CN1336945A - 具有增强效果的包括添加剂共混物的合成聚合物 - Google Patents
具有增强效果的包括添加剂共混物的合成聚合物 Download PDFInfo
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- CN1336945A CN1336945A CN00802672A CN00802672A CN1336945A CN 1336945 A CN1336945 A CN 1336945A CN 00802672 A CN00802672 A CN 00802672A CN 00802672 A CN00802672 A CN 00802672A CN 1336945 A CN1336945 A CN 1336945A
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Abstract
选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂的添加剂在合成聚合物中的分散可通过添加具有两亲性质的至少一种聚合物分散或溶剂化剂来增强。以这种方式加以稳定的合成聚合物突出表现在具有抵抗氧化、热或光诱发的降解的优异稳定性。
Description
本发明涉及包括容易遭受氧化、热或光-诱发的降解的合成聚合物(尤其热塑性聚合物)和作为添加剂的选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的至少一种添加剂和具有两亲性质的至少一种聚合物分散或溶剂化剂的组合物,涉及这些添加剂在合成聚合物、尤其热塑性聚合物中的用途,以及稳定这些合成聚合物的方法,前提条件是至少一种添加剂含有选自稳定剂组中的化合物。
本发明还涉及具有两亲性质的聚合物分散剂或溶剂化剂用于改进选自稳定剂、抗静电剂、成核剂和/或生物杀伤剂组的添加剂在合成聚合物中的分散作用的用途,以及涉及改进选自稳定剂、抗静电剂、成核剂和/或生物杀伤剂组的添加剂在合成聚合物中的分散作用的方法。
合成添加剂的效果取决于,例如,添加剂的化学结构,添加剂掺混物的组成,添加剂在塑料中的分散,添加剂在各聚合物中的溶解度和添加剂与聚合物基质的相容性。添加剂与聚合物基质的增强的相容性,和因此而得的增强的效果,例如能够通过预混物的制备来实现。经常使用所谓的母料或浓缩物,它们是聚合物与高浓度添加剂的预混物,这一母料的随后使用使得该添加剂有可能比它直接添加时更容易和更好地分散在聚合物基质中。虽然这些技术是众所周知的,但仍然在寻求一些可使添加剂的性能进一步改进的方法,即充分利用它们。
因此,本发明的目的是为了提供一种组合物,它增强了现有添加剂在合成聚合物中的效果,尤其有改进的分散作用。
US5,387,467公开了具有酯基和长链烷基(该基团经过碳原子键接于硅原子上)的有机聚硅氧烷用于对微粒如颜料和填料的表面或玻璃纤维的表面进行改性的用途。
现已发现,选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂的添加剂在合成聚合物中的效果可通过添加具有两亲性质的至少一种聚合物分散或溶剂化剂来增强。如此增强的合成聚合物突出表现在具有抵抗氧化、热或光诱发的降解的优异稳定性。
本发明所以涉及一种组合物,它包含
a)容易遭受氧化、热或光诱发的降解的合成聚合物,
b)选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的至少一种添加剂,和
c)具有两亲性质的至少一种聚合物分散或溶剂化剂。
抗静电剂的实例描述在R.Gchter和H.Müller,Hanser Verlag,第三版,1990,749-775页中。特别合适的抗静电剂是选自乙氧基化烷基胺,脂肪酸酯,烷基磺酸盐和基于聚酰胺共聚物的聚合物体系(如Ciba Spezialittenchemie的IrgastatP22)中的那些。
生物杀伤剂的实例描述在R.Gchter和H.Müller,HanserVerlag,第三版,1990,791-809页。特别适宜的生物杀伤剂是从10,10’-氧-双吩噁吡,N-(三卤代甲硫基)苯邻二甲酰亚胺,2-乙基己酸二苯基锑,双(8-羟基喹啉)铜,氧化三丁基锡和其衍生物;卤代酚类,如Irgaguard(Ciba Spezialittenchemie AG的Trichlosan CAS登记号3380-34-5);甲硫基-s-三嗪类,如2-甲硫基-4-环丙基氨基-6-(α,β-二甲基丙基氨基)-s-三嗪,2-甲硫基-4-环丙基氨基-6-叔丁基氨基-s-三嗪和2-甲硫基-4-乙氨基-6-(α,β-二甲基丙基氨基)-s-三嗪。
优选的组合物是其中组分(b)是稳定剂和/或成核剂的那些组合物。
稳定剂的例子是以下这些:
1、抗氧化剂
1.1、烷基化一元酚类,例如,2,6-二叔丁基-4-甲基苯酚,2-叔丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚;壬基苯酚类,它是线型的或在支链上支化,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、次烷基双酚类,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,即该酸与一元或多元醇类,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-硫杂十一烷醇(thiaundecanol),3-硫杂(3-thia)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,即该酸与一元或多元醇类,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]辛烷的酯类。
1.15、β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,即该酸与一元或多元醇类,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]辛烷的酯类。
1.16、3.5-二叔丁基-4-羟基苯基乙酸的酯类,即该酸与一元或多元醇类,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)六亚甲基肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)酰肼,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(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-乙基书已氧基)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的酯基转移产物;
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,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-1,3,5-三嗪的线型或环状缩合物,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,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-双取代的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)草酰二酰肼,N,N’-草酰二苯胺,间苯二甲酰二酰肼,癸二酰双(苯基酰肼),N,N′-二乙酰基己二酰二酰肼,N,N′-双(水杨酰基)草酰二酰肼,N,N′-双(水杨酰基)硫代丙酰基二酰肼。
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,二亚膦酸四(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-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,6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-dioxaphosphocin,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-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-dioxaphophirane。
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,从氢化牛油脂肪胺得到的N,N-二烷基羟基胺。
6.硝酮类,例如N-苄基-α-苯基-硝酮,N-乙基-α-甲基-硝酮,N-辛基-α-庚基-硝酮,N-月桂基-α-十一烷基-硝酮,N-十四烷基-α-十三烷基-硝酮,N-十六烷基-α-十五烷基-硝酮,N-十八烷基-α-十七烷基-硝酮,N-十六烷基-α-十七烷基-硝酮,N-十八烷基-α-十五烷基-硝酮,N-十七烷基-α-十七烷基-硝酮,N-十八烷基-α-十六烷基-硝酮,从氢化牛油脂肪胺衍生而来的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、蓖麻醇酸钠和棕榈酸钾,邻苯二酚锑或邻苯二酚锡。
水滑石系列的化合物可由以下通式III表示:
M2+ 1-x·M3+ x·(OH)2·(Ay-)x/y·pH2O (III),
其中
M2+=Mg,Ca,Sr,Zn,Sn和/或Ni,
M3+=Al,B或Bi,
Ay-是具有价态y的阴离子,
y是1-4中的数值,
x是0-0.5中的数值,和
p是0-20中的数值;
其它例子见于DE-A-4106403。
Ay-优选是OH-,Cl-,Br-,l-,ClO4 -,HCO3 -,CH3COO-,C6H5COO-,CO3 2-,SO4 2-,(-OOC-COO-),(CHOHCOO)2 2-,(CHOH)4CH2OHCOO-,C2H4(COO)2 2-,(CH2COO)2 2-,CH3CHOHCOO-,SiO3 2-,SiO4 4-,Fe(CN)6 3-,Fe(CN)6 4-或HPO4 2-。
可以方便使用的其它水滑石是具有通式IIIa的化合物:
M2+ x·Al2·(OH)2x+6yz·(Ay-)2·pH2O (IIIa),
在通式IIIa中M2+是选自Mg和Zn系列的至少一种金属,Mg是优选的,和Ay-是选自例如CO3 2-,(-OOC-COO-),OH-和S2-系列的阴离子,y是阴离子的价态,p是正数,优选0.5-15,以及x和z是正数,x优选是2-6和z小于2。
水滑石系列的优选化合物是具有以下通式III的那些:
M2+ 1-x·M3+ x·(OH)2·(Ay-)x/y·pH2O (III),
其中M2+是Mg或Mg和Zn的固溶体,Ay-是CO3 2-,x是0-0.5中的数,以及p是0-20中的数。
特别优选的水滑石是具有下式的那些
Al2O3·6MgO·CO2·12H2O,
Mg4.5Al2(OH)13·CO3·3.5H2O,
4MgO·Al2O3·CO2·9H2O,
4MgO·Al2O3·CO2·6H2O,
ZnO·3MgO·Al2O3·CO2·8-9H2O或
ZnO·3MgO·Al2O3·CO2·5-6H2O。
该水滑石能够以例如0.1-20,更适宜0.5-10和优选0.5-5重量份的量使用,基于100重量份的合成聚合物。
优选的沸石可从“《沸石结构类型大全》(Atlas of ZeoliteStructure Types)”,W.M.Meier和D.H.Olson,VerlagButterworths,第二版,1986中获知。
在广义上,该沸石还包括具有沸石结构的磷酸铝。
本身已知的优选沸石具有平均有效值3-5埃的孔径并能够通过已知方法制备。特别优选的沸石是属于NaA型的那些,它们具有平均有效值4埃的孔径,这就是为何它们也被称作沸石4A的原因。
特别优选的是结晶的硅铝酸钠,它的粒度至少主要在1-10μ范围内。特别优选的沸石是:Na12Al12Si12O48·27H2O[沸石A],Na6Al6Si6O24·2NaX·7.5H2O,X=OH、卤素、ClO4[钠沸石]Na6Al6Si30O72·24H2O,Na8Al8Si40O96·24H2O,Na16Al16Si24O80·16H2O,Na16Al16Si32O96·16H2O,Na56Al56Si136O384·250H2O,[沸石Y]Na86Al86Si106O384·264H2O[沸石X],或能够通过钠原子被Li、K、Mg、Ca、Sr或Zn原子部分或完全交换所制备的其它沸石,如
(Na,K)10Al10Si22O64·20H2O。
Ca4.5Na3[(AlO2)12(SiO2)12]·30H2O
K9Na3[(AlO2)12(SiO2)12]·27H2O。
该沸石类能够以例如0.1-20,更适宜0.5-10和优选0.5-5重量份的量使用,基于100重量份的合成聚合物。
11.苯并呋喃酮类和吲哚满酮类,例如在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-4,316,611,D.E-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。
有用的组合物是其中组分(b)是选自以下这些的稳定剂的那些组合物:酚类抗氧剂,胺型抗氧化剂,紫外线吸收剂,光稳定剂,金属减活剂,亚磷酸酯,亚膦酸酯,羟胺,硝酮,硫代协合剂,过氧化物清除性化合物,苯并呋喃-2-酮类型的化合物和/或PVC热稳定剂,如Me(II)-羧酸盐,Me(II)表示Ba、Ca、Mg或Zn,优选Ba/Zn-或Ca/Zn-的羧酸盐的混合物。
成核剂的例子描述在R.Gchter和H.Müller,Hanser Verlag,第三版,1990,863-875页中。特别合适的是苯磺酰胺类,双(对-乙基-亚苄基)山梨糖醇,苯甲酸钠,碳酸氢钠,2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸钠,或下式I的化合物:其中R1,R2,R3和R4相互独立地是氢或C1-C4烷基。
含有1-4个碳原子的烷基是支化或无支链的基团,例如甲基,乙基,正-丙基,异丙基,正丁基,异丁基或叔丁基。R1,R2,R3和R4的优选意义中的一个是甲基。
IrgaclearDM和IrgaclearD是Ciba Spezialittenchemie AG的注册商标。Millad3988是Millken的注册商标。
特别有益的是其中成核剂是IrgaclearDM和苯甲酸钠的那些组合物。
阻燃剂的例子描述在R.Gchter和H.Müller,Hanser Verlag,第三版,1990,709-747页。特别优选的阻燃剂选自四苯基-间苯二酚-二亚磷酸酯(FyrolflexRDP,Akzo Nobel),氯烷基-磷酸酯(AntiblazeAB-100,Albright&Wilson;FyrolFR-2,AkzoNobel),多溴化二苯基醚(DE-60F,Great Lakes Corp.),十溴二苯基醚(DBDPO;Saytex102E),三氧化锑(Sb2O3),五氧化二锑(Sb2O5),磷酸三[3-溴-2,2-(溴甲基)丙基]酯(PB370,FMC Corp.),磷酸三苯基酯,双酚A的双(2,3-二溴丙基醚)(PE68),聚磷酸铵(APP)或(HostaflamAP750),低聚间苯二酚-二磷酸酯(RDP),溴化环氧树脂,亚乙基双(四溴苯邻二甲酰亚胺)(BT93),双(六氯环戊二烯)环辛烷(Declorane plus),硫酸钙,氯化石蜡,碳酸镁,磷酸三聚氰胺,焦磷酸三聚氰胺,三氧化钼,氧化锌,1,2-双(三溴苯氧基)乙烷(FF680),四溴双酚A(SaytexRB100),氢氧化镁,三水合铝,硼酸锌,乙二胺二磷酸盐(EDAP),和通式F1的化合物:其中
G1和G2相互独立地是C1-C4烷基或一起是五亚甲基,
E是C1-C18烷氧基,C5-C12环烷氧基,C7-C25芳烷氧基或C6-C12芳氧基,和
Z1和Z2是甲基,或Z1和Z2一起形成了可另外被酯,醚,酰胺,氨基,羧基或尿烷基团取代的环。通式Fl的化合物也称作NOR化合物并公开在WO-A-99/00450中。
具有两亲性质的聚合物分散或溶剂化剂是在同一分子具有极性和非极性基团的聚合物分散或溶剂化剂,它们例如是以聚乙二醇(PEG),聚丙烯酸酯,聚硅氧烷,聚乙酸乙烯酯或含有至少一种基于丙烯酸酯、丙烯酸或甲基丙烯酸酯的嵌段共聚物的嵌段共聚物为基础的分散剂或溶剂化剂。
具有两亲性质的该新型聚合物分散或溶剂化剂在一个聚合物分子中具有至少两种不同的极性。低聚物结构也是可能的。它们通常是共聚物,例如能够通过已知的聚合反应(例如通过自由基或阴离子聚合反应)、通过缩聚反应(如通过端部官能化的低聚物的反应)制备的无规共聚物或嵌段共聚物,或梳形聚合物,该聚合物例如可通过接枝反应来制备。嵌段共聚物例如是二嵌段共聚物(A-B型)或三嵌段共聚物(A-B-A或A-B-C型)和所谓的递变嵌段结构。
二嵌段共聚物(A-B型)是,例如,聚(苯乙烯-b-甲基丙烯酸甲酯),聚(苯乙烯-b-甲基丙烯酸叔丁基酯),聚(苯乙烯-b-丙烯酸甲酯),聚(苯乙烯-b-丙烯酸正丁基酯),聚(苯乙烯-b-丙烯酸叔丁基酯),聚(苯乙烯-b-丁二烯),聚(苯乙烯-b-异戊二烯[1,4-加成]),递变嵌段共聚物聚(苯乙烯-b-丁二烯),递变嵌段共聚物聚(苯乙烯-b-乙烯),聚(苯乙烯-b-2-乙烯基吡啶),聚(苯乙烯-b-4-乙烯基吡啶),聚(苯乙烯-双叔丁基苯乙烯),聚(苯乙烯-b-二甲基硅氧烷),聚(丁二烯-b-二甲基硅氧烷),聚(丁二烯[1,4-加成]-b-甲基丙烯酸甲酯),聚(异戊二烯[1,4-加成]-b-甲基丙烯酸甲酯),聚(丁二烯-b-甲基丙烯酸叔丁基酯),聚(丁二烯-b-丙烯酸叔丁基酯),聚(异戊二烯-b-2-乙烯基吡啶),聚(丁二烯-b-4-乙烯基吡啶),聚(苯乙烯-b-甲基丙烯酸甲酯),聚(甲基丙烯酸甲酯-b-甲基丙烯酸叔丁基酯),聚(甲基丙烯酸甲酯-b-丙烯酸叔丁基酯),聚(丙烯酸叔丁基酯-b-甲基丙烯酸甲酯),聚(丙烯酸正丁基酯-b-甲基丙烯酸甲酯),聚(2-乙烯基吡啶-b-甲基丙烯酸甲酯),聚(甲基丙烯酸叔丁基酯-b-丙烯酸叔丁基酯),聚(甲基丙烯酸叔丁基酯-b-2-乙烯基吡啶),聚(甲基丙烯酸叔丁基酯-b-4-乙烯基吡啶),聚(丙烯酸叔丁基酯-b-2-乙烯基吡啶),聚(2-乙烯基吡啶-b-4-乙烯基吡啶),聚(乙烯-b-甲基丙烯酸甲酯),聚(乙烯-b-2-乙烯基吡啶)或聚(乙烯-b-4-乙烯基吡啶)。
A-B-A型的三嵌段共聚物是,例如,聚(甲基丙烯酸甲酯-b-苯乙烯-b-甲基丙烯酸甲酯),聚(甲基丙烯酸叔丁基酯-b-苯乙烯-b-甲基丙烯酸叔丁基酯),聚(丙烯酸叔丁基酯-b-苯乙烯-b-丙烯酸叔丁基酯),聚(2-乙烯基吡啶-b-苯乙烯-b-丙烯酸叔丁基酯),聚(4-乙烯基吡啶-b-苯乙烯-b-4-乙烯基吡啶),聚(丁二烯[1,2-加成]-b-苯乙烯-b-丁二烯[1,2-加成]),聚(丁二烯[1,4-加成]-b-苯乙烯-b-丁二烯[1,4-加成]),聚(苯乙烯-b-丁二烯[1,4-和1,2-加成]-b-苯乙烯),聚(甲基丙烯酸甲酯-b-丁二烯[1,4-或1,2-加成]-b-甲基丙烯酸甲酯),聚(甲基丙烯酸叔丁基酯-b-甲基丙烯酸甲酯-b-甲基丙烯酸叔丁基酯),聚(丙烯酸叔丁基酯-b-甲基丙烯酸甲酯-b-丙烯酸叔丁基酯),聚(甲基丙烯酸甲酯-b-2-乙烯基吡啶-b-甲基丙烯酸甲酯),聚(4-乙烯基吡啶-b-甲基丙烯酸甲酯-b-4-乙烯基吡啶),聚(甲基丙烯酸甲酯-b-丙烯酸叔丁基酯-b-甲基丙烯酸甲酯),聚(甲基丙烯酸甲酯-b-丙烯酸正丁基酯-b-甲基丙烯酸甲酯),聚(甲基丙烯酸叔丁基酯-b-丙烯酸叔丁基酯-b-甲基丙烯酸叔丁基酯),聚(2-乙烯基吡啶-b-丙烯酸叔丁基酯-b-2-乙烯基吡啶),聚(4-乙烯基吡啶-b-丙烯酸叔丁基酯-b-4-乙烯基吡啶),聚(苯乙烯-b-丙烯酸正丁基酯-b-苯乙烯),聚(苯乙烯-b-丙烯酸乙酯-b-苯乙烯),聚(苯乙烯-b-乙烯-b-苯乙烯),聚(苯乙烯-b-丁烯-b-苯乙烯),聚(环氧乙烷-b-苯乙烯-b-环氧乙烷),聚(苯乙烯-b-环氧乙烷-b-苯乙烯)或聚(苯乙烯-b-丙烯酸-b-苯乙烯)。
A-B-C型的三嵌段共聚物是,例如,聚(苯乙烯-b-丁二烯-b-2-乙烯基吡啶),聚(苯乙烯-b-丁二烯-b-4-乙烯基吡啶),聚(苯乙烯-b-甲基丙烯酸叔丁基酯-b-2-乙烯基吡啶),聚(苯乙烯-b-甲基丙烯酸叔丁基酯-b-4-乙烯基吡啶),聚(苯乙烯-b-2-乙烯基吡啶-b-4-乙烯基吡啶),聚(丁二烯-b-苯乙烯-b-甲基丙烯酸甲酯),聚(苯乙烯-b-丁二烯-b-甲基丙烯酸甲酯),聚(苯乙烯-b-2-乙烯基吡啶-b-环氧乙烷),聚(苯乙烯-b-丙烯酸叔丁基酯-b-甲基丙烯酸甲酯),聚(苯乙烯-b-丙烯酸-b-甲基丙烯酸甲酯),聚(苯乙烯-b-α-甲基苯乙烯-b-甲基丙烯酸甲酯)或聚(苯乙烯-b-α-甲基苯乙烯-b-丙烯酸叔丁基酯)。
特别优选的长链嵌段共聚物具有超过10碳原子,优选C12~C16个碳原子的链长。
具有两亲性质的特别合适的分散或溶剂化剂是,例如,聚(丁二烯-甲基丙烯酸甲酯),聚(异戊二烯-甲基丙烯酸甲酯),聚(乙烯-甲基丙烯酸甲酯),聚(苯乙烯-4-乙烯基吡啶),聚(苯乙烯-2-乙烯基吡啶),聚(苯乙烯-丙烯酸正丁基酯),聚(苯乙烯-丙烯酸叔丁基酯),聚(苯乙烯-丙烯酸钠),聚(苯乙烯-丙烯酸),聚(甲基丙烯酸甲酯-丙烯酸钠),聚(甲基丙烯酸甲酯-甲基丙烯酸钠),聚(环氧乙烷-ε-己内酯),聚(2-乙烯基吡啶-环氧乙烷),聚(丁二烯-环氧乙烷),聚(丁二烯-丙烯酸钠),聚(乙烯-环氧乙烷),聚(乙烯-环氧丙烷),聚(苯乙烯-丙烯酸乙酯-苯乙烯),聚(环氧乙烷-苯乙烯-环氧乙烷),聚(苯乙烯-丙烯酸-苯乙烯),聚(苯乙烯-丁二烯-甲基丙烯酸甲酯),聚(苯乙烯-乙烯基吡啶-环氧乙烷),聚(苯乙烯-4-乙烯基苯甲酸),聚(苯乙烯-甲基丙烯酸多缩水甘油基酯),聚(乙烯-甲基丙烯酸缩水甘油酯),聚(丙烯-丙烯酸),聚(乙烯-丙烯酸),聚(丙烯-马来酸酐),聚(乙烯-马来酸酐),聚(苯乙烯-马来酸酐),聚甲基丙烯酸-聚烯化氧嵌段共聚物,例如根据EP-A-0859028,聚硅氧烷-聚氧化烯,马来酸酯和苯乙烯或苯乙烯衍生物的共聚物,例如根据EP-A-0791024,聚苯乙烯-聚硅氧烷嵌段共聚物,聚丙烯酸酯-聚硅氧烷嵌段共聚物和环状硅氧烷-星形(radiale)共聚物,例如根据EP-A-0870774使用ATRP技术制得,丙烯酸甲酯-苯乙烯共聚物,甲基丙烯酸甲酯-苯乙烯其聚物,聚丁二烯-丙烯酸甲酯,根据EP-A-0135280通过硝酰基引发的自由基聚合反应制得。
该聚烯化氧优选是聚氧化乙烯,聚氧化丙烯和聚氧化丁烯。
合适的嵌段共聚物是,例如,聚丙烯酸酯/聚苯乙烯,聚甲基丙烯酸酯/聚氧化乙烯,聚丙烯酸酯/聚氧化乙烯,聚丙烯酸酯/聚乙烯,聚醋酸乙烯酯/聚乙烯,聚苯乙烯/聚丁二烯,聚丙烯酸酯/聚丁二烯,聚丙烯酸酯/聚异戊二烯,聚异戊二烯/聚甲基丙烯酸甲酯,聚乙烯/聚甲基丙烯酸甲酯,聚乙烯/聚氧化乙烯或聚乙烯/聚氧化丙烯。
具有两亲性质的特别合适的分散或溶剂化剂是,例如,聚(苯乙烯-bis-丙烯酸钠),聚(苯乙烯-bis-丙烯酸),聚(苯乙烯-bis-甲基丙烯酸钠),聚(苯乙烯-bis-N-甲基-4-乙烯基吡啶鎓碘化物),聚(异戊二烯-bis-N-甲基-2-乙烯基哌啶鎓碘化物),聚(苯乙烯-bis-环氧乙烷),聚(甲基丙烯酸甲酯-bis-丙烯酸钠),聚(甲基丙烯酸甲酯-bis-甲基丙烯酸钠),聚(甲基丙烯酸甲酯-bis-环氧乙烷),聚(甲基丙烯酸叔丁基酯-bis-环氧乙烷),聚(甲基丙烯酸甲酯-bis-N-甲基-4-乙烯基吡啶鎓碘化物),聚(环氧乙烷-bis-乳酸酯),聚(2-乙烯基吡啶-bis-环氧乙烷),聚(丁二烯-bis-丙烯酸钠),聚(丁二烯-bis-甲基丙烯酸钠),聚(丁二烯-bis-N-甲基-4-乙烯基吡啶鎓碘化物),聚(丁二烯-bis-环氧乙烷),聚(乙烯-bis-环氧乙烷)或聚(乙烯-bis-环氧丙烷)。
含有长链侧基的特别优选的聚硅氧烷尤其公开于US-5,387,467中。
基于聚丙烯酸酯的其它同样优选的分散或溶剂化剂尤其描述在US-5,133,898中。
基于丙烯酸酯的特别优选的分散或溶剂化剂例如是Th.Goldschmidt AG,德国的TegomerDA100,TegomerDA102或WaxP121,
特别优选的是其中组分(c)是基于含有长链侧基的聚丙烯酸酯或聚硅氧烷的分散或溶剂化剂的组合物。
组分(b)和(c)的共混物适于稳定所述合成聚合物(尤其是热塑性聚合物,例如聚烯烃类和聚苯乙烯)来抵抗氧化、热或光-诱发的降解。
合成聚合物的例子是:
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),线型低密度聚乙烯(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合物,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。活化剂可以方便地另外用酯,醚,胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为Phillips,Standard Oil Indiana,齐格勒(-纳塔),TNZ(杜邦),金属茂或单点催化剂(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、单烯烃和二烯烃彼此的共聚物,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,线型低密度聚乙烯(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、二聚环戊二烯或亚乙基一降冰片烯的三元共聚物;和此类共聚物相互之间的混合物和与以上1)项中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或无规聚烯/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与另一种聚合物如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元共聚物的混合物;以及苯乙烯的嵌段共聚物,如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
7、苯乙烯或α-甲基苯乙烯的接枝共聚物,例如聚丁二烯上接枝苯乙烯;聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上接枝苯乙烯;聚丁二烯上接枝苯乙烯和丙烯腈(或甲基丙烯腈);聚丁二烯上接枝苯乙烯、丙烯腈和甲基丙烯酸甲酯;聚丁二烯上接枝苯乙烯和马来酸酐;聚丁二烯上接枝苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;聚丁二烯上接枝苯乙烯和马来酰亚胺;聚丁二烯上接枝苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯;乙烯/丙烯/二烯烃三元共聚物上接枝苯乙烯和丙烯腈;聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上接枝苯乙烯和丙烯腈;丙烯酸酯/丁二烯共聚物上接枝苯乙烯和丙烯腈,以及它们与6)项所列举的共聚物的混合物,例如已知为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8、含卤素的聚合物类,如聚氯丁二烯,氯化橡胶,异丁烯-异戊二烯的氯化和溴化共聚物(卤化丁基橡胶),氯化或氯磺化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均-和共聚物,尤其含卤素的乙烯基化合物的聚合物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯、以及它们的共聚物,如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。
9、从α,β-不饱和羧酸和其衍生物得到的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯,用丙烯酸丁酯进行冲击改性的聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈。
10、在9)项中提到的单体相互之间的或与其它不饱和单体的共聚物,例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/卤代乙烯共聚物,或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11、从不饱和醇类和胺类或酰基衍生物或其缩醛类得到的聚合物,例如聚乙烯醇,聚乙酸乙烯酯,聚硬脂酸乙烯酯,聚苯甲酸乙烯酯,聚马来酸乙烯酯,聚乙烯醇缩丁醛,聚邻苯二甲酸烯丙酯或聚烯丙基蜜胺,以及它们与以上1)项中提到的烯烃的共聚物。
12、环醚的均聚物和共聚物,如聚亚烷基二醇,聚环氧乙烷,聚环氧丙烷或它们与双缩水甘油基醚的共聚物。
13、聚缩醛类,如聚甲醛和含有环氧乙烷作为共聚单体的那些聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛类。
14、聚苯醚和聚苯硫醚,聚苯醚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/和对苯二甲酸在有或没有高弹体作为改性剂而制备的聚酰胺,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、聚亚烷基萘二甲酸酯(PAN)和聚羟基苯甲酸酯,以及从羟基封端的聚醚衍生而来的嵌段共聚酯;还有用聚碳酸酯或MBS改性的聚酯类。
19、聚碳酸酯和聚酯-碳酸酯。
20、聚砜,聚醚-砜和聚醚-酮。
21、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、干性和非干性醇酸树脂。
23、从饱和的和不饱和的二羧酸与多元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、从取代的丙烯酸酯衍生而来的可交联丙烯酸树脂,例如环氧丙烯酸酯,聚氨酯丙烯酸酯或聚酯丙烯酸酯。
25、用蜜胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、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、脂环族、杂环族或芳族缩水甘油基化合物衍生而来的交联环氧树脂,例如双酚A和双酚F的二缩水甘油醚的产物,它们用常规的硬化剂如酸酐或胺类加以交联,有或没有促进剂。
27、天然聚合物,如纤维素、橡胶、明胶和它们的化学改性的同源(homologous)衍生物,例如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚类,如甲基纤维素;以及松香和它的衍生物。
28、上述聚合物的共混物(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/PA6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。
合成聚合物的优选组是含卤素的聚合物类。它们优选是含氯的聚合物,例如氯乙烯的聚合物,在其结构中含有氯乙烯单元的乙烯基树脂,氯乙烯的共聚物,和脂族酸的乙烯基酯,尤其乙酸乙烯酯,氯乙烯与丙烯酸和甲基丙烯酸的酯类和与丙烯腈的共聚物,氯乙烯与二烯烃化合物和不饱和二羧酸或它们的酸酐的共聚物,氯乙烯与马来酸二乙基酯、富马酸二乙基酯或马来酸酐的共聚物,氯乙烯的后氯化聚合物和共聚物,氯乙烯和偏二氯乙烯与不饱和醛类、酮类等(如丙烯醛,巴豆醛,乙烯基·甲基(甲)酮,乙烯基·甲基醚,乙烯基·异丁基醚和类似化合物)的共聚物,偏二氯乙烯的聚合物和它与氯乙烯及其它可聚合化合物的共聚物,氯乙酸乙烯基酯和二氯二乙烯基醚的聚合物,乙酸乙烯酯的氯化聚合物,丙烯酸和α-取代丙烯酸的氯化聚合物酯类,氯化苯乙烯(例如二氯苯乙烯)的聚合物,氯化橡胶,乙烯的氯化聚合物,氯丁二烯的聚合物和后氯化聚合物和它们与氯乙烯的共聚物,氢氯化橡胶和氯化氢氯化橡胶,和以上列举的聚合物相互之间的共混物或与其它可聚合化合物的共混物。
还包括在内的是PVC与EVA、ABS和MBS的接枝聚合物。优选的基底也可以是以上列举的均聚-和共聚物(尤其氯乙烯均聚物)与其它热塑性塑料或/和弹性聚合物的共混物,尤其与ABS、MBS、NBR、SAN、EVA、CPE、MBAS、PMA、PMMA、EPDM和聚内酯的共混物。
其它优选的聚合物是悬浮和本体法聚合物,和乳液法聚合物。
含氯聚合物特别优选是聚氯乙烯,尤其悬浮法聚合物和本体法聚合物。
该含氯聚合物优选不含有任何增塑剂。
优选使用含有至少一种无机锌化合物如氧化锌、氢氧化锌、氯化锌、硫化锌或超碱性锌氧化物/氢氧化物加成化合物,或以下各系列的有机锌化合物的如上所述的稳定化含卤素聚合物:脂族饱和C2-C22羧酸盐,脂族不饱和C3-C22羧酸盐,脂族C2-C22羧酸盐,它们可被至少一个OH基团取代或在链中插入至少一个O原子(氧杂酸),含有5-22个碳原子的环状和双环羧酸盐,未被取代或被至少一个OH基团取代和/或被C1-C16烷基取代的苯基羧酸盐,未被取代或被至少一个OH基团取代和/或被C1-C16烷基取代的萘基羧酸盐,苯基-C16-C16烷基羧酸盐,萘基-C1-C16烷基羧酸盐或可被C1-C12烷基取代的酚盐。
可以列举的例子名称是一元羧酸的锌盐,如乙酸,丙酸,丁酸,戊酸,己酸,庚酸,辛酸,新癸酸,2-乙基己酸,壬酸,癸酸,十一烷酸,十二烷酸,十三烷酸,十四烷酸,棕榈酸,异硬脂酸,硬脂酸,12-羟基硬脂酸,9,10-二羟硬脂酸,3,6-二氧杂庚酸,3,6,9-三氧杂癸酸,山萮酸,苯甲酸,对-叔丁基苯甲酸,二甲基羟基苯甲酸,3,5-二叔丁基-4-羟基苯甲酸,甲基苯甲酸,二甲基苯甲酸,乙基苯甲酸,正丙基苯甲酸,水杨酸,对-叔辛基水杨酸和山梨酸;二元羧酸的单酯的锌盐,如草酸,丙二酸,丁二酸,戊二酸,己二酸,富马酸,戊烷-1,5-二羧酸,己烷-1,6-二羧酸,庚烷-1,7-二羧酸,辛烷-1,8-二羧酸,3,6,9-三氧杂癸烷-1,10-二羧酸,聚乙二醇二羧酸(n=10-12),邻苯二甲酸,间苯二酸,对苯二甲酸和羟基邻苯二甲酸;以及三元或四元羧酸的二-或三-酯的锌盐,如苯连三酸,偏苯三酸,苯均四酸,柠檬酸,和单-和二-酯化磷酸或单酯化亚磷酸的锌盐,如在JP3,275,570中所述。
特别优选的是含有7-18个碳原子的羧酸的有机锌羧酸盐(锌皂),例如苯甲酸盐或烷羧酸盐,优选硬脂酸盐,油酸盐,月桂酸盐,棕榈酸盐,山萮酸盐,羟基硬脂酸盐,二羟基硬脂酸盐或(异)辛酸盐。硬脂酸盐,油酸盐,苯甲酸盐,和2-乙基己酸盐是特别优选的。
除了列举的锌化合物外的其它合适化合物还可以是无机或有机铝化合物,以上对于锌化合物给出的说明对它们同样适用。对于可用的和优选的铝化合物的其它细节见于US4,060,512。
除了以上列举的锌化合物之外的其它合适化合物还可以是无机或有机稀土化合物,以上对于锌化合物给出的说明同样适用于它们。该术语稀土元素化合物被理解为指元素铈,镨,钕,钐,铕,钆,铽,镝,钬,铒,铥,镱,镥、镧和钇的化合物,与铈形成的混合物是特别优选的。其它优选的稀土化合物见于EP-A-0108023。
如果合适的话,有可能使用具有不同结构的锌,铝,镧或镧系元素化合物的混合物。还有可能将有机锌,铝,镧或镧系元素化合物涂敷到水滑石,沸石或片钠铝石上;参见DE-A-4031818。
根据本发明加以稳定化的PVC可含有附加的添加剂。这些附加的添加剂是,例如,无机或有机的钙或镁化合物,沸石类,水滑石,片钠铝石,天然水玻璃,水羟硅钠石,canemite,1,3-二酮化合物,多元醇,含氮的化合物,例如β-氨基巴豆酸酯,如在EP-A-0465405的6页9-14行中提及的;α-苯基吲哚,吡咯,空间位阻胺类(HALS),二氢吡啶和它们的聚合物,高氯酸盐,环氧化物,酚类抗氧剂,环烷烃,硫代磷酸盐,增塑剂,填料和增强剂,如碳酸钙,氧化镁,氢氧化镁,硅酸盐,玻璃纤维,滑石,高岭土,白垩,云母,金属氧化物和金属氢氧化物,炭黑或石墨;亚磷酸酯,多价螯合剂,光稳定剂,紫外线吸收剂,润滑剂,耐冲击性改进剂和加工助剂,脂肪酸酯,链烷烃,起泡剂,萤光增白剂,胶凝剂,着色剂,颜料,防烟剂,抗静电剂,防雾剂,生物杀伤剂,硫代二丙酸和它们的酯类,二烷基二硫化物,巯基羧酸盐,过氧化物清除化合物,改性剂和路易斯酸的其它络合物形成体。
优选的合成聚合物也可以是聚烯烃和聚苯乙烯,尤其聚乙烯或聚丙烯。
需要重点强调的是组分(b)和(c)的共混物在抵抗聚烯烃的氧化和热降解(当热塑性塑料被加工和使用时会遇到)上的好效果。本发明的组分(b)和(c)因此特别适合用作长期的热稳定剂。
组分(b)优选以0.01-10%,例如0.01-5%,优选0.025-3%,特别优选0.025-1%的量加入到需要稳定的合成聚合物中,基于需要稳定的合成聚合物的重量。
组分(c)用来以0.005-10%,优选0.01-5%,例如0.02-1%的量加入到需要稳定的合成聚合物中,基于需要稳定的合成聚合物的重量。
除了组分(b)和(c)外,该新型组合物还可含有其它助稳定剂(添加剂),例如填料和增强剂,增塑剂,润滑剂,乳化剂,颜料,流变助剂,催化剂,流动调节剂,萤光增白剂,阻燃剂或起泡剂。
填料和增强剂是,例如,碳酸钙,硅酸盐,玻璃纤维,玻璃珠,滑石,高岭土,云母,硫酸钡,金属氧化物和金属氢氧化物,炭黑,石墨,木屑,其它天然产品的粉料或纤维,或合成纤维。
特别适宜的组合物是除了包含组分(a)、(b)和(c)之外还包含填料,尤其滑石、高岭土、云母或碳酸钙作为其它添加剂的那些组合物。
该填料和增强剂,如滑石、碳酸钙或高岭土,以例如0.01-40%的浓度加入到聚烯烃中,基于需要稳定的聚烯烃的总重量。
在该新型组合物中其它有益的附加添加剂也可以是高级脂肪酸的碱土金属盐,如硬脂酸钙或乳酸的碱土金属盐,例如乳酸钙或硬脂酰-2-乳酸钙。
该组分(b)和(c)和其它任选的添加剂可通过已知的方法,例如在挤塑或模塑之前或过程中,被引入到合成聚合物中,或者,也可通过将溶解或分散的稳定剂共混物施涂到合成聚合物中,如果需要的话随后进行溶剂的蒸发,来引入其中。组分(b)和(c)和其它任选添加剂的添加剂共混物也能够以含有它们的母料,例如以2.5-25wt%的浓度形式加入到需要稳定的聚合物中。
组分(b)和(c)和其它任选添加剂的添加剂共混物也能够在聚合之前或过程中或在交联之前添加。
组分(b)和(c)和其它任选添加剂的添加剂共混物能够以纯净形式或包封在蜡、油或聚合物中的形式被引入到需要稳定的合成聚合物中。
组分(b)和(c)和其它任选添加剂的添加剂共混物也能够喷涂到需要稳定的合成聚合物上。这一共混物能够稀释其它添加剂(例如上述标准添加剂)或它们的熔体,以使它还可以与那些添加剂一起喷涂到需要稳定的合成聚合物上。在聚合催化剂的减活过程中喷涂法添加是特别理想的,例如有可能使用减活用的蒸汽来喷射。
对于球形的聚合的聚烯烃,例如理想的是通过喷涂到组分(b)和(c)上来施涂添加剂共混物,任选与其它添加剂一起喷涂。
如此被稳定的合成聚合物能够以许多形式使用,例如作为箔,纤维,单丝,模塑组合物,异型材或作为涂料体系(尤其粉末涂料组合物、粘合剂或油灰)的粘结剂。
以这种方式稳定的聚烯烃类也能够以许多形式使用,尤其作为与萃取介质永久接触的厚涂层聚烯烃模塑制品,例如液体或气体用的管,箔,纤维,地质处理用膜,单丝,异型材或罐。
优选的厚涂层聚烯烃模塑制品具有1-50mm,优选1-30mm、例如2-1Omm的涂层厚度。
因此,本发明的优选实施方案是使用组分(c)来改进选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂的添加剂在合成聚合物中的分散作用、尤其溶解或相容性增强上的用途。
本发明的另一优选实施方案也是使用组分(b)和(c)的添加剂共混物来稳定合成聚合物以抵抗氧化、热或光诱发降解的用途,限制条件是组分(b)含有稳定剂组中的至少一种化合物。
本发明还涉及添加剂共混物,它包括(α)至少一种选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂的稳定剂,和(β)具有两亲性质的至少一种聚合物分散或溶剂化剂。
还优选的是其中组分(α)∶(β)的重量比是100∶0.01到0.01∶100的添加剂共混物。
本发明还涉及改进选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的添加剂在合成聚合物中的分散作用的方法,该方法包括在其中引入或在向其施加具有两亲性质的至少一种聚合物分散或溶剂化剂。
本发明还涉及稳定合成聚合物以抵抗氧化、热或光诱发降解的方法,它包括在其中引入或向其施加组分(b)和(c)各自至少一种,限制条件是组分(b)含有选自稳定剂组的至少一种化合物。
优选用于以上公开的用途和方法中的组分(b)和(c)与对于含有合成聚合物的组合物所描述的那些相同。
下面实施例用于更详细地说明本发明。份或百分数是按重量计。
实施例1:利用具有两亲性质的聚合物分散或溶剂化剂增强成核剂在聚丙烯中的效果。
1.5kg聚丙烯粉料(Profax6501,Montell)在高速混合机中与0.10%Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05%Irganox1010[四-[3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];0.10%的硬脂酸钙和与表1中列出的添加剂(成核剂和分散或溶剂化剂)混合均匀,这一共混物然后在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。利用注塑机(Arburg320S)在最高250℃的温度下从这些粒料模塑加工80×90mm和2mm厚的试验板。根据Euro-norm(EN)ISO527-1测量这些试验板的E-模量(兆帕(Mpa))、雾度(%)和透明度。E-模量和透明度的值越高,添加剂在聚丙烯中的分散越好和聚丙烯的透明度的越高。雾度的值的越小,添加剂在聚丙烯中的分散越好。
表1:
实施例 | 添加剂 | E-模量(MPa) | 雾度(%) | 透明度(%) |
实施例1aa) | 0.10%IrgaclearDMc) | 1517 | 70.6 | 82.5 |
实施例1ba) | 0.20%Wax P121d) | 1550 | 89.2 | 12.0 |
实施例1ca) | 0.20%TegomerDA100e) | 1520 | 87.8 | 12.0 |
实施例1db) | 0.10%IrgaclearDMc)0.20%Wax P121d) | 1552 | 57.5 | 89.4 |
实施例1eb) | 0.10%IrgaclearDMc)0.20%TegomerDA100e) | 1571 | 53.7 | 89.6 |
脚注a)-e)参见表8(实施例8)的末尾。
实施例2:利用具有两亲性质的聚合物分散或溶剂化剂增强聚丙烯的长期温度稳定性。
1.5kg聚丙烯粉料(Profax6501,Montell)在高速混合机中与0.10%Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05%Irganox1010[四-[3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];0.10%的硬脂酸钙和与表2申列出的添加剂(分散或溶剂化剂)混合均匀,这一共混物然后在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高250℃的温度下从这些粒料模塑加工80×90mm和2mm厚的试验板。这些板的一部分在循环空气烘箱中在135℃下经受人工加速老化试验和其它部分在150℃下进行。测量这些板变脆的时间(天)。时间越长,添加剂的效果越大。结果总结在表2中。
表2:
实施例 | 添加剂 | 到脆裂时的天数 | |
在135℃ | 在150℃ | ||
实施例2aa) | —— | 45 | 14 |
实施例2bb) | 1.00%Wax P121d) | >70 | 31 |
实施例2cb) | 1.00%TegomerDA100e) | >70 | 27 |
实施例2db) | 1.00%TegomerDA102f) | >70 | 31 |
脚注a),b),d),e)和f)参见表8的末尾(实施例8)。
实施例3:具有两亲性质的聚合物分散或溶剂化剂对用滑石填充的聚丙烯的长期温度稳定性的效果。
1.5kg聚丙烯粉料(Profax6501,Montell)在高速混合机中与0.10%Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05%Irganox1010[四-[3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];20%的滑石和0.10%硬脂酸钙和与表3中列出的添加剂(分散或溶剂化剂)混合均匀,这一共混物然后在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高250℃的温度下从这些粒料模塑加工80×90mm和2mm厚的试验板。这些板的一部分在循环空气烘箱中在135℃下经受人工加速老化试验和其它部分在150℃下进行。测量这些板变脆的时间(天)。时间越长,添加剂的效果越大。结果总结在表3中。
表3:
实施例 | 添加剂 | 到脆裂时的天数 | |
在135℃ | 在150℃ | ||
实施例3aa) | —— | 7 | 2 |
实施例3bb) | 3.0%Wax P121d) | 52 | 20 |
实施例3cb) | 3.0%TegomerDA102f) | 59 | 26 |
脚注a),b),d)和f)参见表8的末尾(实施例8)。
实施例4:具有两亲性质的聚合物分散或溶剂化剂对聚丙烯的长期温度稳定性的效果。
1.5kg聚丙烯粉末(PP PolychimB10FB,Polychimie,法国)在高速混合机中与0.10%IrganoxHP225(Ciba SpezialittenchemieAG,由42.5%的Irgafos168[亚磷酸(2,4-二叔丁基苯基)酯],42.5%的Irganox1010[四-[3-(3,5-二叔丁基-4-羟基苯基)丙酸季戊四醇酯]和15%的HP-136[约85重量份3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮和约15重量份3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮的混合物,结构式参见在表8的末尾的脚注g)]组成)和0.05%的DHT4A(Kyowa Chemical Industry Co.,Ltd.[Mg4.5Al2(OH)13CO3·3.5H2O])和与表4中列出的添加剂(分散或溶剂化剂)混合均匀,这一共混物然后在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高220℃的温度下从这些粒料模塑加工80×90mm和2mm厚的试验板。试验板在50℃和95%相对湿度下在条件调节室中贮存30天。根据ASTM D1925-70测定这些试验板的黄度指数(YI)。低YI值表示轻微的变色,高的YI值表示样品的强烈变色。变色越少,稳定剂或稳定剂共混物的效果越高。结果总结在表4中。
表4:
实施例 | 添加剂 | 黄度指数 | |
贮存前 | 贮存后(30天/50℃) | ||
实施例4aa) | —— | 3.01 | 4.48 |
实施例4bb) | 0.02%TegomerDA102f) | 0.42 | 1.89 |
实施例4cb) | 0.01%TegomerDA102f)0.01%Irganox1310h) | 0.29 | 1.90 |
脚注a),b),f)和h)参见表8的末尾(实施例8)。
实施例5:具有两亲性质的聚合物分散或溶剂化剂对聚丙烯的长期温度稳定性的效果。
用0.10%硬脂酸钙代替0.05%的DHT4A(Kyowa ChemicalIndustry Co.,Ltd.[Mg4.5Al2(OH)13CO3·3.5H2O]),按照与实施例4中类似的方法获得了总结在表5中的结果。
表5:
实施例 | 添加剂 | 黄度指数 | |
贮存前 | 贮存后(30天/50℃) | ||
实施例5aa) | —— | -0.14 | 3.62 |
实施例5bb) | 0.05%TegomerDA102f) | 0.07 | 1.72 |
脚注a),b)和f)参见表8的末尾(实施例8)。
实施例6:具有两亲性质的聚合物分散或溶剂化剂对用滑石和炭黑填充的聚丙烯的光泽的作用。
1.5kg聚丙烯粉料(DaplenKS10,Borealis,Hinz,奥地利,含有20%的滑石和1%炭黑)在高速混合机中与0.10%的Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05%的Irganox1010[四-[3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];0.20%的Chimassorb2020[Ciba Speziealittenchemie AG,结构式参见表8的末尾的脚注i)]和与表6中列出的添加剂(分散或溶剂化剂)混合均匀,这一共混物然后在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高250℃的温度下从这些粒料模塑加工40×60mm和2mm厚的试验板。试验板在Atlas天候老化仪Ci65A中在63℃的黑板温度下不喷射水来经受人工老化试验。在每过1000小时后,取样进行表面测量。根据DIN67530测定样品的光泽。百分数值越高,添加剂的效果越好。结果总结在表6中
表6:
实施例 | 添加剂 | 在x个小时人工老化之后的光泽,% | ||
0h | 1000h | 2000h | ||
实施例6aa) | —— | 49 | 45 | 35 |
实施例6bb) | 0.10%TegomerDA102f) | 56 | 51 | 49 |
脚注a),b)和f)参见表8的末尾(实施例8)。
实施例7:利用具有两亲性质的聚合物分散或溶剂化剂增强用滑石和炭黑填充的聚丙烯的长期温度稳定性。
1.5kg聚丙烯粉料(DaplenKS10,Borealis,Linz,奥地利,含有20%的滑石和1%炭黑)在高速混合机中与0.10%的Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05的Irganox1010[四-(3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];0.10%的IrganoxPS802[硫代二丙酸二硬脂基酯],0.20%的Chimassorb2020[CibaSpezialittenchemie AG,结构式参见表8的末尾的脚注i)]和与表7中列出的添加剂(分散或溶剂化剂)混合均匀,然后这一共混物在Berstorff的双螺杆挤出机中在最高250℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高250℃的温度下从这些粒料模塑加工80×90mm和2mm厚的试验板。这些试验板在循环空气烘箱中在150℃下经受人工老化试验。测量这些板变脆的时间(天)。时间越长,添加剂的效果越大。结果列于表7中。
表7:
实施例 | 添加剂 | 在150℃下直至变脆的天数 |
实施例7aa) | —— | 24 |
实施例7bb) | 0.10%TegomerDA102f) | 32 |
脚注a),b)和f)参见表8的末尾(实施例8)。
实施例8:具有两亲性质的聚合物分散或溶剂化剂对低密度线型聚乙烯(LLDPE)的光泽的作用。
1.5kg的LLDPE(LE8001,Borealis,Linz,奥地利)与0.05%的Irgafos168[亚磷酸三(2,4-二叔丁基苯基)酯],0.05%的Irganox1010[四-[3-(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯];和与表8中列出的添加剂(分散或溶剂化剂)混合均匀,然后这一共混物在Collin(德国)的单螺杆挤出机中在最高230℃的温度下挤出。在将挤出物拉伸通过水浴冷却之后,将其造粒。然后利用注塑机(Arburg320S)在最高230℃的温度下从这些粒料模塑加工40×60mm和2mm厚的试验板。这些试验板在Atlas天候老化仪Ci65A中在100℃的黑板温度下不喷射水来经受人工老化试验。在38天后根据DIN67530测定样品的光泽。百分数值越高,添加剂的效果越好。结果总结在表8中。
表8:
实施例 | 添加剂 | 在38天人工老化试验后的光泽,% |
实施例8aa) | —— | 20 |
实施例8bb) | 0.05%TegomerDA102f) | 58 |
a)对比实施例。
b)本发明的实施例。
c)IrgaclearDM(Ciba Spezialittenchemie AG)是成核剂并表示结构式Ia的(1.3:2.4)-二对甲基二苄叉基山梨糖醇。
d)Wax P121(Th.Goldschmidt AG,德国)是含有TegomerDA100e)的分散剂蜡。
e)TegomerDA100(Th.Goldschmidt AG,德国)是丙烯酸酯型聚合物分散或溶剂化剂。
f)TegomerDA102(Th.Goldschmidt AG,德国)是丙烯酸酯型聚合物分散或溶剂化剂。
g)HP136(Ciba Spezialittenchemie AG)是大约85重量份的结构式Va的化合物和大约15重量份的结构式Vb的化合物的混合物。h)Irganox1310(Ciba Spezialittenchemie AG)是结构式AO-1的化合物
Claims (19)
1.一种组合物,它包含
a)易遭受氧化、热或光诱发的降解的合成聚合物,
b)选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的至少一种添加剂,和
c)具有两亲性质的至少一种聚合物分散或溶剂化剂。
2.根据权利要求1的组合物,其中组分(a)是聚烯烃或聚苯乙烯。
3.根据权利要求1的组合物,其中组分(a)是聚乙烯或聚丙烯。
4.根据权利要求1的组合物,其中组分(b)是稳定剂和/或成核剂。
5.根据权利要求4的组合物,其中该稳定剂是酚类抗氧化剂、胺型抗氧化剂、紫外线吸收剂、光稳定剂、金属减活剂、亚磷酸酯、亚膦酸酯、羟胺、硝酮、硫代协合剂、过氧化物清除化合物、苯并呋喃-2-酮型的化合物和/或PVC热稳定剂。
6.根据权利要求4的组合物,其中该成核剂是通式I的化合物:其中R1、R2、R3和R4各自独立地是氢或C1-C4烷基。
7.根据权利要求1的组合物,其中组分(c)是以聚丙烯酸酯、聚硅氧烷、聚乙酸乙烯酯为基础或以含有至少一个基于丙烯酸酯、丙烯酸或甲基丙烯酸酯的嵌段的嵌段共聚物为基础的分散或溶剂化剂。
8.根据权利要求1的组合物,其中组分(c)是基于含有长链侧基团的聚丙烯酸酯类或聚硅氧烷的分散或溶剂化剂。
9.根据权利要求1的组合物,其中组分(b)以基于组分(a)的重量的0.01-10%的量存在。
10.根据权利要求1的组合物,其中组分(c)以基于组分(a)的重量的0.01-10%的量存在。
11.根据权利要求1的组合物,其中还存在除了组分(a)、(b)和(c)之外的附加添加剂。
12.根据权利要求11的组合物,其中附加添加剂是填料。
13.根据权利要求12的组合物,其中填料是滑石、高岭土、云母或碳酸钙。
14.添加剂共混物,它包含
α)选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的至少一种添加剂,和
β)具有两亲性质的至少一种聚合物分散或溶剂化剂。
15.根据权利要求14的添加剂共混物,其中组分(α)∶(β)的重量比是100∶0.01到0.01∶100。
16.改进选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的添加剂在合成聚合物中的分散的方法,该方法包括在其中引入或向其施加根据权利要求1的至少一种组分(c)。
17.稳定合成聚合物以抵抗氧化、热或光诱发的降解的方法,它包括在其中引入或向其施加根据权利要求1的组分(b)和(c)各自的至少一种,限制条件是组分(b)含有选自稳定剂组的至少一种化合物。
18.根据权利要求1的组分(c)用于改进选自稳定剂、抗静电剂、成核剂、生物杀伤剂和/或阻燃剂组的添加剂在合成聚合物中的分散的用途。
19.根据权利要求1的组分(b)和(c)的共混物作为稳定剂用于稳定合成聚合物以抵抗氧化、热或光诱发的降解的用途,限制条件是组分(b)含有稳定剂组中的至少一种化合物。
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JP (1) | JP2002534574A (zh) |
KR (1) | KR100611554B1 (zh) |
CN (1) | CN1165585C (zh) |
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- 2000-01-04 KR KR1020017008419A patent/KR100611554B1/ko not_active IP Right Cessation
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- 2000-01-04 ES ES00901499T patent/ES2215605T3/es not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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DE60009036D1 (de) | 2004-04-22 |
ATE262010T1 (de) | 2004-04-15 |
US6610765B1 (en) | 2003-08-26 |
BR0007415A (pt) | 2001-10-16 |
MY124060A (en) | 2006-06-30 |
CN1165585C (zh) | 2004-09-08 |
EP1149133B1 (en) | 2004-03-17 |
NO20013415L (no) | 2001-09-06 |
KR100611554B1 (ko) | 2006-08-10 |
DE60009036T2 (de) | 2004-07-29 |
WO2000042109A2 (en) | 2000-07-20 |
NO20013415D0 (no) | 2001-07-10 |
CZ20012462A3 (cs) | 2001-11-14 |
ES2215605T3 (es) | 2004-10-16 |
KR20010101350A (ko) | 2001-11-14 |
JP2002534574A (ja) | 2002-10-15 |
EP1149133A2 (en) | 2001-10-31 |
CA2355824C (en) | 2008-12-23 |
TW555795B (en) | 2003-10-01 |
RU2251562C2 (ru) | 2005-05-10 |
AU767538B2 (en) | 2003-11-13 |
AU2287400A (en) | 2000-08-01 |
CA2355824A1 (en) | 2000-07-20 |
WO2000042109A3 (en) | 2000-11-16 |
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