3 '-methylol-5 '-methyl) benzotriazole of reaction raw materials and the generation of 2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole.
After finishing, reaction reaction mixture is washed extraction treatment.Residue carried out drip washing, decolouring, vacuum drying treatment after the organic layer decompression removed solvent benzol.Leacheate is selected 50% aqueous ethanolic solution, and the decolouring processing selecting is utilized charcoal absorption.Purified product after the processing is analyzed through HPLC, its content 〉=98.0%.Can obtain the pure product soup compound of 281.5g after the drying treatment, productive rate is 91%.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 2-(2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-methyl) benzotriazole.Concrete ultimate analysis situation is as follows: measured value (calculated value) C65.99% (66.02%); H4.81% (4.85%); N13.60 (13.59%).
Preparation embodiment two: (process program one)
[preparation of 2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole]
(target compound 2)
Adopt the method identical with embodiment one, with the acid of 90g methacrylic acid instead of propylene, replace tosic acid with the 10g vitriol oil, in this case, the reaction times extends to 8 hours, and reacting yield is 87%.
1HNMR,
13CNMR and MS have proved conclusively the structure of target compound.Concrete ultimate analysis situation is as follows: measured value (calculated value) C66.80% (66.87%); H5.19% (5.26%); N13.06 (13.00%).
Preparation embodiment three: (process program two)
[preparation of 2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole]
Be equipped with thermometer, agitator, gas introduction tube and have in the reaction vessel of distillation tower of recirculation control device at 2000ml and add 255.3g 2-(2 '-hydroxyl-3 '-methylol-5 '-methyl) benzotriazole, 600ml normal hexane, 0.5g p methoxy phenol, heating for dissolving is even.Add 1.0g dibutyltin oxide, 500g methyl methacrylate in said mixture, be warmed up to reflux state under 300mmHg pressure, temperature is 70 ℃ at the bottom of this moment still.Control reflux ratio 10～30, tower top temperature is 38～55 ℃.The form that methyl alcohol will be used as azeotrope is moved out of.React after 4 hours, temperature is elevated to 74 ℃ at the bottom of the still, and tower top temperature can not maintain 55 ℃ or lower temperature levels again.By the HPLC sampling analysis, the transformation efficiency that can learn 2-(2 '-hydroxyl-3 '-methylol-5 '-methyl) benzotriazole 〉=99.5%.
Finish immediately that the reaction back adds paratoluenesulfonic acid sodium salt so that catalyst deactivation, changeing back flow control device is water distilling apparatus, and the 100mmHg that reduces pressure steams excessive methyl methacrylate and entrapment solvent.After finishing, reaction reaction mixture is washed extraction treatment.Unreacted trace benzotriazole reactant and other byproduct can drip washing mode wash-out in addition.Residue is proceeded decolouring, vacuum drying treatment.Leacheate is selected 50% aqueous ethanolic solution, and the decolouring processing selecting is utilized charcoal absorption.Purified product after the processing is analyzed through HPLC, its content 〉=98.0%.Can obtain the pure product soup compound of 297.2g after the drying treatment, productive rate is 92%.By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole.Concrete ultimate analysis situation is as follows: measured value (calculated value) C66.90% (66.87%); H5.21% (5.26%); N13.12 (13.00%).
Preparation embodiment four: (process program two)
[2-(preparation of 2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole]
Adopt the method identical with embodiment three, with 339.3g2-(2 '-hydroxyl-3 '-methylol-5 '-Te Xinji) benzotriazole is a raw material, and remaining remains unchanged, these the reaction time needs 5 hours, productive rate is 90%.
1HNMR,
13CNMR and MS have proved conclusively the structure of target compound.Concrete ultimate analysis situation is as follows: measured value (calculated value) C70.80% (70.76%); H7.10% (7.13%); N10.26 (10.32%).
Preparation embodiment five: (process program two)
[2-(preparation of 2 '-hydroxyl-3 '-(acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole]
Adopt the method identical with embodiment four, catalyzer changes the 0.5g lithium hydroxide into, and the methyl acrylate consumption is adjusted to the 900g while and do not used entrainment agent.In this case, the reaction times extends to 7 hours, and the reaction yield is 83%.
1HNMR,
13CNMR and MS have proved conclusively the structure of target compound.Concrete ultimate analysis situation is as follows: measured value (calculated value) C70.40% (70.23%); H6.79% (6.87%); N10.76 (10.69%).
Preparation embodiment six: (process program three)
[preparation of 2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole]
119.5g methyl methacrylate and 55.5g sodium hydroxide are neutralized, can obtain the anhydrous sodium salt of methacrylic acid of 150.0g by spray-dired mode.In the reaction vessel that is equipped with thermometer, agitator and condenser, add above-mentioned anhydrous sodium salt, 380g2-(2 '-hydroxyl-3 '-chloromethyl-5 '-methyl) benzotriazole, 1000mlDMF, 0.9g tetramethyl ammonium chloride and 0.6g thiodiphenylamine, 110 ℃ of following stirring reactions 4 hours.By the HPLC sampling analysis, the transformation efficiency that can learn 2-(2 '-hydroxyl-3 '-chloromethyl-5 '-methyl) benzotriazole 〉=99.5%.Reaction finishes sodium chloride salt that the back generated can be by in addition filtering of filter type.After removing DMF under the 10mmHg reduced pressure.After finishing, reaction reaction mixture is washed extraction treatment.Unreacted micro-benzotriazole reactant and other byproduct can drip washing mode wash-out in addition.Residue is proceeded decolouring, vacuum drying treatment.Leacheate is selected 50% aqueous ethanolic solution, and the decolouring processing selecting is utilized charcoal absorption.Purified product after the processing is analyzed through HPLC, its content 〉=98.0%.Can obtain the pure product soup compound of 408.2g after the drying treatment, productive rate is 91%.By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 2-(2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-methyl) benzotriazole.Concrete ultimate analysis situation is as follows: measured value (calculated value) C66.78% (66.87%); H5.09% (5.26%); N12.94 (13.00%).
Preparation embodiment seven: (process program three)
[2-(preparation of 2 '-hydroxyl-3 '-(Alpha-Methyl acryloyl yloxymethyl)-5 '-Te Xinji) benzotriazole]
Adopt the method identical with embodiment six, with 497g2-(2 '-hydroxyl-3 '-chloromethyl-5 '-Te Xinji) benzotriazole is a raw material, and remaining remains unchanged, these the reaction time needs 5 hours, productive rate is 90%.
1HNMR,
13CNMR and MS have proved conclusively the structure of target compound.Concrete ultimate analysis situation is as follows: measured value (calculated value) C70.84% (70.76%); H7.05% (7.13%); N10.21 (10.32%).
Can prepare following target compound (seeing Table 1) according to as above process program:
Table 1: the raw material of target compound and structural formula of compound
The Application Example part:
Application Example 1: the light stabilization in polypropylene PP flat filament
A) in turbomixer, be that 3.5 polypropylene powder mixes mutually with each related in the table 2 target compound 1g, 1g three (nonyl is for phenyl) phosphorous acid ester, 0.5g ethylene glycol [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic ester] and 1g calcium stearate with the 1Kg melt index.The extruding under 230 ℃ of this mixture is obtained the PP particle, stretch ratio 1: 6, PP flat filament: 50 μ m.
With above-mentioned flat filament bundle on blank and be exposed in the 65WR weather-o-meter (according to the ASTMD2565-85 standard) 64 ℃ of blackboard temperatures.Remain toughness by the sample of constant speed tensiometer after and measure, record thus and reach original toughness half (T the various time shutter
50) the needed time shutter.
Table 2:
The interpolation situation T of photostabilizer
50(hour)
There is not photostabilizer 400
Target compound 1 2400
Target compound 3 2490
Target compound 5 2700
Target compound 10 2900
B) according to a) method, only the addition with ethylene glycol [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic ester] is increased to the 1.0g/1000gPP powder.Its result such as table 3.
Table 3:
The interpolation situation T of photostabilizer
50(hour)
There is not photostabilizer 400
Target compound 1 3000
Target compound 3 3100
Target compound 5 3300
Target compound 10 3600
C) according to b) method, the addition with photostabilizer is increased to the 1.5g/1000gPP powder again.Its result such as table 4.
Table 4:
The interpolation situation T of photostabilizer
50(hour)
There is not photostabilizer 400
Target compound 1 3600
Target compound 3 3700
Target compound 5 3800
Target compound 10 4000
Application Example 2: the light stabilization in polypropylene PP fiber
The PP fibre-grade I:0.1% calcium stearate+0.05% β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid+0.05% 3 (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester+0.25%TiO2
Multifilament: 130/37dtex, stretch ratio: 1: 3.2,100% extensibility
Accelerated weathering test: xenon lamp aging test [Xenotest 1200], blackboard temperature: 55 ℃
Measure its tensile strength and drop to 50% o'clock required time, concrete outcome is as shown in table 5.
Table 5 photostabilizer type is to the influence of PP fiber optic stability
| Photostabilizer is handled | The tensile strength 50% o'clock required time that descends |
| Do not have | 280 |
| 0.1% target compound 1 | 800 |
| 0.1% target compound 2 | 850 |
| 0.1% target compound 7 | 1100 |
| 0.1% target compound 9 | 1200 |
| 0.15% target compound 3 | 1300 |
| 0.15% target compound 4 | 1380 |
| 0.15% target compound 8 | 1400 |
| 0.15% target compound 10 | 1700 |
Claims (7)
1. benzotriazole compound that has alkenyl ester type structure is characterized in that it is that general formula is the compound of (I):
Wherein, X=3, hydrogen, halogen, alkyl or the alkoxyl group of 4,5,6 replacements; R=alkyl, cycloalkyl, carboxylic acid group, aryl or substituted aryl; R1, R2 and R3 are hydrogen, alkyl or alkenyl independently; M is an alkylene.
2. as the said preparation method who has the benzotriazole compound of alkenyl ester type structure of claim 1, it is characterized in that it is through following process program: by general formula (II) compound of 3-hydroxyalkyl replacement
And general formula (IV) thiazolinyl formic acid
Carrying out alcoholic acid esterification reacts and prepares general formula (I) compound.
Among above-mentioned formula II, the IV, X, R, R1, R2, R3, the definition of M is with the definition in the general formula I.
3. as the said preparation method who has the benzotriazole compound of alkenyl ester type structure of claim 1, it is characterized in that it is through following process program: general formula (II) compound and logical formula V thiazolinyl formic acid lower alkyl ester
Carry out the transesterify reaction and prepare general formula (I) compound.
Among above-mentioned formula II, the V, X, R, R1, R2, R3, the definition of M is with the definition in the general formula I; R4 is C1～C4 alkyl.
4. as the said preparation method who has the benzotriazole compound of alkenyl ester type structure of claim 1, it is characterized in that it is through following process program: by general formula (III) compound that the 3-alkylhalide group replaces or the sulphonyl oxyalkyl replaces
And general formula (IV) thiazolinyl formic acid or its an alkali metal salt react and prepare general formula (I) compound.
Among above-mentioned formula III, the IV, X, R, R1, R2, R3, the definition of M is with the definition in the general formula I; Y is halogen and sulfonyloxy.
5. the compound of Formula I in the claim 1, R
1, R
2, R
3In one or more groups can be to be the unsaturated chain thiazolinyl, general formula I has the ester type structure of polyene-based feature.
6. as claim 1 and the 5 said application that have the benzotriazole compound of alkenyl ester type structure, it is characterized in that being used for the age inhibiting photostabilizer of polymkeric substance.
7. one kind is used claim 1 and the 5 said methods that have the benzotriazole compound of alkenyl ester type as photostabilizer, and the amount of application that it is characterized in that it is 0.05～10%.
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