CN1026118C - 对光诱导的降解稳定的合成聚合物组合物 - Google Patents
对光诱导的降解稳定的合成聚合物组合物 Download PDFInfo
- Publication number
- CN1026118C CN1026118C CN89109348A CN89109348A CN1026118C CN 1026118 C CN1026118 C CN 1026118C CN 89109348 A CN89109348 A CN 89109348A CN 89109348 A CN89109348 A CN 89109348A CN 1026118 C CN1026118 C CN 1026118C
- Authority
- CN
- China
- Prior art keywords
- ester
- acid
- reaction
- melamine
- carbon atom
- 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
- 229920000877 Melamine resin Polymers 0.000 title abstract description 6
- 239000004611 light stabiliser Substances 0.000 title abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title abstract description 4
- 229920003023 plastic Polymers 0.000 title description 3
- 239000004033 plastic Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229920000620 organic polymer Polymers 0.000 claims abstract 4
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 2
- 238000005286 illumination Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 125000003386 piperidinyl group Chemical group 0.000 abstract description 2
- -1 polypropylene Polymers 0.000 description 50
- 150000002148 esters Chemical class 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- DJHGZIHTRHTINN-UHFFFAOYSA-N 2-[[4,6-bis[bis(carboxymethyl)amino]-1,3,5-triazin-2-yl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C1=NC(N(CC(O)=O)CC(O)=O)=NC(N(CC(O)=O)CC(O)=O)=N1 DJHGZIHTRHTINN-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 150000003053 piperidines Chemical class 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005613 synthetic organic polymer Polymers 0.000 description 5
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003490 Thiodipropionic acid Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019303 thiodipropionic acid Nutrition 0.000 description 3
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000001589 carboacyl group Chemical group 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001924 fatty-acyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 230000035935 pregnancy Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical compound CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- GUGQQGROXHPINL-UHFFFAOYSA-N 2-oxobutanoyl chloride Chemical compound CCC(=O)C(Cl)=O GUGQQGROXHPINL-UHFFFAOYSA-N 0.000 description 1
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 description 1
- RYAIMSPHUVXLQI-UHFFFAOYSA-N 4-(aminomethyl)-2-(benzotriazol-2-yl)phenol Chemical compound NCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 RYAIMSPHUVXLQI-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical class OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- DJRCMVCFUPOPKC-UHFFFAOYSA-N CCCCCCCCCCCC(=NO)C1=CC=C(C)C=C1O Chemical compound CCCCCCCCCCCC(=NO)C1=CC=C(C)C=C1O DJRCMVCFUPOPKC-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- IBFHBLOKQVCABG-UHFFFAOYSA-N cyclohexyl 2-chloroacetate Chemical compound ClCC(=O)OC1CCCCC1 IBFHBLOKQVCABG-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 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
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YGTCLOWQFRNAGT-UHFFFAOYSA-N n-chloro-n-ethylformamide Chemical compound CCN(Cl)C=O YGTCLOWQFRNAGT-UHFFFAOYSA-N 0.000 description 1
- TUIAQSKEFHFDRQ-UHFFFAOYSA-N n-chloro-n-methylformamide Chemical compound CN(Cl)C=O TUIAQSKEFHFDRQ-UHFFFAOYSA-N 0.000 description 1
- YSBUANSGDLZTKV-UHFFFAOYSA-N n-phenylcarbamoyl chloride Chemical compound ClC(=O)NC1=CC=CC=C1 YSBUANSGDLZTKV-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- AGUWUIVKDXDKBT-UHFFFAOYSA-N phenyl 2-chloroacetate Chemical compound ClCC(=O)OC1=CC=CC=C1 AGUWUIVKDXDKBT-UHFFFAOYSA-N 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 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 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrogenated Pyridines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
含多个2,2,6,6-四烷基哌啶部分的三聚氰胺基化合物是有机聚合物的光稳定剂。
Description
本发明涉及当暴露于光化辐射时具有抗降解和抗褪色性能的聚合物组合物。具体讲,它涉及用有效量的含2,2,6,6-四烷基哌啶部分的三聚氰胺衍生物稳定的树脂如聚丙烯、聚乙烯等。本发明还涉及一组新的用作合成聚合物添加剂来延缓光降解作用的化合物。
许多合成的有机聚合物当暴露于阳光时都发生迅速劣化。为了防止这种迅速降解,人们已用各种添加剂来稳定这些树脂以抗有害辐射。这些添加剂包括UV吸收剂如羟基二苯甲酮类和羟苯基苯并三唑类、可用来淬灭受激态的有机镍配合物、以及最新的受阻胺光稳定剂(HALS)。HALS具有最通常取代在4-位的2,2,6,6-四烷基哌啶基,它作为自由基消除剂,由此抑制降解过程。
对一种作为有效的光稳定剂的化合物有许多要求,它必须能与掺有它的树脂相溶、具有足够的非挥发性以便在高温加工过程中或加工之后仍保留在树脂中、并且它能抵抗水提取作用。到目前为止所公开的哌啶化合物中,连有三嗪环的那些哌啶化合物在许多情况下是优选的,因为它们较全面地满足了上述标准。
尽管先有技术化合物通常是合成有机聚合物的有效的光稳定剂,但没有一种化合物能完全满足各种形式和用途的聚合物的稳定要求。
对于用于薄型制品如纤维和薄膜的那些聚合物材料来说更是如此。由于这些缺陷,所以就需要一些能更全面地满足所述要求的物质。
本发明公开了把有效量的新的含多烷基哌啶部分的三聚氰胺化合物掺入合成聚合物中来稳定该合成聚合物的方法。三聚氰胺基HALS可选自式Ⅰ所述的化合物。
式中R为下式基团:
Y选自-O-和-NH-;和
B为含1-10个碳原子的、直链或支链的二价亚烷基;
R1选自氢和含1-5个碳原子的烷基如甲基、乙基、正丙基等,优选为氢和甲基,最优选为氢;
R2独立地选自氢,氧,羟基,含1-18个碳原子的直链或支链的通过亚甲基联接的烷基如甲基、乙基、辛基、十八烷基或2-乙基己基,含2-18个碳原子的链烷酰基如乙酰基、丙酰基、丁酰基、异戊酰基或硬脂酰基,含3-4个碳原子的链烯基,含3-6个碳原子
的链烯酰基如丙烯酰基、甲基丙烯酰基、巴豆酰基,含3-6个碳原子的炔基如快丙基或2-丁炔基,氰甲基,2,3-环氧丙基,含7-15个碳原子的苄基或烷基苄基如3,5-二叔丁基-4-羟基苄基、3-叔丁基-4-羟基苄基或3-叔丁基-4-羟基-5-甲基苄基,基团-CH2-CH(OR3)-R4,以及式-(CH2)m-C(O)-Z所示的基团,其中当m为1或0时Z选自-O-R5和-N(R6)(R7),而当m为0时Z还可为-C(O)-OR8;
R3选自氢,含1-18个碳原子的脂族基如上述R2中的那些脂族基,芳脂基如苄基和苯乙基,以及含2-18个碳原子的脂酰基如R2中的那些脂酰基;
R4选自氢,含1-16个碳原子的烷基及苯基;
R5选自含1-18个碳原子的烷基,含5-12个碳原子的环烷基如环戊基、环己基、环辛基、环十二烷基,烯丙基,苄基,苯基,以及其中的R1和R2为上述基团的R;
R6和R7可相同或不同,选自氢,含1-8个碳原子的烷基如甲基、乙基、己基,含5-12个碳原子的环烷基如R2中的那些环烷基,含6-10个碳原子的芳基如4-甲基苯基、2-甲基苯基、4-丁基苯基,以及含7-15个碳原子的芳烷基如苄基、邻-,间-,对-烷基取代的苄基、和苯乙基。此外,R6和R7与它们所连的N-原子一起可形成5-7元环如吡咯烷、哌啶和高哌啶;
R8选自含1-18个碳原子的烷基如R2中的那些烷基,苯基,或苄基,优选为甲基或乙基。
式Ⅰ化合物可由式Ⅱ的官能化三聚氰胺与式Ⅲ的适当取代的醇或胺反应制备,
式中R9为低级烷基如甲基或乙基,
式中Y为-O-或-NH-。
该反应通常在溶剂如溶剂轻油或二甲苯、或任何其它溶剂中进行,这些溶剂应当能使上述反应可在其或接近于其回流温度下得以进行。反应中最好使用催化剂如氨化锂或四异丙氧基钛以及适于反应发生的其它催化剂。本发明的产物可从溶剂溶液中分离,并且通常可通过结晶、研制或任何其它合适的方法纯化。
式Ⅱ化合物可由适当的亚胺基二亚烷基酯或酸与氰尿酰氯反应生成其相应的三聚氰胺六亚烷基化合物来制备。该六元酸在转化成所需的本发明化合物前通常先被转化成六甲基或六乙基酯。
制备式Ⅰ化合物的另一种方法是在溶剂如二恶烷、甲苯或任何其它不妨碍该反应的溶剂中、在或接近于溶剂的回流温度下、在碱如碳酸盐、氢氧化物等(用来除去反应中产生的氯化氢)存在下由式Ⅳ化合物与氰尿酰氯反应,
式Ⅱ中B为亚甲基、Y为-O-和R9为甲基的起始化合物早在Ger.offen.1,935,010(1971)中描述过。合成路线为下述多步程序:
该程序包括由亚胺基二乙腈与氰尿酰氯反应生成三聚氰胺六乙腈,接着水解,然后酯化,得到了六元酯。
然后,在有或无溶剂存在下,在技术上已知的催化剂存在下用所需的醇或胺对这些酯进行酯基转移或酰胺化,得到了本发明化合物。不带来任何限制的合适溶剂的实例有溶剂轻油、二甲苯、甲苯等或其混合物。不带来任何限制的合适催化剂的实例有氨化锂和四异丙氧基钛。
该反应通常在或接近于所用溶剂的回流温度下进行,在其它情
况下,反应温度为100-200℃之间。反应产物通常可通过把反应混合物在水和反应溶剂之间进行分配,然后除去溶剂来分离。该产物可通过重结晶或任何其它合适方法纯化。
从德国专利2,352,658和美国专利3,684,765得知,用来把式Ⅱ酯转化成本发明化合物的4-羟基多烷基哌啶和4-氨基多烷基哌啶是已知的。通常,4-羟基化合物用阮内镍进行催化氢化还原制备,而4-氨基化合物用氨经还原胺化合成。
式Ⅴ的4-氧代哌啶可由氨与脂族酮反应制备。氨与丙酮反应生成三丙酮胺的反应是已知的,先有技术中有多种生产三丙酮胺的方法。氨与甲乙酮的反应已由W.Traube描述在Chem.Ber.,41,777(1908)中,
在2-位和6-位带有其它烷基取代基的式Ⅴ化合物可分两步按Hel.Chem.Acta 30,1114(1947)和Monatsh.Chem.88,464(1957)中概述的方法反应,然后水解所得嘧啶来制备。
烷基、链烯基、炔基、芳烷基及2,3-环氧丙基的引入反应可由最初制备的含游离的哌啶N-H的4-氧代哌啶或衍生化的三聚氰胺与合适的卤化物反应完成。合适的卤化物的实例包括碘甲烷、氯甲烷、溴乙烷、十二烷基氯、十八烷基氯、烯丙基溴、甲基烯丙基氯、丁烯基氯、炔丙基氯、苄基氯、苯乙基溴及表氯醇。生成的卤化氢
可通过于反应混合物中加入无机碱如碳酸盐或氢氧化物或加有机胺如三乙胺来除去。
制备含1-烷基、1-链烯基、1-炔基、1-芳烷基或2,3-环氧丙基的本发明化合物(特别是所需本发明化合物为一种酯时)的另一种方法是按美国专利4,014,887所述制备1-取代的多烷基哌啶-4-醇并按上述方式进行酯基转移。
链烷酰基或链烯酰基的引入反应可由合适的酰卤或方便时用酸酐对N-H基酰化来进行。如用使用酰卤,产生的卤化氢可通过上述同样方法除去。合适的酰化试剂有乙酰氯、乙酐、丙酐、己酰氯、十二烷酰氯及十八烷酰氯。
引入基团-CH2CH(O-R3)-R4时,取代基可通过母体N-H化合物与相应的氧化烯如氧化乙烯、氧化丙烯和氧化苯乙烯的反应来引入。所得羟基化合物可按通常先有技术中已知的方法用合适的酰卤酰化,并且可通过形成烷氧化物和与所需烷基卤反应烷基化。
当R2为基团-(CH2)m-C(O)-Z和m为0时,可由母体N-H化合物与氯甲酸酯如氯甲酸甲酯、氯甲酸乙酯、氯甲酸烯丙酯、氯甲酸己酯、氯甲酸癸酯、氯甲酸十八烷酯及氯甲酸苯酯反应引入适当基团。草酰胺半酯可由N-H化合物与草酰氯单烷基酯如草酰氯单乙酯反应并如上所述除去产生的氯化氢制备。
相应的脲的制备可用合适的氨甲酰卤处理母体N-H化合物完成,所述氨甲酰卤有,例如,甲基氨甲酰氯、乙基氨甲酰氯、二甲基氨甲酰氯、苯基氨甲酰氯、吡咯烷氨甲酰氯及哌啶氨甲酰氯。或者,脲也可以用合适的异氰酸酯处理母体N-H化合物制备。
当R2为氧或羟基时,可将母体N-H化合物在催化剂如钨酸钠存在
下用氧化剂如过氧化氢处理,或用过氧羧酸如间氯过氧苯甲酸处理,若所需的是羟基,则接着用催化氢化法来还原氧基。
当R2为基团-(CH2)m-C(O)-Z和m为1时,可由母体N-H化合物与合适的氯乙酸酯如氯乙酸甲酯、氯乙酸乙酯、氯乙酸烯丙酯、氯乙酸苯酯及氯乙酸环己基酯反应引入适当基团。
本发明的化合物是合成的有机聚合物的有效的光稳定剂。下述非限制性的实例是用来说明本发明的:
三聚氰胺六乙酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(1,2,2,6,6-五甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(1-丁基-2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(1-烯丙基-2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(1-氧-2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(1-乙酰基-2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六乙酸六(4-氨基-2,2,6,6-四甲基哌啶)酰胺
三聚氰胺六丙酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六丙酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六己酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六辛酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六癸酸六(2,2,6,6-四甲基-4-哌啶醇)酯,
三聚氰胺六(十一酸)六(2,2,6,6-四甲基-4-哌啶醇)酯。
本发明的化合物是合成有机聚合物的有效的光稳定剂,除了它们的有效的光稳定性质外,一些本发明化合物也表现出优良的热稳定性能。可用本发明化合物稳定的合成有机聚合物中包括聚烯烃类,它包括烯烃均聚物如聚乙烯、高和低密度聚乙烯、聚丙烯、聚丁二
烯、聚苯乙烯等;和烯烃与其它乙烯型不饱和单体的共聚物如乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-醋酸乙烯共聚物、苯乙烯-丁二烯共聚物等;三元共聚物如丙烯腈-丁二烯-苯乙烯共聚物等;聚氯乙烯,聚偏二氯乙烯,氯乙烯和偏二氯乙烯与醋酸乙烯或其它乙烯型不饱和单体的共聚物;聚缩醛如聚甲醛和聚氧化乙烯;聚酯如聚对苯二甲酸乙二醇酯;聚酰胺如聚酰胺6,聚酰胺6,6,聚酰胺6,10;聚氨酯和由α,β-不饱和酸及其衍生物得到的聚合物;聚碳酸酯;聚丙烯酸酯和聚甲基丙烯酸酯,聚丙烯酰胺和聚丙烯酯,以及丙烯酸和一种或几种它的衍生物与三聚氰胺-甲醛树脂形成的共聚物。
在上述各组聚合物中,特别重要的是聚烯烃的稳定化问题。本发明化合物可很好地用于聚烯烃的稳定作用。通常,按基于所要稳定的聚合物重量的0.01-5.0%(重量)的量把本发明的稳定剂加到要稳定的聚合物中。稳定剂用量为0.5-1%(重量)较好。
本发明化合物还可与其它稳定剂结合使用来制备稳定的组合物。所述其它添加剂可以是抗氧剂,辅助光稳定剂如受阻胺、金属减活剂等,颜料,着色剂,填料,阻燃剂,抗静电剂等。
合适的抗氧剂包括受阻酚型抗氧剂如2,6-二叔丁基对甲酚;4,4′-双(2,6-二异丙基苯酚);2,4,6-三叔丁基苯酚;2,2′-硫双(4-甲基-6-叔丁基酚);2-(3′,5′-二叔丁基-4′-羟基苯基)丙酸十八烷基酯;四(3,5′-二丁基-4-羟基苯基)丙酸季戊四醇酯;1,3,5-三(3,5′-二叔丁基-4′-羟基苄基)异氰脲酸酯;1,3,5-三(3,5′-二叔丁基-4′-羟基苯基)丙酸酯)异氰脲酸酯;1,3,5-三(3,5′-二叔丁基-4′-羟基苄基)-2,4,6-二甲基苄基)-均
三嗪-2,4,6-(1H,3H,5H)-三酮。
也包括硫二丙酸酯如硫二丙酸二月桂酯和硫二丙酸二硬脂基酯。
亚磷酸酯如亚磷酸三苯酯、亚磷酸三壬酯、二亚磷酸二(十二烷醇)季戊四醇酯、亚磷酸二苯基癸基酯、亚磷酸三(2,4-二叔丁基苯基)酯、二亚磷酸二(2,4-二叔丁基苯酚)季戊四醇酯可以被使用。
辅助光稳定剂包括,例如,苯并三唑类,包括2-(2′-羟基-5′-叔辛基苯基)苯并三唑;2-(2′-羟基-3′,5′-二叔丁基)-5-氯苯并三唑;2-(2′-羟基-5′-甲基苯基)苯并三唑;2-(2′-羟基-3′-叔丁基-5′-甲基苯基)苯并三唑;2-(2′-羟基-3′,5′-二叔戊基苯基)苯并三唑;羟基二苯甲酮类如2-羟基-4-甲氧基二苯甲酮;2-羟基-4-辛氧基二苯甲酮;2,2′-二羟基-4,4′-二甲氧基二苯甲酮;
受阻酚的酯类如3,5-二叔丁基-4-羟基苯甲酸正十六烷基酯和3,5-二叔丁基-4-羟基苯甲酸2′,4′-二叔丁基苯基酯;
金属配合物如2,2′-硫二(4,6-辛基苯酚)镍配合物;二丁基氨荒酸镍;4-羟基-3,5-二叔丁基苄基膦酸单烷基酯镍盐,其中烷基为甲基、乙基、丙基和丁基;以及2-羟基-4-甲基苯基十一烷基酮肟的镍配位化合物。
其它合适的辅助光稳定剂的实例可参见美国专利3,488,290和3,496,134。
下述非限制性制备实例用来说明本发明,其中所有比例都用重量表示,除非另有说明。
实例1
三聚氰胺六乙酸六(2,2,6,6-四甲基-4-哌啶醇)酯的制备
将按Ger.Offen.1,935,010中的方法制备的三聚氰胺六乙酸六甲酯(4.26g)和2,2,6,6-四甲基-4-哌啶醇(7.92g)的混合物用50ml溶剂轻油稀释后加热至回流。加入氨化锂(33mg),并加入另外50ml溶剂轻油。用2小时时间逐渐除去馏出液,并将混合物回流16小时,通过加入另外的溶剂,用水洗涤,干燥(MgSO4)并浓缩进行后处理,固体残留物用溶剂轻油重结晶后,得5.4g产物(mp115-188℃)。
实例2
三聚氰胺六乙酸六(1,2,2,6,6-五甲基-4-哌啶醇)酯的制备
将三聚氰胺六乙酸六甲酯(4.0g)和1,2,2,6,6-五甲基-4-哌啶醇(8.1g)的混合物合并在二甲苯(15ml)中并加热至100-105℃。此时加入催化剂四异丙基钛酸钛(0.15ml)。将该均相混合物加热到约140℃,并维持16小时以逐渐除去产生的甲醇。然后,将混合物冷却,溶于CH2Cl2中并用水洗涤。用CH2Cl2反洗水层,将有机提取液干燥(MgSO4)并浓缩后,得白色固体。用溶剂轻油重结晶,得7.8g产物(mp65-75℃)。
实例3-5
为了进一步说明上述化合物作为光稳定剂的效果,把实例1和2所述的物质分别掺到市售的由Hercules Corporation生产的商品Pro-Fax 6301 Polypropylene Resin中。用混有二氯甲烷的溶剂把光稳定剂以0.25%总树脂组合物重量的浓度掺到聚丙烯中。加入主要抗氧剂(β-3.5-二叔丁基-4-羟基苯基丙酸硬脂基酯(浓度0.2%)。然后将树脂在200℃挤塑并在6,000psi和188℃压塑,得
到厚度为5密耳的薄膜。按同样的步骤生产不含该光稳定剂的对照薄膜。将每种薄膜在阿特拉斯天候老化仪中暴露于氙弧光中,直到IR羰基增加0.5,此时被认为是破损点。
表1
实例号 稳定剂 破损时间(hrs)
3 对照 900
4 化合物1 >3500(继续上升)
5 化合物2 >3500(继续上升)
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US284,574 | 1988-12-15 | ||
US07/284,574 US4883831A (en) | 1988-12-15 | 1988-12-15 | Melamine-based light stabilizers for plastics |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1045100A CN1045100A (zh) | 1990-09-05 |
CN1026118C true CN1026118C (zh) | 1994-10-05 |
Family
ID=23090707
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN89109348A Expired - Fee Related CN1026118C (zh) | 1988-12-15 | 1989-12-15 | 对光诱导的降解稳定的合成聚合物组合物 |
Country Status (17)
Country | Link |
---|---|
US (1) | US4883831A (zh) |
EP (1) | EP0373779B1 (zh) |
JP (1) | JP2781036B2 (zh) |
KR (1) | KR0133661B1 (zh) |
CN (1) | CN1026118C (zh) |
AR (1) | AR247883A1 (zh) |
AT (1) | ATE117687T1 (zh) |
AU (1) | AU623957B2 (zh) |
CA (1) | CA2005233C (zh) |
DE (1) | DE68920846T2 (zh) |
DK (1) | DK632589A (zh) |
ES (1) | ES2066002T3 (zh) |
FI (1) | FI95798C (zh) |
GB (1) | GB8926493D0 (zh) |
IL (1) | IL92409A0 (zh) |
NO (1) | NO175432C (zh) |
ZA (1) | ZA898922B (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4883860A (en) * | 1988-12-15 | 1989-11-28 | Ici Americas Inc. | Triazine-based light stabilizers for plastics |
US5256787A (en) * | 1990-09-03 | 1993-10-26 | Ciba-Geigy Corporation | Tri-piperdine compounds as stabilizers for organic materials |
IT1243433B (it) * | 1990-10-03 | 1994-06-10 | Ciba Geigy Spa | Composti piperidin-triazinici atti all'impiego come stabilizzanti per materiali organici |
IT1270975B (it) * | 1993-06-03 | 1997-05-26 | Ciba Geigy Spa | Composti piperidin-triazinici atti all'impiego come stabilizzanti allaluce, al calore e alla ossidazione per materiali organici |
IT1264945B1 (it) * | 1993-07-16 | 1996-10-17 | Ciba Geigy Spa | Composti piperidinici atti all'impiego come stabilizzanti per materiali organici |
JP2009516039A (ja) * | 2005-11-17 | 2009-04-16 | ディーエスエム アイピー アセッツ ビー.ブイ. | 染色性が改善されたポリマーの調製方法 |
CN102051167A (zh) * | 2009-10-28 | 2011-05-11 | 中国科学院福建物质结构研究所 | 一种合成简便的高产率高性能稀土铕荧光材料 |
TWI513762B (zh) * | 2014-04-09 | 2015-12-21 | Fdc Lees Chemical Industry Co | 雙官能型安定劑及其組成物 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3485764A (en) * | 1964-05-22 | 1969-12-23 | American Cyanamid Co | Polymeric photochromic compositions stabilized with ultraviolet light absorbers |
US3496134A (en) * | 1967-06-20 | 1970-02-17 | American Cyanamid Co | Stabilization of rigid poly(vinylchloride) plastics with bis-amides and ultraviolet absorbers |
US3684765A (en) * | 1970-01-08 | 1972-08-15 | Sankyo Co | Stabilization of synthetic polymers |
US4348493A (en) * | 1981-07-20 | 1982-09-07 | American Cyanamid Company | Novel light stabilizers for polymers |
EP0107615B1 (de) * | 1982-09-30 | 1992-10-28 | Ciba-Geigy Ag | Mit Bis- oder Tris-(polyalkylpiperidinyl-amino)-1,3,5-triazine stabilisierte Polyolefine |
CA1266272A (en) * | 1983-05-27 | 1990-02-27 | Masakatsu Yoshimura | A 2,2,6,6-tetramethylpiperidine derivative, its production and a stabilizer for synthetic resins containing the same |
JPS61155368A (ja) * | 1984-12-28 | 1986-07-15 | Sumitomo Chem Co Ltd | ピペリジン誘導体、その製造方法およびこれを有効成分とする有機物質用安定剤 |
JPS6218443A (ja) * | 1985-07-17 | 1987-01-27 | Adeka Argus Chem Co Ltd | 安定化高分子材料組成物 |
EP0314472B1 (en) * | 1987-10-30 | 1994-06-22 | Sankyo Company Limited | Novel piperidyl-triazine derivatives and their use as polymer stabilizers |
US4883860A (en) * | 1988-12-15 | 1989-11-28 | Ici Americas Inc. | Triazine-based light stabilizers for plastics |
EP0389428A3 (en) * | 1989-03-21 | 1991-10-09 | Ciba-Geigy Ag | N,n-bis(l-hydroxycarbyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) amino triazines and stabilized compositions |
-
1988
- 1988-12-15 US US07/284,574 patent/US4883831A/en not_active Expired - Lifetime
-
1989
- 1989-11-22 ZA ZA898922A patent/ZA898922B/xx unknown
- 1989-11-23 DE DE68920846T patent/DE68920846T2/de not_active Expired - Fee Related
- 1989-11-23 IL IL92409A patent/IL92409A0/xx not_active IP Right Cessation
- 1989-11-23 EP EP89312186A patent/EP0373779B1/en not_active Expired - Lifetime
- 1989-11-23 GB GB898926493A patent/GB8926493D0/en active Pending
- 1989-11-23 AT AT89312186T patent/ATE117687T1/de not_active IP Right Cessation
- 1989-11-23 ES ES89312186T patent/ES2066002T3/es not_active Expired - Lifetime
- 1989-11-24 NO NO894691A patent/NO175432C/no unknown
- 1989-12-07 AR AR89315627A patent/AR247883A1/es active
- 1989-12-12 CA CA002005233A patent/CA2005233C/en not_active Expired - Fee Related
- 1989-12-14 JP JP1324853A patent/JP2781036B2/ja not_active Expired - Lifetime
- 1989-12-14 FI FI895985A patent/FI95798C/fi not_active IP Right Cessation
- 1989-12-14 DK DK632589A patent/DK632589A/da not_active Application Discontinuation
- 1989-12-14 AU AU46732/89A patent/AU623957B2/en not_active Ceased
- 1989-12-15 KR KR1019890018616A patent/KR0133661B1/ko not_active IP Right Cessation
- 1989-12-15 CN CN89109348A patent/CN1026118C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0373779A1 (en) | 1990-06-20 |
AR247883A1 (es) | 1995-04-28 |
CN1045100A (zh) | 1990-09-05 |
NO175432C (no) | 1994-10-12 |
CA2005233A1 (en) | 1990-06-15 |
FI95798C (fi) | 1996-03-25 |
US4883831A (en) | 1989-11-28 |
DK632589A (da) | 1990-06-16 |
ES2066002T3 (es) | 1995-03-01 |
ZA898922B (en) | 1990-11-28 |
AU623957B2 (en) | 1992-05-28 |
AU4673289A (en) | 1990-06-21 |
FI95798B (fi) | 1995-12-15 |
NO175432B (no) | 1994-07-04 |
GB8926493D0 (en) | 1990-01-10 |
NO894691D0 (no) | 1989-11-24 |
KR0133661B1 (ko) | 1998-04-23 |
DK632589D0 (da) | 1989-12-14 |
KR900009629A (ko) | 1990-07-05 |
DE68920846D1 (de) | 1995-03-09 |
NO894691L (no) | 1990-06-18 |
ATE117687T1 (de) | 1995-02-15 |
EP0373779B1 (en) | 1995-01-25 |
IL92409A0 (en) | 1990-07-26 |
DE68920846T2 (de) | 1995-05-24 |
JPH02218677A (ja) | 1990-08-31 |
FI895985A0 (fi) | 1989-12-14 |
CA2005233C (en) | 1999-04-13 |
JP2781036B2 (ja) | 1998-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101915874B1 (ko) | 자외선 및 열 분해에 대해 물질을 안정화하기 위한 안정화 조성물 | |
CN1154685C (zh) | 保护聚合物免受紫外光损害的聚合物制品、光稳定添加剂组合物和光稳定添加剂母料 | |
EP1481024B1 (en) | Uv stabilized thermoplastic olefins | |
CN1026118C (zh) | 对光诱导的降解稳定的合成聚合物组合物 | |
JP2017518430A5 (zh) | ||
JPS6341394B2 (zh) | ||
CN1028370C (zh) | 对光诱导的降解稳定的合成聚合物组合物 | |
JP2000512676A (ja) | Nor―hals化合物を使用するポリマーの分解 | |
US6265473B1 (en) | Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials | |
JP5420179B2 (ja) | ポリ乳酸樹脂組成物 | |
CN1875061A (zh) | 紫外稳定添加剂组合物 | |
US5300545A (en) | Process for stabilizing polymer compositions against heat or light effects | |
JPH031304B2 (zh) | ||
CN1045102A (zh) | 四甲基哌啶基终止的三嗪低聚酯和酰胺 | |
US4983738A (en) | Reactive hindered amine light stabilizers | |
CN1045103A (zh) | 含二哌啶基三嗪基团的低聚酯和低聚酰胺 | |
ITMI930661A1 (it) | Composti piperidin-triazinici atti all'impiego come stabilizzanti per materiali organici | |
CA1252596A (en) | Polymeric compounds containing piperidine groups | |
JPS62116584A (ja) | マロン酸エステルを基礎にしたプラスチツク用光安定剤 | |
US5214147A (en) | Process for preparing reactive hindered amine light stabilizers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C53 | Correction of patent of invention or patent application | ||
CB02 | Change of applicant information |
Applicant after: ICI Americas Inc. Applicant before: ICI Americas Inc. |
|
COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: ICI AMERICAS INC. (US) CONCORD PIKE + NEW MURPHY ROAD, WILMINGTON, DE, U.S.A. TO: ZENECA ( AMERICA ) CO., LTD. |
|
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |