CN1224732A - 聚酰胺、聚酯和聚缩醛的稳定处理 - Google Patents
聚酰胺、聚酯和聚缩醛的稳定处理 Download PDFInfo
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- CN1224732A CN1224732A CN 98122394 CN98122394A CN1224732A CN 1224732 A CN1224732 A CN 1224732A CN 98122394 CN98122394 CN 98122394 CN 98122394 A CN98122394 A CN 98122394A CN 1224732 A CN1224732 A CN 1224732A
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- acid
- butyl
- phenyl
- ester
- composition
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Abstract
本发明涉及包含(a)一种聚酰胺、聚酯或聚缩醛,和(b)用作稳定剂的通式Ⅰ化合物的组合物其条件是如果组分(a)是聚酰胺,那么组合物不包含金属次磷酸盐和有机酸铜盐;还涉及通式Ⅰ化合物在稳定聚酰胺、聚酯和聚缩醛,防止其氧化、热和/或光诱导降解中的用途以及涉及一种稳定这些塑料材料的方法。
Description
本发明涉及一种包含聚酰胺、聚酯或聚酮的组合物;还涉及一种具体酚类抗氧剂及其在稳定聚酰胺、聚酯和聚缩醛,防止其氧化、热和/或光诱导降解中的用途;以及涉及一种稳定这些塑料材料的方法。
从美国第3,691,131和3,860,558号专利说明书中可知聚酰胺可在诸如次磷酸钾或次磷酸钠之类的金属次磷酸盐和有机酸铜盐的存在下用酚类抗氧剂稳定化。
对于聚酰胺、聚酯或聚缩醛,这些已知的稳定剂混合物不能满足所有对它们的要求。众所周知这些稳定剂减小了聚酰胺在炉内老化期间的起色(starting color)及其显色,而且进一步增加了聚酰胺在炉内老化及暴露于光照时机械性能的损失。
已经发现一种酚类抗氧剂特别适合用作不存在金属次磷酸盐和有机酸铜盐时聚酰胺、聚酯或聚缩醛的稳定剂,该抗氧剂选自美国第3,691,131和3,860,558号专利说明书。通过这种方法稳定的聚酰胺、聚酯或聚缩醛在抗氧化、热或/和光诱导降解方面的性能得以改进。
因此,本发明涉及包含以下组分的组合物
a)一种经受氧化、热或/和光诱导降解的聚酰胺、聚酯或聚缩醛,和
其条件是如果组分(a)是聚酰胺,那么组合物不包含金属次磷酸盐和有机酸铜盐。
新型组合物的组分(b)或者通式Ⅰ化合物是已知的,并且化学文摘登记号为[37042-77-6]。通式Ⅰ化合物的制备公开于GB-A-1251840第5页的实施例1中。
聚酰胺应理解为脂族和芳香聚酰胺或来自于二胺和二羧酸和/或氨基羧酸或者它们相应内酰胺的共聚酰胺。合适的聚酰胺例如:PA 6,PA 11,PA 12,PA 46,PA 6.6,PA 4.6,PA 6.9,PA 6.10,或者PA 6.12,PA 10.12,PA 12.12以及Trogamid PA 6-3-T和GrilamidTR 55型无定形聚酰胺。所引用的这些聚酰胺通常已知并商业有售。
令人感兴趣的组合物是那些组分(a)为聚酰胺6、聚酰胺6.6、聚酰胺4.6、聚酰胺11或聚酰胺12或者它们的共聚物,尤其是聚酰胺6或聚酰胺6.6或者与聚丙烯共混的弹性体改良聚酰胺6或聚酰胺6.6的组合物。
所用的聚酯可以是由脂族、脂环族或芳香二羧酸和二元醇或羟基羧酸形成的均聚或共聚酯。
脂族二羧酸可以包含2~40个碳原子,脂环族二羧酸包含6~10个碳原子,芳香二羧酸包含8~14个碳原子,脂族羟基羧酸包含2~12个碳原子,而芳香族,例如脂环族羟基羧酸包含7~14个碳原子。
脂族二元醇可包含2~12个碳原子,脂环族二元醇包含5~8个碳原子,而芳香二元醇包含6~16个碳原子。
芳香二元醇即其中两个羟基与一个或不同的芳香烃基相连的醇。
聚酯也可以用少量的超过两个官能基的多官能单体(例如:季戊四醇、偏苯三酸、1,3,5-三(羟苯基)苯、2,4-二羟基苯甲酸或2-(4-羟苯基)-2-(2,4-二羟苯基)丙烷)支化,支化剂的量例如占二羧酸的0.1~3mol%。
由至少两种单体组成的聚酯可以无规分布或它们可以是嵌段共聚物。
合适的二羧酸为直链及支链饱和脂族二羧酸、芳香二羧酸和脂环族二羧酸。
合适的脂族二羧酸包含2~40个碳原子,例如草酸、丙二酸、二甲基丙二酸、丁二酸、庚二酸、己二酸、三甲基己二酸、癸二酸、壬二酸和二聚酸(诸如油酸之类的不饱和脂族羧酸的二聚产物)、烷基化丙二酸和丁二酸,如十八烷基丁二酸。
合适的脂环族二羧酸为:1,3-环丁烷二羧酸、1,3-环戊烷二羧酸、1,3-和1,4-环己烷二羧酸、1,3-和1,4-(二羧基甲基)环己烷、4,4’二环己基二羧酸。
合适的芳香二羧酸为:尤其是对苯二酸、间苯二酸、邻苯二甲酸,以及1,3-、1,4-、2,6-或2,7-萘二甲酸、4,4’-二苯基二羧酸、4,4’-二苯砜二羧酸、4,4’-二苯甲酮二羧酸、1,1,3-三甲基-5-羧基-3-(对羧苯基)二氢化茚、4,4’-二苯醚二羧酸、二-p-(羧苯基)甲烷或二-p-(羧苯基)乙烷。
其中芳香二羧酸优选为对苯二酸、间苯二酸和2,6-萘二甲酸。
其它合适的二羧酸为那些包含-CO-NH基团的二羧酸;它们在DE-A-2 414 349专利中有描述。包含N-杂环的二羧酸也很合适,例如那些来自于羧基烷基化、羧基苯基化或羧基苄化的单胺-S-三嗪二羧酸(参见专利DE-A-2 121 184和2 533 675)、单或乙二酰脲,任选卤代的苯并咪唑或乙二酰脲的二羧酸。这里,羧烷基可包含3~20个碳原子。
合适的脂族二元醇为直链和支链脂族二元醇,尤其是分子中包含2~12,优选2~6个碳原子的二元醇,例如:乙二醇、1,2-和1,3-丙二醇、1,2-、1,3-、2,3-或1,4-丁二醇、庚二醇、新戊二醇、1,6-己二醇、1,12-十二烷二醇。合适的脂环族二醇例如1,4-二羟基环己烷。其它合适的脂族二醇例如1,4-二(羟甲基)环己烷、芳香-脂族二醇例如p-亚二甲苯基二甲醇或2,5-二氯-p-亚二甲苯基二甲醇、2,2-(β-羟乙氧苯基)丙烷和聚亚氧烷基乙二醇,例如乙二醇、三甘醇、聚乙二醇或聚丙二醇。亚烷基二醇优选为直链且包含2~4个碳原子。
优选的二醇为亚烷基二醇、1,4-二羟基环己烷和1,4-二(羟甲基)环己烷。乙二醇、1,4-丁二醇和1,2-和1,3-丙二醇尤为优选。
其它合适的脂族二醇为β-羟烷基化,尤其β-羟乙基化双酚,例如2,2-二[4’(β-羟乙氧基)苯基]丙烷。其它双酚将在下文中举例。
另一组合适的脂族二醇为那些专利DE-A-1 812 003、DE-A-2 342432、DE-A-2 342 372和DE-A-2 453 326中所述的杂环二醇。例如:N,N’-二(β-羟乙基)-5,5-二甲基乙内酰脲、1N,N’-二(β-羟丙基)-5,5-二甲基乙内酰脲、二[N-(β-羟乙基)-5-甲基-5-乙基乙内酰脲]甲烷、二[N-(β-羟乙基)-5,5-二甲基乙内酰脲]甲烷、N,N’-二(β-羟乙基)苯并咪唑、N,N’-二(β-羟乙基)-(四氯)苯并咪唑或N,N’-二(β-羟乙基)-(四溴)苯并咪唑。
合适的芳香二醇为单核二酚,以及特别是在每个芳香环上带有一羟基的双核二酚。术语芳香应理解为优选指芳香烃基,例如亚苯基或亚萘基。除了例如对苯二酚、间苯二酚或1,5-、2,6-和2,7-二羟基萘外,应当提及的尤其是可用下列通式表示的双酚:羟基可以在间位,以及尤其在对位。这些通式中的R’和R”可以是包含1~6个碳原子的烷基、卤素,如氯或溴,以及优选为氢原子。A可以是直接连接键或氧、硫、-SO-、-SO2-、C=O、-P(O)(C1-C20烷基)-、未取代或取代亚烷基(alkylidene)、环亚烷基或亚烷基(alkylene)。
未取代或取代亚烷基(alkylidene)例子(alkylidene)为:1,1-亚乙基、1,1-或2,2-亚丙基、2,2-亚丁基、1,1-亚异丁基、亚戊基、亚己基、亚庚基、亚辛基、二氯1,1-亚乙基、三氯1,1-亚乙基。
未取代或取代亚烷基(alkylene)例子为:亚甲基、1,2-亚乙基、苯亚甲基、二苯基亚甲基、甲基苯基亚甲基。环亚烷基的例子为亚环戊基、亚环己基、亚环庚基和亚环辛基。
双酚的例子为:双〔对羟基苯基〕醚或双〔对羟基苯基〕硫醚、双〔对羟基苯基〕砜、双〔对羟基苯基〕甲烷、双〔4-羟基苯基〕-2,2’-联苯、苯基氢醌、1,2-二〔对羟基苯基〕乙烷、1-苯基-二〔对羟基苯基〕甲烷、二苯基-二〔对羟基苯基〕甲烷、二苯基-二〔对羟基苯基〕乙烷、二〔3,5-二甲基-4-羟基苯基〕砜、二〔3,5-二甲基-4-羟基苯基〕-p-二异丙基苯、二〔3,5-二甲基-4-羟基苯基〕-m-二异丙基苯、2,2-二〔3’,5’-二甲基-4’-羟基苯基〕丙烷、1,1-或2,2-二〔对羟基苯基〕丁烷、2,2-二〔对羟基苯基〕六氟丙烷、1,1-二氯或1,1,1-三氯-2,2-二〔对羟基苯基〕乙烷、1,1-二〔对羟基苯基〕环戊烷以及特别是2,2-二〔对羟基苯基〕丙烷〔双酚A〕和1,1-二〔对羟基苯基〕环己烷(双酚C)。
羟基羧酸的合适聚酯例如聚己内酯、聚新戊内酯或者4-羟基环己烷羧酸或4-羟基苯甲酸的聚酯。
其它除了主要包含酯键外还包含其它键如聚酰胺酯或聚酯酰亚胺的聚合物也较合适。
含有芳香二羧酸的聚酯最为重要,尤其是聚亚烷基二醇对苯二酸酯。因此,发明的成形组合物优选为由下列含量的组分组成的聚酯:占聚酯至少30mol%,优选至少40mol%的芳香二羧酸和至少30mol%,优选至少40mol%的亚烷基二醇,所述亚烷基二醇优选含有2~12个碳原子。
此时亚烷基二醇优选为直链且包含2~6个碳原子,例如乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇,芳香二羧酸是指对苯二酸和/或间苯二酸。
特别合适的聚酯为PET、PETG(二醇改性的聚对苯二酸乙二醇酯)或PBT(对苯二酸丁二醇酯)及其相应的共聚物,PET及其共聚物尤为优选。
聚缩醛例如仲甲醛的均聚物或共聚物,例如尤其是聚甲醛(POM)以及包含诸如环氧乙烷之类的共聚单体的聚甲醛,和经热塑聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
如上所述,有用的组合物为:其中组分(b)的含量占组分(a)重量的0.01~1%,优选为0.02~0.8%,例如0.03~0.6%。
除了组分(a)和(b)外,该新型组合物可以包含附加的添加剂或共稳定剂,如:
1.抗氧剂
1.1.烷基化一元酚,例如2,6-二叔丁基-4-甲基酚、2-叔丁基-4,6-二甲基酚、2,6-二叔丁基-4-乙基酚、2,6-二叔丁基-4-正丁基酚、2,6-二叔丁基-4-异丁基酚、2,6-二环戊基-4-甲基酚、2-(α-甲基环己基)-4,6-二甲基酚、2,6-二十八烷基-4-甲基酚、2,4,6-三环己基酚、2,6-二叔丁基-4-甲氧甲基酚、直链或在侧链支化的壬基酚,例如,2,6-二壬基-4-甲基酚、2,4-二甲基-6-(1’-甲基十一烷-1’-基)酚、2,4-二甲基-6-(1’-甲基十七烷-1’-基)酚、2,4-二甲基-6-(1’-甲基十三-1’-基)酚及其混合物。
1.2.烷基硫代甲基酚,例如2,4-二辛基硫代甲基-6-叔丁基酚、2,4-二辛基硫代甲基-6-甲基酚、2,4-二辛基硫代甲基-6-乙基酚、2,6-二-十二烷基硫代甲基-4-壬基酚。
1.3.氢醌和烷基化氢醌,例如2,6-二叔丁基-4-甲氧基酚、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、二(3,5-二叔丁基-4-羟基苯基)己二酸。
1.4.生育酚,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’-硫代二(6-叔丁基-4-甲基酚)、2,2’-硫代二(4-辛基酚)、4,4’-硫代二(6-叔丁基-3-甲基酚)、4,4’-硫代二(6-叔丁基-2-甲基酚)、4,4’-硫代二(3,6-二仲戊基酚)、4,4’-二(2,6-二甲基-4-羟苯基)二硫化物。
1.6.亚烷基双酚,例如2,2’-亚甲基双(6-叔丁基-4-甲基酚)、2,2’-亚甲基双(6-叔丁基-4-乙基酚)、2,2’-亚甲基双[4-甲基-6-(α-甲基环己基)酚]、2,2’-亚甲基双(4-甲基-6-环己基酚)、2,2’-亚甲基双(6-壬基-4-甲基酚)、2,2’-亚甲基双(4,6-二叔丁基酚)、2,2’-亚乙基双(4,6-二叔丁基-4-苯酚)、2,2’-亚乙基双(6-叔丁基-4-异丁基酚)、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(2,6-二叔丁基酚)、4,4’-亚甲基双(6-叔丁基-2-甲基酚)、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-羟苄基)-4-甲基酚、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、二[3,3-二(3’-叔丁基-4’-羟苯基)丁酸]乙二醇酯、二(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯、二[2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二酸酯、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、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯、三(3,5-二叔丁基-4-羟基苄基)胺、二(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二酸、二(3,5-二叔丁基-4-羟基苄基)硫化物、异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8.羟基苄基化丙二酸酯,例如二-十八烷基-2,2-二(3,5-二叔丁基-2-羟基苄基)丙二酸酯、二-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、二-十二烷基-2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸酯、二[4-(1,1,3,3-四甲基丁基)苯基]-2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳香羟基苄基化合物,例如1,3,5-三-(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,4-二(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)酚。
1.10.三嗪化合物,例如2,4-二(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-4,6-二(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-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)-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,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯、二-十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯、二-十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯、3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12.酰氨基酚,例如4-羟基月桂酰苯胺、4-羟基硬酯酰苯胺、辛基N-(3,5-二叔丁基-4-羟基苯基)甲氨酸酯。
1.13.β-(3,5-二叔丁基-4-羟苯基)丙酸与一元或多元醇形成的酯,所述醇例如:甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-二(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元或多元醇形成的酯,所述醇例如:甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-二(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.15.β-(3,5-二环己基-4-羟苯基)丙酸与一元或多元醇形成的酯,所述醇例如:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-二(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.16.3,5-二叔丁基-4-羟苯基乙酸与一元或多元醇形成的酯,所述醇例如:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-二(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,例如:N,N’-二(3,5-二叔丁基-4-羟基苯基丙酰)六亚甲基二酰胺、N,N’-二(3,5-二叔丁基-4-羟基苯基丙酰)三亚甲基二酰胺、N,N’-二(3,5-二叔丁基-4-羟基苯基丙酰)酰肼、N,N’-二[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰)乙基]草酰胺(Uniroyal供应的NaugardXL-1)。
1.18.抗坏血酸(维生素C)
1.19.胺抗氧剂,例如N,N’-二异丙基-p-苯二胺、N,N’-二仲丁基-p-苯二胺、N,N’-二(1,4-二甲基戊基)-p-苯二胺、N,N’-二(1-乙基-3-甲基戊基)-p-苯二胺、N,N’-二(1-甲基庚基)-p-苯二胺、N,N’-二环己基-p-苯二胺、N,N’-二苯基-p-苯二胺、N,N’-二(2-萘基)-p-苯二胺、N-异丙基-N’-苯基-p-苯二胺、N-(1,3-甲基丁基)-N’-苯基-p-苯二胺、N-(1-甲基庚基)-N’-苯基-p-苯二胺、N-环己基-N’-苯基-p-苯二胺、4-(对甲苯氨磺酰)二苯胺、N,N’-二甲基-N,N’-二仲丁基-p-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-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺,例如p,p’-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰氨基苯酚、4-壬酰氨基苯酚、4-十二酰氨基苯酚、4-十八酰氨基苯酚、二(4-甲氧苯基)胺、2,6-二叔丁基-4-二甲基氨甲基苯酚、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-萘胺、单和二烷基化叔丁基/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/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-苯并四嗪、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-二(2,2,6,6-四甲基哌啶-4-基)六亚甲基二胺、二(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.紫外线吸收剂和光稳定剂
2.1.2-(2’-羟苯基)苯并三唑,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’-二(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-异辛氧羰基乙基)苯基)苯并三唑、2,2’-亚甲基-二[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-羟基二苯酮,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酯,例如:4-叔丁基-苯基水杨酸酯、水杨酸苯基酯、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)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-p-甲氧基肉桂酸甲酯、α-氰基-β-甲基-p-甲氧基肉桂酸丁酯、α-甲酯基-p-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,例如:2,2’-硫代-二[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,象1∶1或1∶2配合物,该配合物可不含也可含有其它配体如: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、单烷基酯的镍盐,例如:4-羟基-3,5-二叔丁基苄基膦酸甲酯或乙酯;酮肟的镍配合物,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-5-羟基吡唑的镍配合物,可含有也可不含附加配体。
2.6.空间位阻胺,例如:癸二酸二(2,2,6,6-四甲基-4-哌啶基)酯、丁二酸二(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、丙二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯、丙二酸正丁基-3,5-二叔丁基-4-羟基苄基酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶与丁二酸的缩合物、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-1,3,5-三嗪的直链或环状缩合物、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-丁烷四羧酸酯、1,1’-(1,2-乙烷二基)-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-硬酯酰氧基-2,2,6,6-四甲基哌啶、丙二酸二(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)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、丁二酸二(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-吗啉代-2,6-二氯-1,3,5-三嗪的直链或环状缩合物、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-硬酯酰氧基-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-1,3,5-三嗪的缩合产物、1,2-二(3-氨丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁氨基-2,2,6,6-四甲基哌啶(CAS Reg.No.[136504-96-6])的缩合产物;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、1,1-二(1,2,2,6,6-五甲基-4-哌啶氧羰基)-2-(4-甲氧苯基)乙烷、N,N’-二-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-氧代-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,例如4,4’-二辛氧草酰二苯胺、2,2’-二乙氧草酰二苯胺、2,2’-二辛氧-5,5’-二叔丁基草酰二苯胺、2,2’-二-十二烷氧-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(3-二甲氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙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、邻位和对位甲氧基二取代的草酰二苯胺的混合物以及邻位和对位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,例如2,4,6-三(2-羟基-4-辛氧苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧苯基)-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-丙氧苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧苯基)-4,6-二(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧苯基)-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/十三烷氧-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-甲氧苯基)-6-苯基-1,3,5-三嗪、2-{2-羟基-4-[3-(2-乙基己-1-氧基)-2-羟基丙氧基]苯基}-4,6-二(2,4-二甲基苯基)-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’-二(水杨酰)肼、N,N’-二(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、二(苯亚甲基)草酰二酰肼、N,N’-草酰二苯胺、间苯二酰二酰肼、癸二酰二苯基酰肼、N,N’-二乙酰基己二酰二酰肼、N,N’-二(水杨酰)草酰二酰肼、N,N’-二(水杨酰)硫代丙酰二酰肼。
4.亚磷酸酯和亚膦酸酯(phosphonites),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、二亚磷酸二硬酯酰季戊四醇酯、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(2,6-二叔丁基-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、三亚磷酸三硬酯酰山梨醇酯、二亚磷酸四(2,4-二叔丁基苯基)-4,4’-二亚苯基酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂phosphocin、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂phosphocin、亚磷酸二〔2,4-二叔丁基-6-甲苯基〕甲酯、亚磷酸二〔2,4-二叔丁基-6-甲苯基〕乙酯、2,2’,2”-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)亚磷酸酯]、2-乙基己基(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)亚磷酸酯。
以下亚磷酸酯特别优选:
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-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、来自于氢化动物酯胺的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、衍生于N,N-二烷基羟胺的硝酮,所述N,N-二烷基羟胺来自于氢化动物酯胺。
7.硫代增效剂,例如:硫代二丙酸二月桂基酯或硫代二丙酸硬酯基酯。
8.过氧化物清除剂,例如:β-硫代二丙酸酯,例如月桂基、硬酯基、十四烷基或十三烷基酯、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、双十八烷基二硫化物、四〔β-十二烷基巯基〕丙酸季戊四醇酯。
9.碱性共稳定剂,例如:三聚氰胺、聚乙烯吡咯烷酮、二氰胺、氰尿酸三烯丙基酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属和碱土金属盐、例如:硬酯酸钙、硬酯酸锌、二十二烷酸镁、硬酯酸镁、蓖麻油酸钠和棕榈酸钾、焦儿茶酸(pyrocatecholate)锑或焦儿茶酸锌。
10.成核剂,例如:无机物如:滑石、诸如二氧化钛或氧化镁之类的金属氧化物、磷酸盐、优选碱土金属的碳酸盐或硫酸盐;有机化合物例如:一元或多元羧酸及其盐,例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、丁二酸钠或苯甲酸钠;高聚化合物例如离子共聚物〔离聚物〕。
11.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,碳黑、石墨、木粉或其它天然产物的纤维、合成纤维的粉末。
12.其它添加剂,例如:增塑剂、滑润剂、乳化剂、颜料、流变添加剂、催化剂、流动调节剂、光学增亮剂、阻燃剂、抗静电剂和发泡剂。
13.苯并呋喃酮和二氢吲哚酮,例如:那些在专利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或EP-A-0591102中公开的此类化合物或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-硬酯酰氧基乙氧基)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。
除了第13项所列的苯并呋喃酮外,共稳定剂的浓度例如可占被稳定聚酰胺、聚酯和聚缩醛总重量的0.01~10%。
其它优选的组合物除了包含组分(a)和(b)外还可进一步包含添加剂,特别是酚类抗氧剂、光稳定剂或/和加工稳定剂。
特别优选的添加剂为酚类抗氧剂(第1项所列)、空间位阻胺(第2.6项所列)、亚磷酸酯和亚膦酸酯(phosphonites)(第4项所列)和过氧化物清除剂(第8项所列)。
特别令人感兴趣的组合物除了包含组分(a)和(b)外还可进一步包含有机亚磷酸酯或亚膦酸酯(第4项所列)类化合物中至少一种添加剂。
其它优选的附加添加剂(稳定剂)为苯并呋喃-2-酮,正如那些特别公开于专利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;DE-A-4 316 622;DE-A-4 316 876;EP-A-0 589 839或EP-A-0 591102的化合物。
其中
R’11为一未取代或取代的碳环或杂环芳环体系;
R’12为氢原子;
R’14为氢原子、1~12碳原子烷基、环戊基、环己基或氯;
其中
R’16为氢原子、1~18碳原子烷基、被氧或硫间隔的2~18碳原子烷基、碳原子总数为3~16的二烷基氨基烷基、环戊基、环己基、苯基或碳原子总数不超过18的被1~3个烷基取代的苯基;
s为0,1或2;
两个R’17取代基彼此独立分别为氢原子、1~18碳原子烷基、碳原子总数为3~16的二烷基氨基烷基、环戊基、环己基、苯基或碳原子总数不超过16的被1~2个烷基取代的苯基;通式-C2H4-O-CtH2t+1或
的基团或者与连接氮原子一起形成的哌啶基或吗啉基;
t为1~18;
R’20为氢原子、1~22碳原子烷基、5~12碳原子的环烷基;
A为可被氮、氧或硫间隔的2~22碳原子亚烷基;
R’18为氢原子、1~18碳原子烷基、环戊基、环己基、苯基;碳原子总数不超过16的被1~2个烷基取代的苯基或苄基;
R’19为1~18碳原子烷基;
D为-O-、-S-、-SO-、-SO2-或-C(R’21)2-;
E是通式如下的基团:其中R’11、R’12和R’14如上所定义;而R’15为氢原子、1~20碳原子烷基、环戊基、环己基、氯或通式或
的基团,其中R’16和R’17如上所定义,或者R’15与R’14一起为四亚甲基。
优选的苯并呋喃-2-酮为其中R’13为氢原子、1~12碳原子烷基、环戊基、环己基、氯、或通式的基团或者-D-E,其中s、R’16、R’17、D和E如上所定义,R’16优选为氢原子、1~18碳原子烷基、环戊基、环己基。
其它优选的苯并呋喃-2-酮为其中R’11为苯基或碳原子总数不超过12的被1~2个烷基取代的苯基;R’12为氢原子;R’14为氢原子或1~12碳原子烷基;R’13为氢原子、1~12碳原子烷基、或者-D-E;R’15为氢原子、1~20碳原子烷基、
或
或者R’15与R’14一起为四亚甲基,s、R’16、R’17、D和E如上文所定义。
特别令人感兴趣的苯并呋喃-2-酮还可以是这些化合物:其中R’13为氢原子、1~12碳原子烷基或者-D-E;R’12和R’14彼此独立分别为氢原子或1~4碳原子烷基;R’15为1~20碳原子烷基,D和E如上文所定义。
最后,最令人感兴趣的苯并呋喃-2-酮还可以是这些化合物其中R’13为1~4碳原子烷基或者-D-E;R’12和R’14为氢原子;R’15为1~4碳原子烷基、环戊基或环己基,D为-C(R’21)2-,E为以下通式的基团
R’21取代基可相同也可不同,分别为1~4碳原子烷基,R’11、R’12、R’14和R’15的定义已给出。
另外添加的苯并呋喃-2-酮的量可在很宽的范围内变化,它们在本发明组合物中的重量百分比例如可以是0.0001~5%,优选为0.001~2%,更优选为0.01~2%。
向组分(a)[聚酰胺、聚酯和聚缩醛]中加入组分(b)及任选的添加剂可按照已知的方法进行,例如可以在模塑前也可在模塑后,或者将溶解或分散的组分(b)加至组分(a),溶剂可蒸去,也可不蒸。组分(b)也可以母料的形式加至被稳定的材料[组分(a)],浓度例如可以是2.5~25%。
组分(b)也可在聚合前或聚合期间或交联前加入。
组分(b)可以纯的形式或用蜡、油或聚合物包封后加至被稳定的组分(a)中。
组分(b)也可以喷至被稳定的组分(a)上。它可以稀释其它添加剂(例如上述传统添加剂)或它们的熔化物,所以它们可与这些添加剂一起喷至被稳定的组分(a)上。聚合催化剂减活期间喷加特别有利,例如可以使用减活用的蒸汽进行喷射。
经过稳定处理的聚酰胺、聚酯和聚缩醛可以以非常广泛的形式使用,典型的包括薄膜、纤维、长丝、模制品、型材、或涂料体系的基料,所述涂料体系尤其是粉末涂料、粘合剂或腻子。
组分(b)特别适合用于加工稳定剂(热稳定剂)。为达此目的,通常在加工前将其加至组分(a)。
因此,本发明的一个优选的实施方案将组分(b)用作稳定剂,更具体地说是用来稳定聚酰胺、聚酯和聚缩醛,防止其氧化、热和/或光诱导降解的加工稳定剂(热稳定剂)。
组分(b)有突出的其颜色特性,即加工期间聚酰胺、聚酯和聚缩醛几乎不脱色。
因此,本发明还涉及稳定聚酰胺、聚酯和聚缩醛,防止其氧化、热和/或光诱导降解的方法,该方法包括向所述材料中加入至少一种组分(b)。
下面的实施例将更为详尽地说明本发明。份数和百分数均按重量计。
实施例1:聚酰胺12的稳定
100份未经稳定的聚酰胺12颗粒(GrilamidL 20 G,瑞士的EMS提供)通过低温研磨粉化并与表1所列稳定剂一起进料。70℃下混合物在海歇尔混合机中混合2分钟。所得粉末在80℃下干燥6小时,最高温度不超过210℃时在一双螺杆挤塑机(Berstorff型)中挤塑,然后造粒。最高温度不超过220℃下,所得颗粒在一注塑装置(Engel型)中注塑,形成1.0毫米厚,67毫米长的哑铃形试片。这些哑铃形试片的黄度指数(YI)根据ASTM D 1925-70测定。低YI是指脱色较少,高YI则指样品强烈脱色。脱色越少,稳定剂或稳定剂混合物的效率越高。结果汇总于表1。
表1:
实施例 | 稳定剂 | 黄度指数(哑铃形试片) |
1aa) | - | 6.7 |
1ba) | 0.25%Irganox245c) | 8.9 |
1ca) | 0.50%Irganox245c) | 9.6 |
1da) | 0.25%Irganox1098d) | 9.2 |
1ea) | 0.50%Irganox1098d) | 10.7 |
1fb) | 0.25%组分(b)e) | 6.3 |
1gb) | 0.50%组分(b)e) | 6.4 |
1ha) | 0.25%Irganox245c)0.25%Irgafos168f) | 6.8 |
1ia) | 0.25%Irganox1098d)0.25%Irgafos168f) | 7.6 |
1jb) | 0.25%组分(b)e)0.25%Irgafos168f) | 5.7 |
1ka) | 0.25%Irganox245c)0.25%Irgafos12g) | 5.3 |
1la) | 0.25%Irganox1098d)0.25%Irgafos12g) | 6.0 |
1mb) | 0.25%组分(b)e)0.25%Irgafos12g) | 3.4 |
a)对比例
b)本发明的实施例
f)Irgafos168(Ciba Spezialittenchemie AG)是指亚磷酸三(2,4-二叔丁基苯基)酯。
g)Irgafos12(Ciba Spezialittenchemie AG)是指亚磷酸2,2’,2”-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-连苯基-2,2’-二基)酯];化学文摘的登记号为:80410-33-9,代表通式B化合物。
实施例2:聚酰胺6的稳定
100份未经稳定的聚酰胺6颗粒(UltramidB3S,BASF提供)通过低温研磨粉化并与表2所列稳定剂一起进料。70℃下混合物在海歇尔混合机中混合2分钟。所得粉末在80℃下干燥6小时,最高温度不超过240℃时在一双螺杆挤塑机(Berstorff型)中挤塑,然后造粒。最高温度不超过240℃下,所得颗粒在一注塑装置中注塑,形成4×6毫米厚,50毫米长的小型棒材。150℃下,这些棒材在一循环空气炉内老化。以小时为单位测出棒材冲击强度降至80KJ/m2所需要的时间。时间越长,越稳定。结果汇总于表2。
表2:150℃下,炉内老化测试中的冲击强度
实施例 | 稳定剂 | 150℃下,冲击强度降至80KJ/m2所需要的时间,小时 |
2aa) | - | 2 |
2ba) | 0.25%Irganox245c) | 28 |
2ca) | 0.25%Irganox1098d) | 30 |
2db) | 0.25%组分(b)e) | 38 |
参见表1结尾处对脚标a)~e)的定义。
实施例3:聚甲醛共聚物的稳定(POM)
100份未经稳定的POM共聚物(HostaformC,Hoechst提供)与0.3%的硬酯酸钙和表3、4和5所列稳定剂混合。最高温度不超过190℃下,对粉末进行挤塑。最高温度不超过200℃下,一部分颗粒在注塑装置中注塑,形成2毫米厚,40毫米宽,60毫米长的板材。最高温度不超过200℃下,另一部分颗粒在注塑装置中注塑,形成4×6毫米厚,50毫米长的小型棒材。
220℃下,在空气流中对一部分板材进行等温热重分析测试。以分钟为单位测出这些板材重量损失3%、6%和10%的时间。时间越长,稳定性越好。结果汇总于表3。
表3:220℃下进行的热重分析测试
实施例 | 稳定剂 | 重量损失以下百分比所需要的时间,分钟 | ||
3% | 6% | 10% | ||
3aa) | 0.30%Irganox245c) | 53 | 70 | 88 |
3ba) | 0.30%Irganox1098d) | 78 | 103 | 127 |
3cb) | 0.30%组分(b)e) | 82 | 114 | 157 |
参见表1结尾处对脚标a)~e)的定义。
140℃时,对另一部分板材进行炉内老化测试。这些板材在一台140℃的循环空气炉内老化,以小时为单位测出板材重量损失2%所需要的时间。时间越长,稳定性越好。结果汇总于表4。
表4:140℃时炉内老化测试中的重量损失
实施例 | 稳定剂 | 重量损失2%所需要的时间,小时 |
3da) | 0.30%Irganox245c) | 1300 |
3ea) | 0.30%Irganox1098d) | 2150 |
3fb) | 0.30%组分(b)e) | 2700 |
参见表1结尾处对脚标a)~e)的定义。
140℃时,在一台循环空气炉中对4×6毫米厚,50毫米长的棒材进行炉内老化测试,以小时为单位测出棒材冲击强度从起始的110KJ/m2降至90KJ/m2所需要的时间。时间越长,稳定性越好。结果汇总于表5。
表5:140℃下,炉内老化测试中的冲击强度
参见表1结尾处对脚标a)~e)的定义。
实施例 | 稳定剂 | 140℃下,冲击强度降至90KJ/m2所需要的时间,小时 |
2ga) | 0.30%Irganox245c) | 770 |
2ha) | 0.30%Irganox1098d) | 800 |
2ib) | 0.30%组分(b)e) | 1250 |
Claims (11)
2.根据权利要求1的组合物,其中聚酰胺为聚酰胺6、聚酰胺6,6、聚酰胺4,6、聚酰胺11或聚酰胺12或者它们的一种共聚物。
3.根据权利要求1的组合物,其中聚酯为PET、PETG或PBT,或者它们的一种共聚物。
4.根据权利要求1的组合物,其中聚缩醛为一种均聚物或共聚物。
5.根据权利要求1的组合物,其中组分(b)占组分(a)重量的0.01~1%。
6.根据权利要求1的组合物,除了组分(a)和(b)外还可进一步包括其它添加剂。
7.根据权利要求6的组合物,其中其它添加剂为酚类抗氧剂、光稳定剂或/和加工稳定剂。
8.根据权利要求6的组合物,其中其它添加剂为有机亚磷酸酯或亚烷基膦酸酯(phosphonites)中至少一种化合物。
9.根据权利要求6的组合物,其中其它添加剂为至少一种苯并呋喃-2-酮型化合物。
10.一种稳定聚酰胺、聚酯和聚缩醛,防止其氧化、热和/或光诱导降解的方法,它包括向所述材料中加入或施用至少一种根据权利要求1的组分(b)。
11.根据权利要求1的组分(b)作为稳定剂保护聚酰胺、聚酯或聚缩醛,防止其氧化、热和/或光诱导降解的用途。
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CN105283509A (zh) * | 2013-06-13 | 2016-01-27 | 株式会社可乐丽 | 聚酰胺树脂组合物和包含该组合物的成形品 |
CN101600822B (zh) * | 2006-12-27 | 2016-05-25 | 西巴控股有限公司 | 复丝,单丝,无纺织物或条带 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN101600822B (zh) * | 2006-12-27 | 2016-05-25 | 西巴控股有限公司 | 复丝,单丝,无纺织物或条带 |
CN105283509A (zh) * | 2013-06-13 | 2016-01-27 | 株式会社可乐丽 | 聚酰胺树脂组合物和包含该组合物的成形品 |
CN105283509B (zh) * | 2013-06-13 | 2018-06-08 | 株式会社可乐丽 | 聚酰胺树脂组合物和包含该组合物的成形品 |
US10364339B2 (en) | 2013-06-13 | 2019-07-30 | Kuraray Co., Ltd. | Polyamide resin composition and molded article produced therefrom |
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