CN103210031B - 用于聚合物的稳定剂组合物 - Google Patents
用于聚合物的稳定剂组合物 Download PDFInfo
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- CN103210031B CN103210031B CN201180053878.6A CN201180053878A CN103210031B CN 103210031 B CN103210031 B CN 103210031B CN 201180053878 A CN201180053878 A CN 201180053878A CN 103210031 B CN103210031 B CN 103210031B
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- butyl
- acid
- ester
- bis
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种组合物,该组合物包含:(a)式(A-I)化合物,(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,其中Z1为线性C12烷基或线性C18烷基,和(c)为另一位阻酚类抗氧化剂的化合物。该组合物用于稳定有机聚合物对抗由热、光和/或氧化所引起的降解。该有机聚合物例如为苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯共聚物或聚丁二烯。
Description
发明描述
聚合物易于降解,其可例如由热、光和/或氧化诱发。
为了降低所述降解,提出了许多关于添加稳定剂或稳定剂组合的解决方法。
EP-A-0238140尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
EP-A-0243956尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
JP-A-07196868尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
US-62844374尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
JP-A-2002/241574尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
US-A-2006/0183829尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
JP-A-2010/077382尤其公开了用于稳定聚合物的包含酚类抗氧化剂和硫醚的组合物。
仍需要关于热稳定性、光稳定性和/或氧化稳定性的聚合物稳定的其他技术解决方法。
现已发现本发明稳定剂的某些特殊组合在较大程度上满足上述热、光和/或氧化稳定性标准。
本发明涉及一种组合物,该组合物包含:
(a)式(A-I)化合物
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物
其中Z1为线性C12烷基或线性C18烷基,
(c)式(C-I)、(C-II)或(C-III)化合物
其中
n=1或4,
当n=1时,R1为C1-C18烷基,
当n=4时,R1为2,2-二甲基丙-1,3,1',1''-四基,
C1-C18烷基例如为甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、异辛基、2-乙基己基、壬基、异壬基、癸基、十一烷基、十二烷基、十三烷基、支化十三烷基、十四烷基、十五烷基、支化十五烷基、十六烷基和十八烷基[=硬脂基]。
优选甲基、C7-C9烷基、C13-15烷基和十八烷基。尤其优选十八烷基,特别是线性十八烷基。
式(B-III)化合物为2,4-二(辛基硫基甲基)-6-甲基苯酚且含于市售Irganox1520(RTM BASF)中。
式(B-IV)化合物为2,4-二(十二烷基硫基甲基)-6-甲基苯酚且含于市售Irganox1726(RTM BASF)中。
式(C-I)化合物,其中当n=4时,R1为2,2-二甲基丙-1,3,1',1''-四基,为四[3-(3,5-二叔丁基-4-羟基苯基)丙酰氧基甲基]甲烷,其含于市售Irganox1010(RTM BASF)中且如下所述:
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)化合物,和
(c)式(C-I)、(C-II)或(C-III)化合物。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)化合物,和
(c)式(C-I)化合物。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)化合物,和
(c)式(C-I)化合物,
其中n=1且R1为C1-C18烷基。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)化合物,和
(c)式(C-I)化合物,
其中n=1且R1为线性十八烷基。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-II)化合物,和
(c)式(C-I)、(C-II)或(C-III)化合物。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-III)或(B-IV)化合物,和
(c)式(C-I)、(C-II)或(C-III)化合物。
添加剂组合物可用于稳定有机聚合物对抗由热、光和/或氧化引起的降解。
热稳定性例如与加工有机聚合物的高温有关。热稳定性对有机聚合物的长期热稳定性而言也是重要的。
优选稳定化,其提供聚合物在短期高温加工期间的稳定性与聚合物在长期储存期间的稳定性之间的平衡。
适合用于测定上述平衡的测试为Brabender诱导时间试验程序和烘箱老化。温度例如为160℃的Brabender诱导时间试验程序模拟在高温、剪切和低氧含量下的短期加工,而在升高的温度如70℃或80℃下的烘箱老化模拟聚合物的长期储存。可通过测量黄度指数(即希望几乎不变黄)和测量凝胶含量(即希望几乎不含胶)来测定聚合物在烘箱老化期间对抗降解的稳定性。
光稳定性尤其与有机聚合物的长期使用期间有关。
氧化可伴随地发生且通常加重光和/或热的有害作用。
本发明添加剂组合物还提供光和热稳定性的组合,例如在加工的高温期间的热稳定性与长期光稳定性组合或长期热稳定性与长期光稳定性组合。
另一技术优势为添加剂组合物本身具有低发射潜力,且因此含有该添加剂组合物的有机聚合物具有较低发射潜力。
如本文中所定义的有机聚合物可为天然、半天然或合成聚合物。
有机聚合物的实例为:
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,以及环烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(其任选可为交联的),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,即前面段落中例举的单烯烃聚合物,优选聚乙烯和聚丙烯,可以通过不同方法制备,尤其通过下列方法制备:
a)自由基聚合(通常在高压和升高的温度下)。
b)使用通常含有一种或一种以上周期表第IVb、Vb、VIb或VIII族金属的催化剂的催化聚合。这些金属通常具有一个或一个以上配体,通常是可为π-或σ-配位的氧化物、卤化物、醇化物、酯、醚、胺、烷基、链烯基和/或芳基。这些金属配合物可为游离形式或固定在基材上,通常在活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可溶于或不溶于聚合介质中。所述催化剂本身可用于聚合或者可使用其他活化剂,通常为烷基金属、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基氧烷(alkyloxane),其中所述金属为周期表第Ia、IIa和/或IIIa族的元素。所述活化剂可方便地用其他酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常称为Philips、Standard Oil Indiana、齐格勒(-纳塔)、TNZ(杜邦)、茂金属或单中心催化剂(SSC)。
2.1.下提及的聚合物的混合物,例如聚丙烯与聚异丁烯、聚丙烯与聚乙烯的混合物(例如PP/HDPE、PP/LDPE)以及不同种类聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃相互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)以及乙烯与丙烯和二烯如己二烯、二环戊二烯或亚乙基-降冰片烯的三元共聚物,和这些共聚物相互之间及与上述1.下提及聚合物的混合物,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和交替或无规聚烯烃/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),包括其氢化改性物(例如增粘剂)以及聚烯烃和淀粉的混合物。
来自1.-4.的均聚物和共聚物可以具有任何立体结构,包括间规、等规、半等规或无规立构;其中优选无规立构聚合物。还包括立构嵌段聚合物。
5.聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.衍生于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,尤其是对乙烯基甲苯,乙基苯乙烯、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽的所有异构体及其混合物。均聚物和共聚物可具有任何立体结构,包括间规、等规、半等规或无规立构;其中优选无规立构聚合物。还包括立构嵌段聚合物。
6a.包括上述乙烯基芳族单体和选自乙烯、丙烯、二烯、腈、酸、马来酸酐、马来酰亚胺、乙酸乙烯酯和氯乙烯或丙烯酸衍生物及其混合物的共聚单体的共聚物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(共聚体)、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;高冲击强度的苯乙烯共聚物和其他聚合物如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物的混合物;苯乙烯的无规共聚物,例如苯乙烯-丁二烯-苯乙烯无规共聚物(=S-SBR),以及苯乙烯的嵌段共聚物,例如苯乙烯-丁二烯-苯乙烯嵌段共聚物(=SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(=SIS)、苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(=SEBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物或苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物。
6b.衍生于6.)下所提到的聚合物的氢化的氢化芳族聚合物,尤其包括通过氢化无规立构聚苯乙烯得到的聚环己基乙烯(PCHE),也常称为聚乙烯基环己烷(PVCH)。
6c.衍生于6a.下所提到的聚合物的氢化的氢化芳族聚合物。
均聚物和共聚物可以具有任何立体结构,包括间规、等规、半等规或无规立构;其中优选无规立构聚合物。还包括立构嵌段聚合物。
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,例如苯乙烯接枝聚丁二烯,苯乙烯接枝聚丁二烯-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)接枝聚丁二烯;苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝聚丁二烯;苯乙烯和马来酸酐接枝聚丁二烯;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝聚丁二烯;苯乙烯和马来酰亚胺接枝聚丁二烯;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝聚丁二烯;苯乙烯和丙烯腈接枝乙烯/丙烯/二烯三元共聚物;苯乙烯和丙烯腈接枝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丙烯酸酯/丁二烯共聚物,及其与6)下所列共聚物的混合物,例如称作ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素的聚合物,例如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化和溴化共聚物(卤丁基橡胶)、氯化或磺基氯化聚乙烯、乙烯和氯代乙烯的共聚物、表氯醇均聚物和共聚物,尤其是含卤素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,及其共聚物如氯乙烯/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.衍生于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;用丙烯酸丁酯冲击改性的聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈。
10.9.下所提到的单体相互之间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/卤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.衍生于不饱和醇和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蜜胺;以及它们与上面1.中所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、聚氧乙烯、聚氧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。
15.一方面衍生于羟基封端的聚醚、聚酯或聚丁二烯且另一方面衍生于脂族或芳族多异氰酸酯的聚氨酯,以及其前体。
16.衍生于二胺和二羧酸和/或衍生于氨基羧酸或相应内酰胺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,来源于间苯二甲胺和己二酸的芳族聚酰胺;由六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的聚酰胺(含或不含作为改性剂的弹性体),例如聚对苯二甲酰2,4,4,-三甲基六亚甲基二胺或聚间苯二甲酰间苯二胺;还有上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键合或接枝弹性体的嵌段共聚物;或与聚醚如聚乙二醇、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、聚乙内酰脲类和聚苯并咪唑类。
18.衍生自二羧酸和二醇和/或衍生于羟基羧酸或相应内酯或交酯的聚酯,例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、聚萘二甲酸亚烷基二醇酯和聚羟基苯甲酸酯以及衍生于羟基封端的聚醚的共聚醚酯,还有用聚碳酸酯或MBS改性的聚酯。共聚酯例如可以包括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、聚己二酸四亚甲基二醇酯/对苯二甲酸四亚甲基二醇酯、聚琥珀酸丁二醇酯/己二酸丁二醇酯、聚琥珀酸丁二醇酯/碳酸丁二醇酯、聚-3-羟基丁酸酯/辛酸酯共聚物、聚-3-羟基丁酸酯/己酸酯/癸酸酯三元共聚物。此外,脂族聚酯例如可以包括但不限于聚(羟基链烷酸酯)类,尤其是聚丙内酯、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、聚琥珀酸六亚甲基二醇酯、聚己二酸乙二醇酯、聚己二酸丙二醇酯、聚己二酸丁二醇酯、聚己二酸六亚甲基二醇酯、聚草酸乙二醇酯、聚草酸丙二醇酯、聚草酸丁二醇酯、聚草酸六亚甲基二醇酯、聚癸二酸乙二醇酯、聚癸二酸丙二醇酯、聚癸二酸丁二醇酯和聚乳酸(PLA)以及用聚碳酸酯或MBS改性的对应聚酯。术语“聚乳酸(PLA)”表示优选聚-L-交酯的均聚物以及其与其他聚合物的共混物或掺合聚合物;乳酸或交酯与其他单体如羟基羧酸,例如乙醇酸、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的共聚物;术语“乳酸”或“丙交酯”包括L-乳酸、D-乳酸、其混合物和二聚体,即L-交酯、D-交酯、内消旋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。
22.一方面衍生于醛和另一方面衍生于酚、脲和蜜胺类的交联聚合物,例如苯酚/甲醛树脂、脲/甲醛树脂和蜜胺/甲醛树脂。
23.干性和不干性醇酸树脂。
24.衍生于饱和和不饱和二羧酸与多元醇的共聚酯和作为交联剂的乙烯基化合物的不饱和聚酯树脂,以及具有低可燃性的其含卤素改性物。
25.衍生于取代丙烯酸酯的可交联丙烯酸系树脂,例如环氧丙烯酸酯、尿烷丙烯酸酯或聚酯丙烯酸酯。
26.用蜜胺树脂、脲树脂、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.衍生于脂族、脂环族、杂环或芳族缩水甘油基化合物的交联环氧树脂,例如双酚A和双酚F的二缩水甘油醚的产物,它们用常规硬化剂如酸酐或胺交联,使用或不使用促进剂。
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(高分子共混物),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。优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,
(c)式(C-I)、(C-II)或(C-III)化合物,和
(d)有机聚合物。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,
(c)式(C-I)、(C-II)或(C-III)化合物,和
(d)有机聚合物,其选自如6a.项所述的共聚物和聚丁二烯。
优选如下组合物,其中有机聚合物(d)选自苯乙烯共聚物和聚丁二烯。
优选如下组合物,其中有机聚合物(d)选自丁二烯-苯乙烯共聚物、异戊二烯-苯乙烯共聚物和聚丁二烯。
优选如下组合物,其中有机聚合物(d)选自丁二烯-苯乙烯共聚物和异戊二烯-苯乙烯共聚物。
优选如下组合物,其中有机聚合物(d)选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯无规共聚物和聚丁二烯。
优选如下组合物,其中有机聚合物(d)选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物和苯乙烯-丁二烯-苯乙烯无规共聚物。
存在已知用于单体的不同类型的聚合方法,例如溶液聚合,其中将单体溶解于有机溶剂如环己烷中,和乳液聚合,特别是水性乳液聚合,其中通常将水不溶性单体乳化于水中。
优选如下组合物,其中有机聚合物(d)由溶液聚合方法或水性乳液聚合方法得到。
优选如下组合物,其中有机聚合物(d)由溶液聚合方法得到。
优选如下组合物,其中有机聚合物(d)由溶液聚合得到且其中有机聚合物(d)选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物和苯乙烯-乙烯-丁二烯嵌段共聚物。
优选如下组合物,其中有机聚合物(d)为苯乙烯-丁二烯-苯乙烯嵌段共聚物且由溶液聚合方法得到,其中反应单体苯乙烯与丁二烯的重量比为1:4-4:1,即1份苯乙烯:4份丁二烯至4份苯乙烯:1份丁二烯。
优选如下组合物,其中包含组分(a)、组分(b)和组分(c)的组合物在20℃的室温下可溶于环己烷。
组分(a)(其为式(A-I)化合物)与组分(b)(其为式(B-I)、(B-II)、(B-III)或(B-IV)化合物)的重量比可为2:1-1:20,特别是1:3-1:20,尤其是1:4-1:10,非常特别是1:4-1:8。
优选如下组合物,其中组分(a)与组分(b)的重量比为2:1-1:20。
组分(a)(其为式(A-I)化合物)与组分(c)(其为式(C-I)、(C-II)或(C-III)化合物)的重量比可为1:1-1:60,特别是1:3-1:25,尤其1:5-1:25,非常特别是1:5-1:15。
优选如下组合物,其中组分(a)与组分(c)的重量比为1:1-1:60。
优选如下组合物,其中组分(a)与组分(b)的重量比为2:1-1:20且组分(a)与组分(c)的重量比为1:1-1:60。
优选如下组合物,其中组分(a)与组分(b)的重量比为1:3-1:20且组分(a)与组分(c)的重量比为1:5-1:60。
优选如下组合物,其中组分(a)与组分(b)的重量比为1:4-1:10且组分(a)与组分(c)的重量比为1:5-1:25。
优选如下组合物,其中组分(a)与组分(b)的重量比为1:4-1:6且组分(a)与组分(c)的重量比为1:5-1:8。
稳定剂通常以相对于待稳定的物质少量使用。在包含组分(a)、组分(b)、组分(c)和组分(d)的组合物中,组分(a)、组分(b)和组分(c)的组合重量为组分(d)重量的0.01%至20%,特别是0.02%至10%,尤其0.1%至1.3%,非常特别是0.3%至0.8%。
优选如下组合物,其中组分(a)、组分(b)和组分(c)的组合重量为组分(d)重量的0.02%至10%。
优选如下组合物,其中
组分(a)的重量为组分(d)重量的0.015%至0.1%,
组分(b)的重量为组分(d)重量的0.045%至0.3%,和
组分(c)的重量为组分(d)重量的0.1%至0.8%。
优选如下组合物,其中
组分(a)的重量为组分(d)重量的0.02%至0.04%,
组分(b)的重量为组分(d)重量的0.1%至0.2%,和
组分(c)的重量为组分(d)重量的0.2%至0.5%。
优选如下组合物,其包含
(a)式(A-I)化合物,
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,
(c)式(C-I)、(C-II)或(C-III)化合物,和
(d)有机聚合物,其选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯无规共聚物和聚丁二烯,
其中
组分(a)的重量为组分(d)重量的0.015%至0.1%,
组分(b)的重量为组分(d)重量的0.045%至0.3%,和
组分(c)的重量为组分(d)重量的0.1%至0.8%。
包含组分(a)、组分(b)和组分(c)的组合物可含有其他添加剂。
其他添加剂的实例为:
1.抗氧化剂
1.1.烷基化单酚,选自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,2,6-二-十八烷基-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苯酚如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)苯酚和2,4-二甲基-6-(1'-甲基十三烷-1'-基)苯酚及其混合物。
1.2.烷硫基甲基酚类,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-乙基苯酚、2,6-二-十二烷硫基甲基-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-羟基苯基酯,己二酸二(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.羟基化硫二苯基醚类,例如2,2'-硫二(6-叔丁基-4-甲基苯酚)、2,2'-硫二(4-辛基苯酚)、4,4'-硫二(6-叔丁基-3-甲基苯酚)、4,4'-硫二(6-叔丁基-2-甲基苯酚)、4,4'-硫二(3,6-二仲戊基苯酚)、4,4'-二(2,6-二甲基-4-羟基苯基)二硫化物。
1.6.亚烷基双酚类,例如2,2'-亚甲基二(6-叔丁基-4-甲基苯酚),2,2'-亚甲基二(6-叔丁基-4-乙基苯酚),2,2'-亚甲基二[4-甲基-6-(α-甲基环己基)苯酚],2,2'-亚甲基二(4-甲基-6-环己基苯酚),2,2'-亚甲基二(6-壬基-4-甲基苯酚),2,2'-亚甲基二(4,6-二叔丁基苯酚),2,2'-亚乙基二(4,6-二叔丁基苯酚),2,2'-亚乙基二(6-叔丁基-4-异丁基苯酚),2,2'-亚甲基二[6-(α-甲基苄基)-4-壬基苯酚],2,2'-亚甲基二[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4'-亚甲基二(2,6-二叔丁基苯酚),4,4'-亚甲基二(6-叔丁基-2-甲基苯酚),1,1-二(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-二(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,1,1-二(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,乙二醇二[3,3-二(3'-叔丁基-4'-羟基苯基)丁酸酯],二(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯,对苯二甲酸二[2-(3'-叔丁基-2'-羟基-5'-甲基苄基)-6-叔丁基-4-甲基苯基]酯,1,1-二(3,5-二甲基-2-羟基苯基)丁烷,2,2-二(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-二(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,二硫代对苯二甲酸二(4-叔丁基-3-羟基-2,6-二甲基苄基)酯,二(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.羟苄基化丙二酸酯类,例如2,2-二(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,2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸二-十二烷基巯基乙基酯,2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸二[4-(1,1,3,3-四甲基丁基)苯基]酯。
1.9.芳族羟基苄基化合物,选自1,4-二(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯和2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。
1.10.三嗪化合物,选自2-辛硫基-4,6-二(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛硫基-4,6-二(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-1,3,5-三嗪和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-羟基苄基膦酸二甲基酯,3,5-二叔丁基-4-羟基苄基膦酸二乙基酯,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-羟基苄基膦酸单乙基酯的钙盐。
1.12.酰胺基酚类,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)氨基甲酸辛基酯。
1.13.β-(3,5-二叔丁基-4-羟基苯基)丙酸与选自如下的一元或多元醇的酯: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、三(羟乙基)异氰脲酸酯、N,N'-二(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、三羟甲基丙烷和4-羟甲基-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)丙酸与一元或多元醇的酯,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、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-二(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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;3,9-二[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)丙酸与一元或多元醇的酯,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、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-二(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-羟基苯基乙酸与一元或多元醇的酯,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、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-二(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'-二(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺,N,N'-二(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二酰胺,N,N'-二(3,5-二叔丁基-4-羟基苯基丙酰基)酰肼,N,N'-二[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1),(RTM,由Uniroyal供应)。
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'-二(1,4-二甲基戊基)对苯二胺,N,N'-二(1-乙基-3-甲基戊基)对苯二胺,N,N'-二(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'-二(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-(对甲苯氨磺酰)二苯基胺,N,N'-二甲基-N,N'-二仲丁基对苯二胺,二苯基胺,N-烯丙基二苯基胺,4-异丙氧基二苯基胺,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,辛基化二苯基胺如4,4'-二叔辛基二苯基胺,4-正丁胺基苯酚,4-丁酰胺基苯酚,4-壬酰胺基苯酚,4-十二烷酰胺基苯酚,4-十八烷酰胺基苯酚,二(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,1,2-二[(2-甲基苯基)氨基]乙烷,1,2-二(苯基氨基)丙烷,(邻甲苯基)双胍,二[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/叔辛基二苯基胺的混合物,单-和二烷基化壬基二苯基胺的混合物,单-和二烷基化十二烷基二苯基胺的混合物,单-和二烷基化异丙基/异己基二苯基胺的混合物,单-和二烷基化叔丁基二苯基胺的混合物,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/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***类,例如2-(2'-羟基-5'-甲基苯基)苯并***,2-(3',5'-二叔丁基-2'-羟基苯基)苯并***,2-(5'-叔丁基-2'-羟基苯基)苯并***,2-(2'-羟基-5'-(1,1,3,3-四甲基丁基)苯基)苯并***,2-(3',5'-二叔丁基-2'-羟基苯基)-5-氯苯并***,2-(3'-叔丁基-2'-羟基-5'-甲基苯基)-5-氯苯并***,2-(3'-仲丁基-5'-叔丁基-2'-羟基苯基)苯并***,2-(2'-羟基-4'-辛氧基苯基)苯并***,2-(3',5'-二叔戊基-2'-羟基苯基)苯并***,2-(3',5'-二(α,α-二甲基苄基)-2'-羟基苯基)苯并***,2-(3'-叔丁基-2'-羟基-5'-(2-辛氧羰基乙基)苯基)-5-氯苯并***,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***,2-(3'-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)苯基)-5-氯苯并***,2-(3'-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)苯基)苯并***,2-(3'-叔丁基-2'-羟基-5'-(2-辛氧羰基乙基)苯基)苯并***,2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羟基苯基)苯并***,2-(3'-十二烷基-2'-羟基-5'-甲基苯基)苯并***,2-(3'-叔丁基-2'-羟基-5'-(2-异辛氧羰基乙基)苯基苯并***,2,2'-亚甲基-二[4-(1,1,3,3-四甲基丁基)-6-苯并***-2-基苯酚];2-[3'-叔丁基-5'-(2-甲氧羰基乙基)-2'-羟基苯基]-2H-苯并***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***-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***;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***。
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'-二甲氧基的衍生物。
2.3.取代和未取代苯甲酸的酯,例如水杨酸4-叔丁基苯基酯、水杨酸苯酯、水杨酸辛基苯基酯、二苯甲酰基间苯二酚、二(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,例如α-氰基-β,β-二苯基丙烯酸乙基酯、α-氰基-β,β-二苯基丙烯酸异辛基酯、α-甲酯基肉桂酸甲酯、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’-硫二[4-(1,1,3,3-四甲基丁基)苯酚]的镍络合物,例如1:1或1:2络合物,有或没有额外配体如正丁胺、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基或乙基酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍络合物,1-苯基-4-月桂酰基-5-羟基吡唑的镍络合物,有或没有额外配体。
2.6.位阻胺,例如碳酸二[2,2,6,6-四甲基-1-(十一烷氧基)哌啶-4-基]酯、癸二酸二(2,2,6,6-四甲基-4-哌啶基)酯、琥珀酸二(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯、癸二酸二(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯、正丁基-3,5-二叔丁基-4-羟基苄基丙二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物、N,N'-二(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-1,3,5-三嗪的线性或环状缩合物、次氮基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四甲酸四(2,2,6,6-四甲基-4-哌啶基)酯、1,1'-(1,2-乙二基)二(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、2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸二(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、癸二酸二(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、琥珀酸二(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、N,N'-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-二(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1,2-二(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'-二(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、1,2-二(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[136504-96-6]);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(CAS登记号[192268-64-7]);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、1,1-二(1,2,2,6,6-五甲基-4-哌啶氧羰基)-2-(4-甲氧基苯基)乙烯、N,N'-双甲酰基-N,N'-二(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-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、2,4-二[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)-4-十八酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧甲基-3,3,5-三甲基-2-吗啉酮、Sanduvor(RTM,Clariant;CAS登记号106917-31-1)、5-(2-乙基己酰基)氧甲基-3,3,5-三甲基-2-吗啉酮、2,4-二[(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'-二(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。
2.7.草酰胺,例如4,4'-二辛氧基草酰二苯胺、2,2'-二乙氧基草酰二苯胺、2,2'-二辛氧基-5,5'-二叔丁基草酰二苯胺、2,2'-二(十二烷氧基)-5,5'-二叔丁基草酰二苯胺、2-乙氧基-2'-乙基草酰二苯胺、N,N'-二(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2'-乙氧基草酰二苯胺及其与2-乙氧基-2'-乙基-5,4'-二叔丁基草酰二苯胺的混合物、邻-和对甲氧基二取代的草酰二苯胺的混合物以及邻-和对乙氧基二取代的草酰二苯胺的混合物。
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)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2,4-二(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)-4,6-二(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-二(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]-4,6-二(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]-4,6-二(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]-4,6-二(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]-4,6-二(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)-2-羟基丙氧基]苯基}-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪、2,4-二(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.金属去活化剂,例如N,N'-二苯基草酰胺、N-水杨醛基-N'-水杨酰基肼、N,N'-二(水杨酰基)肼、N,N'-二(3,5-二叔丁基-4-羟基苯基丙酰基)肼、3-水杨酰氨基-1,2,4-***、二(亚苄基)草酰二肼、草酰二苯胺、间苯二甲酰二肼、癸二酰二苯基肼、N,N'-二乙酰基己二酰二肼、N,N'-二(水杨酰基)草酰二肼、N,N'-二(水杨酰基)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、二亚磷酸二(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸二(2,4-二枯基苯基)季戊四醇酯、二亚磷酸二(2,6-二叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸氧基季戊四醇酯、二亚磷酸二(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸二(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂基山梨醇酯、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(dioxaphosphocin)、亚磷酸二(2,4-二叔丁基-6-甲基苯基)甲基酯、亚磷酸二(2,4-二叔丁基-6-甲基苯基)乙基酯、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]、亚磷酸2-乙基己基(3,3',5,5'-四叔丁基-1,1'-联苯-2,2'-二基)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)。
尤其优选以下亚磷酸酯:
亚磷酸三(2,4-二叔丁基苯基)酯(Irgafos168(RTM,Ciba Inc))、亚磷酸三(壬基苯基)酯,
5.羟胺类,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-二(十四烷基)羟胺、N,N-二(十六烷基)羟胺、N,N-二(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.硝酮类,例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、由衍生自氢化牛油脂肪胺的N,N-二烷基羟胺衍生的硝酮。
7.硫增效剂,选自硫代二丙酸二肉豆蔻基酯、硫代二丙酸二-十三烷基酯或二硬脂基二硫醚。
8.过氧化物清除剂,选自巯基苯并咪唑或2-巯基苯并咪唑的锌盐和二丁基二硫代氨基甲酸锌。
9.聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物的组合以及二价锰盐。
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、焦儿茶酚锑或焦儿茶酚锌。
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;有机化合物如单羧酸或多羧酸及其盐,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;聚合化合物如离子性共聚物(离聚物)或Irgaclear XT386(RTM,BASF)。尤其优选1,3:2,4-二(3',4'-二甲基亚苄基)山梨醇、1,3:2,4-二(对甲基二亚苄基)山梨醇和1,3:2,4-二(亚苄基)山梨醇。
12.填充剂和增强剂,例如碳酸钙、硅酸盐、玻璃纤维、玻璃珠、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和氢氧化物、炭黑、石墨、木粉以及其他天然产物的粉或纤维、合成纤维。
13.其他添加剂,例如颜料如炭黑,呈金红石或锐钛矿晶型的二氧化钛、彩色颜料;增塑剂;润滑剂;乳化剂;流变添加剂;防滑/防粘添加剂;催化剂;流动控制剂;荧光增白剂;抗静电剂和发泡剂。
14.苯并呋喃酮类和吲哚满酮类,例如公开于U.S.4,325,863;U.S.4,338,244;U.S.5,175,312;U.S.5,216,052;U.S.5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839;EP-A-0591102;EP-A-1291384中的那些或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'-二[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。
本发明的另一实例为如下组合物,其额外包含亚磷酸酯或亚膦酸酯作为其他添加剂。
本发明的另一实例为如下组合物,其不含亚磷酸三(壬基苯基)酯。
本发明的另一实例为如下组合物,其不含如上述列举中4.项所定义的亚磷酸酯或亚膦酸酯。
优选如下组合物,其中其他添加剂的重量在组分(a)、组分(b)和组分(c)的组合重量的50%以下。
如文中所述本发明包含其他实施方案,以上对组合物所述的优选情形同样适用于这些实施方案。
本发明的另一实施方案为稳定有机聚合物对抗由热、光和/或氧化引起的降解的方法,其特征在于将组合物掺入有机聚合物中,
其中该组合物包含
(a)式(A-I)化合物,
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,和
(c)式(C-I)、(C-II)或(C-III)化合物。
已知掺入有机聚合物中的许多可行性。例如,对于热塑性聚合物已知在升高的温度下掺入,例如熔体挤出。对于通过其单体于溶剂中聚合而合成的其他聚合物,理想地在聚合时或聚合结束之后掺入添加剂。
优选在有机聚合物的聚合步骤中或结束之后掺入包含组分(a)、组分(b)和组分(c)的组合物。
组分(a)、组分(b)和组分(c)可溶于亲脂性溶剂。因此,向有机聚合物(其仍悬浮于亲脂性溶剂中)中添加组合物提供通过正常搅拌进行的简单掺入方案。通常,对于包含组分(a)、组分(b)和组分(c)的组合物,当其掺入悬浮于亲脂性溶剂中的有机聚合物时,不需要乳化剂。
在有机聚合物的溶剂型溶液聚合的情况下,优选在有机聚合物的聚合步骤中或结束之后且在悬浮的有机聚合物的凝聚步骤之前掺入包含组分(a)、组分(b)和组分(c)的组合物。
本发明的另一实施方案为组合物在稳定有机聚合物对抗由热、光和/或氧化引起的降解的用途,该组合物包含
(a)式(A-I)化合物,
(b)式(B-I)、(B-II)、(B-III)或(B-IV)化合物,和
(c)式(C-I)、(C-II)或(C-III)化合物。
实施例中使用以下物质。
-“聚合物-1”为苯乙烯-丁二烯-苯乙烯嵌段共聚物(=SBS),其由溶液聚合得到且其中反应单体的重量比为30份苯乙烯和70份丁二烯。
-“Phos-1”可以Irgafos TNPP(RTM BASF)市购且含有亚磷酸三(壬基苯基)酯:
-“Stab-a-1”可以Irganox565(RTM BASF)市购且含有2,4-二(正辛基硫基)-6-(3,5-二叔丁基-4-羟苯基氨基)三嗪:
-“Stab-b-1”可以Seenox412s(RTM Shipro Kasei Kaisha)市购且含有四[(3-(正十二烷基硫基)丙酰氧基)甲基]甲烷(=2,2-双[[3-十二烷基硫基)-1-氧代丙氧基]甲基]丙-1,3-二基双[3-(十二烷基硫基)丙酸酯]):
-“Stab-c-1”可以Irganox1076(RTM BASF)市购且含有3-(3,5-二叔丁基-4-羟基苯基)丙酸硬脂基酯:
制备测试板:
将添加剂溶解于作为溶剂的环己烷中,得到浓度为10%重量的添加剂溶液。
将相应量的添加剂溶液添加至SBS混凝物(cement)(17%固体含量的SBS聚合物,在环己烷中,通常批料大小为294g混凝物[=SBS在环己烷中的溶液/悬浮液])。
在80-90℃下将与混凝物的混合物于去离子水中凝结,得到SBS颗粒。
在室温下在二辊磨机上将SBS颗粒脱水且在110℃下在二辊磨机上加工这些干燥SBS颗粒2分钟,得到SBS橡胶薄片。在115℃下将SBS橡胶片压塑8分钟,得到厚度为2mm的测试板。
表1:测试板的组成
测试板 | 聚合物-1[份] | Phos-1[份] | Stab-a-1[份] | Stab-b-1[份] | Stab-c-1[份] |
com-1a) | 100 | 0.4 | 0.2 | ||
com-2a) | 100 | 0.2 | 0.2 | ||
com-3a) | 100 | 0.2 | 0.2 | ||
com-4a) | 100 | 0.2 | 0.2 | ||
inv-1b) | 100 | 0.03 | 0.15 | 0.2 |
a)比较
b)本发明
根据ASTM E313用C光测定黄度指数。低黄度指数值是希望的。
根据CIELAB体系测定明度(L*)。高明度值是希望的。
黄度指数增加表明降解。
通过在80℃下烘箱老化来测试热稳定性。
表2:在80℃下烘箱老化前后测试板的颜色
a)比较
b)本发明
c)黄度指数
d)明度
结果表明在具有0.2份Stab-c1的组合中,由0.03份Stab-a1和0.15份Stab-b1代替0.2份Stab-a1或0.2份Stab-b1引起的黄度指数增加有限,其表明较少降解。
可通过曝露于UV光来测试光稳定性。例如,可在由Q-Lab公司供应的装置中进行“QUV”测试,其中在60℃的温度下以UV光(340nm,0.77W/m2)连续照射测试板指定时段。
Claims (9)
1.一种组合物,包含
(a)式(A-I)化合物
(b)式(B-I)化合物
(c)式(C-I)化合物
其中n=1,R1为C18烷基,和
(d)有机聚合物,其中所述有机聚合物(d)选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯无规共聚物和聚丁二烯。
2.根据权利要求1的组合物,其中所述有机聚合物(d)由溶液聚合方法或乳液聚合方法得到。
3.根据权利要求1的组合物,其中组分(a)与组分(b)的重量比为2:1-1:20。
4.根据权利要求1的组合物,其中组分(a)与(b)的重量比为2:1-1:20且组分(a)与组分(c)的重量比为1:1-1:60。
5.根据权利要求1的组合物,其中组分(a)、组分(b)和组分(c)的组合重量为组分(d)重量的0.02%至10%。
6.根据权利要求1的组合物,其中
组分(a)的重量为组分(d)重量的0.015%至0.1%,
组分(b)的重量为组分(d)重量的0.045%至0.3%,和
组分(c)的重量为组分(d)重量的0.1%至0.8%。
7.根据权利要求1的组合物,其中存在其他添加剂。
8.一种用于稳定有机聚合物对抗由热、光和/或氧化引起的降解的方法,其特征在于将如权利要求1所定义的包含组分(a)、组分(b)和组分(c)的组合物掺入如权利要求1所定义的所述有机聚合物中。
9.如权利要求1所定义的包含组分(a)、组分(b)和组分(c)的组合物在稳定如权利要求1所定义的有机聚合物对抗由热、光和/或氧化引起的降解中的用途。
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