CN1257495A - 可用作有机材料稳定剂的含有1-烃氧基-2,2,6,6-四甲基-4-哌啶基基团的嵌段低聚物 - Google Patents
可用作有机材料稳定剂的含有1-烃氧基-2,2,6,6-四甲基-4-哌啶基基团的嵌段低聚物 Download PDFInfo
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- CN1257495A CN1257495A CN98805445A CN98805445A CN1257495A CN 1257495 A CN1257495 A CN 1257495A CN 98805445 A CN98805445 A CN 98805445A CN 98805445 A CN98805445 A CN 98805445A CN 1257495 A CN1257495 A CN 1257495A
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- group
- alkyl
- general formula
- phenyl
- replaces
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- 239000011368 organic material Substances 0.000 title claims abstract description 19
- 239000003381 stabilizer Substances 0.000 title abstract description 6
- -1 oxyl Chemical group 0.000 claims abstract description 178
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002978 peroxides Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 113
- 150000001875 compounds Chemical class 0.000 claims description 93
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 28
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- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 18
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical class 0.000 claims description 13
- 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 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 11
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
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- 239000001257 hydrogen Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 229960005141 piperazine Drugs 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims 3
- WAJQTBOWJRUOOO-UHFFFAOYSA-N 3-benzylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)CC1=CC=CC=C1 WAJQTBOWJRUOOO-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000004611 light stabiliser Substances 0.000 abstract 1
- 230000000306 recurrent effect Effects 0.000 abstract 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 48
- 239000002585 base Substances 0.000 description 44
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000011572 manganese Substances 0.000 description 21
- 150000001412 amines Chemical group 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 150000001408 amides Chemical class 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229960003742 phenol Drugs 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
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- 230000007246 mechanism Effects 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
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- 238000005406 washing Methods 0.000 description 8
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- 229920001903 high density polyethylene Polymers 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
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- 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
- 238000012360 testing method Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000003513 alkali Substances 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
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Abstract
通过将在多分散性Mw/Mn为1-1.7且对应于通式(Ⅰ)的嵌段低聚物中存在的通式(G-Ⅰ)的基团转变成通式(G-Ⅱ)的基团所获得的产物;其中R1是烃基或-O-R1是氧基;该转变是通过嵌段低聚物与氢过氧化物在烃溶剂中在过氧化物分解催化剂存在下的反应来进行;n是2-14中的数;R2例如是C2-C12亚烷基;A例如是-N(R4)(R5);R4和R5例如是C1-C18烷基;R优选是通式(G-Ⅰ)的基团以及B和B*具有对于A给出的一个定义;前提条件是在通式(Ⅰ)的各重复单元中,基团B,R和R2中每一个具有相同或不同的定义。所指定的化合物可用作有机材料、尤其合成聚合物的光稳定剂,热稳定剂和氧化稳定剂。
Description
本发明涉及含有1-烃氧基-2,2,6,6-四甲基-4-哌啶基基团的一种特定的嵌段低聚物,涉及它们作为有机材料尤其合成聚合物的光稳定剂、热稳定剂和氧化稳定剂的用途,以及涉及被稳定的有机材料。
用2,2,6,6-四甲基哌啶的衍生物稳定合成聚合物的方法已经描述在,例如,US-A-4,086,204,US-A-4,331,586,US-A-4,335,242,US-A-4,234,707,US-A-4,459,395,US-A-4,492,791,US-A-5,204,473,EP-A-53 775,EP-A-357,223,EP-A-377,324,EP-A-462,069,EP-A-782 994和GB-A-2301106。
其中R1是烃基或-O-R1是氧基;
该转变是由对应于通式(I)的嵌段低聚物与氢过氧化物在烃溶剂中在过氧化物分解催化剂存在下的反应进行的;
n是2-14中的数;
R2相互独立地是C2-C12亚烷基,C4-C12亚链烯基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被1,4-哌嗪二基,-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有以下给出的R4的一个定义;或R2是通式(a),(b)或(c)的基团; m是2或3,X2是C1-C18烷基,C5-C12环烷基,该环烷基是未取代的或被1,2或3个C1-C4烷基取代;苯基,它是未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它未被取代或在苯基上被1,2或3个C1-C4烷基取代;和基团X3相互独立地是C2-C12亚烷基;基团A相互独立地是-OR3,-N(R4)(R5)或以下通式(II)的基团,
R3,R4和R5可以相同或不同,是C1-C18烷基,C5-C12环烷基,该环烷基是未被取代的或被1,2或3个C1-C4烷基取代;C3-C18链烯基,苯基,它是未被取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它是未取代的或在苯环上被1,2或3个C1-C4烷基取代;四氢糠基或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或以下通式(III)的基团所取代,其中Y是-O-,-CH2-,-CH2CH2-或>N-CH3,R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;X是-O-或>N-R6;R6是C1-C18烷基,C3-C18链烯基,C5-C12环烷基,该环烷基是未取代或被1,2或3个C1-C4烷基取代;C7-C9苯基烷基,它是未取代的或在苯基上被1,2或3个C1-C4烷基取代;四氢糠基,通式(G-I)的基因,或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或通式(III)的基团取代;
R相互独立地具有一个对于R6所给出的定义;以及基团B和B*相互独立地具有一个对于A给定的定义;
其前提是在通式(I)的各重复单元中,基团B,R和R2中每一个具有相同的或不同的定义。
通式(G-I)的基团向通式(G-II)的基团的转变例如可按照与US-A-4921 962中所述方法类似地进行,该文献被引入本文供参考。
多分散性表示聚合化合物的分子量分布。在本申请中,多分散性是重均分子量(
Mw)和数均分子量(
Mn)之比。
Mw/
Mn的值等于1意味着该化合物是单分散性的并具有仅仅一个分子量和没有分子量分布。窄分子量分布由接近1的多分散性
Mw/
Mn表征。
当多分散性
Mw/
Mn是1时,n优选是2,3,4,5,6,7,8,9,10,11或12,尤其2,3,4,5或6,例如2,4或6。
通式(I)的优选嵌段低聚物具有多分散性
Mw/
Mn为1.1-1.7。该嵌段低聚物是多分散性的并具有分子量分布。更具体地说,该嵌段低聚物对应于含有通式(I)的至少三种不同单分散性化合物(仅仅由变量n发生变化)的混合物,该混合物具有多分散性为1.1-1.7。
当多分散性
Mw/
Mn高于1时,n优选是2-12中、尤其2-6中的数。
优选的嵌段低聚物具有多分散性
Mw/
Mn为1.1-1.65,1.1-1.6,1.1-1.55,1.1-1.5,1.1-1.45,1.1-1.40或1.1-1.35。1.1-1.55,例如1.1-1.5的多分散性
Mw/
Mn是特别优选的。
多分散性
Mw/
Mn的其它例子是1.15-1.7,例如1.15-1.65,1.15-1.6,1.15-1.55,1.15-1.5,1.15-1.45,1.15-1.40,1.15-1.35。1.15-1.55例如1.15-1.5的多分散性
Mw/
Mn也是特别优选的。
R1的定义取决于所使用的烃溶剂。R1优选是具有5-18个碳原子的烃基。
R1尤其是C5-C18烷基,C5-C18链烯基,C5-C18炔基,未取代或被C1-C4烷基取代的C5-C12环烷基;未取代或被C1-C4烷基取代的C5-C12环链烯基;具有6-10个碳原子的双环或三环烃基或未取代或在苯基上被C1-C4烷基取代的C7-C9苯基烷基;和
烃溶剂(取决于R1)因此是C5-C18链烷烃,C5-C18链烯烃,C5-C18炔烃,未取代或被C1-C4烷基取代的C5-C12环烷烃;未取代的或被C1-C4烷基取代的C5-C12环烯烃;具有6-10个碳原子的双环或三环烃类或未取代或在苯基上被C1-C4烷基取代的C7-C9苯基烷烃。
含有不超过18个碳原子的烷基的实例是甲基,乙基,丙基,异丙基,丁基,2-丁基,异丁基,叔丁基,戊基,2-戊基,己基,庚基,辛基,2-乙基己基,叔辛基,壬基,癸基,十一烷基,十二烷基,十三烷基,十四烷基,十六烷基和十八烷基。R1优选是C6-C12烷基,尤其庚基或辛基。R4,R5和R6优选是C1-C8烷基,尤其C1-C4烷基。
被-OH取代的C2-C4烷基例如是2-羟基乙基。
被C1-C8烷氧基,优选C1-C4烷氧基,尤其甲氧基或乙氧基所取代的C2-C4烷基的实例是2-甲氧基乙基,2-乙氧基乙基,3-甲氧基丙基,3-乙氧基丙基,3-丁氧基丙基,3-辛氧基丙基和4-甲氧基丁基。
被二(C1-C4烷基)氨基,优选被二甲基氨基或二乙基氨基所取代的C2-C4烷基的实例是2-二甲氨基乙基,2-二乙氨基乙基,3-二甲氨基丙基,3-二乙氨基丙基,3-二丁氨基丙基和4-二乙氨基丁基。通式(III)的基团优选是被通式(III)的基团取代的C2-C4烷基的优选实例是式的基团。基团是特别优选的。
未取代的或被1,2或3个C1-C4烷基取代的C5-C12环烷基的实例是环戊基,甲基环戊基,二甲基环戊基,环己基,甲基环己基,二甲基环己基,三甲基环己基,叔丁基环己基,环辛基,环癸基和环十二烷基。未取代或被取代的环己基是优选的。
具有6-10个碳原子的双环或三环烃基的优选实例是1,2,3,4-四氢萘次甲基。
未取代的或被C1-C4烷基取代的C5-C12环链烯基的优选实例是环己烯基。
含有不超过18个碳原子的链烯基的实例是烯丙基,2-甲基烯丙基,丁烯基,己烯基,十一碳烯基和十八碳烯基。1-位上的碳原子是饱和的链烯基是优选的,且烯丙基是特别优选的。
C5-C18炔基的优选实例是辛炔基。
被1,2或3个C1-C4烷基或C1-C4烷氧基取代的苯基的实例是甲基苯基,二甲基苯基,三甲基苯基,叔丁基苯基,二叔丁基苯基,3,5-二叔丁基-4-甲基苯基,甲氧基苯基,乙氧基苯基和丁氧基苯基。
未被取代或在苯环上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基的实例是苄基,甲基苄基,二甲基苄基,三甲基苄基,叔丁基苄基和2-苯基乙基。苄基是优选的。
含有不超过12个碳原子的酰基(脂族、环脂族或芳族)的实例是甲酰基,乙酰基,丙酰基,丁酰基,戊酰基,己酰基,庚酰基,辛酰基和苯甲酰基。C1-C8链烷酰基和苯甲酰基是优选的。乙酰基是尤其优选的。
(C1-C12烷氧基)羰基的实例是甲氧基羰基,乙氧基羰基,丙氧基羰基,丁氧基羰基,戊氧基羰基,己氧基羰基,庚氧基羰基,辛氧基羰基,壬氧基羰基,癸氧基羰基,十一烷氧基羰基和十二烷氧基羰基。
含有不超过12个碳原子的亚烷基的实例是亚乙基,亚丙基,三亚甲基,四亚甲基,五亚甲基,六亚甲基,八亚甲基,十亚甲基和十二亚甲基。R2例如是C2-C8亚烷基或C4-C8亚烷基,尤其C2-C6亚烷基,优选六亚甲基。
C4-C12亚链烯基的实例是3-亚己烯基。
C5-C7亚环烷基的实例是亚环己基。
被1,4-哌嗪二基间断的C4-C12亚烷基的实例是
被-O-,例如1,2或3个-O-间断的C4-C12亚烷基的实例是3-氧杂戊烷-1,5-二基,4-氧杂庚烷-1,7-二基,3,6-二氧杂辛烷-1,8-二基,4,7-二氧杂癸烷-1,10-二基,4,9-二氧杂十二烷-1,12-二基,3,6,9-三氧杂十一烷-1,11-二基和4,7,10-三氧杂十三烷-1,13-二基。
被>N-X1间断的C4-C12亚烷基的实例是-CH2CH2CH2-N(X1)-CH2CH2-N(X1)-CH2CH2CH2-,尤其-CH2CH2CH2-N(CH3)-CH2CH2-N(CH3)-CH2CH2CH2-。
C5-C7亚环烷基二(C1-C4亚烷基)的实例是亚环己基二亚甲基。
C1-C4亚烷基二(C5-C7亚环烷基)的实例是亚甲基二亚环己基和异亚丙基二亚环己基。
亚苯基二(C1-C4亚烷基)的实例是亚苯基二亚甲基。
R1优选是庚基,辛基,环己基,甲基环己基,环辛基,环己烯基,α-甲基苄基或1,2,3,4-四氢萘次甲基,和烃溶剂(取决于R1)因此是庚烷,辛烷,环己烷,甲基环己烷,环辛烷,环己烯,乙基苯或四氢萘。
根据本发明的另一个优选实施方案,R1是环己基或辛基,和烃溶剂(取决于R1)是环己烷或辛烷。
当-O-R1是氧基时,烃溶剂相应地是惰性有机溶剂,优选甲苯或1,2-二氯乙烷。
过氧化物分解催化剂例如是金属羰基化物,金属氧化物,金属乙酰丙酮化物或金属醇盐,其中金属选自元素周期表的IVb,Vb,VIb,VIIb和VIII族元素,优选乙酰丙酮酸钒(III),羰基钴,氧化铬(VI),异丙氧基钛(IV),四丁氧基钛,六羰基钼,三氧化钼和类似物。最优选的催化剂是三氧化钼。
合适的氢过氧化物是叔丁基过氧化氢,叔戊基过氧化氢,叔己基过氧化氢,叔辛基过氧化氢,乙基苯过氧化氢,1,2,3,4-四氢萘过氧化氢或枯烯(=异丙基苯)过氧化氢。最优选的氢过氧化物是叔丁基过氧化氢。
例如可使用2-8摩尔,优选3-6摩尔的氢过氧化物,0.001-0.1摩尔,优选0.005-0.05摩尔的过氧化物分解催化剂和5-30摩尔,优选10-20摩尔的烃溶剂,对于每摩尔在对应于嵌段低聚物中存在的通式为(G-I)的位阻胺结构部分:通式(G-I)的位阻胺结构部分向以下通式的基团的转变例如可在75℃-160℃,优选100-150℃下进行。
当通式(G-I)的位阻胺结构部分首先用氢过氧化物水溶液在惰性有机溶剂中在过氧化物分解催化剂存在下处理时(与US-A-4 691 015中所述方法类似),在较短时间内获得的初始反应产物是相应的N-氧基中间体(-OR1=氧基),它是高度着色并本身能够被分离出来。
当有机溶剂是具有不稳定氢原子的烃时,当保留了足够的摩尔过量的氢过氧化物(超过了将胺转化成相应N-氧基衍生物所需要的量),和当反应混合物在中等温度(优选100-150℃)下加热另外的时间时,则在N-氧基化合物(它就地从起始胺制备或在该方法中用作最初的起始中间体)和烃溶剂之间发生进一步的反应而得到相应的N-烃氧基衍生物。
初始反应混合物是无色的,但随着N-氧基中间体的形成而变深了颜色。随着N-氧基化合物被转化成无色的N-烃氧基产物时该颜色会消失。实质上该方法内置了颜色显示器来显示反应的程度。当反应混合物变无色时,则表明着色的N-氧基中间体完全转化成N-烃氧基产物。
如果需要,根据本发明的产物能够由下述方法中的一种提纯:
a)残余的过氧化物被分解和溶剂被蒸发而获得粗的固体产物。固体物与惰性溶剂如环己烷,辛烷,己烷,石油醚,二甲苯,甲苯,丙酮,丁酮,乙酸乙酯,乙酸丁酯,叔丁醇,叔戊醇,异丙醇,乙醇,甲醇,氯仿,二氯甲烷,乙腈,乙醚,丁醚和/或水一起搅拌。混合物在搅拌的同时被加热。在搅拌之后,混合物被冷却和固体产物通过过滤收集并加以干燥。
b)残余的过氧化物被分解和溶剂被部分地蒸发出来。残余物经过滤获得固体,用惰性溶剂如以上溶剂中的一种进行洗涤,然后冷却和干燥。
c)残余过氧化物被分解和在升高的温度下蒸发溶剂获得熔体。温热的熔体与惰性溶剂如以上所述溶剂中的一种进行混合,然后冷却,所得到的沉淀物通过过滤收集下来并加以干燥。该操作程序的变化包括将温热熔体与溶剂混合和然后将混合物冷却获得沉淀物,或将温热熔体与溶剂混合,加热使任何固体溶解,然后冷却而获得沉淀物。
d)残余过氧化物被分解和溶剂在升高的温度下被蒸发出来而获得熔体。将熔体溶于惰性溶剂如以上所述溶剂中的一种中,加热或无需加热,然后,所得到的溶液通过蒸馏出一些过量的溶剂来浓缩。然后在使产物沉淀的温度下溶液与第二种溶剂如以上所述的一种混合。通过过滤收集固体并加以干燥。
更具体地说,根据本发明的产物优选按以下方法提纯:
在反应结束后,粗反应混合物被冷却至50℃并用20%亚硫酸钠处理,直至残余过氧化物的浓度低于0.5%为止。水层被分离出来,通过在降低的压力下加热产物溶液来浓缩有机层。粗产物被溶于过量的叔丁醇中,通过在降低的压力下加热该溶液直至固体浓度为50%时为止来除去溶剂。将该溶液缓慢地加入到冷却的甲醇中。所得到的沉淀物被过滤,用甲醇洗涤,和在真空下加热干燥。
多分散性为1-1.7的通式(I)的嵌段低聚物起始原料被描述在US专利申请序列号No.08/756 225和EP-A-782 994中。
具有大于1至1.7的多分散性
Mw/
Mn值的嵌段低聚物起始原料可例如根据以下方法来制备:
2)让通式(C)的化合物与通式(B)的化合物按摩尔比例1∶2-1∶3、优选1∶2进行反应,获得通式(D)的至少三种不同单分散性化合物的混合物,其中n是2,3,4,5,6,7,8,9,10,11,12,13或14,尤其2,4和6;
3)让在2)中获得的混合物与通式(E)的化合物按化学计量比例进行反应,获得具有指定的多分散性的所需产物;反应1)至3)是在无机碱存在下在有机溶剂中进行的。
合适有机溶剂的例子是甲苯,二甲苯,三甲基苯,异丙基苯,二异丙基苯和尤其水不溶性有机酮类,如甲基乙基酮和甲基异丁基酮。二甲苯是优选的。
无机碱的实例是氢氧化钠,氢氧化钾,碳酸钠和碳酸钾。氢氧化钠是优选的。
反应1)例如可在40-70℃、优选50-60℃的温度下进行。
反应2)例如可在110-180℃、优选140-160℃的温度下进行。
反应3)例如可在110-180℃、优选140-160℃的温度下进行。
这些化合物中的每一种(从US-A-4 108 829和US-A-4 442 250中可知)能够以例如至多30mol%,优选至多20mol%或至多10mol%尤其至多8mol%的量(相对于整个混合物)存在于混合物中。
通式(A)的化合物例如能够在有机溶剂和无机碱存在下由氰脲酰氯与化合物B-H按化学计量比进行反应来制备。
此外,通式(E)的化合物例如能够在有机溶剂和无机碱存在下由氰脲酰氯与通式A-H和B*-H的化合物按化学计量比例进行反应来制备。
适宜的是对于通式(A)和(E)的化合物的制备可使用与以上反应1)至3)中同样的溶剂和同样的无机碱。
在以上方法中使用的起始原料是已知的。对于无法通过商业途径获得的情况,它们能够与已知方法类似地制备。例如通式(B)的一些起始原料描述在WO-A-95/21157,US-A-4 316 837和US-A-4 743 688中。
特别优选的起始原料是多分散性
Mw/
Mn为1.1-1.7的产物或更佳是具有所指定多分散性的混合物,该混合物含有至少三种仅仅重复单元数不同的单分散性化合物且它们是:a)通式(S-Ia)的化合物b)通式(S-Ib)的化合物和c)通式(S-Ic)的化合物,基团A,B,B*,R和R2如以上所定义,通式(S-Ia)与(S-Ib)与(S-Ic)的化合物的摩尔比是2∶1.6∶1至2∶0.4∶0.04,优选2∶1.2∶0.5至2∶0.4∶0.04,尤其2∶1∶0.4至2∶0.45∶0.04。
多分散性
Mw/
Mn为1的通式(I)的起始原料可一步步地构造该化合物来制备。此类操作程序的一些代表性实例是以下所示这些:I)其中R是通式(G-1)和n是2的通式(I)的化合物可方便地根据反应历程I-1由通式(E)的化合物与大大过量的通式(B)的化合物反应获得通式(F)的化合物来制备。通式(E)的化合物与通式(B)的化合物的摩尔比例如是1∶4。反应历程I-1:
随后,如反应历程I-2所示,通式(F)的化合物与通式(C)的化合物按化学计量比例进行反应而获得所需化合物:反应历程I-2:II)其中R是通式(G-I)和n是3的通式(I)的化合物可方便地根据反应历程II-1由通式(F)的化合物与通式(A)的化合物按照化学计量比例进行反应而获得通式(G)的化合物来制备。反应历程II-1:
随后,通式(H)的化合物可与通式(A)的化合物按照化学计量比例进行反应而获得通式(K)的化合物,按照反应历程II-3。反应历程II-3:III)其中R是通式(G-I)和n是4的通式(I)的化合物可方便地由通式(H)的化合物与通式(C)的化合物按照化学计量比例进行反应而获得通式(L)的化合物来制备。
反应I)至III)例如在有机溶剂如甲苯,二甲苯,三甲基苯中在无机碱如氢氧化钠存在下在110℃至180℃、优选140℃-160℃之间的温度下进行。
本发明的优选产物是其中R是通式(G-I)的基团的那些化合物。
本发明的优选产物也是满足以下条件的那些化合物:其中
R2是C2-C12亚烷基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有R4的一个定义;或R2是通式(b)的基团;
R3,R4和R5,可以相同或不同,是C1-C18烷基,未取代或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代的苯基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;和R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;
R6是C1-C18烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;或通式(G-I)的基团。
本发明的又一个优选实施方案涉及满足以下条件的那些产物,其中:
n是2-12的数;
R2是C2-C12亚烷基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基)或亚苯基二(C1-C4亚烷基);
R6是C1-C18烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;或通式(G-I)的基团;和
R是通式(G-I)的基团。
满足以下条件的那些产物是适宜的,其中:
R2是C2-C10亚烷基,亚环己基,亚环己基二(C1-C4亚烷基),C1-C4亚烷基二亚环己基或亚苯基二(C1-C4亚烷基);
R3,R4和R5,可以相同或不同,是C1-C12烷基,未取代或被1,2或3个C1-C4烷基取代的C5-C7环烷基;未取代的或被1,2或3个C1-C4烷基取代的苯基;未取代或在苯基上被1,2或3个C1-C4烷基取代的苄基;或
-N(R4)(R5)另外是通式(III)的基团;和
R6是C1-C12烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C7环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的苄基;或通式(G-I)的基团。
也适宜的是满足以下条件的那些产物,其中:
R2是C2-C8亚烷基;
R3,R4和R5,可以相同或不同,是C1-C8烷基,未取代或被甲基取代的环己基;未取代的或被甲基取代的苯基;或苄基;或
-N(R4)(R5)另外是4-吗啉基;和
R6是C1-C8烷基,未取代的或被甲基取代的环己基;苄基;或通式(G-I)的基团。
也适宜的是满足以下条件的那些产物,其中:
n是2-6的数;
R2是C2-C6亚烷基;
A是-N(R4)(R5)或通式(II)的基团;
R4和R5,可以相同或不同,是C1-C8烷基;
或-N(R4)(R5)另外是4-吗啉基;
X是>NR6;
R6是C1-C4烷基;和
基团B和B*相互独立地是对于A给出的一个定义。
其它优选的产物是满足以下条件的那些:其中,B*不同于B以及基团B、R和R2中每一个在通式(I)的各个重复单元中具有同样的意义。
氢化是根据已知方法例如在有机溶剂如甲醇或乙醇中在氢化催化剂(优选钯/碳或PtO2)存在下进行的,如US-A-4 691 015中所述。
本发明的另一个实施方案是一种混合物,它含有:
通式(Ia)、(Ib)和(Ic)的化合物仅仅在重复单元的数目上不同,通式(Ia)与(Ib)与(Ic)的化合物的摩尔比是2∶1.6∶1至2∶0.4∶0.04,优选2∶1.2∶0.5至2∶0.4∶0.04,尤其2∶1∶0.4至2∶0.45∶0.04;和
R1是氢或烃基或-O-R1是氧基;
R2是C2-C12亚烷基,C4-C12亚链烯基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被1,4-哌嗪二基,-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有以下给出的R4的一个定义;或R2是通式(a),(b)或(c)的基团;其中,m是2或3,X2是C1-C18烷基,C5-C12环烷基,该环烷基是未取代的或被1,2或3个C1-C4烷基取代;苯基,它是未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它未被取代或在苯基上被1,2或3个C1-C4烷基取代;和基团X3独立地是C2-C12亚烷基;A*是-OR3,-N(R4)(R5)或以下通式(G-IV)的基团,
R3,R4和R5可以相同或不同,是C1-C18烷基,C5-C12环烷基,该环烷基是未被取代的或被1,2或3个C1-C4烷基取代;C3-C18链烯基,苯基,它是未被取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它是未取代的或在苯环上被1,2或3个C1-C4烷基取代;四氢糠基或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或以下通式(III)的基团所取代,其中Y是-O-,-CH2-,-CH2CH2-或>N-CH3;和R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;X*是-O-或>N-R6 *;R6 *是C1-C18烷基,C3-C18链烯基,C5-C12环烷基,该环烷基是未取代或被1,2或3个C1-C4烷基取代;C7-C9苯基烷基,它是未取代的或在苯基上被1,2或3个C1-C4烷基取代;四氢糠基,通式(G-II)的基团,或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或通式(III)的基团取代;
R*具有一个对于R6 *所给出的定义;和
基团B*和B**独立地具有一个对于A*给出的定义。
在将多分散性为例如1.1-1.7的嵌段低聚物起始原料(含有通式(S-Ia),(S-Ib)和(S-Ic)的化合物的混合物)中存在的通式(G-I)的基团转化成通式(G-II)的基团之后,通式(Ia)与(Ib)与(Ic)的化合物的比例对应于以上所示的通式(S-Ia)与(S-Ib)与(S-Ic)的初始化合物的比例,因为在反应过程中这些化合物的骨架不受影响。
优选的是满足以下条件的混合物,其中:
R1是环己基或辛基;
R2是C2-C6亚烷基;
B*是通式(G-IV-1)的基团;和
R*是通式(G-II)的基团。
R1 *的意义能够从R1的意义推断。在这两个基团之间的唯一差别是R1 *具有一个或两个附加的价键。因此,作为环己基的R1对应于作为环己烷二基或环己烷三基的R1 *以及作为辛基的R1对应于作为辛烷二基或辛烷三基的R1 *。
本发明的产物以及所述的混合物在改进有机材料尤其合成聚合物和共聚物的耐光、热和氧化性能上非常有效。尤其是,在聚丙烯,尤其聚丙烯纤维中,尤其在阻燃剂存在下以及在农用的低密度聚乙烯(LDPE)膜中观察到低的颜料相互作用以及非常良好的色彩。还十分突出的是,本发明的产物和所述混合物本身是阻燃剂。
能够被稳定的有机材料的实例是:
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)。
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,和优选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底上,典型地在活化氯化镁、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。该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),该金属是元素周期表的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菲利普(Phillips),美孚印第安那(Standard Oil Indiana),齐格勒(-纳塔)(Ziegler(-Natta)),TNZ(杜邦(Dupont)),金属茂或单一“位”(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、二环戊二烯或亚乙基-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,如氯丁橡胶,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-或共聚物,尤其含卤素的乙烯基化合物的聚合物,例如聚氯乙烯,聚偏氯乙烯,聚氟乙烯,聚偏氟乙烯,以及它们的共聚物,如氯乙烯/偏氯乙烯,氯乙烯/乙酸乙烯酯或偏氯乙烯/乙酸乙烯酯共聚物。
9、从α,β-不饱和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、聚苯氧和聚苯硫,聚苯氧与苯乙烯聚合物或聚酰胺的混合物。
15、从羟基封端的聚醚、聚酯或聚丁二烯与脂族或芳族多异氰酸酯衍生而来的聚氨酯,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高弹体作为改性剂的聚酰胺,例如聚-2,4,4-三甲基亚己基对苯二甲酰二胺或聚间亚苯基间苯二甲酰二胺;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醚酯;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、从醛与酚类、脲和三聚氰胺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、干燥和非干燥醇酸树脂。
23、从饱和的和不饱和的二羧酸与多羟基醇的共聚酯和作为交联剂的乙烯基化合物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(例如环氧丙烯酸酯,尿烷丙烯酸酯或聚酯丙烯酸酯)衍生而来的可交联丙烯酸树脂。
25、用蜜胺树脂,尿素树脂,异氰酸酯,异氰脲酸酯,聚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在有或没有促进剂的情况下加以交联。
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;以及松香和它们的衍生物。
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、天然的和合成的有机材料,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,磷酸酯或偏苯三酸酯)的油、脂肪和蜡,还有合成酯与矿物油按任何重量比例的混合物,典型地用作纺丝组合物的那些材料,以及此类材料的水乳液。
30、天然或合成橡胶的水乳液,例如天然胶乳或羧化苯乙烯/丁二烯共聚物的乳胶。
本发明因而也涉及包含有机材料(该材料易遭受由光、热或氧化诱发的降解)和根据本发明的产物或混合物的组合物。
有机材料优选是合成聚合物,更优选选自上述各组的聚合物。聚烯烃是优选的且聚乙烯和聚丙烯是特别优选的。
本发明的又一实施方案是使有机材料稳定化以防止由光、热或氧化诱发的降解的方法,它包括向该有机材料中引入根据本发明的产物或混合物。
本发明的产物或混合物能够以各种比例使用,这取决于被稳定的材料的性质,取决于最终用途和取决于其它添加剂的存在。
一般来说,例如使用0.01-5重量%的本发明的产物或混合物是合适的(相对于被稳定的材料的重量来说),优选0.05-2重量%,特别是0.05-1wt%。
根据本发明的产物或混合物可以例如在该材料的聚合反应或该材料的交联反应之前、期间或之后加入到聚合物材料中。此外,它们还能够以纯净的形式或以包裹在蜡、油或聚合物中的形式引入聚合物材料中。
一般来说,根据本发明的产物或混合物能够通过各种方法被引入聚合物材料中,例如以粉末形式干混方法,或者以溶液或悬浮液的形式或以母料的形式湿混,母料含有2.5-25wt%的本发明产物或混合物;在这类操作中,聚合物能够以粉末、粒料、溶液、悬浮液的形式或以乳胶的形式使用。
用本发明的产物或混合物稳定的材料能够用于生产模制品,薄膜,带材,单丝,纤维,表面涂层等等。
如果需要,其它常用于合成聚合物的添加剂,如抗氧化剂,UV吸收剂,镍稳定剂,颜料,填料,增塑剂,缓蚀剂或金属减活剂能够加入到含有本发明产物或混合物的有机材料中。
这类常规的添加剂的具体例子是:
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,它们是线性的或在支链上支化,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,与单羟基或多羟基醇类,例如与甲醇,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]辛烷的酯类。
1.14、β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,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]辛烷的酯类。
1.15、β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,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]辛烷的酯类。
1.16、3,5-二叔丁基-4-羟基苯基乙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,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]辛烷的酯类。
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,N,N’-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基1草酰胺(NaugardXL-1,由Uniroyal提供)。
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-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化二苯胺(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-萘基胺,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
2.1、2-(2′-羟基苯基)苯并三唑类,例如2-(2′-羟基-5′-甲基苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)苯并三唑,2-(5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基)-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑,2-(3′-仲丁基-5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-4′-辛氧基苯基)苯并三唑,2-(3′,5′-二叔戊基-2′-羟基苯基)苯并三唑,2-(3′,5′-双-(α,α-二甲基苄基)-2′-羟基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑,和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];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯基转移产物;[R-CH2CH2-COO-CH2CH2-]2-其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基,2-[2′-羟基-3′-(α,α-二甲基苄基)-5′-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2′-羟基-3′-(1,1,3,3-四甲基丁基)-5′-(α,α-二甲基苄基)苯基]苯并三唑。
2.2、2-羟基二苯甲酮类,例如4-羟基,4-甲氧基,4-辛氧基,4-癸氧基,4-十二烷氧基,4-苄氧基,4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3、取代的和未取代的苯甲酸的酯类,例如水杨酸4-叔丁基-苯基酯,水杨酸苯酯,水杨酸辛基苯酯,二苯甲酰基间苯二酚,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,3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
2.4、丙烯酸酯类,例如α-氰基-β,β-二苯基丙烯酸乙酯,α-氰基-β,β-二苯基丙烯酸异辛酯,α-甲酯基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸丁酯,α-甲酯基-对甲氧基肉桂酸甲酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。
2.5、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。
2.6、空间位阻胺;例如癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯,琥珀酸双(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯,癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯,双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯。1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的缩合物,次氮基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯,1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯,1,1′-(1,2-亚乙基)双(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂酰氧基-2,2,6,6-四甲基哌啶,2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,琥珀酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,N,N′-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线型或环状缩合物,2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-硬脂酰氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-双(3-氨基-丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪的缩合物,以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS登记号[136504-96-6]);N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基4-哌啶基)正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷和表氯醇的反应产物,1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N′-双甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基-亚甲基-丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7、草酰胺类,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′-二叔丁氧基N,N’-草酰二苯胺(2,2′-dioctyloxy-5,5′-di-tert-butoxanilide),2,2′-二(十二烷氧基)-5,5′-二叔丁氧基N,N′-草酰二苯胺(2,2′-didodecyloxy-5,5′-di-tert-butoxanilide),2-乙氧基-2′-乙基N,N′-草酰二苯胺,N,N′-双(3-二甲氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙氧基N,N′-草酰二苯胺(2-ethoxy-5-tert-butyl-2′-ethoxanilide)和它与2-乙氧基-2′-乙基-5,4′-二叔丁氧基N,N′-草酰二苯胺(2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide)的混合物以及邻-和对-甲氧基双取代的N,N′-草酰二苯胺类的混合物和邻-和对-乙氧基-二取代的N,N′草酰二苯胺类的混合物。
2.8、2-(2-羟基苯基)-1,3,5-三嗪类,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基-丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
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,二亚磷酸二异癸基氧基季戊四醇酯,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,二膦酸四(2,4-二叔丁基苯基)4,4′-亚联苯基酯,6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂膦辛(dioxaphosphocin),6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂膦辛(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,2,2′,2″-次氮基[三乙基三(3,3′,5,5′-四叔丁基-1,1′-二苯基-2,2′-二基)亚磷酸酯],亚磷酸2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-二苯基-2,2′-二基)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,从氢化牛胺得到的N,N-二烷基羟基胺。
6、硝酮类,例如N-苄基-α-甲基-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,从氢化牛胺衍生而来的N,N-二烷基羟基胺获得的硝酮。
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、聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物的混合物,和二价锰的盐。
10、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,蓖麻酸钠和棕榈酸钾,邻苯二酚锑或邻苯二酚锌。
11、成核剂类,例如,无机物质,如滑石,金属氧化物例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”)。
12、填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃球,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。
13、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。
14、苯并呋喃酮类和二氢吲哚酮类,例如在US-A-4,325,863,US-A-4338244,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-0589839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,3-(3,4-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮。
根据本发明的产物或混合物与常规的添加剂的重量比可以是例如1∶0.5-1∶5。
根据本发明的产物或混合物还可以用作在照相复制技术和其它复制技术中几乎所有已知的材料的稳定剂,尤其光稳定剂,例如在ResearchDisclosure,1990,31429(474-480页)中所描述的。
通过下面的实施例将更详细地解释本发明。所有的百分数和份数都是按重量计的,除非另有说明。
下面的实施例S-1和实施例S-2是起始原料的制备方法的代表。实施例1-4是根据本发明的产物的制备方法的代表。
GPC(凝胶渗透色谱法)用作分析程序,用来根据它们的尺寸差异分离分子并获得分子量平均值(
Mw,
Mn)或有关聚合物的分子量分布的信息。
该技术是已知的并描述在,例如,“Modern Size-Exclusion LiquidChromatogrphy”W.W.Yan等人,由J.Wiley & Sons,N.Y.,USA编辑,1979,页码4-8,249-283和315-340。
由多分散性(
Mw/
Mn)接近1来表征窄的分子量分布。
在下面的实施例S-1和S-2中给出的GPC分析是通过使用装有Perkin-Elmer RI检测仪LC 30和装有Perkin-Elmer烘箱LC 101的GPC色谱仪Perkin-Elmer LC 250来进行的。
所有的分析是通过使用3根柱PLGEL 3μm Mixed E 300mm长×7.5mm i.d.(内尺寸)(购自Polymer Laboratories Ltd.Shropshire,U.K.)在45℃下进行的。
四氢呋喃用作洗脱液(流速0.40ml/分钟)和样品溶于四氢呋喃中(2%)(%w/v)。
在0℃下将74.3g(0.35mol)的N-(2,2,6,6-四甲基-4-哌啶基)-正丁基胺在50ml水中的溶液缓慢地加入到64.5g(0.35mol)氰脲酰氯在500ml二甲苯中的溶液中,在加料过程中保持该温度并保持另外1小时。
在室温下2小时之后,混合物被冷却至0℃和然后添加14.7g(0.368mol)的氢氧化钠在50ml水中的水溶液。在0℃下1/2小时和在室温下另外2小时之后,分离出水溶液和添加69.2g(0.175mol)的N,N′-双[2,2,6,6-四甲基-4-哌啶基]-1,6-己烷二胺。
混合物被加热至50℃保持1小时,然后添加48.4g(0.35mol)的研磨碳酸钾并加热至60℃保持4小时。
在用水洗涤之后,有机相在60-70℃/10毫巴下真空浓缩,回收250ml二甲苯。
添加138.1g(0.35mol)的N,N′-双[2,2,6,6-四甲基-4-哌啶基]-1,6-己烷二胺,混合物被加热至150℃保持2小时,再次冷却和添加14g(0.35mol)的研磨氢氧化钠。
混合物被加热至140℃保持另外4小时,反应的残余水以共沸方式除去,并在160℃保持另外4小时。
在冷却至60℃后,混合物用300ml二甲苯稀释,过滤和用100ml乙二醇洗涤3次。
在60℃/10毫巴下真空浓缩后,添加78.7g(0.147mol)的2-氯-4,6-双[N-(2,2,6,6-四甲基-4-哌啶基)-正丁基胺基)-1,3,5-三嗪。
混合物被加热至140℃保持3小时,然后添加5.9g(0.147mol)的研磨氢氧化钠,混合物被加热回流,反应水以共沸方式消除。
混合物被加热至160℃保持4小时,添加另外5.9g(0.147mol)的研磨氢氧化钠,再次加热至160℃保持2小时。
在冷却至60℃后,混合物用300ml二甲苯稀释,过滤和在140℃/1毫巴下真空浓缩。
在干燥之后获得了熔点为166-170℃的固体。
Mn(由GPC)=3360g/mol。
多分散性
Mw/
Mn=1.18。
GPC分析结果显示了色谱图,如图1中所示。
所获得的多分散性产物的三种主要单种组分的摩尔比((n′=2)∶(n′=4):(n′=6))是2∶0.53∶0.05。实施例S-2:具有下式的产物的制备:
在0℃下将74.3g(0.35mol)的N-(2,2,6,6-四甲基-4-哌啶基)-正丁基胺在50ml水中的溶液缓慢地加入到64.5g(0.35mol)氰脲酰氯在500ml二甲苯中的溶液中,在加料过程中保持该温度并保持另外1小时。
在室温下2小时之后,混合物被冷却至0℃和然后添加14.7g(0.368mol)的氢氧化钠在50ml水中的水溶液。
在0℃下1/2小时和在室温下另外2小时之后,分离出水溶液和添加69.2g(0.175mol)的N,N′-双[2,2,6,6-四甲基-4-哌啶基]-1,6-己烷二胺。
混合物被加热至50℃保持1小时,然后添加48.4g(0.35mol)的研磨碳酸钾并加热至60℃保持4小时。
在用水洗涤之后,有机相在60-70℃/10毫巴下真空浓缩,回收250ml二甲苯。
添加138.1g(0.35mol)的N,N′-双[2,2,6,6-四甲基-4-哌啶基]-1,6-己烷二胺,混合物被加热至150℃保持2小时,再次冷却和添加14g(0.35mol)的研磨氢氧化钠。
混合物被加热至140℃保持另外4小时,反应的残余水以共沸方式除去,并在160℃保持另外4小时。
在冷却至60℃后,混合物用300ml二甲苯稀释,过滤和用100ml乙二醇洗涤3次。
在60℃/10毫巴下真空浓缩后,添加54.4g(0.147mol)的2-氯-4,6-双(二丁基氨基)-1,3,5-三嗪。
混合物被加热至140℃保持3小时,然后添加20.3g(0.147mol)的研磨碳酸钾,混合物被加热回流,反应水以共沸方式消除。
混合物被加热至160℃保持4小时,添加另外20.3g(0.147mol)的研磨碳酸钾,再次加热至160℃保持2小时。在冷却至60℃后,混合物用300ml二甲苯稀释,过滤和在140℃/1毫巴下真空浓缩。
在干燥之后获得了熔点为130-136℃的固体。
Mn(由GPC)=2830g/mol。
多分散性
Mw/
Mn=1.22。
GPC分析结果显示了色谱图,如图2中所示。
在磁力搅拌式500ml四颈圆底烧瓶中加入25.0g(0.115mol)的实施例S-1的产物和200ml环己烷。混合物被加热回流,然后添加0.10g的三氧化钼。经3小时添加51.9g(0.403mol)的70%叔丁基过氧化氢,通过共沸蒸馏分离出水分。在该加料过程中添加三份各0.10g的三氧化钼。内容物被转移至磁力搅拌式Fisher-Porter耐压瓶中,在125℃下加热4小时,然后冷却至60℃以下和过滤出三氧化钼。滤液在200ml5%亚硫酸钠存在下搅拌90分钟。将两相分离,有机相用水和饱和氯化钠水溶液洗涤。有机相用硫酸镁干燥,蒸发成浅黄色固体。
产率:35.7g(理论值的99%)。
熔化范围:130-170℃
1H-NMR:0.85-2.40ppm(复杂混合物);3.20-3.45ppm(s,宽,NCH2);3.54-3.70ppm(s,宽,NOCH);4.90-5.50ppm(s,宽,NCH)。
在3.20,3.54和4.90ppm处的质子比率:2∶1∶1。
13C-NMR:82ppm(NOC);165ppm(三嗪C)实施例2:具有下式的产物的制备:
在磁力搅拌式500ml四颈圆底烧瓶中加入25.0g(0.0962mol)的实施例S-2的产物和200ml环己烷。混合物被加热回流,添加0.10g三氧化钼。然后,经2小时的时间添加43.3g(0.337mol)的70%叔丁基过氧化氢,同时以共沸蒸馏方法分离出水分。在该加料过程中添加另外两份各0.10g的三氧化钼。内容物与附加的0.3g三氧化钼被转移至磁力搅拌式Fisher-Porter耐压瓶中,在125℃下加热11小时,然后冷却至60℃以下,和过滤出三氧化钼。在200ml的5%亚硫酸钠存在下将滤液搅拌90分钟。将两相分离,有机相用水和饱和氯化钠水溶液洗涤。有机相用硫酸镁干燥和蒸发成浅黄色固体。
产率:34.4g(99%理论值)。
熔化范围:128-169℃。
1H-NMR:0.80-2.50ppm(复杂混合物);3.20-3.40ppm(s,宽,NCH2);3.40-3.50ppm(s,宽,NC4H9的NCH2);3.54-3.70ppm(s,宽,NOCH);4.90-5.40ppm(s,宽,NCH)。
在3.20,3.54和4.90ppm处的质子比率:2∶1∶1。
将885g(3.39mol)实施例S-2的产物,6000g(71.4mol)的环己烷和2.2g的三氧化钼的混合物加热回流。经1-2小时向回流混合物中添加3360g的70%叔丁基过氧化氢(26.1mol)水溶液,通过共沸蒸馏除去水。反应物料被转移至耐压反应器中,在125℃下在30-50psig(2.1-3.5巴)下加热直至显红色为止。粗的反应物料被冷却和用亚硫酸钠水溶液处理来破坏残余过氧化物。分离出水层,有机层在减压下浓缩成熔体,将其加入到冷甲醇中,在过滤后获得灰白色的固体产物。
平均透光值(10%甲苯):425nm=44.2%;450nm=56.0%;
475nm=67.5%实施例2-B:具有下式的产物的制备
重复实施例2-A的操作程序,只是在后处理过程中,在除去环己烷之后所获得的熔体用叔丁醇稀释,浓缩至50%固体含量。溶液被冷却,将冷甲醇缓慢地加入,在过滤之后获得了灰白色的固体产物。
平均透光值(10%甲苯):425nm=46.5%;450nm=63.30%;
在500ml四颈圆底烧瓶中加入30.0g(0.138mol)的实施例S-1的产物,240ml正辛烷,36g(0.27mol)的70%叔丁基过氧化氢和0.2g的三氧化钼。反应混合物被加热至回流,通过共沸蒸馏除去水分。在15分钟后添加另外35.1g(0.27mol)叔丁基过氧化氢和0.1g三氧化钼,回流继续进行下去,直至反应温度升高至110℃。在此时反应混合物被转移至磁力搅拌式Fisher-Porter耐压瓶中,在150℃下加热3.5小时,过滤出催化剂,滤液与200ml 5%亚硫酸钠一起经2小时搅拌成於浆状。有机相用水和饱和氯化钠水溶液洗涤,用硫酸镁干燥,蒸发至浅黄色固体。
产率:43.3g(91%理论值)。
熔化范围:93-117℃。
1H-NMR:0.70-2.50ppm(复杂混合物);3.20-3.45ppm(s,宽,NCH2);3.55-3.95ppm(宽,NOCH,异构体在C8H17中的混合物);4.90-5.50ppm(s,宽,NCH)。
在3.20,3.55和4.90ppm处的质子比率:2∶1∶1。
13C-NMR:78-84ppm(NOC,异构体在C8H17中的混合物);165ppm(三嗪C)。实施例3-B:具有下式的产物的制备(方法2)
在500ml四颈圆底烧瓶中加入25.0g(0.115mol)的实施例S-1的产物,200ml正辛烷和0.3g三氧化钼。混合物被加热至回流。经45分钟的时间添加59.2g(0.46mol)的70%叔丁基过氧化氢,同时通过共沸蒸馏连续分离出水分。在5小时后添加另外22.2g(0.17mol)的叔丁基过氧化氢和0.2g三氧化钼之后,在9小时的总反应时间之后,过滤出催化剂,滤液与200ml 5%亚硫酸钠一起经2小时搅拌成於浆状。有机相用水和饱和氯化钠水溶液洗涤,用硫酸镁干燥,蒸发至浅黄色固体。
产率:37.3g(99%理论值)。
熔化范围:108-124℃。
在500ml四颈圆底烧瓶中加入30.0g(0.115mol)的实施例S-2的产物,240ml正辛烷,30g(0.23mol)的70%叔丁基过氧化氢和0.2g的三氧化钼。反应混合物被加热至回流,通过共沸蒸馏除去水分。在30分钟后添加另外29.4g(0.23mol)叔丁基过氧化氢和0.2g三氧化钼,回流继续进行下去,直至反应温度升高至110℃。在此时反应混合物被转移至磁力搅拌式Fisher-Porter耐压瓶中,在150℃下加热3.5小时。过滤出催化剂,滤液与200ml 5%亚硫酸钠一起经2小时搅拌成於浆状。有机相用水和饱和氯化钠水溶液洗涤,用硫酸镁干燥,蒸发至浅黄色固体。
产率:41.0g(92%理论值)。
熔化范围:95-125℃。
1H-NMR:0.80-2.50ppm(复杂混合物);3.20-3.41ppm(s,宽,NCH2);3.41-3.55ppm(s,宽,NC4H9的NCH2);3.55-3.95(宽,NOCH,异构体在C8H17中的混合物);4.90-5.50ppm(s,宽,NCH)。
在3.20,3.55和4.90ppm处的质子比率:2∶1∶1。
13C-NMR:76-84ppm(NOC,异构体在C8H17中的混合物);165ppm(三嗪C)。实施例4-A:具有下式的产物的制备
将1304g(5.0mol)的实施例S-2的产物,10.3kg(90.2mol)的辛烷和8.95g三氧化钼的混合物加热至回流。经1-2小时向回流混合物中添加3873g的70%叔丁基过氧化氢水溶液(30.1mol),通过共沸蒸馏除去水分。反应物料在常压下加热回流,直至显红色为止。粗的反应物料进行冷却并用亚硫酸钠水溶液处理来破坏残余的过氧化物。水层被分离出来,有机层在减压下浓缩成熔体,将其缓慢地加入到冷甲醇中,在过滤后获得灰白色固体产物。
平均透光值(10%甲苯):425nm=47.7%;450nm=76.0%;
475nm=84.6%实施例4-B:具有下式的产物的制备:
重复实施例4-A的操作程序,只是在后处理中,在除去辛烷之后获得的熔体用叔丁醇稀释并浓缩至50%固体。冷却溶液,快速地将甲醇加入,在过滤之后获得灰白色的固体产物。
平均透光值(10%甲苯):425nm=47.6%;450nm=80.0%;
475nm=91.4%实施例A:
通过将聚烯烃共混物(含有乙烯-丙烯高聚物的聚丙烯;PolytropeTPP 518-01,购自A.Schulman,Inc.;Akron,Ohio,USA)与以下所列添加剂在具有通用型螺杆(24∶1 L/D)的Superior/MPM 1”单螺杆挤出机中在200℃下进行混合,在水浴中冷却和切粒,来制备含颜料的热塑性烯烃(TPO)粒料。在挤出和模塑之前,添加剂在转鼓干燥器中进行干混。添加剂:
0.25%*)的Red 3B(颜料Red 177,色度指数65300)。
0.2%*)的2-(2′-羟基-3′,5′-二叔戊基苯基)苯并三唑。
0.2%*)的癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯。
0.1%*)的硬脂酸钙,
大约10%*)的滑石和
列于表1中的稳定剂
—————————————————
*)基于聚烯烃共混物的重量百分数
所得到的粒料在BOY 30M注塑机中在约190℃下被模塑成1.524mm厚的2″×2″板材。
将试验板材安放在金属框内并暴露于70℃黑板温度下的Atlas Ci65氙气弧灯耐候试验仪中,在340纳米下0.55W/m2和50%相对湿度,间歇进行光照/黑暗周期和水喷雾(Society of Automotive Engineers-SAE J1960试验程序-Exterior Automotive conditions)。
根据ASTM D 523,在BYK-GARDNER Haze/Gloss Meter上在60℃对试样进行光泽测量。
结果示于表1中。
表1
稳定剂 | 在耐候性试验仪中数小时后光泽保持率 | |
0小时(≌0KJ/m2**)) | 1890小时(≌2500KJ/m2**)) | |
0.05%*)的四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.05%*)的亚磷酸三[2,4-二叔丁基苯基]酯0.20%*)的实施例2的化合物 | 100.0% | 87.1% |
0.05%*)的四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.05%*)的亚磷酸三[2,4-二叔丁基苯基]酯0.20%*)的实施例4的化合物 | 100.0% | 89.3% |
0.05%*)的二(氢化牛脂)羟基胺0.20%*)的实施例2的化合物 | 100.0% | 88.3% |
0.05%*)的二(氢化牛脂)羟基胺0.20%*)的实施例4的化合物 | 100.0% | 83.4% |
*)基于聚烯烃共混物的重量百分数
**)指在340nm下测得的入射能,以KJ/m2表达
含有表1中列出的稳定剂的配方比没有该稳定剂的配方显示了更高的耐光致降解性能。在以上所列出的UV曝光下未稳定化的试样快速破坏。实施例B:聚丙烯带材的稳定化
1.0g实施例2或4的化合物,0.5g的四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和1g的硬脂酸钙在汽轮式混合机中与1000g熔体流动指数为2.1(在230℃和2.16kg下测得)的聚丙烯粉末(PPMOPLEN S 30 S)进行混合。
混合物在200-230℃下挤出获得粒料,然后通过使用半工业应用型装置(Leonard;Sumirago/VA,意大利)和在下述条件下进行操作,将粒料转变成50μm厚和2.5mm宽的拉伸带:
挤出机温度: 210-230℃
机头温度: 240-260℃
拉伸比: 1∶6
如此预处理的带材被安放在白色的板上并暴露于65WR Weather-O-Meter(耐候性试验仪)(ASTM D2565-85),其中黑板温度为63℃。
对于在各种暴光时间之后取出的样品,通过使用恒速张力仪测定残留韧度,然后从它计算出具有初始韧度值的一半时(T50)所需要的暴光时间(小时)。
结果揭示了,实施例2或4的化合物以优异的方式稳定了聚丙烯带材。实施例C:聚乙烯膜的稳定化-用农药处理或未处理。
实施例2或4的化合物以母料方式与低密度聚乙烯(LDPE)粒料(RibleneFF29,由ENICHEM,Milano,意大利销售;密度:0.921g/cm3;在190℃和2.16kg下熔体流动指数:0.60g/10min)在慢速混合机中进行混合。
通过用双螺杆挤出机在200℃下将粉末状LDPE和5wt%的实施例2或4的化合物挤出来预先制备母料。
混合物在200℃下吹塑。获得150μm厚度的膜,含有0.2%的实施例2或4的化合物。
一些膜按以下方法用农药处理:
在耐候性试验仪中曝照之前该膜在VAPAM在水中的浓溶液(1∶1比率,体积份数)上方贮存,不与该溶液直接接触。(VAPAM(BASLINISpA,Treviglio/BG,意大利)是结构式为CH3-NH-CS-SNa的威百亩(Metam)-钠的浓度为382g/升的水溶液。
在上述处理之后,膜试样在耐候性试验仪Weather-O-Meter型65WR中在白板上曝照,其中黑板温度为63℃。未处理的膜在同样条件下曝照。通过用傅立叶转换红外光谱仪测量样品中羰基的增加来监测降解过程。羰基提高得多则表示降解程度也高。通过使用恒速张力仪对于各种曝照时间后取的试样测定残留伸长率来监测降解率。计算具有初始伸长率的一半时(T50)所需要的曝照时间(小时)。
结果表明,实施例2或4的化合物以优异的方式稳定聚乙烯膜。实施例D:温室应用
实施例2或4的化合物以母料方式与低密度聚乙烯(LDPE)粒料(RibleneEF2100 V,由ENICHEM,Milano,意大利销售;密度:0.921g/cm3;在190℃和2.16kg下熔体流动指数:0.25)在慢速混合机中进行混合。
通过将粉末状LDPE和10wt%的实施例2或4的化合物挤出来预先制备母料。
混合物在200℃下吹塑。获得150μm厚度的膜,含有0.3%或0.4%的实施例2或4的化合物。
该膜在Pontecchio Marconi(Bologna,意大利)的没有背板(backing)的温室的朝南屋顶上,在白铁片上和在松木背板上曝照。
将下述农药施加于温室中:
(VAPAM(BASLINI SpA,Treviglio/BG,意大利),它是结构式为CH3-NH-CS-SNa的Metam-钠的浓度为382g/升的水溶液。
温室用4升VAPAM在10升水中的溶液每6个月和用SESMETRIN(5g在5升水中的溶液)每月进行处理。
在曝照过程中,由测力计在恒定速度下测量残余伸长率(按聚乙烯膜的初始伸长率的%计)来定期评价其性能。
结果揭示,实施例2或4的化合物以优异的方式稳定LDPE膜。实施例E:低密度聚乙烯膜的稳定化-户外曝照
实施例2或4的化合物以母料方式与低密度聚乙烯(LDPE)粒料(RibleneEF2100 V,由ENICHEM,Milano,意大利销售;密度:0.921g/cm3;在190℃和2.16kg下熔体流动指数:0.25)在慢速混合机中进行混合。
通过将粉末状LDPE和10wt%的实施例2或4的化合物挤出来预先制备母料。
混合物在200℃下吹塑。获得150μm厚度的膜,含有0.3%或0.4%的实施例2或4的化合物。
该膜在没有支持板的Pontecchio Marconi(约110k Lys(赖氨酸)/年辐射)内,在白铁片上和在松木支持板上曝照,不使用农药。膜表面在朝南的45°入射角方向被固定。
在曝照过程中,由测力计在恒定速度下测量残余伸长率(按聚乙烯膜的初始伸长率的%计)来定期评价其性能。
结果揭示,实施例2或4的化合物以优异的方式稳定LDPE膜。实施例F:
含有0.05wt%的硬脂酸钙和0.05wt%的二(氢化牛脂)羟基胺作为碱性稳定剂的纤维级聚丙烯与表2中列出的稳定剂进行干混,然后在234℃熔化加工成粒料。使用Hills实验室模型纤维挤出机在246℃或274℃下将造粒的全配方的树脂纺丝成纤维。41根单丝纤维的纺出丝束以1∶3.2的比率进行拉伸,得到最终旦尼尔为615/41。
在Lawson-Hemphill Analysis Knitter上从稳定化的聚丙烯编织出“短袜”,然后使用SAE J1885 Interior Automotive条件在89℃bpt下,在340nm波长下以0.55kW/cm2功率,无需喷雾周期,在Atlas Xenon-Arc-Weather-Ometer中曝照。当用钝的玻璃棒“刮擦”时,由观察到短袜的物理损坏来决定该试验是否失败。发生破坏性的损坏需要越长的时间,则稳定剂越具有有效。结果示于表2中。
表2
稳定剂 | 在246℃下纺丝纤维的破坏性损坏时间 | 在274℃下纺丝纤维的破坏性损坏时间 |
无 | 192小时 | 96小时 |
0.25wt%的实施例2的化合物 | 408小时 | 408小时 |
0.25wt%的实施例4的化合物 | 600小时 | 408小时 |
Claims (26)
其中R1是烃基或-O-R1是氧基;
该转变是由对应于通式(I)的嵌段低聚物与氢过氧化物在烃溶剂中在过氧化物分解催化剂存在下进行;
n是2-14中的数;
各R2独立地是C2-C12亚烷基,C4-C12亚链烯基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被1,4-哌嗪二基,-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有以下给出的R4的一个定义;或R2是通式(a),(b)或(c)的基团;其中,m是2或3,X2是C1-C18烷基,C5-C12环烷基,该环烷基是未取代的或被1,2或3个C1-C4烷基取代;苯基,它是未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它未被取代或在苯基上被1,2或3个C1-C4烷基取代;和基团X3相互独立地是C2-C12亚烷基;基团A相互独立地是-OR3,-N(R4)(R5)或以下通式(II)的基团,
R3,R4和R5,可以相同或不同,是C1-C18烷基,C5-C12环烷基,该环烷基是未被取代的或被1,2或3个C1-C4烷基取代;C3-C18链烯基,苯基,它是未被取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它是未取代的或在苯环上被1,2或3个C1-C4烷基取代;四氢糠基或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或以下通式(III)的基团所取代,其中Y是-O-,-CH2-,-CH2CH2-或>N-CH3,且R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;X是-O-或>N-R6;R6是C1-C18烷基,C3-C18链烯基,C5-C12环烷基,该环烷基是未取代或被1,2或3个C1-C4烷基取代;C7-C9苯基烷基,它是未取代的或在苯基上被1,2或3个C1-C4烷基取代;四氢糠基,通式(G-I)的基团,或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或通式(III)的基团取代;和
R相互独立地具有一个对于R6所给出的定义;以及基团B和B*相互独立地具有一个对于A给定的定义;
其前提是在通式(I)的各重复单元中,基团B,R和R2中每一个具有相同的或不同的定义。
2、根据权利要求1的产物,其中:
R1是C5-C18烷基,C5-C18链烯基,C5-C18炔基,未取代或被C1-C4烷基取代的C5-C12环烷基;未取代或被C1-C4烷基取代的C5-C12环链烯基;具有6-10个碳原子的双环或三环烃基或未取代或在苯基上被C1-C4烷基取代的C7-C9苯基烷基;和
烃溶剂,取决于R1,是C5-C18链烷烃,C5-C18链烯烃,C5-C18炔烃,未取代或被C1-C4烷基取代的C5-C12环烷烃;未取代或被C1-C4烷基取代的C5-C12环烯烃;具有6-10个碳原子的双环或三环烃类或未取代或在苯基上被C1-C4烷基取代的C7-C9苯基烷烃。
3、根据权利要求1的产物,其中:
R1优选是庚基,辛基,环己基,甲基环己基,环辛基,环己烯基,α-甲基苄基或1,2,3,4-四氢萘次甲基,和
烃溶剂,取决于R1,是庚烷,辛烷,环己烷,甲基环己烷,环辛烷,环己烯,乙基苯或四氢萘。
4、根据权利要求1的产物,其中R1是环己基或辛基,和
烃溶剂是环己烷或辛烷,而这取决于R1。
5、根据权利要求1的产物,其中
基团-O-R1是氧基和烃溶剂是惰性有机溶剂。
6、根据权利要求1的产物,其中
过氧化物分解催化剂是金属羰基化物,金属氧化物,金属乙酰基丙酮酸盐或金属醇盐,其中金属选自元素周期表的IVb,Vb,VIb,VIIb和VIII族。
7、根据权利要求1的产物,其中
氢过氧化物是叔丁基过氧化氢和过氧化物分解催化剂是三氧化钼。
9、根据权利要求1的产物,其中对应于通式(I)的嵌段低聚物的多分散性
Mw/
Mn是1.1-1.7。
10、根据权利要求1的产物,其中R是通式(G-1)的基团。
11、根据权利要求1的产物,其中R2是C2-C12亚烷基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有R4的一个定义;或R2是通式(b)的基团;
R3,R4和R5,可以相同或不同,是C1-C18烷基,未取代或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代的苯基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;
和R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;
R6是C1-C18烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;或通式(G-I)的基团。
12、根据权利要求1的产物,其中:
n是2-12的数;
R2是C2-C12亚烷基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基);
R6是C1-C18烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C12环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的C7-C9苯基烷基;或通式(G-I)的基团;和
R是通式(G-I)的基团。
13、根据权利要求1的产物,其中:
R2是C2-C10亚烷基,亚环己基,亚环己基二(C1-C4亚烷基),C1-C4亚烷基二亚环己基或亚苯基二(C1-C4亚烷基);
R3,R4和R5,可以相同或不同,是C1-C12烷基,未取代或被1,2或3个C1-C4烷基取代的C5-C7环烷基;未取代的或被1,2或3个C1-C4烷基取代的苯基;或未取代或在苯基上被C1-C4烷基取代的苄基;或
-N(R4)(R5)另外是通式(III)的基团;和
R6是C1-C12烷基,未取代的或被1,2或3个C1-C4烷基取代的C5-C7环烷基;未取代或在苯基上被1,2或3个C1-C4烷基取代的苄基;或通式(G-I)的基团。
14、根据权利要求1的产物,其中:
R2是C2-C8亚烷基;
R3,R4和R5,可以相同或不同,是C1-C8烷基,未取代或被甲基取代的环己基;未取代的或被甲基取代的苯基;或苄基;或
-N(R4)(R5)另外是4-吗啉基;和
R6是C1-C8烷基,未取代的或被甲基取代的环己基;苄基;或通式(G-I)的基团。
15、根据权利要求1的产物,其中:
n是2-6的数;
R2是C2-C6亚烷基;
A是-N(R4)(R5)或通式(II)的基团;
R4和R5,可以相同或不同,是C1-C8烷基;
或-N(R4)(R5)另外是4-吗啉基;
X是>NR6;
R6是C1-C4烷基;和
基团B和B*相互独立地是对于A给出的一个定义。
16、根据权利要求1的产物,其中B*不同于B以及基团B,R和R2在通式(I)的各重复单元中具有同样的定义。
17、一种产物,它是由将其中通式(G-II)中的-OR1为氧基的权利要求1的产物进行氢化得到具有通式(G-III)的基团的嵌段低聚物而获得的。
18、一种混合物,它含有:
通式(Ia)、(Ib)和(Ic)的化合物仅仅在重复单元的数目上不同,通式(Ia)与(Ib)与(Ic)的化合物的摩尔比是2∶1.6∶1至2∶0.4∶0.04;和
R1是氢或烃基或-O-R1是氧基;
R2是C2-C12亚烷基,C4-C12亚链烯基,C5-C7亚环烷基,C5-C7亚环烷基二(C1-C4亚烷基),C1-C4亚烷基二(C5-C7亚环烷基),亚苯基二(C1-C4亚烷基)或C4-C12亚烷基,它们被1,4-哌嗪二基,-O-或>N-X1间断,其中X1是C1-C12酰基或(C1-C12烷氧基)羰基,或者具有以下给出的R4的一个定义;或R2是通式(a),(b)或(c)的基团; 其中,m是2或3,X2是C1-C18烷基,C5-C12环烷基,该环烷基是未取代的或被1,2或3个C1-C4烷基取代;苯基,它是未取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它未被取代或在苯基上被1,2或3个C1-C4烷基取代;和基团X3独立地是C2-C12亚烷基;A*是-OR3,-N(R4)(R5)或以下通式(G-IV)的基团,
R3,R4和R5可以相同或不同,是C1-C18烷基,C5-C12环烷基,该环烷基是未被取代的或被1,2或3个C1-C4烷基取代;C3-C18链烯基,苯基,它是未被取代的或被1,2或3个C1-C4烷基或C1-C4烷氧基取代;C7-C9苯基烷基,它是未取代的或在苯环上被1,2或3个C1-C4烷基取代;四氢糠基或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或以下通式(III)的基团所取代,其中Y是-O-,-CH2-,-CH2CH2-或>N-CH3;和R3另外是氢或-N(R4)(R5)另外是通式(III)的基团;X*是-O-或>N-R6 *;R6 *是C1-C18烷基,C3-C18链烯基,C5-C12环烷基,该环烷基是未取代或被1,2或3个C1-C4烷基取代;C7-C9苯基烷基,它是未取代的或在苯基上被1,2或3个C1-C4烷基取代;四氢糠基,通式(G-II)的基团,或C2-C4烷基,它在2,3或4位上被-OH,C1-C8烷氧基,二(C1-C4烷基)氨基或通式(III)的基团取代;和
R*具有一个对于R6 *所给出的定义;和
基团B*和B**独立地具有一个对于A*给出的定义。
19、根据权利要求18的混合物,其中通式(Ia)与(Ib)与(Ic)的化合物的摩尔比是2∶1.2∶0.5至2∶0.4∶0.04。
20、根据权利要求18的混合物,其中通式(Ia)与(Ib)与(Ic)的化合物的摩尔比是2∶1∶0.4至2∶0.45∶0.04。
22、一种组合物,该组合物含有易遭受光、热或氧化诱导的降解作用的有机材料和权利要求1的产物。
23、根据权利要求22的组合物,其中有机材料是合成聚合物。
24、根据权利要求22的组合物,其中有机材料是聚乙烯或聚丙烯。
25、一种组合物,该组合物含有易遭受光、热或氧化诱导的降解作用的有机材料和权利要求18的混合物。
26、稳定有机材料使之抵抗光、热或氧化诱导的降解作用的方法,它包括在该有机材料中引入根据权利要求1的产物。
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CN114853733A (zh) * | 2022-05-07 | 2022-08-05 | 宿迁联盛科技股份有限公司 | 骨架法制备光稳定剂2020的方法 |
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ITMI980366A1 (it) | 1998-02-25 | 1999-08-25 | Ciba Spec Chem Spa | Preparazione di eteri amminici stericamente impediti |
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DE10152228A1 (de) * | 2001-10-20 | 2003-05-08 | Clariant Gmbh | Mischungen aus Wachsen und Polymeradditiven |
EP2993168B1 (en) * | 2004-11-02 | 2017-05-17 | Basf Se | Process for the synthesis of n-alkoxyamines |
MX2007008152A (es) * | 2005-01-03 | 2007-09-12 | Univ Texas | Metodo para la transformacion de polimeros convencionales y comercialmente importantes en materiales polimericos antimicrobianos durables y recargables. |
US20070062884A1 (en) | 2005-08-11 | 2007-03-22 | Board Of Regents, The University Of Texas System | N-halamines compounds as multifunctional additives |
US8486428B2 (en) * | 2006-03-27 | 2013-07-16 | Board Of Regents, The University Of Texas System | Compositions and methods for making and using acyclic N-halamine-based biocidal polymeric materials and articles |
CA2700259A1 (en) * | 2007-09-19 | 2009-03-26 | Board Of Regents, The University Of Texas System | Colorants based n-halamines compositions and method of making and using |
ES2541284T3 (es) | 2010-10-20 | 2015-07-17 | Basf Se | Fotoestabilizadores a base de aminas estéricamente impedidas con funcionalización mixta |
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CN114853733A (zh) * | 2022-05-07 | 2022-08-05 | 宿迁联盛科技股份有限公司 | 骨架法制备光稳定剂2020的方法 |
CN114853733B (zh) * | 2022-05-07 | 2023-09-01 | 宿迁联盛科技股份有限公司 | 骨架法制备光稳定剂2020的方法 |
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DE19882402T1 (de) | 2000-08-10 |
FR2763947B1 (fr) | 2001-03-30 |
JP2002501520A (ja) | 2002-01-15 |
GB9926845D0 (en) | 2000-01-12 |
KR100536923B1 (ko) | 2005-12-16 |
CN1106398C (zh) | 2003-04-23 |
CA2287325A1 (en) | 1998-12-03 |
CA2287325C (en) | 2008-03-18 |
JP4366668B2 (ja) | 2009-11-18 |
KR20010012911A (ko) | 2001-02-26 |
DE19882402B9 (de) | 2013-05-29 |
WO1998054175A1 (en) | 1998-12-03 |
BE1011939A3 (fr) | 2000-03-07 |
DE19882402B3 (de) | 2012-12-20 |
ITMI981135A1 (it) | 1999-11-21 |
TW428008B (en) | 2001-04-01 |
US6409941B1 (en) | 2002-06-25 |
ES2165791B1 (es) | 2003-10-01 |
GB2340118B (en) | 2001-07-04 |
ES2165791A1 (es) | 2002-03-16 |
AU7072398A (en) | 1998-12-30 |
FR2763947A1 (fr) | 1998-12-04 |
GB2340118A (en) | 2000-02-16 |
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