CN117203272A - 稳定剂混合物 - Google Patents
稳定剂混合物 Download PDFInfo
- Publication number
- CN117203272A CN117203272A CN202280025536.1A CN202280025536A CN117203272A CN 117203272 A CN117203272 A CN 117203272A CN 202280025536 A CN202280025536 A CN 202280025536A CN 117203272 A CN117203272 A CN 117203272A
- Authority
- CN
- China
- Prior art keywords
- tert
- butyl
- bis
- hydroxyphenyl
- tris
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000003381 stabilizer Substances 0.000 title abstract description 45
- 150000001875 compounds Chemical class 0.000 abstract description 93
- 239000003963 antioxidant agent Substances 0.000 abstract description 39
- 230000003078 antioxidant effect Effects 0.000 abstract description 32
- 239000011368 organic material Substances 0.000 abstract description 23
- 230000000087 stabilizing effect Effects 0.000 abstract description 5
- -1 polyethylenes Polymers 0.000 description 190
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 48
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- 125000000217 alkyl group Chemical group 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 37
- 235000006708 antioxidants Nutrition 0.000 description 35
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 33
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 25
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- 239000007983 Tris buffer Substances 0.000 description 18
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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 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
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- 239000001257 hydrogen Substances 0.000 description 15
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- 238000009472 formulation Methods 0.000 description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
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- 239000004952 Polyamide Substances 0.000 description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 13
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
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- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
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- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
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- 150000001993 dienes Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 8
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- 125000001931 aliphatic group Chemical group 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229940116351 sebacate Drugs 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
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- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 7
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- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 7
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- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
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- 239000003054 catalyst Substances 0.000 description 6
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 6
- 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 6
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- 125000000623 heterocyclic group Chemical group 0.000 description 6
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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 6
- VMDYMJSKWCVEEB-UHFFFAOYSA-N 1-[3,5-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]-1,3,5-triazinan-1-yl]-3-(3,5-ditert-butyl-4-hydroxyphenyl)propan-1-one Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)N2CN(CN(C2)C(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VMDYMJSKWCVEEB-UHFFFAOYSA-N 0.000 description 5
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
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- SLYJXPKHTZCZOG-UHFFFAOYSA-N n-tetradecyltetradecan-1-imine oxide Chemical compound CCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCC SLYJXPKHTZCZOG-UHFFFAOYSA-N 0.000 description 1
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- 125000005591 trimellitate group Chemical group 0.000 description 1
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Abstract
本发明涉及一种稳定剂混合物,其包含至少一种选自式(A)化合物和式(B)化合物的化合物,和至少一种抗氧化剂化合物,其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2‑1:20。此外,本发明涉及一种包含有机材料和稳定剂混合物的组合物。此外,本发明还涉及该稳定剂混合物在稳定暴露于光的有机材料中的用途。
Description
发明领域
本发明涉及一种稳定剂混合物,其包含至少一种选自式(A)化合物和式(B)化合物的化合物,和至少一种抗氧化剂化合物,其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2-1:20。此外,本发明涉及一种包含有机材料和稳定剂混合物的组合物。本发明还涉及该稳定剂混合物在稳定暴露于光的有机材料中的用途。
发明背景
有机材料(即合成聚合物如聚烯烃、聚乙烯等)由于其在制造多种挤出和模塑制品中的易用性而广泛用于多种应用中。然而,这些制品由于反复暴露于UV光而经常遭受一般稳定性的影响。为防止UV光对由该有机材料制备的制品的不利影响,使用不同添加剂或添加剂混合物。然而,一些类别的添加剂(例如抗氧化剂)不是光稳定的。
因此,本发明的目的为提供一种稳定剂混合物以稳定非光稳定添加剂。
发明概述
令人惊讶地,已发现本发明的稳定剂混合物在暴露于光时稳定制品中的非光稳定添加剂。
因此,在一个方面中,本发明涉及一种稳定剂混合物,其包含:
(i)至少一种选自式(A)化合物和式(B)化合物的化合物:
其中
E1为C1-C18烷基;和
E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
其中
L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基;
E6、E7、E8、E9、E10、E11、E12、E13彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
(ii)至少一种抗氧化剂化合物,其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2-1:20。
在另一方面中,本发明涉及一种组合物,其包含有机材料和如上定义的稳定剂混合物。
在又一方面中,本发明涉及如上定义的稳定剂混合物在稳定暴露于光的有机材料中的用途。
发明详述
在描述本发明的本发明组合物和配制剂之前,应当理解,本发明不限于所描述的特定组合物和配制剂,因为该组合物和配制剂当然可以变化。还应理解,此处使用的术语并非意欲进行限制,因为本发明的范围仅受所附权利要求的限制。
如果在下文中将组定义为包括至少一定数量的实施方案,则这意味着还包括优选地仅由这些实施方案组成的组。此外,说明书和权利要求中的术语“第一”、“第二”、“第三”或“(a)”、“(b)”、“(c)”、“(d)”等用于区分相似的要素,而不一定用于描述次序或时间顺序。应当理解,如此使用的术语在适当的情况下是可互换的,并且本文所述的本发明实施方案能够以不同于本文所述或示意的其他顺序操作。如果术语“第一”、“第二”、“第三”或“(A)”、“(B)”和“(C)”、或“(a)”、“(b)”、“(c)”、“(d)”、“i”、“ii”等涉及方法或用途或测定方法的步骤,则步骤之间没有时间或时间间隔的相干性,即,步骤可同时实施或者该类步骤之间可能有数秒、数分钟、数小时、数天、数周、数月或者甚至数年的时间间隔,除非上文或下文所述申请中另有说明。
在以下段落中,更详细地定义了本发明的不同方面。除非明确相反地指出,否则如此定义的每个方面可以与任何其他一个方面或多个方面相结合。特别地,指示为优选或有利的任何特征可以与一个或多个指示为优选或有利的任何其他特征组合。
在本说明书通篇中对“一个实施方案”或“优选实施方案”的引用意味着结合该实施方案描述的特定特征、结构或特征被包括在本发明的至少一个实施方案中。因此,说明书通篇中各个地方出现的短语“在一个实施方案中”或“在优选实施方案中”或“在另一个实施方案中”不一定都指同一个实施方案,而是可以指同一个实施方案。此外,特定特征、结构或特征可以以任何合适的方式组合在一个或多个实施方案中,如本领域技术人员从本公开内容中知悉的那样。此外,尽管本文描述的一些实施方案包括其他实施方案中包括的一些特征,但不包括其他特征,然而不同实施方案的特征的组合意味着落入本发明的范围内,并且形成本领域技术人员所理解的不同实施方案。例如,在所附权利要求中,任何要求保护的实施方案都可以以任何组合使用。
此外,说明书通篇中定义的范围也包括端值,即1-10的范围意味着1和10都包括在该范围内。为避免疑义,申请人有权根据适用法律获得任何等同方案。
首先定义某些术语,以便可以更容易地理解本公开内容。除非另有定义,否则本文使用的所有技术和科学术语具有与本发明实施方案所属领域的普通技术人员通常理解的相同含义。
在一个方面中,本发明涉及一种稳定剂混合物,其包含:
(i)至少一种选自式(A)化合物和式(B)化合物的化合物:
其中
E1为C1-C18烷基;和
E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
其中
L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基;
E6、E7、E8、E9、E10、E11、E12、E13彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
(ii)至少一种抗氧化剂化合物,其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2-1:20,优选1:2-1:15,更优选1:2-1:10。
在示例性实施方案中,至少一种式(A)化合物与至少一种抗氧化剂的重量比为1:3.33。
在一个实施方案中,本发明涉及一种稳定剂混合物,其包含:i.至少一种选自式(A)化合物的化合物:
其中
E1为C1-C18烷基;和
E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
ii.至少一种抗氧化剂,
其中至少一种式(A)化合物与至少一种抗氧化剂的重量比为1:2-1:20,优选1:2-1:15,更优选1:2-1:10。
式(A)化合物:
在一个实施方案中,该稳定剂混合物包含至少一种式(A)化合物:
在一个实施方案中,E1为C1-C18烷基,优选C1-C8烷基。
在一个实施方案中,E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基,优选E2、E3、E4和E5彼此独立地为氢、C1-C4烷基或苯基。
具有至多18个碳原子的烷基的实例为甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、2-乙基丁基、正戊基、异戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基十一烷基、十二烷基、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、十七烷基和十八烷基。
在一个优选实施方案中,至少一种式(A)化合物选自式(A-1)、(A-2)和(A-3):
大多数式(A)化合物为已知的且可以类似于本领域熟练技术人员已知的方法制备。
式(A)化合物可例如以类似于US-B-6,255,483中所述的方法制备。
式(B)化合物:
在一个实施方案中,该稳定剂混合物包含至少一种式(B)化合物:
在一个实施方案中,L为ROCOR’,其中R与R’彼此独立地为C1-C18亚烷基。
在一个实施方案中,E6、E7、E8、E9、E10、E11、E12和E13彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基,优选E6、E7、E8、E9、E10、E11、E12和E13彼此独立地为氢、C1-C4烷基或苯基。
具有至多18个碳原子的亚烷基的实例为亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基、亚十二烷基、亚十三烷基、亚十四烷基、亚十五烷基、亚十六烷基、亚十七烷基和亚十八烷基。
具有至多4个碳原子的烷基的实例为甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基和2-乙基丁基。
在一个优选实施方案中,至少一种式(B)化合物选自式(B-1):
抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)、4,6-双(辛基硫代甲基)-邻甲酚、双(十八烷基)羟胺、苯胺、N-苯基、与2,4,4-三甲基戊烯的反应产物、3,3'-硫代二丙酸双(正十八烷基)酯、3,3'-硫代二丙酸双(十二烷基)酯、4,4'-双(α,α-二甲基苄基)二苯胺、3,3'-硫代二丙酸二肉豆蔻酯、双(十八烷基)二硫醚和2,2-双[[3-(十二烷基硫)-1-氧代丙氧基]甲基]丙烷-1,3-二基双[3-(十二烷基硫)丙酸酯]。
在一个优选实施方案中,该抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)和4,6-双(辛基硫代甲基)-邻甲酚。
在一个更优选实施方案中,该抗氧化剂选自:1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯和1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯。
在一个实施方案中,该稳定剂混合物进一步包含至少一种硫增效剂。该至少一种硫增效剂选自:硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻基酯、季戊四醇四[3-(十二烷基硫)丙酸酯]、硫代二丙酸二硬脂酯和二硬脂基二硫醚,优选硫代二丙酸二硬脂酯。
在另一方面中,本发明涉及一种组合物,其包含:
a.有机材料,和
b.如上定义的稳定剂混合物。
在一个实施方案中,所述有机材料选自:
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基环己烷、聚异戊二烯或聚丁二烯、以及环烯烃的聚合物,例如环戊烯或降冰片烯的聚合物,聚乙烯(可任选交联),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,即前段中所例示的单烯烃聚合物(优选聚乙烯和聚丙烯)可通过不同方法,尤其是通过下述方法制得:
a)自由基聚合(通常在高压和升高的温度下)。
b)使用催化剂的催化聚合,所述催化剂通常包含一种或多种周期表第IVb、Vb、VIb或VIII族的金属。这些金属通常具有一个或多个配体,典型地为氧化物、卤化物、醇盐、酯、醚、胺、烷基、链烯基和/或芳基,其可为p-或s-共轭的。这些金属配合物可呈游离形式或固定在基体上,典型地固定在活化氯化镁、氯化钛(III)、氧化铝或二氧化硅上。这些催化剂可溶于或不溶于聚合介质中。所述催化剂自身可单独用于聚合反应中或可使用其他活化剂,典型的为烷基金属、金属氢化物、烷基金属卤化物、烷基金属氧化物或烷基金属烷(metalalkyloxane),所述金属为周期表第Ia、IIa和/或IIIa族的元素。活化剂可用其他酯、醚、胺或甲硅烷基醚基团方便地改性。这些催化剂体系通常称为Philips、Standard OilIndiana、Ziegler(-Natta)、TNZ(杜邦)、茂金属或单中心催化剂(SSC)。
2.1)中提及的聚合物的混合物,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)以及不同类型聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃彼此之间或与其他乙烯基单体的共聚物,例如乙烯/丙烯共聚物、线性低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、乙烯/乙烯基环己烷共聚物、乙烯/环烯烃共聚物(例如乙烯/降冰片烯,例如COC)、乙烯/1-烯烃共聚物(其中1-烯烃原位产生);丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/乙烯基环己烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物及其盐(离聚物)、以及乙烯与丙烯及二烯(例如己二烯、二环戊二烯或亚乙基降冰片烯)的三元共聚物;和这些共聚物彼此之间的混合物以及与上述1)中提及的聚合物的混合物,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(polyalkylene)/一氧化碳共聚物及其与其他聚合物(如聚酰胺)的混合物。
4.烃树脂(例如C5-C9),包括其氢化改性产物(例如增粘剂)及聚亚烷基和淀粉的混合物。
1.)-4.)的均聚物及共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
5.聚苯乙烯、聚对甲基苯乙烯、聚α-甲基苯乙烯。
6.衍生自乙烯基芳族单体的芳族均聚物和共聚物,所述单体包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯的所有异构体,特别是对乙烯基甲苯、乙基苯乙烯的所有异构体、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽及其混合物。均聚物和共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
6a.包括上述乙烯基芳族单体及选自下述共聚单体的共聚物:乙烯、丙烯、二烯、腈、酸、马来酸酐类、马来酰亚胺类、乙酸乙烯酯和氯乙烯或丙烯酸系衍生物及其混合物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(共聚物)、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;苯乙烯共聚物与其他聚合物(例如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物)的高抗冲混合物;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。
6b.由上述6.)中提及的聚合物氢化衍生的氢化芳族聚合物,尤其是包括由无规聚苯乙烯氢化制得的聚环己基乙烯(PCHE),通常称为聚乙烯基环己烷(PVCH)。
6c.由上述6a.)中提及的聚合物氢化衍生的氢化芳族聚合物。
均聚物和共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
7.乙烯基芳族单体(如苯乙烯或α-甲基苯乙烯)的接枝共聚物,例如苯乙烯接枝的聚丁二烯、苯乙烯接枝的聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物;苯乙烯和丙烯腈(或甲基丙烯腈)接枝的聚丁二烯;苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝的聚丁二烯;苯乙烯和马来酸酐接枝的聚丁二烯;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝的聚丁二烯;苯乙烯和马来酰亚胺接枝的聚丁二烯;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝的聚丁二烯;苯乙烯和丙烯腈接枝的乙烯/丙烯/二烯三元共聚物;苯乙烯和丙烯腈接枝的聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯;苯乙烯和丙烯腈接枝的丙烯酸酯/丁二烯共聚物、及其与6)中所列共聚物的混合物,例如称为ABS、MBS、ASA或AES聚合物的共聚物的混合物。
8.含卤素的聚合物,例如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化或溴化共聚物(卤丁橡胶)、氯化或氯磺化聚乙烯、乙烯和氯化乙烯的共聚物、表氯醇均聚物及共聚物,尤其是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;及其共聚物如氯乙烯/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.衍生自α,β-不饱和酸及其衍生物的聚合物,例如聚丙烯酸酯和聚甲基丙烯酸酯;聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈,其用丙烯酸丁酯进行抗冲击改性。
10.9.)中所提及的单体彼此之间的共聚物或与其他不饱和单体的共聚物,例如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷基酯共聚物、丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/乙烯基卤共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和醇及胺或其酰基衍生物或缩醛的聚合物,例如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙基酯或聚烯丙基三聚氰胺;及其与上述1.)中所提及的烯烃的共聚物。
12.环醚的均聚物和共聚物,例如聚亚烷基二醇、聚氧化乙烯、聚氧化丙烯或其与二缩水甘油基醚的共聚物。
13.聚缩醛如聚甲醛和含有氧化乙烯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。
14.聚苯醚和聚苯硫醚、以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15.聚氨酯,其一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯,另一方面衍生自脂族或芳族多异氰酸酯及其前体。
16.聚酰胺和共聚酰胺,其衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺,例如聚酰胺4、聚酰胺6、聚酰胺6/6、6/10、6/9、6/12、4/6、12/12、聚酰胺11、聚酰胺12、由间二甲苯二胺和己二酸获得的芳族聚酰胺;在存在或不存在作为改性剂的弹性体下由六亚甲基二胺与间苯二甲酸和/或对苯二甲酸制备的聚酰胺,例如聚-2,4,4-三甲基六亚甲基对苯二甲酰胺或聚间亚苯基间苯二甲酰胺;以及上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键合或接枝的弹性体的嵌段共聚物;或与聚醚,例如与聚乙二醇、聚丙二醇或聚四亚甲基二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;以及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、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑。
18.聚酯,其衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯,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、聚萘二甲酸亚烷基酯和聚羟基苯甲酸酯以及衍生自羟基封端聚醚的共聚醚酯;以及用聚碳酸酯或MBS改性的聚酯。
共聚酯可包括,例如(但不限于):聚琥珀酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸四亚甲基酯/对苯二甲酸四亚甲基酯、聚琥珀酸丁二醇酯/己二酸丁二醇酯、聚琥珀酸丁二醇酯/碳酸酯、聚-3-羟基丁酸酯/3-羟基辛酸酯共聚物、聚-3-羟基丁酸酯/3-羟基己酸酯/3-羟基癸酸酯三元共聚物。此外,脂族聚酯可包括,例如(但不限于):聚(羟基链烷酸酯)类,尤其为聚丙内酯、聚丁内酯、聚新戊内酯、聚戊内酯和聚己内酯、聚琥珀酸乙二醇酯、聚琥珀酸丙二醇酯、聚琥珀酸丁二醇酯、聚琥珀酸六亚甲基酯、聚己二酸乙二醇酯、聚己二酸丙二醇酯、聚己二酸丁二醇酯、聚己二酸六亚甲基酯、聚草酸乙二醇酯、聚草酸丙二醇酯、聚草酸丁二醇酯、聚草酸六亚甲基酯、聚癸二酸乙二醇酯、聚癸二酸丙二醇酯、聚癸二酸丁二醇酯及聚乳酸(PLA)以及用聚碳酸酯或MBS改性的相应聚酯。术语“聚乳酸(PLA)”表示优选为聚-L-丙交酯的均聚物及其与其他聚合物的任何共混物或合金;乳酸或丙交酯与其他单体的共聚物,所述其他单体例如羟基羧酸如乙醇酸、3-羟基丁酸、4-羟基丁酸、4-羟基戊酸、5-羟基戊酸、6-羟基己酸及其环状形式;术语“乳酸”或“丙交酯”包括L-乳酸、D-乳酸、其混合物及二聚物,即L-丙交酯、D-丙交酯、内消旋丙交酯及其任何混合物。
19.聚碳酸酯和聚酯碳酸酯。
20.聚酮。
21.聚砜、聚醚砜和聚醚酮。
22.交联聚合物,其一方面衍生自醛,另一方面衍生自酚类、脲类和三聚氰胺类,例如苯酚/甲醛树脂、尿素/甲醛树脂及三聚氰胺/甲醛树脂。
23.干性和非干性醇酸树脂。
24.不饱和聚酯树脂,其衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯,及其低可燃性的含卤改性产物。
25.可交联丙烯酸系树脂,其衍生自取代的丙烯酸酯,例如丙烯酸环氧酯、氨基甲酸酯丙烯酸酯或聚酯丙烯酸酯。
26.用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
27.交联环氧树脂,其衍生自脂族、脂环族、杂环族或芳族缩水甘油基化合物,例如双酚A及双酚F的二缩水甘油醚的产物,其在存在或不存在促进剂下使用常规硬化剂如酸酐或胺交联。
28.天然聚合物如纤维素、橡胶、明胶及其化学改性的同系衍生物,例如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚,例如甲基纤维素;以及松香及其衍生物。
29.上述聚合物的共混物(聚合物共混物),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/PA 6,6及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
30.天然和合成的有机材料,其为纯单体化合物或这些化合物的混合物,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、以及合成酯与矿物油的任意重量比的混合物,典型地为用作纺丝组合物的那些、以及这些材料的水性乳液。
31.天然或合成橡胶的水性乳液,例如天然胶乳或羧化苯乙烯/丁二烯共聚物的胶乳。
该有机材料优选选自单烯烃和二烯烃的聚合物;单烯烃和二烯烃与彼此或与其他乙烯基单体的共聚物;烃树脂,和聚烯烃与淀粉的混合物;聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯);乙烯基芳族单体(例如苯乙烯或α-甲基苯乙烯)的接枝共聚物;含卤素的聚合物;衍生自α,β-不饱和酸及其衍生物的聚合物;衍生自不饱和醇和胺或其酰基衍生物或缩醛的聚合物;环醚的均聚物和共聚物;聚苯醚和聚苯硫醚;一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯且另一方面衍生自脂族或芳族多异氰酸酯的聚氨酯;衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺的聚酰胺和共聚酰胺;聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑;衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯的聚酯;聚碳酸酯和聚酯碳酸酯;聚酮;聚砜、聚醚砜和聚醚酮;一方面衍生自醛且另一方面衍生自酚类、脲类和三聚氰胺类的交联聚合物;干性和非干性醇酸树脂;衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯的不饱和聚酯树脂;衍生自取代的丙烯酸酯的可交联丙烯酸系树脂;用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂;衍生自脂族、脂环族、杂环或芳族缩水甘油基化合物的交联环氧树脂;天然聚合物如纤维素、橡胶、明胶及其化学改性的同系衍生物;天然或合成橡胶的含水乳液;线性低密度聚乙烯、低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸丁酯共聚物、聚丙烯均聚物和聚丙烯共聚物。
根据本发明的稳定剂混合物在待稳定的有机材料中以相对于该有机材料的重量为优选0.005-10%或0.005-5%,特别是0.01-2.5%或0.05-2%的量存在。
本稳定剂混合物的各组分可单独或彼此混合地添加到待稳定的有机材料中。它们可在聚合之前、期间或之后或者在交联之前或之后添加到聚合物中。
根据本发明的稳定剂混合物或其单独的组分可以通过已知的方法掺入到待稳定的有机材料中,例如在成型之前或期间,或者通过将溶解或分散的稳定剂施加到有机材料,如果需要,随后蒸发溶剂。稳定剂可以以粉末、颗粒或母料的形式添加到有机材料中。
根据本发明稳定的材料的加工或转化的实例为:
注射吹塑、挤出、吹塑、滚塑、模内装饰(反向注射)、泥浆模塑、注塑、共注射模塑、成型、压缩模塑、压制、膜挤出(流延膜;吹塑膜)、纤维纺丝(纺织、非纺织)、拉伸(单轴、双轴)、退火、深拉伸、压延、机械变形、烧结、共挤出、涂覆、层压、交联(辐射、过氧化物、硅烷)、气相沉积、焊接、胶接、硫化、热成型、管材挤出、型材挤出、片材挤出;片材铸造、旋涂、捆扎、发泡、回收/返工、挤压涂覆、减粘(过氧化物、热)、纤维熔喷、纺粘、表面处理(电晕放电、火焰、等离子体)、灭菌(通过γ射线、电子束)、浇铸聚合(R&M工艺、RAM挤压)、凝胶涂层、带挤出、GMT工艺、SMC工艺、增塑溶胶和浸渍(PVC、乳胶)。
在一个实施方案中,所述组合物进一步包含至少一种位阻胺光稳定剂。
该至少一种位阻胺光稳定剂选自双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)碳酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、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-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N'-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-双(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与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)六亚甲基二胺与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)乙烷与2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;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]癸烷与表氯醇的反应产物、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、2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N'-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、4-正丁基-2-N,4-N-双(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)氨基]己基]-1,3,5-三嗪-2,4-二胺、N,N'-双(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲酰基六亚甲基二胺及其混合物。
在一个优选实施方案中,该位阻胺光稳定剂为1,6-己二胺和2,4,6-三氯-1,3,5-三嗪以及N,N-二丁基胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物。
在一个实施方案中,该组合物进一步包含至少一种选自通式(I)、通式(II)、通式(III)、通式(IV)及其混合物的化合物(C)。
通式(I)的化合物(C):
其中
A1选自线性或支化的取代或未取代的C2-C18亚烷基、取代或未取代的C5-C7亚环烷基和C1-C4亚烷基双(C5-C7亚环烷基),
A2独立地选自H、线性或支化的取代或未取代的C1-C12烷基、C1-C12烷氧基、取代或未取代的C5-C12环烷基和C5-C12环烷氧基,
A3和A4独立地选自H、线性或支化的取代或未取代的C1-C12烷基、取代或未取代的C5-C12环烷基和式(a-1)的基团:
或
A3和A4与它们所键合的氮原子一起形成5-10元杂环;且
a为1-20的整数,并且重复单元相同或不同。
在本发明的上下文中,本文所用的术语烷基是指无环饱和脂族基团,包括线性或支化烷基。
如本文所用,“支化”表示带有一个或多个与其连接的侧链的原子链。支化通过用共价键合的脂族结构部分代替取代基(例如氢原子)而发生。
线性和支化的未取代C1-C12烷基的代表性实例包括但不限于甲基、乙基、正丙基、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、1,1,1,3-四甲基己基、1-甲基庚基、3-甲基庚基、2-丙基庚基、正辛基、2-乙基己基、1,3,3-三甲基己基、1,1,3,3-四甲基戊基、正壬基、正癸基、正十一烷基、异十一烷基、1-甲基十一烷基、正十二烷基、异十二烷基和1,1,3,3,5,5-六甲基己基。
C1-C12烷氧基的代表性实例包括但不限于甲氧基、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、壬氧基、癸氧基、十一烷氧基和十二烷氧基。
在优选实施方案中,烷氧基选自甲氧基、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、庚氧基和辛氧基。在更优选的实施方案中,烷氧基为丙氧基。
C5-C12环烷基的代表性实例为环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环十一烷基和环十二烷基。
C5-C12环烷氧基的代表性实例为环戊氧基、环己氧基、环庚氧基、环辛氧基、环壬氧基、环癸氧基、环十一烷氧基和环十二烷氧基。
在优选实施方案中,环烷氧基为环己氧基。
被1、2或3个C1-C4烷基取代的苯基的优选实例为2,4-二甲基苯基。
优选的C2-C18亚烷基为亚乙基、异丙基、三亚甲基、四亚甲基、五亚甲基、2,2-二甲基三亚甲基和六亚甲基。在更优选的实施方案中,亚烷基为六亚甲基。
C5-C7亚环烷基的实例为亚环己基。
C1-C4亚烷基双(C5-C7亚环烷基)的实例为亚甲基二亚环己基。
与它们所键合的氮原子一起形成的5-10元杂环的基团A3和A4的实例为1-吡咯烷基、哌啶基、吗啉基、1-哌嗪基、4-甲基-1-哌嗪基,1-六氢氮杂基、5,5,7-三甲基-1-高哌嗪基或4,5,5,7-四甲基-1-高哌嗪基,优选吗啉基。
在通式(I)的化合物(A)中,连接到二氨基上的端基例如为氢或下式的基团:
并且连接到三嗪基的端基例如为下式的基团或式的基团。
在优选实施方案中,A1为六亚甲基,A2为氢和丙氧基。
在优选实施方案中,A3为丁基、
在优选实施方案中,A4为丁基。
在优选实施方案中,a为1-10的整数。
通式(II)的化合物(C):
其中
x1和x2独立地选自C1-C30烷氧基。
在优选实施方案中,x1和x2独立地选自线性或支化的未取代的C1-C30烷氧基。
线性或支化的未取代C1-C30烷氧基的代表性实例为甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基,十三烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基、十八烷氧基、十九烷氧基、二十烷氧基、二十一烷氧基、二十二烷氧基、二十三烷氧基、二十四烷氧基、二十五烷氧基、二十六烷氧基、二十七烷氧基、二十八烷氧基和二十九烷氧基。
在优选实施方案中,x1和x2各自为十一烷氧基。
通式(III)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y2为C1-C30烷基;和
在优选实施方案中,Y1为线性或支化的未取代的C3-C20烷基。
在一个实施方案中,Y1选自甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基和二十烷基。
在优选实施方案中,Y1选自丙基和十二烷基。
在优选实施方案中,Y2为线性或支化的未取代的C1-C30烷基。
在一个实施方案中,Y2选自甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、二十五烷基、二十六烷基、二十七烷基、二十八烷基、二十九烷基和三十烷基。
在优选实施方案中,Y2选自十五烷基和十七烷基。
通式(IV)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y3独立地选自线性或支化的取代或未取代的C3-C20烷基和C3-C20亚烷基,
X为C2-C5烷基,
n为1-8的整数。
在优选实施方案中,Y3选自线性或支化的未取代的C3-C20烷基和C3-C20亚烷基。
具有至多20个碳原子的亚烷基的代表性实例为亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基、亚十二烷基、亚十三烷基、亚十四烷基、亚十五烷基、亚十六烷基、亚十七烷基、亚十八烷基、亚十九烷基和亚二十烷基。
在优选实施方案中,Y1选自癸基。
在优选实施方案中,Y3选自癸基和亚壬基。
在优选实施方案中,化合物(C)选自式(C-I)、(C-II)、(C-III)、(C-IV)、(C-V)、(C-VI)、(C-VII)和(C-VIII):
其中a为1-10的整数;和
其中n为2。
在一个实施方案中,该组合物进一步包含至少一种选自助滑剂、防结块剂、热填料、颜料、防水雾剂(anti-fog)和防烟雾剂(anti-mist)的添加剂。
在一个实施方案中,该组合物进一步包含金属氢氧化物作为填料和/或除酸剂。
该组合物也可额外含有多种已知添加剂,例如:
1.抗氧化剂
1.1烷基化单酚,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,侧链为线性或支化的壬基酚例如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)苯酚及其混合物。
1.2.烷硫基甲基苯酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚、2,4-二辛硫基甲基-6-甲基苯酚、2,4-二辛硫基甲基-6-乙基苯酚、2,6-双(十二烷硫基)甲基-4-壬基苯酚。
1.3.氢醌类和烷基化氢醌类,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-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸3,5-二叔丁基-4-羟基苯酯、己二酸双(3,5-二叔丁基-4-羟基苯基)酯。
1.4.生育酚类,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(维生素E)。
1.5.羟基化硫代二苯醚,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,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-壬基酚]、2,2'-亚甲基双[6-(α,α-二甲基苄基)-4-壬基酚]、4,4'-亚甲基双(2,6-二叔丁基苯酚)、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、乙二醇双[3,3-双(3'-叔丁基-4'-羟基苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯、双[2-(3'-叔丁基-2'-羟基-5'-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双(3,5-二甲基-2-羟基苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-、N-和S-苄基化合物,例如3,5,3',5'-四叔丁基-4,4'-二羟基二苄基醚、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、双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯、双(3,5-二叔丁基-4-羟基苄基)硫化物、3,5-二叔丁基-4-羟基苄基巯基乙酸异辛基酯。
1.8.羟基苄基化丙二酸酯,例如2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸双(十八烷基)酯、2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸双(十八烷基)酯、2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸双(十二烷基巯基乙基)酯、双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟基苄基化合物,例如1,4-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,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(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,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-羟基苄基膦酸双(十八烷基)酯、5-叔丁基-4-羟基-3-甲基苄基膦酸双(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.酰氨基苯酚类,例如4-羟基月桂酰替苯胺、4-羟基硬脂酰替苯胺、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)丙酸与如下一元醇或多元醇的酯: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、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与如下一元醇或多元醇的酯: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、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷、3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷的酯。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯: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、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.16. 3,5-二叔丁基-4-羟基苯基乙酸与如下一元醇或多元醇的酯: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、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.17.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺,例如N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰基)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]草酰胺(XL-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'-二异丙基对苯二胺、N,N'-二仲丁基对苯二胺、N,N'-双(1,4-二甲基戊基)对苯二胺、N,N'-双(1-乙基-3-甲基戊基)对苯二胺、N,N'-双(1-甲基庚基)对苯二胺、N,N'-二环己基对苯二胺、N,N'-二苯基对苯二胺、N,N'-双(2-萘基)对苯二胺、N-异丙基-N'-苯基对苯二胺、N-(1,3-二甲基丁基)-N'-苯基对苯二胺、N-(1-甲基庚基)-N'-苯基对苯二胺、N-环己基-N'-苯基对苯二胺、4-(对甲苯胺磺酰基)二苯胺、N,N'-二甲基-N,N'-二仲丁基对苯二胺、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、辛基化二苯胺如p,p'-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰基氨基苯酚、4-十二烷酰基氨基苯酚、4-十八烷酰基氨基苯酚、双(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲基氨基甲基苯酚、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-烷基化叔丁基二苯胺/叔辛基二苯胺的混合物、单-和二-烷基化壬基二苯胺的混合物、单-和二-烷基化十二烷基二苯胺的混合物、单-和二-烷基化异丙基二苯胺/异己基二苯胺的混合物、单-和二-烷基化叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单-和二-烷基化叔丁基吩噻嗪/叔辛基吩噻嗪的混合物、单-和二-烷基化叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N',N'-四苯基-1,4-二氨基丁-2-烯。
2.UV吸收剂和光稳定剂
2.1. 2-(2'-羟基苯基)苯并三唑类,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-甲氧羰基乙基)苯基)-5-氯苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)苯基)苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-辛氧基羰基乙基)苯基)苯并三唑、2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羟基苯基)苯并三唑、2-(3'-十二烷基-2'-羟基-5'-甲基苯基)苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-异辛氧基羰基乙基)苯基苯并三唑、2,2'-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];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的酯交换产物;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.取代和未取代苯甲酸的酯,例如水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯酯、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、N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚、四(α-氰基-β,β-二苯基丙烯酸新戊基酯。
2.5.镍化合物,例如2,2'-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,例如1:1或1:2配合物,其具有或不具有其他配体如正丁胺、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如甲酯或乙酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,其具有或不具有其他配体。
2.6.草酰胺,例如4,4'-二辛氧基草酰替苯胺、2,2'-二乙氧基草酰替苯胺、2,2'-二辛氧基-5,5'-二叔丁基草酰替苯胺、2,2'-双(十二烷氧基)-5,5'-二叔丁基草酰替苯胺、2-乙氧基-2'-乙基草酰替苯胺、N,N'-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2'-乙基草酰替苯胺及其与2-乙氧基-2'-乙基-5,4'-二叔丁基草酰替苯胺的混合物、邻-和对-甲氧基二取代草酰替苯胺的混合物以及邻-和对-乙氧基二取代草酰替苯胺的混合物。
2.7. 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-(2,4-二羟基苯基)-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-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、2,4-双(4-[2-乙基己氧基]-2-羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪。
3.金属减活剂,例如N,N'-二苯基草酰胺、N-水杨醛-N'-水杨酰肼、N,N'-双(水杨酰)肼、N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰二肼、草酰替苯胺、间苯二甲酰二肼、癸二酰双苯基肼、N,N'-二乙酰己二酰二肼、N,N'-双(水杨酰)草酰二肼、N,N'-双(水杨酰)硫代丙酰二肼。
4.亚磷酸酯和亚膦酸酯,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、二硬脂基季戊四醇二亚磷酸酯、亚磷酸三(2,4-二叔丁基苯基)酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、4,4'-亚联苯基二亚膦酸四(2,4-二叔丁基苯基)酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷杂八环、亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙酯、6-氟-2,4,8,10-四叔丁基-12-甲基二苯并[d,g]-1,3,2-二氧杂磷杂八环、2,2',2”-次氮基[三乙基三(3,3',5,5'-四叔丁基-1,1'-联苯-2,2'-二基)亚磷酸酯]、(3,3',5,5'-四叔丁基-1,1'-联苯-2,2'-二基)亚磷酸2-乙基己酯、5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷(dioxaphosphirane)、亚磷酸混合2,4-双(1,1-二甲基丙基)苯基和4-(1,1-二甲基丙基)苯基三酯(CAS:939402-02-5)、亚磷酸三苯酯、具有α-氢-ω-羟基聚(氧基(甲基-1,2-乙烷二基)]C10-16烷基酯(CAS:1227937-46-3)。
尤其优选如下亚磷酸酯:亚磷酸三(2,4-二叔丁基苯基)酯(168,CibaSpecialty Chemicals Inc.)、亚磷酸三(壬基苯基)酯,
5.羟胺,例如N,N-二苄基羟胺、N,N-二乙基羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-双(十四烷基)羟胺、N,N-双(十六烷基)羟胺、N,N-双(十八烷基)羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、衍生自氢化牛油脂肪胺的N,N-二烷基羟胺。
6.硝酮,例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、衍生自N,N-二烷基羟胺(衍生自氢化牛油脂肪胺)的硝酮。
7.硫代协合剂,例如硫代二丙酸二月桂基酯、硫代二丙酸二肉豆蔻基酯、季戊四醇四[3-(十二烷基硫)丙酸酯]、硫代二丙酸二硬脂基酯或二硬脂基二硫醚。
8.过氧化物清除剂,例如β-硫代二丙酸的酯,例如月桂基酯、硬脂基酯、肉豆蔻基酯或十三烷基酯、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、双(十八烷基)二硫醚、季戊四醇四(β-十二烷基巯基)丙酸酯。
9.聚酰胺稳定剂,例如与碘和/或磷化合物组合的铜盐和二价锰盐。
10.碱性共稳定剂,例如三聚氰胺、聚乙烯吡咯烷酮、双氰胺、氰脲酸三烯丙基酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙、硬脂酸锌、山萮酸镁、硬脂酸镁、蓖麻醇酸钠和棕榈酸钾、焦儿茶酸锑或焦儿茶酸锌。
11.成核剂,例如无机物质如滑石,金属氧化物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-或聚羧酸及其盐,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)。尤其优选为1,3:2,4-双(3',4'-二甲基亚苄基)山梨糖醇、1,3:2,4-双(对甲基二亚苄基)山梨糖醇和1,3:2,4-双(亚苄基)山梨糖醇。
12.填料和增强剂,例如碳酸钙、硅酸盐、表面处理的二氧化硅(例如如US-A-2007/60,697和US-A-2009/111,918所述)、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、木粉和其他天然产物的粉或纤维、合成纤维。
优选的金属氢氧化物为羟基碳酸镁铝。
13.其他添加剂,例如增塑剂、润滑剂、乳化剂、颜料、流变添加剂、催化剂、流动调节剂、荧光增白剂、阻燃剂、抗静电剂和发泡剂。此外,
也可使用除酸剂。
优选的除酸剂为羟基碳酸镁铝。
14.苯并呋喃酮类和吲哚满酮类,例如US4,325,863、US4,338,244、US5,175,312、US5,216,052、US5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839、EP-A-0591102、EP-A-1291384中所公开的那些,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、3-(2-乙酰基-5-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
本发明的稳定剂混合物与常规添加剂的总量的重量比可例如为100:1-1:1000或10:1-1:100或20:1-1:20或10:1-1:10
根据本发明稳定的材料可以以各种形式使用,例如作为膜、纤维、带、模塑组合物、型材或作为油漆、胶粘剂或腻子的基料。
更详细地,根据本发明稳定的材料可用于制备以下装置:I-1)汽车应用,特别是保险杠、仪表板、电池、后和前衬板、引擎盖下的模
塑零件、帽架、车厢衬板、车内衬板、气囊覆盖物、配件(照明)用的电子模制品、仪表板用的窗格、头灯玻璃、仪器面板、车外衬板、车内装饰、汽车照明、头灯、边灯、尾灯、停车灯、车内外装饰;门板;油箱;
前侧玻璃;后车窗;椅背、外部面板、电线绝缘件、密封用型材挤出物、覆盖层、支柱机盖、底盘零件、排气系统、燃料过滤器/填料、燃油泵、燃料箱、车身模制品、可折叠顶盖、车外后视镜、外部装饰、紧固/固定装置、前端模件、玻璃、铰链、车锁系统、行李/车顶架、压制/冲压零件、密封件、防侧撞梁、隔音装置/隔热装置和天窗。
I-2)飞机、铁道、机动车(汽车、摩托车)用装置,包括陈设。
I-3)太空应用的装置,特别是火箭和卫星,例如重返防护罩。
I-4)建筑与设计用装置、采矿用具、静音系统、街道安全岛和庇护所。II-1)电器,特别是洗衣机、滚筒、烤箱(微波炉)、洗碗机、混合器和熨斗。II-2)用于冷凝器、冰箱、加热装置、空调、电子封装、半导体、咖啡机和真空清洁器的箔片。
III-1)工业制品,例如嵌齿轮(齿轮)、滑动配件、垫片、螺钉、螺栓、把手和按钮。
III-2)转子叶片、通风机和风车轮叶、太阳能装置、游泳池、游泳池盖、泳池衬里、水池衬里、壁橱、衣柜、隔墙、板条墙、折叠墙、屋顶、百叶窗(例如卷帘)、配件、管道之间的连接、套管和输送带。
III-3)任何几何形状(窗格)和壁板的型材。
III-4)玻璃代用品,特别是挤出板,用于建筑物(整体、双壁或多壁)、飞机、学校、挤出板、建筑玻璃装配用窗膜、火车、运输、卫生制品和温室的玻璃。
III-5)板(墙壁、砧板)、挤出涂层(相纸、利乐包和管道涂层)、筒仓、木材代替物、塑料木材、木材复合物、墙壁、表面、家具、装潢箔、地板覆盖物(内部和外部应用)、地板、沟槽板道和瓷砖。
III-6)水泥-、混凝土-、复合材料应用和覆盖物、壁板和覆层、扶手、栏杆、厨房工作台、屋顶、屋顶板、瓷砖和防水布。
IV-1)板(墙壁和砧板)、盘、人工草皮、阿斯特罗特夫尼龙草皮(astroturf)、用于体育馆圆形场地(运动)的人工覆盖物、用于体育馆圆形场地(运动)的人工地板,和胶带。
V-1)通用塑料膜(包装、垃圾堆、层压、游泳池盖、废物袋、壁纸、拉伸和收缩包装、酒椰、淡化膜、电池组和连接器)。
V-2)农用膜(温室覆盖物、隧道、覆盖物、青贮饲料、捆包包装),尤其是在农业化学品的密集施用的情况下。
VI-1)食品包装和包装材料(柔韧和坚固型)、BOPP、BOPET、瓶。
VI-2)药筒、注射器、医疗器具、用于任何运输的容器、垃圾篮和废品箱、废品袋、箱、垃圾箱、箱衬里、轮箱、常规容器、用于水/用后水/化学品/气体/油/汽油/柴油的罐;罐衬层、箱、板条箱、电池箱、水槽、医学装置如活塞、眼科用具、诊断装置和药剂泡罩包装。
VII-1)填充聚合物(滑石、粉笔、陶土(高岭土)、硅酸钙岩矿、颜料、炭黑、TiO2、云母、纳米复合材料、白云石、硅酸盐、玻璃、石棉)的装置。
因此,本发明的另一实施方案为一种由如上定义的组合物制成的制品。
在另一方面中,本发明涉及如上定义的至少一种式(A)化合物和/或式(B)化合物在防止如上定义的抗氧化剂化合物降解中的用途。
在又一方面中,本发明涉及如上定义的稳定剂混合物在稳定暴露于光的有机材料中的用途。
本发明提供以下一个或多个优点:
1.本发明的稳定剂混合物稳定在暴露于光时制品中的非光稳定添加剂。
2.由于使用本发明的稳定剂混合物,该非光稳定添加剂可用于暴光制品中,从而延长最终制品的耐久性。
下文描述了本发明的具体实施方案:
1.一种稳定剂混合物,其包含:
i.至少一种选自式(A)化合物和式(B)化合物的化合物:
其中
E1为C1-C18烷基;和
E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
其中
L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基;
E6、E7、E8、E9、E10、E11、E12、E13彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
ii.至少一种抗氧化剂化合物,
其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2-1:20。
2.根据实施方案1所述的稳定剂混合物,其中E1为C1-C8烷基,且E2、E3、E4和E5彼此独立地为氢、C1-C4烷基或苯基。
3.根据实施方案1或2所述的稳定剂混合物,其中L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基,且E6、E7、E8、E9、E10、E11、E12和E13彼此独立地为氢、C1-C4烷基或苯基。
4.根据实施方案1-3中一项或多项所述的稳定剂混合物,其中至少一种式(A)化合物选自式(A-1)、(A-2)和(A-3):
5.根据实施方案1或3中一项或多项所述的稳定剂混合物,其中式(B)化合物为式(B-1)化合物:
6.根据实施方案1所述的稳定剂混合物,其中抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)、4,6-双(辛基硫代甲基)-邻甲酚、双(十八烷基)羟胺、苯胺、N-苯基、与2,4,4-三甲基戊烯的反应产物、3,3'-硫代二丙酸双(正十八烷基)酯、3,3'-硫代二丙酸双(十二烷基)酯、4,4'-双(α,α-二甲基苄基)二苯胺、3,3'-硫代二丙酸二肉豆蔻酯、双(十八烷基)二硫醚和2,2-双[[3-(十二烷基硫)-1-氧代丙氧基]甲基]丙烷-1,3-二基双[3-(十二烷基硫)丙酸酯]。
7.根据实施方案1和6中一项或多项所述的稳定剂混合物,其中抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)和4,6-双(辛基硫代甲基)-邻甲酚。
8.根据实施方案1、6和7中一项或多项所述的稳定剂混合物,其中抗氧化剂选自:1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯和1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯。
9.根据实施方案1-8中一项或多项所述的稳定剂混合物,其进一步包含至少一种硫增效剂,其中该至少一种硫增效剂选自:硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻基酯、季戊四醇四[3-(十二烷基硫)丙酸酯]、硫代二丙酸二硬脂酯和二硬脂基二硫醚。
10.根据实施方案1-9中一项或多项所述的稳定剂混合物,其中该硫增效剂为硫代二丙酸二硬脂酯。
11.一种组合物,其包含:
c.有机材料,和
d.根据实施方案1-10中一项或多项所述的稳定剂混合物。
12.根据实施方案11所述的组合物,其进一步包含至少一种位阻胺光稳定剂。
13.根据实施方案11和12中一项或多项所述的组合物,其中该至少一种位阻胺光稳定剂选自双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)碳酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、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-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N'-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-双(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与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)六亚甲基二胺与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)乙烷与2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;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]癸烷与表氯醇的反应产物、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、2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N'-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、4-正丁基-2-N,4-N-双(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)氨基]己基]-1,3,5-三嗪-2,4-二胺、N,N'-双(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲酰基六亚甲基二胺及其混合物。
14.根据实施方案11-13中一项或多项所述的组合物,其进一步包含至少一种选自通式(I)、通式(II)、通式(III)、通式(IV)及其混合物的化合物(C):-通式(I)的化合物(C):
其中
A1选自线性或支化的取代或未取代的C2-C18亚烷基、取代或未取代的C5-C7亚环烷基和C1-C4亚烷基双(C5-C7亚环烷基),
A2独立地选自H、线性或支化的取代或未取代的C1-C12烷基、C1-C12烷氧基、取代或未取代的C5-C12环烷基和C5-C12环烷氧基,
A3和A4独立地选自H、线性或支化的取代或未取代的C1-C12烷基、取代或未取代的C5-C12环烷基和式(a-1)的基团:
或
A3和A4与它们所键合的氮原子一起形成5-10元杂环;且
a为1-20的整数,并且重复单元相同或不同;
-通式(II)的化合物(C):
其中
x1和x2独立地选自C1-C30烷氧基,
-通式(III)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y2为C1-C30烷基;和
-通式(IV)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y3独立地选自线性或支化的取代或未取代的C3-C20烷基和C3-C20亚烷基,
X为C2-C5烷基,
n为1-8的整数。
15.根据实施方案11-14中一项或多项所述的组合物,其中化合物(C)选自式(C-I)、(C-II)、(C-III)、(C-IV)、(C-V)、(C-VI)、(C-VII)和(C-VIII):
其中a为1-10的整数;和
其中n为2。
16.根据实施方案11-15中一项或多项所述的组合物,其进一步包含至少一种选自UV稳定剂、助滑剂、防结块剂、热填料、颜料、防水雾剂和防烟雾剂的添加剂。
17.根据实施方案11-16中一项或多项所述的组合物,其进一步包含除酸剂。
18.根据实施方案16所述的组合物,其UV稳定剂选自2-(2'-羟基苯基)苯并三唑、2-羟基二苯甲酮、2-(2-羟基苯基)-1,3,5-三嗪、氰基丙烯酸酯、草酰苯胺、苯并噁嗪及其混合物。
19.根据实施方案11所述的组合物,其中该有机材料选自单烯烃和二烯烃的聚合物;单烯烃和二烯烃与彼此或与其他乙烯基单体的共聚物;烃树脂,和聚烯烃与淀粉的混合物;聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯);乙烯基芳族单体(例如苯乙烯或α-甲基苯乙烯)的接枝共聚物;含卤素的聚合物;衍生自α,β-不饱和酸及其衍生物的聚合物;衍生自不饱和醇和胺或其酰基衍生物或缩醛的聚合物;环醚的均聚物和共聚物;聚苯醚和聚苯硫醚;一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯且另一方面衍生自脂族或芳族多异氰酸酯的聚氨酯;衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺的聚酰胺和共聚酰胺;聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑;衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯的聚酯;聚碳酸酯和聚酯碳酸酯;聚酮;聚砜、聚醚砜和聚醚酮;一方面衍生自醛且另一方面衍生自酚类、脲类和三聚氰胺类的交联聚合物;干性和非干性醇酸树脂;衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯的不饱和聚酯树脂;衍生自取代的丙烯酸酯的可交联丙烯酸系树脂;用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂;衍生自脂族、脂环族、杂环或芳族缩水甘油基化合物的交联环氧树脂;天然聚合物如纤维素、橡胶、明胶及其化学改性的同系衍生物;天然或合成橡胶的含水乳液;线性低密度聚乙烯、低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸丁酯共聚物、聚丙烯均聚物和聚丙烯共聚物。
20.根据实施方案11-19中一项或多项所述的组合物,其中有机材料与稳定剂混合物的重量比为0.005:10。
21.一种制品,其包含根据实施方案11-20中一项或多项所述的组合物。
22.根据实施方案1所述的至少一种式(A)化合物和/或式(B)化合物在防止根据实施方案1的抗氧化剂化合物降解中的用途。
23.根据实施方案1-10中一项或多项的稳定剂混合物在稳定暴露于光的有机材料中的用途。
以下实施例更详细地说明了本发明。除非另有说明,所有百分比和份均以重量计。
实施例
下表1、2、3、4和5中所列的稳定剂:
化合物(A-1)
化合物(A-2)
化合物(A-3)
化合物D:1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物
抗氧化剂-1:季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯
抗氧化剂-2:1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯
抗氧化剂-3:1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯
抗氧化剂-4:硫代二丙酸二硬脂酯
化合物E:三(2,4-二叔丁基苯基)亚磷酸酯
化合物F:羟基碳酸镁铝
(A)膜样品的制备
将10g Plexiglas 7N与0.203g表1-5的化合物(由0.103g抗氧化剂或0.100g抗氧化剂加0.003g羟基苯基-三嗪构成)溶解于40g二氯甲烷中。所有化合物也含有0.1g HALS(1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物)作为碱稳定剂以用于制得的膜的完整性。
在刀片速度为12mm/sec且间隙高度为120mm的自动刀片(Erichsen)的帮助下绘制膜。将制得的膜使用Atlas 5000装置暴露于DIN ISO 4892-2Cyclus 1(有Boro S/Boro S滤光片的氙灯,60W/m2@300-400nm(相当于0.51W/(m2·nm)@340nm),BPT 65±2℃,50+/-5%相对湿度,干块温度38+/-3℃,102min,光,18min,水喷雾)或使用Atlas CI 65装置暴露于DIN EN ISO 4892-2Cyclus 5(有Boro S/碱石灰滤光片的氙灯,50W/m2@300-400nm(相当于0.43W/(m2·nm)@340nm),BPT 65±3℃,50+/-10%相对湿度,干块温度38+/-3℃,持续光照,无水喷雾)或暴露于ASTM G 155Cyclus 1。主要UV的吸收%为通常使用Perkin Elmer的Lambda 20UV-vis光谱测量(250-500nm)。在AO的最大吸收下观测光学吸收光谱,测得该最大吸收在约270-290nm。对于暴露于DIN ISO 4892-2Cyclus 5(干)的样品,抗氧化剂吸收百分比(%Abs)的降低结果显示于表1中,和对于暴露于DIN EN ISO 4892-2Cyclus 1(湿)的样品,显示于表2中,和对于暴露于ASTM G 155Cyclus 1(干)的样品,显示于表3中,有BoroS/Boro S滤光片的氙灯,0.35W/(m2·nm)@340nm,BPT 63℃,50+/-10%相对湿度,干块温度42+/-4℃,使用Atlas装置。
该表显示单独的主要抗氧化剂相比于该相同抗氧化剂加羟基苯基三嗪化合物的经时效率和固有稳定性
表1-3:暴露于ISO 4892-2cyclus 1(湿)的膜中的抗氧化剂的UV吸收的减少(以%计)
配制剂 | 1000小时 |
0.13%抗氧化剂-1 | 76 |
0.03%化合物(A-1)+0.1%抗氧化剂-1 | 100 |
0.03%化合物(A-3)+0.1%抗氧化剂-1 | 82 |
含1%化合物D的PMMA溶液膜
在275nm下测量的抗氧化剂-1的UV光谱
表2:
配制剂 | 350小时 |
0.13%抗氧化剂-2 | 83 |
0.03%化合物(A-1)+0.1%抗氧化剂-2 | 100 |
0.03%化合物(A-2)+0.1%抗氧化剂-2 | 93 |
含1%化合物D的PMMA溶液膜
在280nm下测量的抗氧化剂-2的UV光谱
表3:
配制剂 | 350小时 |
0.13%抗氧化剂-3 | 89 |
0.03%化合物(A-2)+0.1%抗氧化剂-3 | 100 |
含1%化合物D的PMMA溶液膜
在275nm下测量的抗氧化剂-3的UV光谱
从表1-3中可知,与单独的抗氧化剂相比,当暴露于光时,羟基苯基三嗪化合物与抗氧化剂一起使用提高该抗氧化剂在膜中的稳定性。
表4:暴露于ASTM G 155Cyclus 1(干)的膜中的抗氧化剂的UV吸收的减少(以%计)
配制剂 | 1100小时 |
0.13%抗氧化剂-1 | 87 |
0.03%化合物(A-1)+0.1%抗氧化剂-1 | 100 |
0.03%化合物(A-3)+0.1%抗氧化剂-1 | 92 |
含1%化合物D的PMMA溶液膜
在275nm下测量的抗氧化剂-1的UV光谱
表5:暴露于ASTM G 155Cyclus 1(干)的膜中的抗氧化剂的UV吸收的减少(以%计)
含1%化合物D的PMMA溶液膜
在270nm下测量的抗氧化剂-4的UV光谱
从表4和5中可知,与单独的抗氧化剂相比,当暴露于光时,羟基苯基三嗪化合物与抗氧化剂一起使用提高该抗氧化剂在膜中的稳定性。
(B)测试样品的制备:
用Mixaco Lab CM12高速混合器装置混合非稳定化高密度聚乙烯(HDPE;CRP-100;天然归类于LyondellBasell的PE100下;熔体流动速率:190℃/5.0Kg:0.23g/10min(ISO 1133);密度:0.95g/cm3(ISO 1183))和表6中所列的添加剂的混合物。
随后将所得完整配制剂在Collin 25X42D挤出机上在240℃下配混,和随后在Engel HL65注塑机上在230℃下注塑。
使用ASTM G 154-C1(不带滤光片的UV-A荧光灯,0.77W/(m2·nm)@340nm和BPT A:60±3C和B:50±3C),将40mm x 60mm x 2mm的注塑试片暴露于来自QLab的QUV-SE。
所测量的参数为在最大氧化峰下的时间和热流,在1600小时QUV-SE(ASTM G 154-C1)后,使用DSC Q2000 von TA仪器(Waters)在200℃下在O2下测得。结果列于表7中。
所测量的参数为HP-OIT(@150℃和500psi),在1600小时QUV-SE(ASTM G 154-C1)后,使用带有压敏组件的DSC Q2000 von TA仪器(Waters)TA测得。结果列于表8中。
表6:
添加剂配制剂 | 编号 |
0.3%抗氧化剂-1+0.1%化合物E | 1 |
0.3%抗氧化剂-3+0.1%化合物E+0.1%化合物(A-2) | 2 |
0.3%抗氧化剂-3+0.1%化合物E+0.1%化合物F | 3 |
0.3%抗氧化剂-3+0.1%化合物E+0.1%化合物F+0.1%化合物(A-2) | 4 |
0.3%抗氧化剂-3+0.1%化合物E+0.1%化合物F+0.05%化合物(A-1) | 5 |
表7:最大氧化峰下的时间和热流
配制剂编号 | 最大氧化峰下的时间(min.) | 最大氧化峰下的热流(W/g) |
1:对照1 | 27 | 0.7 |
2 | 44 | 1.4 |
3:对照2 | 17 | 0.6 |
4 | 58 | 1.3 |
5 | 40 | 1.1 |
表7显示,与不含化合物(A)的配方配制剂相比,本发明的配制剂在最大氧化峰下提供更长时间和更高热流,在暴露于QUV时显示样品的优异稳定性。
表8:在150℃和500psi下以分钟计的HP-OIT
配制剂编号 | HP-OIT(min.) |
3:对照2 | 70 |
4 | 140 |
5 | 426 |
表8显示,与不含该化合物(A)的配制剂相比,本发明的配制剂产生更长HP-OIT(在150℃和500psi下),在暴露于QUV时显示样品的优异稳定性。
Claims (23)
1.一种稳定剂混合物,其包含:
i.至少一种选自式(A)化合物和式(B)化合物的化合物:
其中E1为C1-C18烷基;和
E2、E3、E4和E5彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
其中
L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基;
E6、E7、E8、E9、E10、E11、E12、E13彼此独立地为氢、C1-C18烷基、苯基或被1、2或3个C1-C4烷基取代的苯基;和
ii.至少一种抗氧化剂化合物,
其中至少一种式(A)化合物和/或式(B)化合物与至少一种抗氧化剂的重量比为1:2-1:20。
2.根据权利要求1所述的稳定剂混合物,其中E1为C1-C8烷基,且E2、E3、E4和E5彼此独立地为氢、C1-C4烷基或苯基。
3.根据权利要求1或2所述的稳定剂混合物,其中L为ROCOR’,其中R和R’彼此独立地为C1-C18亚烷基,且E6、E7、E8、E9、E10、E11、E12和E13彼此独立地为氢、C1-C4烷基或苯基。
4.根据权利要求1-3中一项或多项所述的稳定剂混合物,其中至少一种式(A)化合物选自式(A-1)、(A-2)和(A-3):
5.根据权利要求1或3中一项或多项所述的稳定剂混合物,其中式(B)化合物为式(B-1)化合物:
6.根据权利要求1所述的稳定剂混合物,其中抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)、4,6-双(辛基硫代甲基)-邻甲酚、双(十八烷基)羟胺、苯胺、N-苯基、与2,4,4-三甲基戊烯的反应产物、3,3'-硫代二丙酸双(正十八烷基)酯、3,3'-硫代二丙酸双(十二烷基)酯、4,4'-双(α,α-二甲基苄基)二苯胺、3,3'-硫代二丙酸二肉豆蔻酯、双(十八烷基)二硫醚和2,2-双[[3-(十二烷基硫)-1-氧代丙氧基]甲基]丙烷-1,3-二基双[3-(十二烷基硫)丙酸酯]。
7.根据权利要求1和6中一项或多项所述的稳定剂混合物,其中抗氧化剂选自:2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-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、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯、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、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、辛基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)-N-[6-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氨基]己基]丙烯酰胺、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸]钙、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3,5-二叔丁基-4-羟基氢化肉桂酸1,3,5-三(2-羟乙基)-s-三嗪三酮酯、3-叔丁基-2-羟基-5-甲基苯硫醚、2-甲基-4,6-双(正辛基硫烷基甲基)苯酚、2,2'-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、4-((4,6-双(辛基硫基)-1,3,5-三嗪-2-基)氨基)-2,6-二叔丁基苯酚、双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯、α-生育酚、3-(3,5-二叔丁基-4-羟基苯基)-N'-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙烷酰肼、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、亚乙基双[3,3-双[3-(1,1-二甲基乙基)-4-羟基苯基]丁酸酯]、苄基-2-乙酰氨基-2-脱氧-α-D-半乳吡喃糖苷、2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)单丙烯酸酯、2-丙烯酸,2-(1,1-二甲基乙基)-6-[1-[3-(1,1-二甲基乙基)-5-(1,1-二甲基丙基)-2-羟基苯基]乙基]-4-(1,1-二甲基丙基)苯基酯、三[2-叔丁基-4-(5-叔丁基-4-羟基-2-甲基苯基)硫烷基-5-甲基苯基]亚磷酸酯、(1,2-二氧亚乙基)双(亚氨基亚乙基)双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、苯酚、2,6-双[[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]八氢-4,7-甲桥基-1H-茚基]-4-甲基-,4,4'-硫代双(2-叔丁基-5-甲基苯酚)和4,6-双(辛基硫代甲基)-邻甲酚。
8.根据权利要求1、6和7中一项或多项所述的稳定剂混合物,其中抗氧化剂选自:1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、季戊四醇四[3-[3,5-二叔丁基-4-羟基苯基]丙酸酯和1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯。
9.根据权利要求1-8中一项或多项所述的稳定剂混合物,其进一步包含至少一种硫增效剂,其中所述至少一种硫增效剂选自:硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻基酯、季戊四醇四[3-(十二烷基硫)丙酸酯]、硫代二丙酸二硬脂酯和二硬脂基二硫醚。
10.根据权利要求1-9中一项或多项所述的稳定剂混合物,其中所述硫增效剂为硫代二丙酸二硬脂酯。
11.一种组合物,其包含:
a.有机材料,和
b.根据权利要求1-10中一项或多项所述的稳定剂混合物。
12.根据权利要求11所述的组合物,其进一步包含至少一种位阻胺光稳定剂。
13.根据权利要求11和12中一项或多项所述的组合物,其中所述至少一种位阻胺光稳定剂选自双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)碳酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、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-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N'-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-双(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与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)六亚甲基二胺与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)乙烷与2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物;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]癸烷与表氯醇的反应产物、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、2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N'-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、4-正丁基-2-N,4-N-双(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)氨基]己基]-1,3,5-三嗪-2,4-二胺、N,N'-双(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲酰基六亚甲基二胺及其混合物。
14.根据权利要求11-13中一项或多项所述的组合物,其进一步包含至少一种选自通式(I)、通式(II)、通式(III)、通式(IV)及其混合物的化合物(C):
-通式(I)的化合物(C):
其中
A1选自线性或支化的取代或未取代的C2-C18亚烷基、取代或未取代的C5-C7亚环烷基和C1-C4亚烷基双(C5-C7亚环烷基),
A2独立地选自H、线性或支化的取代或未取代的C1-C12烷基、C1-C12烷氧基、取代或未取代的C5-C12环烷基和C5-C12环烷氧基,
A3和A4独立地选自H、线性或支化的取代或未取代的C1-C12烷基、取代或未取代的C5-C12环烷基和式(a-1)的基团:
或
A3和A4与它们所键合的氮原子一起形成5-10元杂环;且
a为1-20的整数,并且重复单元相同或不同;
-通式(II)的化合物(C):
其中
x1和x2独立地选自C1-C30烷氧基,
-通式(III)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y2为C1-C30烷基;和
-通式(IV)的化合物(C):
其中
Y1为线性或支化的取代或未取代的C3-C20烷基,
Y3独立地选自线性或支化的取代或未取代的C3-C20烷基和C3-C20亚烷基,
X为C2-C5烷基,
n为1-8的整数。
15.根据权利要求11-14中一项或多项所述的组合物,其中化合物(C)选自式(C-I)、(C-II)、(C-III)、(C-IV)、(C-V)、(C-VI)、(C-VII)和(C-VIII):
其中a为1-10的整数;和
其中n为2。
16.根据权利要求11-15中一项或多项所述的组合物,其进一步包含至少一种选自UV稳定剂、助滑剂、防结块剂、热填料、颜料、防水雾剂和防烟雾剂的添加剂。
17.根据权利要求11-16中一项或多项所述的组合物,其进一步包含除酸剂。
18.根据权利要求16所述的组合物,其UV稳定剂选自2-(2'-羟基苯基)苯并三唑、2-羟基二苯甲酮、2-(2-羟基苯基)-1,3,5-三嗪、氰基丙烯酸酯、草酰苯胺、苯并噁嗪及其混合物。
19.根据权利要求11所述的组合物,其中所述有机材料选自单烯烃和二烯烃的聚合物;单烯烃和二烯烃与彼此或与其他乙烯基单体的共聚物;烃树脂,和聚烯烃与淀粉的混合物;聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯);乙烯基芳族单体如苯乙烯或α-甲基苯乙烯的接枝共聚物;含卤素的聚合物;衍生自α,β-不饱和酸及其衍生物的聚合物;衍生自不饱和醇和胺或其酰基衍生物或缩醛的聚合物;环醚的均聚物和共聚物;聚苯醚和聚苯硫醚;一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯且另一方面衍生自脂族或芳族多异氰酸酯的聚氨酯;衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺的聚酰胺和共聚酰胺;聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑;衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯的聚酯;聚碳酸酯和聚酯碳酸酯;聚酮;聚砜、聚醚砜和聚醚酮;一方面衍生自醛且另一方面衍生自酚类、脲类和三聚氰胺类的交联聚合物;干性和非干性醇酸树脂;衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯的不饱和聚酯树脂;衍生自取代的丙烯酸酯的可交联丙烯酸系树脂;用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂;衍生自脂族、脂环族、杂环或芳族缩水甘油基化合物的交联环氧树脂;天然聚合物如纤维素、橡胶、明胶及其化学改性的同系衍生物;天然或合成橡胶的含水乳液;线性低密度聚乙烯、低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸丁酯共聚物、聚丙烯均聚物和聚丙烯共聚物。
20.根据权利要求11-19中一项或多项所述的组合物,其中有机材料与稳定剂混合物的重量比为0.005:10。
21.一种制品,其包含根据权利要求11-20中一项或多项所述的组合物。
22.根据权利要求1所述的至少一种式(A)化合物和/或式(B)化合物在防止根据权利要求1所述的抗氧化剂化合物降解中的用途。
23.根据权利要求1-10中一项或多项所述的稳定剂混合物在稳定暴露于光的有机材料中的用途。
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TW206220B (zh) | 1991-07-01 | 1993-05-21 | Ciba Geigy Ag | |
US5252643A (en) | 1991-07-01 | 1993-10-12 | Ciba-Geigy Corporation | Thiomethylated benzofuran-2-ones |
GB2267490B (en) | 1992-05-22 | 1995-08-09 | Ciba Geigy Ag | 3-(Carboxymethoxyphenyl)benzofuran-2-one stabilisers |
TW260686B (zh) | 1992-05-22 | 1995-10-21 | Ciba Geigy | |
NL9300801A (nl) | 1992-05-22 | 1993-12-16 | Ciba Geigy | 3-(acyloxyfenyl)benzofuran-2-on als stabilisatoren. |
MX9305489A (es) | 1992-09-23 | 1994-03-31 | Ciba Geigy Ag | 3-(dihidrobenzofuran-5-il)benzofuran-2-onas, estabilizadores. |
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DE19630599A1 (de) * | 1996-07-31 | 1998-02-05 | Hoechst Ag | Polyethylenterephthalat-Platte mit verbesserter Hydrolysestabilität, Verfahren zur Herstellung und Verwendung |
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GB2384486B (en) * | 2000-07-26 | 2004-04-21 | Ciba Sc Holding Ag | Hydroxyphenyltriazines |
CO5231248A1 (es) * | 2000-07-26 | 2002-12-27 | Ciba Sc Holding Ag | Articulos transparentes de polimero de baja consistencia |
TW593303B (en) | 2001-09-11 | 2004-06-21 | Ciba Sc Holding Ag | Stabilization of synthetic polymers |
AU2002348236A1 (en) * | 2001-12-27 | 2003-07-24 | Cytec Technology Corp. | Uv stabilized thermoplastic olefins |
ZA200301683B (en) * | 2002-03-04 | 2004-09-06 | Ciba Sc Holding Ag | Synergistic combinations of UV absorbers for pigmented polyolefins. |
AU2003246417A1 (en) * | 2002-06-19 | 2004-01-06 | Ciba Specialty Chemicals Holding Inc. | Stabilized polyamide compositions |
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KR100836363B1 (ko) * | 2007-07-11 | 2008-06-09 | 현대자동차주식회사 | 내후성이 우수한 폴리카보네이트 얼로이 수지 조성물 |
US7897663B2 (en) | 2007-10-25 | 2011-03-01 | Kuo Ching Chemical Co., Ltd. | Clarifying agent composition and manufacturing method thereof |
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CA3214135A1 (en) | 2022-10-06 |
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