CN1432042A - 稳定剂混合物 - Google Patents
稳定剂混合物 Download PDFInfo
- Publication number
- CN1432042A CN1432042A CN01810328A CN01810328A CN1432042A CN 1432042 A CN1432042 A CN 1432042A CN 01810328 A CN01810328 A CN 01810328A CN 01810328 A CN01810328 A CN 01810328A CN 1432042 A CN1432042 A CN 1432042A
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- China
- Prior art keywords
- component
- classification
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- general formula
- alkyl
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 239000003381 stabilizer Substances 0.000 title claims abstract description 22
- -1 amine compound Chemical class 0.000 claims abstract description 142
- 150000001875 compounds Chemical class 0.000 claims description 78
- 239000000049 pigment Substances 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 39
- 239000011368 organic material Substances 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 230000001939 inductive effect Effects 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 48
- 150000002148 esters Chemical class 0.000 description 25
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 25
- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 19
- 239000002585 base Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 150000001408 amides Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 229960003742 phenol Drugs 0.000 description 11
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 10
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 10
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- CMXLJKWFEJEFJE-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound C1=CC(OC)=CC=C1C=C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(=O)OC1CC(C)(C)N(C)C(C)(C)C1 CMXLJKWFEJEFJE-UHFFFAOYSA-N 0.000 description 8
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229940059574 pentaerithrityl Drugs 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 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 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- PMNGNPRHPYYVNM-UHFFFAOYSA-N 1-hydroxyundecane-3-sulfonic acid Chemical compound CCCCCCCCC(CCO)S(O)(=O)=O PMNGNPRHPYYVNM-UHFFFAOYSA-N 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ICHKVCYUNCKCGL-UHFFFAOYSA-N CN(C)C.OCCCCCCO Chemical compound CN(C)C.OCCCCCCO ICHKVCYUNCKCGL-UHFFFAOYSA-N 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- COVMBDWAODLWIB-UHFFFAOYSA-N n'-(2-hydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCCO COVMBDWAODLWIB-UHFFFAOYSA-N 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 2
- HWRLEEPNFJNTOP-UHFFFAOYSA-N 2-(1,3,5-triazin-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC=NC=N1 HWRLEEPNFJNTOP-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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Abstract
稳定剂混合物,其含有(I)一种低分子量烷基化位阻胺化合物;和(II)一种高分子量烷基化位阻胺化合物。
Description
本发明涉及含有一种特定的低分子量烷基化位阻胺化合物和一种特定的高分子量位阻胺化合物的稳定剂混合物,这一混合物用于稳定有机材料(尤其聚烯烃)以抵抗由光、热或氧化诱导的降解的用途和如此被稳定的有机材料。
聚烯烃类的稳定被描述在很多出版物中,例如在US-A-4,692,468,US-A-4,863,981,US-A-5,719,217,US-A-6,015,849,US-A-6,020,406,US-A-5,965,643,US-A-5,980,783,US-A-5,919,399,US-A-5,817,821,US-A-6,126,861和EP-A-345,220.中。用于太阳能电池组件和层压玻璃的紫外线稳定添加剂包已公开在WO-A-99/05,206中。
更详细地,本发明涉及稳定剂混合物,其含有(I)选自类别(α-1),(α-2),(α-3),(α-4)和(α-5)中的一种位阻胺化合物;和(II)选自类别(β-1),(β-2),(β-3)和(β-4)中的一种位阻胺化合物;(α-1)通式(A-1)的化合物:其中E1是C1-C4烷基,m1是1,2或4,如果m1是1,则E2是C1-C25烷基,如果m1是2,则E2是C1-C14亚烷基或通式(a-I)的基团:其中E3是C1-C10烷基或C2-C10链烯基,E4是C1-C10亚烷基,和E5和E6彼此独立地是C1-C4烷基,环己基或甲基环己基,和如果m1是4,则E2是C4-C10链烷四基;(α-2)通式(A-2)的化合物:其中两个基团E7是-COO-(C1-C20烷基),和两个基团E7是通式(a-II)的基团:其中E8具有E1的意义中的一个;(α-3)通式(A-3)的化合物:其中E9是C1-C24烷基,和E10具有E1的意义中的一个:(α-4)通式(A-4)的化合物:其中该基团E11彼此独立地具有E1的意义中的一个,和E12是氢,C1-C12烷基或C1-C12烷氧基;(α-5)通式(A-5)的化合物:其中E13具有E1的意义中的一个,和E14是通式(a-III)的基团:其中该基团E15彼此独立地是C2-C12亚烷基,和基团E16彼此独立地是C1-C12烷基或C5-C12环烷基;(β-1)通式(B-1)的化合物:其中R1,R3,R4和R5彼此独立地是氢,C1-C12烷基,C5-C12环烷基,C1-C4-烷基取代的C5-C12环烷基,苯基,被-OH和/或C1-C10烷基取代的苯基;C7-C9苯基烷基,在苯基上被-OH和/或C1-C10烷基取代的C7-C9苯基烷基;或下式(b-I)的基团:R2是C2-C18亚烷基,C5-C7亚环烷基或C1-C4亚烷基二(C5-C7亚环烷基),或基团R1,R2和R3与它们所键接的氮原子一起构成了5-到10-员杂环,或
R4和R5与它们所连接的氮原子一起构成了5-到10-员杂环,R6是C1-C4烷基,和b1是2-50的数,前提条件是基团R1,R3,R4和R5中至少一个是通式(b-I)的基团;(β-2)通式(B-2)的化合物:其中R7和R11彼此独立地是氢或C1-C12烷基,R8,R9和R10彼此独立地是C2-C10亚烷基,和X1,X2,X3,X4,X5,X6,X7和X8彼此独立地是通式(b-II)的基团,其中R12是氢,C1-C12烷基,C5-C12环烷基,C1-C4-烷基取代的C5-C12环烷基,苯基,-OH和/或C1-C10烷基取代的苯基;C7-C9苯基烷基,在苯基上被-OH和/或C1-C10烷基取代的C7-C9苯基烷基;或如以上所定义的通式(b-I)的基团,和R13具有R6的意义中的一个;(β-3)通式(B-3)的化合物:其中R14,R15,R16,R17和R18彼此独立地是直接的键或C1-C10亚烷基,R19具有R6的意义中的一个,和b2是1到50的数;(β-4)可由通式(B-4-1)的多胺与氰尿酰氯反应获得的产物再与通式(B-4-2)的化合物进行反应来获得的产物(B-4) 其中b′3,b″3和b3彼此独立地是2-12的数,R20是氢,C1-C12烷基,C5-C12环烷基,苯基或C7-C9苯基烷基,和R21具有R6的意义中的一个。
具有至多25个碳原子的烷基的例子是甲基,乙基,丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,2-乙基丁基,正戊基,异戊基,1-甲基戊基,1,3-二甲基-丁基,正己基,1-甲基己基,正庚基,异庚基,1,1,3,3-四甲基丁基,1-甲基庚基,3-甲基庚基,正辛基,2-乙基己基,1,1,3-三甲基己基,1,1,3,3-四甲基戊基,壬基,癸基,十一基,1-甲基十一烷基,十二烷基,1,1,3,3,5,5-六甲基己基,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,二十烷基和二十二烷基。E1,E8,E10,E11,E13,R6,R13,R19和R21优选是甲基。R20优选是丁基。
具有至多12个碳原子的烷氧基的例子是甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,异丁氧基,戊氧基,异戊氧基,己氧基,庚氧基,辛氧基,癸氧基和十二烷氧基。
C5-C12环烷基的例子是环戊基,环己基,环庚基,环辛基和环十二烷基。C5-C8环烷基,尤其环己基,是优选的。
C1-C4烷基取代的C5-C12环烷基例如是甲基环己基或二甲基环己基。
-OH-和/或C1-C10烷基取代的苯基例如是甲基苯基,二甲基苯基,三甲基苯基,叔丁基苯基或3,5-二叔丁基-4-羟苯基。
C7-C9苯基烷基的例子是苄基和苯基乙基。
在苯基上被-OH和/或被具有至多10个碳原子的烷基取代的C7-C9苯基烷基例如是甲基苄基,二甲基苄基,三甲基苄基,叔丁基苄基或3,5-二叔丁基-4-羟基苄基。
具有至多10个碳原子的链烯基的例子是烯丙基,2-甲基烯丙基,丁烯基,戊烯基和己烯基。烯丙基是优选的。在1位上的碳原子优选是饱和的。
具有至多18个碳原子的亚烷基的例子是亚甲基,亚乙基,亚丙基,三亚甲基,四亚甲基,五亚甲基,2,2-二甲基三亚甲基,六亚甲基,三甲基六亚甲基,八亚甲基和十亚甲基。
C4-C10链烷四基的例子是1,2,3,4-丁烷四基。
C5-C7亚环烷基的例子是亚环己基。
C1-C4亚烷基二(C5-C7亚环烷基)的例子是亚甲基二亚环己基。
6-员杂环是优选的。
当基团R4和R5与它们所连接的氮原子一起形成5-到10-员杂环时,该环例如是1-吡咯烷基,哌啶基,吗啉代,1-哌嗪基,4-甲基-1-哌嗪基,1-六氢吖庚因基,5,5,7-三甲基-1-高哌嗪基或4,5,5,7-四甲基-1-高哌嗪基。吗啉代是特别优选的。
R15优选是直接的键。
b1优选是2到25,尤其2到20的数。
b2优选是1到25,尤其1到20的数。
B′3和b3优选是3和b″3优选是2。
以上作为组分(I)和(II)描述的化合物是基本上已知的。它们当中的大多数是市场上可买到的。它们全部能够通过已知方法制备。
组分(I)的化合物的制备公开在例如US-A-5,679,733,US-A-3,640,928,US-A-4,198,334,US-A-4,619,958,US-A-4,619,956,GB-A-2,269,819和US-A-5,071,981中。
组分(II)的制备公开在例如US-A-4,086,204,US-A-6,046,304,US-A-4,331,586,US-A-4,108,829,US-A-4,529,760和US-A-4,477,615中。
该产物(B-4)能够用与已知方法类似的方法制备,例如由通式(B-4-1)的多胺与氰尿酰氯按1∶2到1∶4的摩尔比率在有机溶剂如1,2-二氯乙烷,甲苯,二甲苯,苯,二噁烷或叔戊醇中在无水碳酸锂、碳酸钠或碳酸钾存在下,在-20℃到+10℃,优选-10℃到+10℃,尤其0℃到+10℃的温度下,进行反应2-8小时,随后让所获得的产物与通式(B-4-2)的2,2,6,6-四甲基-4-哌啶基胺反应。2,2,6,6-四甲基-4-哌啶基胺与所用通式(B-4-1)的多胺的摩尔比是例如4∶1到8∶1。2,2,6,6-四甲基-4-哌啶基胺的量能够分为一份添加或在几个小时的间隔中作为一个以上的份数添加。
通式(B-4-1)的多胺与氰尿酰氯与通式(B-4-2)的2,2,6,6-四甲基-4-哌啶基胺的摩尔比优选是1∶3∶5到1∶3∶6。
下列实施例指明制备该优选的产物(B-4-a)的一个途径。
实施例:23.6g(0.128mol)的氰尿酰氯,7.43g(0.0426mol)的N,N′-双[3-氨基丙基]乙二胺和18g(0.13mol)无水碳酸钾在5℃和搅拌下在250ml 1,2-二氯乙烷中进行反应3小时。混合物在室温下温热另外4小时。添加29.0g(0.128mol)的N-(1,2,2,6,6-五甲基-4-哌啶基)丁胺,所获得的混合物在60℃加热2小时。添加另外18g(0.13mol)的无水碳酸钾,混合物在60℃下加热另外6小时。溶剂通过在轻微的真空(200毫巴)下蒸馏被除去并被二甲苯置换。添加19.4g(0.085mol)的N-(1,2,2,6,6-五甲基-4-哌啶基)丁胺和5.2g(0.13mol)的研磨氢氧化钠,混合物在回流下加热2小时,和在另外的12小时中,在反应过程中所形成的水通过共沸蒸馏被除去。混合物被过滤。溶液用水洗涤和在Na2SO4上干燥。溶剂被蒸发掉,残留物在120-130℃和真空(0.1毫巴)条件下干燥。获得了无色树脂形式的所需产物。
一般,产物(B-4)例如能够由通式(B-4-α),(B-4-β)或(B-4-γ)的化合物表示。它也能够是这三种化合物的混合物形式。 通式(B-4-α)的优选定义是通式(B-4-β)的优选定义是通式(B-4-γ)的优选定义是在以上通式(B-4-α)至(B-4-γ)中,b3优选是2-20,尤其2-10。优选地,组分(I)的位阻胺化合物选自以下商购产品:TINUVIN765(RTM),TINUVIN144(RTM),ADK STAB LA-52(RTM),ADK STABLA-62(RTM),SANDUVOR3056(RTM),SANDUVOR PR31(RTM)和GOODRITE UV 3159(RTM).
商购产品DASTIB845(RTM)的N-甲基化形式(在2,2,6,6-四甲基-4-哌啶基中氮的甲基化)能够容易地通过已知方法,例如用与US-A-6,046,304,实施例2中描述的方法类似的方法来获得。所获得的化合物也优选用作组分(I)。
优选地,组分(II)的位阻胺化合物选自以下商购产品:CYASORB UV 3529(RTM),CHIMASSORB 119(RTM)和ADK STAB LA-63(RTM).
商购产品CHIMASSORB 944(RTM),CHIMASSORB 2020(RTM)和UVASORB HA 88(RTM)的N-甲基化形式(在2,2,6,6-四甲基-4-哌啶基中氮的甲基化)也能够容易通过已知方法,例如用与以上所述的同样方法类似的方法来获得。所获得的化合物同样地优选用作组分(II)。
饱和了通式(B-1),(B-3),(B-4-α),(B-4-β)和(B-4-γ)的化合物中的自由价的端基的意义取决于用于制备它们的方法。该端基也能够在化合物的制备之后改性。
如果通式(B-1)的化合物通过下式的化合物其中X是例如卤素,尤其氯,及R4和R5如以上所定义,与下式的化合物反应来制得,其中R1,R2和R3如以上所定义,键接于二氨基基团上的端基是氢或和键接到三嗪基团上的端基是X或
如果X是卤素,理想的是当反应完成时让它例如被-OH或氨基取代。可提及的氨基的例子是吡咯烷-1-基,吗啉代,-NH2,-N((C1-C8)烷基)2和-NR(C1-C8烷基),其中R是氢或通式(b-I)的基团。
其中R1,R2,R3,R4,R5和b1如以上所定义,和R4 *具R4的意义中的一个和R5 *具有R5的意义中的一个。
优选的稳定剂混合物是符合下列条件的一种混合物:组分(I)选自类别(α-1),和组分(II)选自类别(β-1);或组分(I)选自类别(α-1),和组分(II)选自类别(β-2);或组分(I)选自类别(α-1),和组分(II)选自类别(β-3);或组分(I)选自类别(α-1),和组分(II)选自类别(β-4);或组分(I)选自类别(α-2),和组分(II)选自类别(β-1);或组分(I)选自类别(α-2),和组分(II)选自类别(β-2);或组分(I)选自类别(α-2),和组分(II)选自类别(β-3);或组分(I)选自类别(α-2),和组分(II)选自类别(β-4);或组分(I)选自类别(α-3),和组分(II)选自类别(β-1);或组分(I)选自类别(α-3),和组分(II)选自类别(β-2);或组分(I)选自类别(α-3),和组分(II)选自类别(β-3);或组分(I)选自类别(α-3),和组分(II)选自类别(β-4);或组分(I)选自类别(α-4),和组分(II)选自类别(β-1);或组分(I)选自类别(α-4),和组分(II)选自类别(β-2);或组分(I)选自类别(α-4),和组分(II)选自类别(β-3);或组分(I)选自类别(α-4),和组分(II)选自类别(β-4);或组分(I)选自类别(α-5),和组分(II)选自类别(β-1);或组分(I)选自类别(α-5),和组分(II)选自类别(β-2);或组分(I)选自类别(α-5),和组分(II)选自类别(β-3);或组分(I)选自类别(α-5),和组分(II)选自类别(β-4)。
根据优选的实施方案,
m1是1,2或4,
如果m1是1,则E2是C12-C20烷基,
如果m1是2,则E2是C2-C10亚烷基或通式(a-I)的基团,
E3是C1-C4烷基,
E4是C1-C6亚烷基,和
E5和E6彼此独立地是C1-C4烷基,和
如果m1是4,则E2是C4-C8链烷四基:
两个基团E7是-COO-(C10-C15烷基),和
两个基团E7是通式(a-II)的基团;
E9是C10-C14烷基;
E12是C1-C4烷氧基;
基团E15彼此独立地是C2-C6亚烷基,和
基团E16彼此独立地是C1-C4烷基或C5-C8环烷基;
R1和R3彼此独立地是通式(b-I)的基团,
R2是C2-C8亚烷基,
R4和R5彼此独立地是氢,C1-C12烷基,C5-C8环烷基或通式(b-I)的基团,或基团R4和R5与它们所连接的氮原子一起形成5-到10-员杂环,和
b1是2-25的数;
R7和R11彼此独立地是氢或C1-C4烷基,
R8,R9和R10彼此独立地是C2-C4亚烷基,和
X1,X2,X3,X4,X5,X6,X7和X8彼此独立地是通式(b-II)的基团,
R12是氢,C1-C4烷基,C5-C8环烷基或通式(b-I)的基团;
R14,R15,R16,R17和R18彼此独立地是直接的键或C1-C4亚烷基,和
b2是1到25的数;
b′3,b″3和b3彼此独立地是2-4的数,和
R20是氢,C1-C4烷基,C5-C8环烷基,苯基或苄基。
其它优选的实施方案对应于稳定剂混合物,其中
组分(I)是通式(A-1-a),(A-1-b),(A-1-c),(A-1-d),(A-2-a),(A-3-a),(A-4-a)或(A-5-a)的化合物;和
组分(II)是通式(B-1-a),(B-1-b),(B-1-c),(B-2-a),(B-3-a)的化合物或产物(B-4-a); 其中两个基团E7是-COO-C13H27,和两个基团E7是 其中b1是2-20的数;其中b2是1-20的数;可通过由通式(B-4-1-a)的多胺与氰尿酰氯反应所获得的产物再与通式(B-4-2-a)的化合物反应来获得的产物(B-4-a)。
组分(I)优选是通式(A-1-a),(A-1-b),(A-1-c),(A-1-d),(A-2-a),(A-3-a),(A-4-a)或(A-5-a)的化合物;和
组分(II)优选是通式(B-1-c)或(B-2-a)的化合物。
组分(I)尤其是通式(A-1-b)的化合物和组分(II)尤其是通式(B-1-c)或(B-2-a)的化合物。
根据本发明的稳定剂混合物的优选的实例是:1.通式(A-1-a)的化合物+CHIMASSORO 119(RTM)2.TINUVIN 765(RTM)+CHIMASSORB 119(RTM)3.TINUVIN 144(RTM)+CHIMASSORB 119(RTM)4.ADK STAB LA-52(RTM)+CHIMASSORB 119(RTM)5.ADK STAB LA-62(RTM)+CHIMASSORB 119(RTM)6.SANDUVOR 3056(RTM)+CHIMASSORB 119(RTM)7.SANDUVOR PR 31(RTM)+CHIMASSORB 119(RTM)8.GOODRITE UV 3159(RTM)+CHIMASSORB 119(RTM)9.通式(A-1-a)的化合物+CYASORB UV 3529(RTM)10.TINUVIN 765(RTM)+CYASORB UV 3529(RTM)11.TINUVIN 144(RTM)+CYASORB UV 3529(RTM)12.ADK STAB LA-52(RTM)+CYASORB UV 3529(RTM)13.ADK STAB LA-62(RTM)+CYASORB UV 3529(RTM)14.SANDUVOR 3056(RTM)+CYASORB UV 3529(RTM)15.SANDUVOR PR 31(RTM)+CYASORB UV 3529(RTM)16.GOODRITE UV 3159(RTM)+CYASORB UV 3529(RTM)17.通式(A-1-a)的化合物+ADK STAB LA-63(RTM)18.TINUVIN 765(RTM)+ADK STAB LA-63(RTM)19.TINUVIN 144(RTM)+ADK STAB LA-63(RTM)20.ADK STAB LA-52(RTM)+ADK STAB LA-63(RTM)21.ADK STAB LA-62(RTM)+ADK STAB LA-63(RTM)22.SANDUVOR 3056(RTM)+ADK STAB LA-63(RTM)23.SANDUVOR PR 31(RTM)+ADK STAB LA-63(RTM)24.GOODRITE UV 3159(RTM)+ADK STAB LA-63(RTM)25.通式(A-1-a)的化合物+通式(B-1-a)的化合物26.TINUVIN 765(RTM)+通式(B-1-a)的化合物27.TINUVIN 144(RTM)+通式(B-1-a)的化合物28.ADK STAB LA-52(RTM)+通式(B-1-a)的化合物29.ADK STAB LA-62(RTM)+通式(B-1-a)的化合物30.SANDUVOR 3056(RTM)+通式(B-1-a)的化合物31.SANDUVOR PR 31(RTM)+通式(B-1-a)的化合物32.GOODRITE UV 3159(RTM)+通式(B-1-a)的化合物33.通式(A-1-a)的化合物+通式(B-1-b)的化合物34.TINUVIN 765(RTM)+通式(B-1-b)的化合物35.TINUVIN 144(RTM)+通式(B-1-b)的化合物36.ADK STAB LA-52(RTM)+通式(B-1-b)的化合物37.ADK STAB LA-62(RTM)+通式(B-1-b)的化合物38.SANDUVOR 3056(RTM)+通式(B-1-b)的化合物39.SANDUVOR PR 31(RTM)+通式(B-1-b)的化合物40.GOODRITE UV 3159(RTM)+通式(B-1-b)的化合物41.通式(A-1-a)的化合物+产物(B-4-a)42.TINUVIN 765(RTM)+产物(B-4-a)43.TINUVIN 144(RTM)+产物(B-4-a)44.ADK STAB LA-52(RTM)+产物(B-4-a)45.ADK STAB LA-62(RTM)+产物(B-4-a)46.SANDUVOR 3056(RTM)+产物(B-4-a)47.SANDUVOR PR 31(RTM)+产物(B-4-a)48.GOODRITE UV 3159(RTM)+产物(B-4-a)
商品TINUVIN 765(RTM)对应于通式(A-1-b)的化合物。
商品TINUVIN 144(RTM)对应于通式(A-1-c)的化合物。
商品ADK STAB LA-52(RTM)对应于通式(A-1-d)的化合物。
商品ADK STAB LA-62(RTM)对应于通式(A-2-a)的化合物。
商品SANDUVOR 3056(RTM)对应于通式(A-3-a)的化合物。
商品SANDUVOR PR 31(RTM)对应于通式(A-4-a)的化合物。
商品GOODRITE UV 3159(RTM)对应于通式(A-5-a)的化合物。
商品CHIMASSORB 119(RTM)对应于通式(B-2-a)的化合物。
商品CYASORB UV 3529(RTM)对应于通式(B-1-c)的化合物。
商品ADK STAB LA-63(RTM)对应于通式(B-3-a)的化合物。
本发明的其它优选的实施方案涉及另外含有下列组分的稳定剂混合物(X-1)颜料或(X-2)UV吸收剂或(X-3)颜料和UV吸收剂。
颜料(组分(X-1))可以是无机或有机颜料。
无机颜料的例子是二氧化钛,氧化锌,炭黑,硫化镉,硒化镉,氧化铬,氧化铁,氧化铅等等。
有机颜料的例子是偶氮颜料,蒽醌,酞菁,四氯异二氢吲哚酮,喹吖啶酮,异二氢吲哚,苝,吡咯并吡咯(如颜料红254)等。
在“Gchter/Müller:Plastics Additives Handbook,第三版,Hanser Publishers,Munich Vienna New York”,647到659页,11.2.1.1到11.2.4.2点中描述的全部颜料能够用作组分(X-1)。
特别优选的颜料是二氧化钛,任选与有机颜料结合。
此类有机颜料的例子是:
C.I.(颜色索引)颜料黄93,C.I.颜料黄95,C.I.颜料黄138,C.I.颜料黄139,C.I.颜料黄155,C.I.颜料黄162,C.I.颜料黄168,C.I.颜料黄180,C.I.颜料黄183,C.I.颜料红44,C.I.颜料红170,C.I.颜料红202,C.I.颜料红214,C.I.颜料红254,C.I.颜料红264,C.I.颜料红272,C.I.颜料红48∶2,C.I.颜料红48∶3,C.I.颜料红53∶1,C.I.颜料红57∶1,C.I.颜料绿7,C.I.颜料蓝15∶1,C.I.颜料蓝15∶3和C.I.颜料紫19.
UV吸收剂(组分(X-2))的例子是2-(2′-羟苯基)苯并三唑,2-羟基二苯甲酮,取代或未被取代的苯甲酸的酯,丙烯酸酯,草酰胺,2-(2-羟苯基)-1,3,5-三嗪,间苯二酚的单苯甲酸酯或甲脒。
2-(2′-羟苯基)苯并三唑是,例如,2-(2′-羟基-5′-甲基苯基)-苯并三唑,2-(3′,5′-二-叔丁基-2′-羟苯基)苯并三唑,2-(5′-叔丁基-2′-羟苯基)苯并三唑,2-(2′-羟基-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3′,5′-二-叔丁基-2′-羟苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑,2-(3′-仲丁基-5′-叔丁基-2′-羟苯基)苯并三唑,2-(2′-羟基-4′-辛氧基苯基)苯并三唑,2-(3′,5′-二-叔戊基-2′-羟苯基)苯并三唑,2-(3′,5′-双(α,α-二甲基苄基)-2′-羟苯基)苯并三唑,以下成分的混合物:2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2′-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚]或,2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;[R-CH2CH2-COO(CH2)3-]2,其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基。
2-(3′,5′-二-叔丁基-2′-羟苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑和2-(3′,5′-二-叔戊基-2′-羟苯基)-苯并三唑是优选的。
2-羟基二苯甲酮是例如4-羟基,4-甲氧基,4-辛氧基,4-癸氧基,4-十二烷氧基,4-苄氧基,4,2′,4′-三羟基或2′-羟基-4,4′-二甲氧基衍生物。
2-羟基-4-辛氧基二苯甲酮是优选的。
取代或未被取代的苯甲酸的酯是例如水杨酸4-叔丁基-苯基酯,水杨酸苯基酯,水杨酸辛基苯基酯,二苯甲酰间苯二酚,双(4-叔丁基苯甲酰基)间苯二酚,苯甲酰基间苯二酚,3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯,3,5-二叔丁基-4-羟基苯甲酸十六烷基酯,3,5-二叔丁基-4-羟基-苯甲酸十八烷基酯或3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯和3,5-二叔丁基-4-羟基苯甲酸十六烷基酯是优选的。
该丙烯酸酯是例如α-氰基-β,β-二苯基丙烯酸乙基酯,α-氰基-β,β-二苯基丙烯酸异辛基酯,α-甲酯基肉桂酸甲基酯,α-氰基-β-甲基-对-甲氧基-肉桂酸甲基酯,α-氰基-β-甲基-对-甲氧基-肉桂酸丁基酯,α-甲酯基-对-甲氧基肉桂酸甲基酯或N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。该草酰胺是例如4,4′-二辛氧基N,N’草酰二苯胺,2,2′-二乙氧基N,N’草酰二苯胺,2,2′-二辛氧基-5,5′-二叔丁基-N,N’草酰二苯胺,2,2′-双十二烷氧基-5,5′-二叔丁基N,N’草酰二苯胺,2-乙氧基-2′-乙基N,N’草酰二苯胺,N,N′-双(3-二甲基氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙基N,N’草酰二苯胺或它与2-乙氧基-2′-乙基-5,4′-二叔丁基N,N’草酰二苯胺的混合物,或邻-和对-甲氧基-双取代的N,N’草酰二苯胺的混合物或邻-和对-乙氧基-双取代的N,N’草酰二苯胺的混合物。
2-(2-羟苯基)-1,3,5-三嗪是例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-(4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基-丙氧基)苯基]-4,6-双(2,4-二甲基-苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪或2-(2-羟苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪。
2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪和2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪是优选的。
该UV吸收剂尤其是2-(2′-羟苯基)苯并三唑,2-羟基二苯甲酮或羟基苯基三嗪。
本发明的稳定剂混合物适合于稳定有机材料以抵抗由光,热或氧化诱导的降解。此类有机材料的例子是下列这些:1、单烯烃和二烯烃的聚合物,例如聚丙烯,聚异丁烯,聚丁烯-1,聚-4-甲基戊烯-1,聚异戊二烯或聚丁二烯,以及环状烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(任选地加以交联),例如高密度聚乙烯(HDPE),高密度和高分子量聚乙烯(HDPE-HMW),高密度和超高分子量聚乙烯(HDPE-UHMW),中等密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),(VLDPE)和(ULDPE),或聚乙烯基环己烷。
聚烯烃,即在前面的段落中例举的单烯烃的聚合物,优选聚乙烯和聚丙烯,能够通过不同的方法,和尤其是通过下面的方法来制备:
a)自由基聚合反应(一般在高压和升高的温度下)。
b)使用一般含有一种或一种以上的元素周期表的第IVb,Vb,VIb或VIII族的金属的催化剂的催化聚合反应。这些金属通常具有一个或一个以上的配位体,典型的是π键或σ键配位的氧化物,卤化物,醇化物,酯类,醚类,胺类,烷基类,链烯基类和/或芳基类。这些金属配合物可以是游离形式或被固定在基体上,典型地在被活化的氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以溶于或不溶于聚合反应介质中。这些催化剂本身可用于聚合反应或另外使用活化剂,典型的是金属烷基化物,金属氢化物,金属烷基卤化物,金属烷基氧化物或金属烷基噁烷(alkyloxanes),这些金属是元素周期表的第Ia,IIa和/或IIIa族的元素。活化剂可以方便地用另外的酯,醚,胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(DuPont),金属茂或单“位点”(single site)催化剂(SSC)。2、在以上1)项提到的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(例如PP/HDPE,PP/LDPE)和不同类型的聚乙烯的混合物(例如LDPE/HDPE)。3、单烯烃和二烯烃的共聚物,或单烯烃和二烯烃与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)和它与低密度聚乙烯(LDPE)的混合物,丙烯/丁烯-1共聚物,丙烯/异丁烯共聚物,乙烯/丁烯-1共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯酯共聚物和它们与一氧化碳的共聚物或乙烯/丙烯酸共聚物和它们的盐类(离聚物类)以及乙烯与丙烯和二烯烃如己二烯、双环戊二烯或亚乙基一降冰片烯的三元共聚物;和此类共聚物相互之间的混合物和与以上1)项中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或无规聚亚烷基/一氧化碳共聚物和它们与其它聚合物如聚酰胺的混合物。4、烃类树脂(例如C5-C9),包括它们的氢化改性物(例如增粘剂)和聚亚烷基类(polyalkylenes)和淀粉的混合物。5、聚苯乙烯,聚(对-甲基苯乙烯),聚(α-甲基苯乙烯)。6、苯乙烯或α-甲基苯乙烯与二烯烃或丙烯酸衍生物的共聚物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/甲基丙烯酸烷基酯,苯乙烯/丁二烯/丙烯酸烷基酯,苯乙烯/丁二烯/甲基丙烯酸烷基酯,苯乙烯/马来酸酐,苯乙烯/丙烯腈/丙烯酸甲酯,高抗冲击强度的苯乙烯共聚物和另一种聚合物如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元共聚物的混合物;以及苯乙烯的嵌段共聚物,如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。7、苯乙烯或α-甲基苯乙烯的接枝共聚物,例如聚丁二烯上接枝苯乙烯,聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上接枝苯乙烯;聚丁二烯上接枝苯乙烯和丙烯腈(或甲基丙烯腈);聚丁二烯上接枝苯乙烯、丙烯腈和甲基丙烯酸甲酯;聚丁二烯上接枝苯乙烯和马来酸酐;聚丁二烯上接枝苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;聚丁二烯上接枝苯乙烯和马来酰亚胺;聚丁二烯上接枝苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯;乙烯/丙烯/二烯烃三元共聚物上接枝苯乙烯和丙烯腈;聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上接枝苯乙烯和丙烯腈;丙烯酸酯/丁二烯共聚物上接枝苯乙烯和丙烯腈,以及它们与6)项所列举的共聚物的混合物,例如已知为ABS、MBS、ASA或AES聚合物的共聚物混合物。8、含卤素的聚合物类,如聚氯丁二烯,氯化橡胶,异丁烯-异戊二烯的氯化和溴化共聚物(卤代丁基橡胶),氯化或氯磺化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均-和共聚物,尤其含卤素的乙烯基化合物的聚合物,例如聚氯乙烯,聚偏二氯乙烯,聚氟乙烯,聚偏二氟乙烯,以及它们的共聚物,如氯乙烯/偏二氯乙烯,氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。9、从α,β-不饱和羧酸和其衍生物得到的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯;用丙烯酸丁酯进行冲击改性的聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈。10、在9)项中提到的单体相互之间的或与其它不饱和单体的共聚物例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/卤代乙烯共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。11、从不饱和醇类和胺类或酰基衍生物或其缩醛类得到的聚合物,例如聚乙烯醇,聚乙酸乙烯酯,聚硬脂酸乙烯酯,聚苯甲酸乙烯酯,聚马来酸乙烯酯,聚乙烯醇缩丁醛,聚邻苯二甲酸烯丙酯或聚烯丙基蜜胺;以及它们与以上1)项中提到的烯烃的共聚物。12、环醚的均聚物和共聚物,如聚亚烷基二醇,聚环氧乙烷,聚环氧丙烷或它们与双缩水甘油基醚的共聚物。13、聚缩醛类,如聚甲醛和含有环氧乙烷作为共聚单体的那些聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛类。14、聚苯醚和聚苯硫,聚苯醚与苯乙烯聚合物或聚酰胺的混合物。15、以羟基封端的聚醚、聚酯或聚丁二烯为一部分和脂族或芳族多异氰酸酯为另一部分衍生而来的聚氨酯,以及它的前体。16、从二胺和二羧酸和/或氨基羧酸或相应的内酰胺衍生而来的聚酰胺和共聚酰胺,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,以间-二甲苯二胺和己二酸为原料的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的和有或没有弹性体作为改性剂的聚酰胺,例如聚对苯二甲酰-2,4,4-三甲基亚己基二胺或聚间苯二甲酰间苯二胺;还有上述聚酰胺与聚烯烃,烯烃共聚物,离聚物或化学键连接的或接枝的弹性体,或与聚醚类,如聚乙二醇、聚丙二醇或聚丁二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。17、聚脲,聚酰亚胺,聚酰胺-酰亚胺,聚醚酰亚胺,聚酰亚胺酯,聚乙内酰脲和聚苯并咪唑。18、从二羧酸和二醇和/或羟基羧酸或相应的内酯衍生而来的聚酯,例如聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯,聚1,4-二羟甲基环己烷对苯二甲酸酯,聚萘二甲酸亚烷基二醇酯(PAN)和聚羟基苯甲酸酯,以及从羟基封端的聚醚衍生而来的嵌段共聚酯;还有用聚碳酸酯或MBS改性的聚酯类。19、聚碳酸酯和聚酯-碳酸酯。20、聚砜,聚醚-砜和聚醚-酮。21、以醛为一部分和酚类、脲和三聚氰胺为另一部分衍生而来的交联聚合物,例如酚醛树脂,脲醛树脂和三聚氰胺/甲醛树脂。22、干性和非干性醇酸树脂。23、从饱和的和不饱和的二羧酸与多羟基醇的共聚酯和乙烯基化合物作为交联剂衍生而来的不饱和聚酯树脂,以及它们的具有低可燃性的含卤素的改性产物。24、从取代的丙烯酸酯衍生而来的可交联丙烯酸树脂,例如环氧丙烯酸酯,聚氨酯丙烯酸酯或聚酯丙烯酸酯。25、用蜜胺树脂,尿素树脂,异氰酸酯,异氰脲酸酯,多异氰酸酯或环氧树脂加以交联的醇酸树脂,聚酯树脂和丙烯酸酯树脂。26、从脂族、环脂族、杂环族或芳族缩水甘油基化合物衍生而来的交联环氧树脂,例如双酚A和双酚F的二缩水甘油醚的产物,它们用常规的硬化剂如酸酐或胺类加以交联,有或没有促进剂。27、天然聚合物,如纤维素、橡胶、明胶和它们的化学改性的同源(homologous)衍生物,例如乙酸纤维素,丙酸纤维素和丁酸纤维素,或纤维素醚类,如甲基纤维素;以及松香和它的衍生物。28、上述聚合物的共混物(多元共混物),例如PP/EPDM,聚酰胺/EPDM或ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PBTP/ABS,PC/ASA,PC/PBT,PVC/CPE,PVC/丙烯酸酯,POM/热塑性PUR,PC/热塑性PUR,POM/丙烯酸酯,POM/MBS,PPO/HIPS,PPO/PA6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。29、天然和合成有机材料,它们是纯单体化合物或此类化合物的混合物,例如,矿物油,动物和植物脂肪、油和蜡,或基于合成酯(例如邻苯二甲酸酯、己二酸酯、磷酸酯或1,2,4-苯三酸酯类)的油、脂肪或蜡,还有合成酯与矿物油按任何重量比的混合物,典型地用作纺丝组合物的那些,以及此类材料的水乳液。30、天然或合成橡胶的水乳液,例如羧基化苯乙烯/丁二烯共聚物的天然乳胶或胶乳类。
本发明因此另外涉及一种含有经受由光、热或氧化诱导的降解的有机材料和以上所述的稳定剂混合物的组合物。
本发明的再一个实施方案是使有机材料稳定化以防止由光、热或氧化诱导的降解的方法,它包括在有机材料中引入以上所述的稳定剂混合物。
该有机材料优选是合成聚合物,尤其是以上列举的各组中的一种。聚烯烃是优选的,而聚乙烯、聚丙烯、聚乙烯共聚物或聚丙烯共聚物是特别优选的。含有滑石和/或其它填料(例如碳酸钙)的聚丙烯也是优选的。有颜料的聚烯烃和有颜料的聚酰胺也是优选的。丙烯腈/丁二烯/苯乙烯也优选作为有机材料。
组分(I)、(II)和任选(X-1)和/或(X-2)可以单独一种或彼此混合的方式加入到需要稳定的有机材料中。
两种空间位阻胺化合物(组分(I)和(II))在需要稳定化的有机材料中的总量优选是0.005-5%,尤其0.01-1%或0.05-1%,相对于有机材料的重量。
颜料(组分(X-1))任选地存在于有机材料中的量优选是相对于有机材料重量的0.01-10%,尤其0.05-1%。
UV吸收剂(组分(X-2))任选地存在于有机材料中的量优选是相对于有机材料重量的0.01-1%,尤其0.05-0.5%。
组分(X-3)(颜料与UV吸收剂的结合物)的总量优选是0.01-10%,相对于有机材料的重量。UV吸收剂与颜料的重量比是例如2∶1至1∶10。
当所用颜料是二氧化钛与以上所述的有机颜料的组合时,二氧化钛优选以相对于有机材料重量的0.01-5%的量存在于有机材料中,和有机颜料以例如相对于有机材料重量的0.01-2%的量存在。
组分(I)∶(II)的重量比是例如1∶10至10∶1,优选1∶5至5∶1,尤其1∶2至2∶1。
组分(I)和(II)∶(X-1)的重量比是例如1∶100至10∶1,优选1∶5至5∶1,尤其1∶2至2∶1。
组分(I)和(II)∶(X-2)的重量比是例如1∶5至20∶1,优选1∶2至2∶1。
组分(I)和(II)∶(X-3)的重量比是例如1∶100至10∶1,优选1∶5至5∶1,尤其1∶2至2∶1。
以上组分通过已知方法,例如在加工成形之前或过程中,或通过将溶解或分散的化合物施加于有机材料中,如果需要,随后蒸发溶剂,被引入到需要稳定化的有机材料中。这些组分能够以粉末、粒状或母料的形式加入到有机材料中,后者含有例如2.5-25wt%浓度的这些组分。
如果需要,组分(I)和(II)和任选的(X-1)和/或(X-2)能够在引入到有机材料中之前彼此熔融掺混。它们能够在聚合之前或过程中或在交联之前被加入到聚合物中。
本发明需要稳定的材料能够以各种各样的形式被使用,例如膜、纤维、带、模塑组合物、异型材或作为漆料、粘合剂或腻子的粘结剂。
需要稳定的材料另外也可含有各种普通的添加剂,例如:
1、抗氧化剂1.1、
烷基化一元酚类,例如,2,6-二叔丁基-4-甲基苯酚,2-叔丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚;壬基苯酚类,它是线性的或在侧链上支化,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1′-甲基十一烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十七烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十三烷-1′-基)苯酚;以及它们的混合物。1.2、烷基硫代甲基酚类,例如2,4-二辛基硫代甲基-6-叔丁基苯酚,2,4-二辛基硫代甲基-6-甲基苯酚,2,4-二辛基硫代甲基-6-乙基苯酚,2,6-双十二烷基硫代甲基-4-壬基苯酚。1.3、氢醌类或烷基化氢醌类,例如,2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二叔戊基氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,硬脂酸3,5-二叔丁基-4-羟基苯基酯,己二酸双(3,5-二叔丁基-4-羟基苯基)酯。1.4、生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和它们的混合物(维生素E)。1.5、羟基化硫代二苯基醚类,例如,2,2′-硫代双(6-叔丁基-4-甲基苯酚),2,2′-硫代双(4-辛基苯酚),4,4′-硫代双(6-叔丁基-3-甲基苯酚),4,4′-硫代双(6-叔丁基-2-甲基苯酚),4,4′-硫代双(3,6-二仲戊基苯酚),4,4’-双(2,6-二甲基-4-羟基苯基)二硫醚。1.6、亚烷基双酚类,例如,2,2′-亚甲基双(6-叔丁基-4-甲基苯酚),2,2′-亚甲基双(6-叔丁基-4-乙基苯酚),2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基双(4-甲基-6-环己基苯酚),2,2′-亚甲基双(6-壬基-4-甲基苯酚),2,2′-亚甲基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基双(2,6-二叔丁基苯酚),4,4′-亚甲基双(6-叔丁基-2-甲基苯酚),1,1′-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,双[3,3-双(3′-叔丁基-4′-羟基苯基)丁酸]乙二醇酯,双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯,对苯二甲酸双[2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基]酯,1,1-双(3,5-二甲基-2-羟基苯基)丁烷,2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。1.7.O-、N-和S-苄基化合物类,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,4-羟基-3,5-二甲基苄基巯基乙酸十八烷基酯,4-羟基-3,5-二叔丁基苄基巯基乙酸十三烷基酯,三(3,5-二叔丁基-4-羟基苄基)胺,二硫代对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄基)酯,双(3,5-二叔丁基-4-羟基-苄基)硫醚,3,5-二叔丁基-4-羟基苄基巯基乙酸异辛基酯。1.8、羟苄基化丙二酸酯类,例如,2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸二(十八烷基)酯,2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二(十八烷基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二(十二烷基巯基乙基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸双[4-(1,1,3,3-四甲基丁基)苯基]酯。1.9、芳族羟苄基化合物类,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。1.10、三嗪化合物类,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-异氰脲酸酯,2,4,6-三(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。1.11、苄基膦酸酯类,例如2,5-二叔丁基-4-羟基苄基膦酸二甲酯,3,5-二叔丁基-4-羟基苄基膦酸二乙酯,3,5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯,5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯,3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。1.12、酰基氨基酚类,例如4-羟基月桂酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。1.13、β-(3,5-二叔丁基-4-羟基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。1.14、β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。1.15、β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。1.16、3,5-二叔丁基-4-羟基苯基乙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。1.17、β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺类,例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼。1.18、抗坏血酸(维生素C)1.19、胺类抗氧化剂,例如N,N′-二异丙基-对-亚苯基二胺,N,N′-二仲丁基-对-亚苯基二胺,N,N′-双(1,4-二甲基戊基)-对-亚苯基二胺,N,N′-双(1-乙基-3-甲基戊基)-对-亚苯基二胺,N,N’-双(1-甲基庚基)-对亚苯基二胺,N,N’-二环己基-对亚苯基二胺,N,N′-二苯基-对-亚苯基二胺,N,N′-双(2-萘基)-对-亚苯基二胺,N-异丙基-N′-苯基-对-亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-对-亚苯基二胺,N-(1-甲基庚基)-N′-苯基-对-亚苯基二胺,N-环己基-N′-苯基-对-亚苯基二胺,4-(对甲苯氨磺酰基)二苯胺,N,N′-二甲基-N,N′-二仲丁基-对亚苯基二胺,二苯胺,N-烯丙基二苯胺,4-异丙氧基-二苯胺,N-苯基-1-萘胺,N-(4-叔辛基苯基)-1-萘胺,N-苯基-2-萘胺,辛基化二苯胺(例如p,p′-二叔辛基二苯胺),4-正丁基氨基苯酚,4-丁酰氨基苯酚,4-壬酰氨基苯酚,4-十二酰氨基苯酚,4-十八酰氨基苯酚,双(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲氨基甲基苯酚,2,4′-二氨基二苯基甲烷,4,4′-二氨基二苯基甲烷,N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷,1,2-双[(2-甲基苯基)氨基]乙烷,1,2-双(苯基氨基)丙烷,(邻甲苯基)双胍,双[4-(1′,3′-二甲基丁基)苯基]胺,叔辛基化N-苯基-1-萘胺,单和二烷基化叔丁基/叔辛基二苯基胺类的混合物,单和二烷基化壬基二苯基胺类的混合物,单和二烷基化十二烷基二苯基胺类的混合物,单和二烷基化异丙基/异己基二苯基胺类的混合物,单和二烷基化叔丁基二苯基胺类的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单和二烷基化叔丁基/叔辛基吩噻嗪的混合物,单和二烷基化叔辛基吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯,N,N-双(2,2,6,6-四甲基-哌啶-4-基-六亚甲基二胺,双(2,2,6,6-四甲基-哌啶-4-基)癸二酸酯,2,2,6,6-四甲基哌啶-4-酮,2,2,6,6-四甲基哌啶-4-醇。2.UV吸收剂和光稳定剂 镍化合物类,例如2,2′-硫代-双[4-(1,1,3,3-四甲基-丁基)苯酚]的镍配合物,如1∶1或1∶2配合比,有或没有附加的配位体如正丁基胺,三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯(例如甲酯或乙酯)类的镍盐,酮肟例如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物类,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,有或没有附加的配位体。3.金属减活剂类,例如N,N′-二苯基草酰胺,N-水杨醛-N′-水杨酰基肼,N,N′-双(水杨酰基)肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,3-水杨酰基氨基-1,2,4-三唑,双(亚苄基)草酰二肼,N,N’-草酰二苯胺,间苯二甲酰二肼,癸二酰双(苯基肼),N,N′-二乙酰基己二酰二肼,N,N′-双(水杨酰基)草酰二肼,N,N′-双(水杨酰基)硫代丙酰基二肼。4.亚磷酸酯类和亚膦酸酯类,例如亚磷酸三苯酯,亚磷酸二苯基烷基酯,亚磷酸苯基二烷基酯,亚磷酸三(壬基苯基)酯,亚磷酸三月桂基酯,亚磷酸三(十八烷基)酯,二亚磷酸二硬脂基季戊四醇酯,亚磷酸三(2,4-二叔丁基苯基)酯,二亚磷酸二异癸基季戊四醇酯,二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯,二亚磷酸双(2,6-二叔丁基-4-甲基苯基)-季戊四醇酯,二亚磷酸二异癸氧基季戊四醇酯,二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯,二亚磷酸双(2,4,6-三叔丁基苯基)季戊四醇酯,三亚磷酸三硬脂基山梨糖醇酯,二亚膦酸四(2,4-二叔丁基苯基)4,4′-双亚苯基酯,6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷辛(dioxaphosphocin),6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂磷辛(dioxaphosphocin),亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯,亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙基酯。5.羟基胺类,例如N,N-二苄基羟基胺,N,N-二乙基羟基胺,N,N-二辛基羟基胺,N,N-二月桂基羟基胺,N,N-二(十四烷基)羟基胺,N,N-二(十六烷基)羟基胺,N,N-二(十八烷基)羟基胺,N-十六烷基-N-十八烷基羟基胺,N-十七烷基-N-十八烷基羟基胺,从氢化牛脂胺衍生的N,N-二烷基羟基胺。6.硝酮类,例如N-苄基-α-苯基-硝酮,N-乙基-α-甲基-硝酮,N-辛基-α-庚基-硝酮,N-月桂基-α-十一烷基-硝酮,N-十四烷基-α-十三烷基-硝酮,N-十六烷基-α-十五烷基-硝酮,N-十八烷基-α-十七烷基-硝酮,N-十六烷基-α-十七烷基-硝酮,N-十八烷基-α-十五烷基-硝酮,N-十七烷基-α-十七烷基-硝酮,N-十八烷基-α-十六烷基-硝酮,从氢化牛脂胺衍生而来的N,N-二烷基羟基胺衍生的硝酮。7.硫代协合剂,例如硫代二丙酸二月桂基酯或硫代二丙酸二硬脂基酯。8.过氧化物清除剂,例如β-硫代二丙酸的酯类,例如月桂基、硬脂基、十四烷基或十三烷基酯类,巯基苯并咪唑或2-巯基苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二(十八烷基)二硫醚,四(β-十二烷基巯基)丙酸季戊四醇酯。9.碱性助稳定剂,例如三聚氰胺,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰脲酸酯,脲衍生物,肼衍生物,胺类,聚酰胺类,聚氨酯类,高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙,硬脂酸锌,二十二烷酸镁,硬脂酸镁,蓖麻酸钠,棕榈酸钾,邻苯二酚锑或邻苯二酚锡。10.成核剂类,例如,无机物质,如滑石,金属氧化物类如二氧化钛或氧化镁,优选碱土金属的磷酸盐、碳酸盐或硫酸盐;有机化合物如单或多羧酸类和它们的盐类,例如4-叔丁基苯甲酸,己二酸,二苯基乙酸,琥珀酸钠或苯甲酸钠;聚合化合物如离子共聚物(离聚物)。11.填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃珠,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,炭黑,石墨,木粉和其它天然产物的粉末或纤维,合成纤维。12.其它添加剂,例如增塑剂,润滑剂,乳化剂,颜料,流变添加剂,催化剂,流动控制剂,荧光增白剂,阻燃剂,抗静电剂和发泡剂。13.苯并呋喃酮类和二氢吲哚酮类,例如在US-A-4,325,863,US-A-4,338,244,US-A-5,175,312,US-A-5,216,052,US-A-5,252,643,DE-A-4,316,611,DE-A-4,316,622,DE-A-4,316,876;EP-A-0589 839或EP-A-0591102中公开的那些,或3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基-苯并呋喃-2-酮,5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮,3,3′-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮],5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮,3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基-苯并呋喃-2-酮。
组分(I)和(II)和任选(X-1)和/或(X-2)的总量与常规添加剂的总量的重量比是,例如,100∶1到1∶100。
下面的实施例用于详细说明本发明。除非另作说明,全部的份数和百分数是按重量计。
实施例1:聚丙烯均聚物膜的光稳定化。
100份的未稳定化的聚丙烯粉末(熔体流动指数:2.4g/10分钟,在230℃和2160g下)在Brabender塑性计中于200℃下与0.05份的季戊四醇基-四{3-(3,5-二叔丁基-4-羟苯基)丙酸酯},0.05份的三{2,4-二叔丁基苯基}亚磷酸酯,0.1份的硬脂酸钙,0.25份的二氧化钛(锐钛矿型)和表1中指定的光稳定剂体系一起均化10分钟。所获得的材料在实验室压制机中在两铝箔之间于260℃下加压模塑6分钟而形成0.5mm厚的膜,它然后立即在水冷却的压制机中冷却至室温。这些0.5mm的膜被切成60mm×25mm的样品,并暴露于WEATHER-OMETER Ci65(黑板温度63±2℃,没有喷水)中。
周期性地,这些样品从暴露试验装置中取出,用红外分光光度计测量它们的羰基含量。形成0.1的羰基吸光率对应的暴露时间(以小时计)(T0.1)是稳定剂体系的效率的量度。
两种助添加剂((α)和(β))的协同作用可通过比较计算的T0.1值与实际测量的T0.1值来确定。根据下面等式,以相加定律为基础来计算T0.1值(B.Ranby and J.F.Rabek;Photodegradation,Photo-oxidation and Photostabilization of Polymers,Principles andApplications,John Wiley & Sons,London,New York,Sydney,Toronto,1975,418和419页):
预期的稳定化活性=(
100%(α)的稳定化活性+100%(β)的 稳定化活性)/2当T0.1测量>T0.1计算时,所述的两种助添加剂有协同作用。表1:
光稳定剂体系 | T0.1(h)(测量) | [(T0.1)α+(T0.1)β]/2(h)(=T0.1计算值) |
没有 | 390 | |
0.2%的化合物(A-1-b) | 4630 | |
0.2%的化合物(B-2-a) | 2460 | |
0.1%的化合物(A-1-b)+0.1%的化合物(B-2-a) | >5475 | 3545 |
化合物(A-1-b)和(B-2-a)的组合显示出协同作用。
Claims (14)
1.一种稳定剂混合物,其含有
(I)选自类别(α-1),(α-2),(α-3),(α-4)和(α-5)中的一种位阻胺化合物;和
(II)选自类别(β-1),(β-2),(β-3)和(β-4)中的一种位阻胺化合物;
其中
E1是C1-C4烷基,
m1是1,2或4,
如果m1是1,则E2是C1-C25烷基,
如果m1是2,则E2是C1-C14亚烷基或通式(a-I)的基团:
其中E3是C1-C10烷基或C2-C10链烯基,E4是C1-C10亚烷基,和
E5和E6彼此独立地是C1-C4烷基,环己基或甲基环己基,和
如果m1是4,则E2是C4-C10链烷四基;
(α-2)通式(A-2)的化合物:其中两个基团E7是-COO-(C1-C20烷基),和两个基团E7是通式(a-II)的基团:其中E8具有E1的意义中的一个;(α-3)通式(A-3)的化合物:其中E9是C1-C24烷基,和E10具有E1的意义中的一个;(α-4)通式(A-4)的化合物:
其中
该基团E11彼此独立地具有E1的意义中的一个,和E12是氢,C1-C12烷基或C1-C12烷氧基;
(α-5)通式(A-5)的化合物:
其中
E13具有E1的意义中的一个,和
其中该基团E15彼此独立地是C2-C12亚烷基,和基团E16彼此独立地是C1-C12烷基或C5-C12环烷基;
其中
R1,R3,R4和R5彼此独立地是氢,C1-C12烷基,C5-C12环烷基,C1-C4-烷基取代的C5-C12环烷基,苯基,被-OH和/或C1-C10烷基取代的苯基;C7-C9苯基烷基,在苯基上被-OH和/或C1-C10烷基取代的C7-C9苯基烷基;或下式(b-I)的基团:
R2是C2-C18亚烷基,C5-C7亚环烷基或C1-C4亚烷基二(C5-C7亚环烷基),
或
基团R1,R2和R3与它们所键接的氮原子一起构成了5-到10-员杂环,或
R4和R5与它们所连接的氮原子一起构成了5-到10-员杂环,
R6是C1-C4烷基,和
b1是2-50的数,
前提条件是基团R1,R3,R4和R5中至少一个是通式(b-I)的基团;
(β-2)通式(B-2)的化合物:
其中
R7和R11彼此独立地是氢或C1-C12烷基,
R8,R9和R10彼此独立地是C2-C10亚烷基,和
其中R12是氢,C1-C12烷基,C5-C12环烷基,C1-C4-烷基取代的C5-C12环烷基,苯基,-OH和/或C1-C10烷基取代的苯基;C7-C9苯基烷基,在苯基上被-OH和/或C1-C10烷基取代的C7-C9苯基烷基;或如以上所定义的通式(b-I)的基团,和
R13具有R6的意义中的一个;
其中
R14,R15,R16,R17和R18彼此独立地是直接的键或C1-C10亚烷基,
R19具有R6的意义中的一个,和
b2是1到50的数;
(β-4)可由通式(B-4-1)的多胺与氰尿酰氯反应获得的产物再与通式(B-4-2)的化合物进行反应来获得的产物(B-4)
其中
b′3,b″3和b3彼此独立地是2-12的数,
R20是氢,C1-C12烷基,C5-C12环烷基,苯基或C7-C9苯基烷基,和
R21具有R6的意义中的一个。
2.根据权利要求1的稳定剂混合物,其中组分(I)选自类别(α-1),和组分(II)选自类别(β-1);或组分(I)选自类别(α-1),和组分(II)选自类别(β-2);或组分(I)选自类别(α-1),和组分(II)选自类别(β-3);或组分(I)选自类别(α-1),和组分(II)选自类别(β-4);或组分(I)选自类别(α-2),和组分(II)选自类别(β-1);或组分(I)选自类别(α-2),和组分(II)选自类别(β-2);或组分(I)选自类别(α-2),和组分(II)选自类别(β-3);或组分(I)选自类别(α-2),和组分(II)选自类别(β-4);或组分(I)选自类别(α-3),和组分(II)选自类别(β-1);或组分(I)选自类别(α-3),和组分(II)选自类别(β-2);或组分(I)选自类别(α-3),和组分(II)选自类别(β-3);或组分(I)选自类别(α-3),和组分(II)选自类别(β-4);或组分(I)选自类别(α-4),和组分(II)选自类别(β-1);或组分(I)选自类别(α-4),和组分(II)选自类别(β-2);或组分(I)选自类别(α-4),和组分(II)选自类别(β-3);或组分(I)选自类别(α-4),和组分(II)选自类别(β-4);或组分(I)选自类别(α-5),和组分(II)选自类别(β-1);或组分(I)选自类别(α-5),和组分(II)选自类别(β-2);或组分(I)选自类别(α-5),和组分(II)选自类别(β-3);或组分(I)选自类别(α-5),和组分(II)选自类别(β-4)。
3.根据权利要求1的稳定剂混合物,其中
m1是1,2或4,
如果m1是1,则E2是C12-C20烷基,
如果m1是2,则E2是C2-C10亚烷基或通式(a-I)的基团,
E3是C1-C4烷基,
E4是C1-C6亚烷基,和
E5和E6彼此独立地是C1-C4烷基,和
如果m1是4,则E2是C4-C8链烷四基:
两个基团E7是-COO-(C10-C15烷基),和
两个基团E7是通式(a-II)的基团;
E9是C10-C14烷基;
E12是C1-C4烷氧基;
基团E15彼此独立地是C2-C6亚烷基,和
基团E16彼此独立地是C1-C4烷基或C5-C8环烷基;
R1和R3彼此独立地是通式(b-I)的基团,
R2是C2-C8亚烷基,
R4和R5彼此独立地是氢,C1-C12烷基,C5-C8环烷基或通式(b-I)的基团,或基团R4和R5与它们所连接的氮原子一起形成5-到10-员杂环,和
b1是2-25的数;
R7和R11彼此独立地是氢或C1-C4烷基,
R8,R9和R10彼此独立地是C2-C4亚烷基,和
X1,X2,X3,X4,X5,X6,X7和X8彼此独立地是通式(b-II)的基团,
R12是氢,C1-C4烷基,C5-C8环烷基或通式(b-I)的基团;
R14,R15,R16,R17和R18彼此独立地是直接的键或C1-C4亚烷基,和
b2是1到25的数;
b′3,b″3和b3彼此独立地是2-4的数,和
R20是氢,C1-C4烷基,C5-C8环烷基,苯基或苄基。
5.根据权利要求4的稳定剂混合物,其中
组分(I)是通式(A-1-a),(A-1-b),(A-1-c),(A-1-d),(A-2-a),(A-3-a),(A-4-a)或(A-5-a)的化合物;和
组分(II)是通式(B-1-c)或(B-2-a)的化合物。
6.根据权利要求4的稳定剂混合物,其中
组分(I)是通式(A-1-b)的化合物和组分(II)是通式(B-1-c)的化合物;或其中
组分(I)是通式(A-1-b)的化合物和组分(II)是通式(B-2-a)的化合物。
7.根据权利要求1的稳定剂混合物,其中E1,E8,E10,E11,E13,R6,R13,R19和R21是甲基。
8.根据权利要求1的稳定剂混合物,它另外含有作为附加组分的
(X-1)颜料或
(X-2)UV吸收剂或
(X-3)颜料和UV吸收剂。
9.一种含有经受由光、热或氧化诱导的降解的有机材料和根据权利要求1的稳定剂混合物的组合物。
10.根据权利要求9的组合物,其中该有机材料是合成聚合物。
11.根据权利要求9的组合物,其中该有机材料是聚烯烃。
12.根据权利要求9的组合物,其中该有机材料是聚乙烯,聚丙烯,聚乙烯共聚物或聚丙烯共聚物。
13.根据权利要求9的组合物,其中该有机材料是丙烯腈/丁二烯/苯乙烯(ABS)。
14.一种使有机材料稳定化以抵抗由光、热或氧化诱导的降解的方法,包括在有机材料中引入根据权利要求1的稳定剂混合物。
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-
2001
- 2001-05-22 DE DE10196267T patent/DE10196267T1/de not_active Ceased
- 2001-05-22 US US10/276,091 patent/US20030191239A1/en not_active Abandoned
- 2001-05-22 GB GB0228156A patent/GB2378951B/en not_active Expired - Fee Related
- 2001-05-22 CA CA2408651A patent/CA2408651C/en not_active Expired - Fee Related
- 2001-05-22 BR BRPI0111240-6A patent/BR0111240B1/pt not_active IP Right Cessation
- 2001-05-22 KR KR1020027015925A patent/KR100786241B1/ko not_active IP Right Cessation
- 2001-05-22 AU AU6231101A patent/AU6231101A/xx active Pending
- 2001-05-22 MX MXPA02011759 patent/MX283566B/es active IP Right Grant
- 2001-05-22 CN CNB018103286A patent/CN1222565C/zh not_active Expired - Lifetime
- 2001-05-22 WO PCT/EP2001/005870 patent/WO2001092393A2/en active IP Right Grant
- 2001-05-22 AU AU2001262311A patent/AU2001262311B2/en not_active Ceased
- 2001-05-22 ES ES200250072A patent/ES2208129B1/es not_active Expired - Fee Related
- 2001-05-22 JP JP2002500999A patent/JP5111712B2/ja not_active Expired - Lifetime
- 2001-05-29 IT IT2001MI001133 patent/IT1324892B/it active
- 2001-05-30 FR FR0107072A patent/FR2809739B1/fr not_active Expired - Fee Related
- 2001-05-31 BE BE2001/0371A patent/BE1014206A3/fr active
- 2001-05-31 NL NL1018187A patent/NL1018187C2/nl not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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ES2208129B1 (es) | 2005-08-01 |
BR0111240A (pt) | 2003-06-10 |
FR2809739A1 (fr) | 2001-12-07 |
US20060270763A1 (en) | 2006-11-30 |
FR2809739B1 (fr) | 2004-06-25 |
KR20030007694A (ko) | 2003-01-23 |
NL1018187C2 (nl) | 2001-12-28 |
WO2001092393A3 (en) | 2002-04-04 |
GB2378951A (en) | 2003-02-26 |
US7652081B2 (en) | 2010-01-26 |
GB2378951B (en) | 2003-12-31 |
WO2001092393A2 (en) | 2001-12-06 |
MXPA02011759A (es) | 2003-04-25 |
DE10196267T1 (de) | 2003-05-15 |
CA2408651A1 (en) | 2001-12-06 |
BE1014206A3 (fr) | 2003-06-03 |
CA2408651C (en) | 2012-10-16 |
ES2208129A1 (es) | 2004-06-01 |
CN1222565C (zh) | 2005-10-12 |
AU6231101A (en) | 2001-12-11 |
NL1018187A1 (nl) | 2001-12-03 |
ITMI20011133A0 (it) | 2001-05-29 |
IT1324892B (it) | 2004-12-02 |
US20030191239A1 (en) | 2003-10-09 |
GB0228156D0 (en) | 2003-01-08 |
JP2003535206A (ja) | 2003-11-25 |
GB2378951A8 (en) | 2003-03-18 |
MX283566B (es) | 2011-02-01 |
AU2001262311B2 (en) | 2006-08-31 |
KR100786241B1 (ko) | 2007-12-17 |
ITMI20011133A1 (it) | 2002-11-29 |
BR0111240B1 (pt) | 2011-12-13 |
JP5111712B2 (ja) | 2013-01-09 |
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