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CN101952262B - 用于高tg应用的无卤苯并噁嗪基可固化组合物 - Google Patents

用于高tg应用的无卤苯并噁嗪基可固化组合物 Download PDF

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CN101952262B
CN101952262B CN2009801058933A CN200980105893A CN101952262B CN 101952262 B CN101952262 B CN 101952262B CN 2009801058933 A CN2009801058933 A CN 2009801058933A CN 200980105893 A CN200980105893 A CN 200980105893A CN 101952262 B CN101952262 B CN 101952262B
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R·逖特泽
Y-L·戈余恩
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Abstract

本发明提供包括苯并

Description

用于高TG应用的无卤苯并噁嗪基可固化组合物
相关申请的交叉引用
本申请要求于2008年2月21日提交的美国专利申请号60/030,366的优先权，该文献引入本文供参考。
关于联邦资助的研究或开发的声明
本发明是根据美国能源部授予的契约号DE-FG 36-07G017012在政府支持下完成的。因此，美国政府享有本发明中的某些权力。
发明领域
本发明涉及苯并
Figure BPA00001206121700012
嗪基无卤组合物，它可以固化而形成易燃并显示改进的热性能的聚合物网络。所述苯并
Figure BPA00001206121700013
嗪基无卤可固化组合物可以用于各种应用，包括汽车、航天、电子和工业应用。
发明背景
通过浸渍操作或浸泡处理，苯并
Figure BPA00001206121700014
嗪化合物已应用于生产半固化片、层压材料、PWB、模塑料、密封剂、烧结粉末、铸塑制品、结构复合材料部件以及电气和电子元件。为了制备阻燃性含苯并
Figure BPA00001206121700015
嗪化合物的组合物，可以添加含溴、磷或氯的化合物和/或填料(参见例如，EP0458739、EP 356379、US 5,200,452、US 5,152,939、EP 1366053或JP2001220455)。然而，此类添加剂的使用具有数种缺点。例如，它们不可溶于溶剂并因此引起加工方面的问题；它们在高温下显示差的氧化稳定性；它们提供通常具有差的物理性能的固化树脂；并且当暴露于火焰中时，特别是当卤化化合物存在时，有毒燃烧气体可能形成。因此，产生不表现出这些缺点，但仍可以用于高温环境的苯并
Figure BPA00001206121700016
嗪基组合物是合乎需要的。
发明概述
本发明提供无卤可固化组合物，它含有：
(a)下式(I)的苯并
Figure BPA00001206121700017
嗪单体
Figure BPA00001206121700021
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基；
(b)至少一种环氧树脂；
(c)催化剂；
(d)增韧剂；和
(e)溶剂。
这种无卤可固化组合物可以用于各种应用，包括要求这种组合物在固化后显示高玻璃化转变温度的那些应用。因此，这种无卤可固化组合物特别适合用作其中通常需要高玻璃化转变温度的汽车或航天应用中的涂层或模制品。
发明详述
一般而言，本发明提供无卤可固化组合物，它包括：
(a)苯并
Figure BPA00001206121700022
嗪单体；(b)环氧树脂；(c)催化剂；(d)增韧剂；和(e)溶剂。本发明的可固化组合物在固化后提供具有机械和化学性能(包括例如，高玻璃化转变温度(Tg)、分解温度(Td)、高拉伸强度、低热膨胀系数、良好挠性和阻燃性)的优异平衡的固化产物。
苯并
Figure BPA00001206121700023
嗪单体
本发明的无卤可固化组合物包括大约10-90重量份，优选大约30-50重量份，更优选大约35-45重量份苯并
Figure BPA00001206121700024
嗪单体/100重量份无卤可固化组合物。本文所使用的术语″苯并
Figure BPA00001206121700025
嗪单体″是指具有至少一个取代或未取代的苯并
Figure BPA00001206121700026
嗪基的单体。该苯并嗪单体可以是单官能化、二官能化或三官能化苯并
Figure BPA00001206121700028
嗪化合物。此外，当使用术语″苯并
Figure BPA00001206121700029
嗪单体″时，应该理解的是，可以一起使用一种或多种苯并
Figure BPA00001206121700031
嗪单体。
苯并嗪单体可以由以下通式表示：
Figure BPA00001206121700033
其中b是0-3的整数；R是取代或未取代的C1-C20烷基、取代或未取代的C2-C20烯基、取代或未取代的C6-C20芳基、取代或未取代的C2-C20杂芳基、取代或未取代的C4-C20碳环基、取代或未取代的C2-C20杂环基或C3-C8环烷基；R1是氢、烷基或烯基；和Z是直接键(当b＝2时)、取代或未取代的C1-C20亚烷基、取代或未取代的C6-C20亚芳基、取代或未取代的C2-C20杂亚芳基或C＝O。
在一个实施方案中，苯并
Figure BPA00001206121700034
嗪单体是以下通式(I)的化合物
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基。R基上的适合的取代基包括氨基、C1-C4烷基和烯丙基。R基上可以存在1-4个取代基。优选地，R基是相同的并且更优选是苯基。
苯并
Figure BPA00001206121700036
嗪单体可从数种来源包括Huntsman Advanced MaterialsAmericas Inc.、Georgia Pacific Resins Inc.和Shikoku ChemicalsCorporation商购的。苯并
Figure BPA00001206121700037
嗪单体还可以如下获得：使酚化合物，例如，双酚A或酚酞与醛，例如，甲醛，和伯胺在其中除去水的条件下反应。酚化合物与醛的摩尔比可以是大约1∶3-1∶10，优选大约1∶4-1∶7，更优选大约1∶4.5-1∶5。酚化合物与伯胺反应物的摩尔比可以是大约1∶1-1∶3，优选大约1∶1.4-1∶2.5，更优选大约1∶2.1-1∶2.2。伯胺的实例包括：芳族单或二-胺，脂族胺，环脂族胺和杂环单胺；例如，苯胺，邻、间和对苯二胺，联苯胺，4，4′-二氨基二苯基甲烷，环己胺，丁胺，甲胺，己胺，烯丙胺，糠胺，乙二胺和丙二胺。胺在它们的相应的碳部分中可以被C1-C8烷基或烯丙基取代。优选的伯胺按照通式RaNH2，其中Ra是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基。Ra基团上的适合的取代基包括氨基、C1-C4烷基和烯丙基。通常，Ra基团上可以存在1-4个取代基。优选地，Ra是苯基。
环氧树脂
本发明的无卤可固化组合物还包括大约2-60重量份，优选大约20-40重量份至少一种环氧树脂/100重量份无卤可固化组合物。这些环氧树脂的实例包括聚缩水甘油环氧化合物、非缩水甘油基环氧化合物、环氧基甲酚酚醛清漆和环氧基苯酚酚醛清漆化合物。
在一个实施方案中，环氧树脂是非缩水甘油基环氧化合物。非缩水甘油基环氧化合物结构方面可以是直链、支链或环状的。例如，可以包括一种或多种其中环氧化物基团形成脂环或杂环体系的一部分的环氧树脂。其它包括具有至少一个环氧基环己基的含环氧基化合物，该环氧基环己基直接地或间接地与含至少一个硅原子的基团键合。实例公开在美国专利号5,639,413中，该文献引入本文供参考。还有的其它包括含一个或多个氧化环己烯基团的环氧树脂和含一个或多个氧化环戊烯基团的环氧化物。
尤其适合的非缩水甘油基环氧化合物包括以下其中环氧化物基团形成脂环或杂环体系的一部分的双官能化非缩水甘油基环氧化物化合物：双(2，3-环氧基环戊基)醚、1，2-双(2，3-环氧基环戊氧基)乙烷、3，4-环氧基环己烷羧酸3，4-环氧基环己基-甲酯、3，4-环氧基-6-甲基环己烷羧酸3，4-环氧基-6-甲基-环己基甲酯、二(3，4-环氧基环己基甲基)己二酸酯、二(3，4-环氧基-6-甲基环己基甲基)己二酸酯、亚乙基双(3，4-环氧基环己烷羧酸酯)、乙二醇二(3，4-环氧基环己基甲基)醚、二氧化乙烯基环己烯、二环氧化双环戊二烯或2-(3，4-环氧基环己基-5，5-螺-3，4-环氧基)环己烷-1，3-二烷和2，2′-双-(3，4-环氧基-环己基)-丙烷。
催化剂
无卤可固化组合物还含有大约0.1-20重量份，优选大约0.5-15重量份催化剂/100重量份无卤可固化组合物，以加速无卤可固化组合物的固化。
在一个实施方案中，催化剂是酚类化合物，优选具有两个或更多个官能团。此类酚类化合物的实例包括：a)由酚类或烷基化酚类与甲醛的反应获得的树脂，例如酚醛清漆树脂或甲阶酚醛树脂；和b)多羟基芳族材料例如：三(羟苯基)甲烷；三(羟苯基)乙烷；1，3，5-三羟基苯和四苯酚乙烷。
增韧剂
本发明的无卤可固化组合物还包括大约0.1-40重量份，优选大约0.5-20重量份增韧剂/100重量份无卤可固化组合物。
在一个实施方案中，增韧剂是以下通式的化合物
Figure BPA00001206121700052
其中m是1或2，n是2-6，R0是弹性预聚物在脱除端异氰酸酯、氨基或羟基后的n-价基团，该弹性预聚物可溶或可分散在环氧树脂中，X和Y彼此独立地为-O-或-NR3-，至少一个X或Y是-NR3-，R2是多酚或氨基酚在除去酚羟基和任选的氨基后的m+1价基团，R3是氢、C1-C6烷基或酚。
式(II)的增韧剂的详细描述给出在美国专利号5,278,257第4栏第20行至第16栏第20行中，该文献的公开内容引入本文供参考。增韧剂的实例是Flexibilizer DY 965(可以从Huntsman AdvancedMaterials Americas Inc.获得，根据美国专利号5,278,257的实施例16制备)。
溶剂
除了组分(a)-(d)之外，本发明的无卤可固化组合物还含有大约1-50重量份，优选大约5-40重量份，更优选大约20-30重量份溶剂/100重量份无卤可固化组合物。
在一个实施方案中，溶剂选自甲乙酮、丙酮、N-甲基-2-吡咯烷酮、N，N-二甲基甲酰胺、戊醇、丁醇、二氧戊环、异丙醇、甲氧基丙醇、甲氧基丙醇乙酸酯、二甲基甲酰胺、乙二醇、乙二醇乙酸酯、甲苯、二甲苯和它们的混合物。
任选的添加剂
除了上面给出的组分(a)-(e)之外，如果有必要的话，无卤可固化组合物还可以包括用于提高强度、释放性能、耐水解性、导电性及其它特性的添加剂。可以按少于大约50重量份，优选少于大约30重量份，最优选少于大约20重量份/100重量份无卤可固化组合物的量将这些添加剂添加到无卤可固化组合物中。
这些任选的添加剂可以包括增强纤维，例如：金属纤维(例如铁、铜、黄铜、青铜、铝)陶瓷纤维，玻璃纤维，碳纤维，石膏纤维，石棉，硅灰石，海泡石，坡缕石，合成矿物纤维，芳族聚酰胺纤维，聚酰亚胺纤维，聚酰胺纤维，酚类纤维，纤维素纤维和丙烯酸系纤维；填料；微或中空球体；增塑剂；炭黑或石墨；染料和金属粉末。
本发明的无卤可固化组合物可以按已知的方式，例如，如下制备：将各组分预混合，然后混合这些预混合物，或使用常用的设备，例如搅拌容器、搅拌棒、球磨机、样品混合器、静态混合器或螺条拌合器将所有组分混合在一起。一旦配制好，就可以将本发明的无卤可固化组合物包装在各种容器例如钢、锡、铝、塑料、玻璃或卡纸容器中。
根据一个实施方案，如下制备本发明的无卤可固化组合物：将大约10-90重量份苯并
Figure BPA00001206121700061
嗪单体，大约2-60重量份环氧树脂，大约0.1-20重量份催化剂，大约0.1-40重量份增韧剂和大约1-50重量份溶剂混合在一起，按100重量份无卤可固化组合物计。在另一个实施方案中，如下制备本发明的无卤可固化组合物：将大约30-50重量份苯并嗪单体，大约20-40重量份环氧树脂，大约0.5-15重量份催化剂，大约0.5-20重量份增韧剂和大约5-40重量份溶剂混合在一起，按100重量份无卤可固化组合物计。一旦混合，则可以将该无卤可固化组合物施涂于基材上并在大于150℃的温度下固化以形成复合制品。
在另一个实施方案中，无卤可固化组合物在混合和固化后提供玻璃化转变温度大于120℃，优选大于160℃，最优选大于200℃，特别优选大于230℃的固化复合制品。
因此，在另一个实施方案中，本发明提供无卤可固化组合物，其包含：
(a)10-90重量份以下式(I)的苯并
Figure BPA00001206121700072
嗪单体
Figure BPA00001206121700073
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基；
(b)2-60重量份至少一种环氧树脂；
(c)0.1-20份催化剂；
(d)0.1-40重量份增韧剂；和
(e)1-50重量份溶剂，按100重量份无卤可固化组合物计，其中
该无卤可固化组合物在固化后具有大于160℃，优选大于200℃，更优选大于230℃的玻璃化转变温度。
本发明的无卤可固化组合物可以用于许多应用，例如浇铸，层压，浸渍，涂覆，粘附或胶粘，涂漆，粘结，绝缘或嵌入，压制，注塑，挤出，砂模粘结泡沫和烧蚀材料。
因此，在本发明的另一个实施方案中，无卤可固化组合物可以用作粘合剂以便胶粘或粘附由相同或不同的基材制成的部件以形成制品。首先将该无卤可固化组合物置于与待粘结的两个或更多个相同或不同的基材中的至少一个接触。可以按各种方法，例如通过挤出，喷涂，印刷或涂覆将该无卤可固化组合物施涂于基材上。在一个实施方案中，将该无卤可固化组合物夹持在第一和第二基材之间。然后在大于150℃的温度下加热该无卤可固化组合物和基材。通过施用热，形成粘着键以致使基材粘附在一起并形成制品。其中可以施涂无卤可固化组合物的基材包括塑料、金属、陶瓷、玻璃、石墨和纤维素材料。
本发明的无卤可固化组合物特别适合用于其中要求高热稳定性的应用，例如，用于形成用作燃料电池的复合制品，该燃料电池用于：在常规汽车、混合动力轿车、小艇中供应电力；用于小规模局部电力产生；家庭发电；隔离设施例如营地的简单电力供给；和用作卫星、空间开发和计算机的电力供给。
因此，在另一个实施方案中，可以将无卤可固化组合物施涂于石墨上并模塑而制备燃料电池。在混合器中将石墨、无卤可固化组合物和任选的松脱剂，例如，巴西棕榈蜡、脂肪酸酯、硬脂酸或褐煤酸的金属盐共混，捏合和注射模塑、转移模塑或压缩模塑而制备燃料电池。
实施例
A)苯并
Figure BPA00001206121700081
嗪基无卤可固化组合物的制备
将表1中的以下组分添加到玻璃容器中并充分地混合至均匀：
表1
Figure BPA00001206121700091
然后将实施例1-6浇铸并从200℃-255℃固化1-5小时，然后从200℃-240℃后固化1-4小时。根据ASTM E1545-05、ASTME1641-07、ASTME831-05和AMTM-0046用分析法试验固化产物并提供以下性能：
表2
Figure BPA00001206121700092
虽然上面已经详细地描述了本发明各种实施方案的制造和使用，但是不言而喻的是本发明提供可以按各种各样的特定背景实施的许多可适用的发明构思。本文论述的特定实施方案仅是构造和使用本发明的特定方法的示例并且不限定本发明的范围。

Claims (12)

1.无卤可固化组合物，其包含：每100重量份的无卤可固化组合物，
(a)10-90重量份的式(I)的苯并
Figure FSB00000715576100011
嗪单体
Figure FSB00000715576100012
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基；
(b)2-60重量份的至少一种环氧树脂；
(c)0.1-20重量份的包含酚类化合物的催化剂；
(d)0.1-40重量份的下式(II)的增韧剂
Figure FSB00000715576100013
其中m是1或2，n是2-6，R0是弹性预聚物在脱除端异氰酸酯、氨基或羟基后的n-价基团，该弹性预聚物可溶或可分散在环氧树脂中，X和Y彼此独立地为-O-或-NR3-，至少一个X或Y是-NR3-，R2是多酚或氨基酚在除去酚羟基和任选的氨基后的m+1价基团，R3是氢、C1-C6烷基或酚；和
(e)1-50重量份的溶剂。
2.根据权利要求1的无卤可固化组合物，其中R是苯基。
3.根据权利要求1的无卤可固化组合物，其中所述酚类化合物具有两个或更多个官能团。
4.根据权利要求1的无卤可固化组合物，其中所述环氧树脂是非缩水甘油基化合物。
5.根据权利要求1的无卤可固化组合物，其中所述溶剂选自甲乙酮、丙酮、N-甲基-2-吡咯烷酮、N，N-二甲基甲酰胺、戊醇、丁醇、二氧戊环、异丙醇、甲氧基丙醇、甲氧基丙醇乙酸酯、二甲基甲酰胺、乙二醇、乙二醇乙酸酯、甲苯、二甲苯和它们的混合物。
6.无卤可固化组合物，其包含：
(a)10-90重量份的式(I)的苯并
Figure FSB00000715576100021
嗪单体
Figure FSB00000715576100022
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基；
(b)2-60重量份的至少一种环氧树脂；
(c)0.1-20重量份的包含酚类化合物的催化剂；
(d)0.1-40重量份的增韧剂；和
(e)1-50重量份的溶剂，按100重量份无卤可固化组合物计，其中所述无卤可固化组合物在固化后具有大于160℃的玻璃化转变温度。
7.根据权利要求6的无卤可固化组合物，其中所述玻璃化转变温度大于200℃。
8.根据权利要求6的无卤可固化组合物，其中所述玻璃化转变温度大于230℃。
9.无卤可固化组合物的制备方法，包括将以下组分混合在一起，其中每100重量份的无卤可固化组合物，
(a)10-90重量份的式(I)的苯并
Figure FSB00000715576100023
嗪单体
Figure FSB00000715576100031
其中每个R彼此独立地是烯丙基、未取代或取代的苯基、未取代或取代的C1-C8烷基或未取代或取代的C3-C8环烷基；
(b)2-60重量份的至少一种环氧树脂；
(c)0.1-20重量份的包含酚类化合物的催化剂；
(d)0.1-40重量份的增韧剂；和
(e)1-50重量份的溶剂，以生产无卤可固化组合物。
10.根据权利要求9的方法制备的无卤可固化组合物。
11.复合制品的制备方法，包括将根据权利要求1的无卤可固化组合物施涂到至少一种基材上并在大于150℃的固化温度下加热该基材和无卤可固化组合物以制备复合制品。
12.根据权利要求11的方法，其中该基材是石墨。
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WO2009137144A2 (en) 2009-11-12
RU2480465C2 (ru) 2013-04-27
JP2011528042A (ja) 2011-11-10
US20150147508A1 (en) 2015-05-28
KR101591537B1 (ko) 2016-02-03
JP5438035B2 (ja) 2014-03-12
TWI437037B (zh) 2014-05-11
KR20100116636A (ko) 2010-11-01
EP2254875A2 (en) 2010-12-01
CN101952262A (zh) 2011-01-19
EP2254875A4 (en) 2012-10-10
US20100330287A1 (en) 2010-12-30
US8975318B2 (en) 2015-03-10
US9416271B2 (en) 2016-08-16
WO2009137144A3 (en) 2010-01-21

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