CN114516208A - 阻燃环氧/有机硅杂化层压覆铜板的制备方法 - Google Patents

阻燃环氧/有机硅杂化层压覆铜板的制备方法 Download PDF

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CN114516208A
CN114516208A CN202111551169.2A CN202111551169A CN114516208A CN 114516208 A CN114516208 A CN 114516208A CN 202111551169 A CN202111551169 A CN 202111551169A CN 114516208 A CN114516208 A CN 114516208A
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陈明
詹浩
王林祥
李联伟
蔡鹏�
倪伶俐
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Jiuyao Electronic Technology Jiangsu Co ltd
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Abstract

本发明涉及功能高分子材料制备技术领域，公开了一种阻燃环氧/有机硅杂化层压板的制备方法，将含氢硅烷、乙烯基环氧树脂和氯铂酸异丙醇溶液搅拌混合回流后，得环氧基团封端的有机硅树脂；将环氧基团封端的有机硅树脂、多官能度环氧树脂、填料和活性小分子环氧树脂混合均匀后，加入氨基改性的三嗪化合物固化剂混合搅拌均匀得胶液；将玻纤布在胶液中浸渍1‑2min后取出烘干，然后在其两面覆盖铜箔，热压得双面覆铜的阻燃环氧/有机硅杂化层压板。本发明使用活性小分子环氧树脂稀释剂替代传统的有机溶剂，使得其制备过程更加绿色环保；获得的覆铜板具有较低的介电常数、很好的耐热和阻燃性能，同时具有一定的疏水性。

Description

阻燃环氧/有机硅杂化层压覆铜板的制备方法
技术领域
本发明涉及功能高分子材料制备技术领域，特别涉及一种阻燃环氧/有机硅杂化层压板的制备方法。
背景技术
覆铜板是电子工业的基础材料，由其加工制造的印制电路板，已广泛应用于电子通讯和仪器仪表。环氧树脂因其优异的力学性能、电气性能、耐化学性及尺寸稳定性，是制作印刷电路板基材的理想材料。但是，环氧树脂的主要成分包括C、H、O等原子，导致其极易燃烧，严重限制了其应用。
目前，制作环氧树脂覆铜板的阻燃处理以通过卤化方法为主，但是卤化的环氧树脂材料在燃烧和废弃处理中将释放出有毒甚至致癌的物质。随着人们对环保意识的强化，环保要求的提高，以及市场对环保产品需求的日益递增，亟需开发一种对环境更友好的环氧树脂覆铜板材料。
近年来，氮、硅、硼系阻燃环氧树脂的研究取得了一定的进展。但是在环氧覆铜板的阻燃应用方面，因成本过高、使用性能差的缺点，导致其工业化生产困难。此外，电子通讯、仪器仪表和国防工业等的迅速发展，对无卤型环氧覆铜板的阻燃性能和综合性能均提出了更高的要求。
本质阻燃聚合物是指利用其自身特有的化学结构，使其在不加阻燃剂的情况下也具有良好的阻燃性。在环氧树脂分子内引入阻燃元素，获得本质阻燃的环氧树脂高聚物，阻燃效率高且持久，无挥发、溶出和渗出之缺点，对环境友好。此外，如果在这类环氧树脂高聚物分子中同时引入多种阻燃元素，则可产生分子内协同阻燃效应。但是本质阻燃的环氧树脂高聚物因其特殊的化学结构，存在加工困难、成本昂贵等缺陷，目前只能应用于某些特殊领域。
发明内容
发明目的：针对现有技术中存在的问题，本发明提供一种阻燃环氧/有机硅杂化层压覆铜板的制备方法，通过硅氢加成反应合成了有机硅改性的环氧树脂，进一步与多官能度环氧树脂、填料和小分子环氧树脂稀释剂，利用氨基改性的三嗪化合物进行交联固化，形成有机硅改性的本质阻燃的具有三维网状结构的聚合物，并进一步提高环氧树脂的玻璃化温度和介电性能，降低吸水率。
技术方案：本发明提供了一种阻燃环氧/有机硅杂化层压覆铜板的制备方法，包括下列步骤：S1：将含氢硅烷、乙烯基环氧树脂和氯铂酸异丙醇溶液搅拌混合后，80~100°C回流2~6h，得环氧基团封端的有机硅树脂；S2：将所述环氧基团封端的有机硅树脂、多官能度环氧树脂、填料和活性小分子环氧树脂，按一定比例混合均匀后，进一步加入计量的氨基改性的三嗪化合物固化剂混合，搅拌均匀后，得胶液；S3：将玻纤布在所述胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，热压得到双面覆铜的阻燃环氧/有机硅杂化层压板。
优选地，在所述S1中，含氢硅烷、乙烯基环氧树脂和氯铂酸异丙醇溶液的用量比例为：10mol：21~22 mol：2 mL。氯铂酸异丙醇溶液的摩尔浓度为0.05mol/L。
优选地，在所述S2中，环氧基团封端的有机硅树脂、多官能度环氧树脂、填料、活性小分子环氧树脂以及氨基固化剂的用量比例为：10：0.5~1mol：20~50g：7~10mol：11.8~14mol。
优选地，在所述S3中，热压的条件为：温度为160-200 °C，压力为4~6MPa，时间为25~35min。
优选地，所述含氢硅烷为1,1,3,3,5,5-六甲基三硅氧烷或1,1,3,3-四甲基二硅氧烷。
优选地，所述乙烯基环氧树脂为以下任意一种：3,4-环氧-1-丁烯、1,2-环氧基-5-己烯、1,2-环氧-7-辛烯、1,2-环氧-9-葵烯。
优选地，所述多官能度环氧树脂为以下任意一种：丙三醇三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、双间苯二酚缩甲醛四缩水甘油醚。
优选地，所述填料为以下任意一种：陶瓷粉、氧化锌、凹凸棒石黏土、蒙脱土。
优选地，所述活性小分子环氧树脂为以下任意一种：1,2,5,6- 二环氧己烷、1,2,7,8-二环氧辛烷、1,2,9,10-二环氧癸烷。
优选地，所述氨基改性的三嗪化合物固化剂为以下任意一种：1,3,5-三嗪-2,4,6-三胺、2-乙烯基-4,6-二氨基-1,3,5-三嗪。
有益效果：本发明与现有技术相比具有下列优点：
1、通过硅氢加成反应合成的具有阻燃、耐温特性的环氧基团封端的有机硅树脂，混合一定量的多官能度环氧树脂、填料和作为稀释剂的活性小分子环氧树脂，并进一步利用氨基改性的三嗪化合物固化剂在聚合物骨架中引入阻燃性能优异的三嗪基团，形成有机硅改性的本质阻燃的具有三维网状结构的聚合物，并进一步提高环氧树脂的玻璃化温度和介电性能，降低吸水率。通过层压，得到具有低的介电常数和介电损耗的双面覆铜的阻燃环氧/有机硅杂化层压板。
2、该工艺使用活性小分子环氧树脂稀释剂替代传统的有机溶剂，使得其制备过程更加绿色环保；而且获得的覆铜板具有较低的介电常数、很好的耐热和阻燃性能，同时具有一定的疏水性。工艺简单、绿色环保，设备要求低，具有广阔的应用前景。
具体实施方式
下面结合具体实施方式对本发明进行详细的介绍。
实施方式1：
S1：混合10mol的1,1,3,3,5,5-六甲基三硅氧烷、21mol的3,4-环氧-1-丁烯和2 mL氯铂酸异丙醇溶液（0.05mol/L）加入到三颈烧瓶中，搅拌混合10min后，90°C回流4h后，得到环氧基团封端的有机硅树脂；
S2：将步骤1制备的环氧基团封端的有机硅树脂、0.5mol丙三醇三缩水甘油醚、20g凹凸棒石黏土和7mol的1,2,5,6-二环氧己烷，混合均匀后，进一步加入11.8mol的1,3,5-三嗪-2,4,6-三胺作为固化剂后混合，搅拌均匀后，得胶液；
S3：将玻纤布在步骤2得到的胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，然后160-200 °C下，5MPa下热压30min，得到双面覆铜的阻燃环氧/有机硅杂化层压板。
实施方式2：
S1：混合10mol的1,1,3,3,5,5-六甲基三硅氧烷、22mol的1,2-环氧-7-辛烯和2 mL氯铂酸异丙醇溶液（0.05mol/L）加入到三颈烧瓶中，搅拌混合10min后，90°C回流4h后，得到环氧基团封端的有机硅树脂；
S2：将步骤1制备的环氧基团封端的有机硅树脂、1mol的丙三醇三缩水甘油醚、50g凹凸棒石黏土和10mol的1,2,7,8-二环氧辛烷稀释剂，混合均匀后，进一步加入14mol的1,3,5-三嗪-2,4,6-三胺固化剂混合，搅拌均匀后，得胶液；
S3：将玻纤布在步骤2得到的胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，然后160-200 °C下，5MPa下热压30min，得到双面覆铜的阻燃环氧/有机硅杂化层压板。
实施方式3：
S1：混合10mol的1,1,3,3-四甲基二硅氧烷、22mol的1,2-环氧-7-辛烯和2 mL氯铂酸异丙醇溶液（0.05mol/L）加入到三颈烧瓶中，搅拌混合10min后，90°C回流4h后，得到环氧基团封端的有机硅树脂；
S2：将步骤1制备的环氧基团封端的有机硅树脂、0.5mol的丙三醇三缩水甘油醚、50g陶瓷粉和8mol的1,2,5,6- 二环氧己烷稀释剂，混合均匀后，进一步加入12.5mol的1,3,5-三嗪-2,4,6-三胺固化剂混合，搅拌均匀后，得胶液；
S3：将玻纤布在步骤2得到的胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，然后160-200 °C下，5MPa下热压30min，得到双面覆铜的阻燃环氧/有机硅杂化层压板。
实施方式4：
S1：混合10mol的1,1,3,3-四甲基二硅氧烷、21mol的1,2-环氧基-5-己烯和2 mL氯铂酸异丙醇溶液（0.05mol/L）加入到三颈烧瓶中，搅拌混合10min后，90°C回流4h后，得到环氧基团封端的有机硅树脂；
S2：将步骤1制备的环氧基团封端的有机硅树脂、0.5mol的双间苯二酚缩甲醛四缩水甘油醚、35g蒙脱土和10mol的1,2,5,6- 二环氧己烷稀释剂，混合均匀后，进一步加入14mol的1,3,5-三嗪-2,4,6-三胺固化剂混合，搅拌均匀后，得胶液；
S3：将玻纤布在步骤2得到的胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，然后160-200 °C下，5MPa下热压30min，得到双面覆铜的阻燃环氧/有机硅杂化层压板。
表1 实施例1至4中制备的双面覆铜的阻燃环氧/有机硅杂化层压板的测试结果
Figure DEST_PATH_IMAGE002
上述实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，包括下列步骤：
S1：将含氢硅烷、乙烯基环氧树脂和氯铂酸异丙醇溶液搅拌混合后，80~100°C回流2~6h，得环氧基团封端的有机硅树脂；
S2：将所述环氧基团封端的有机硅树脂、多官能度环氧树脂、填料和活性小分子环氧树脂，按一定比例混合均匀后，进一步加入计量的氨基改性的三嗪化合物固化剂混合，搅拌均匀后，得胶液；
S3：将玻纤布在所述胶液中浸渍1-2min后取出烘干，然后在其两面覆盖铜箔，热压得到双面覆铜的阻燃环氧/有机硅杂化层压板。
2. 根据权利要求1所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，在所述S1中，含氢硅烷、乙烯基环氧树脂和氯铂酸异丙醇溶液的用量比例为：10mol：21~22 mol：2 mL。
3.根据权利要求1所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，在所述S2中，环氧基团封端的有机硅树脂、多官能度环氧树脂、填料、活性小分子环氧树脂以及氨基固化剂的用量比例为：10mol：0.5~1mol：20~50g：7~10mol：11.8~14mol。
4. 根据权利要求1所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，在所述S3中，热压的条件为：温度为160-200 °C，压力为4~6MPa，时间为25~35min。
5.根据权利要求1至4中任一项所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述含氢硅烷为1,1,3,3,5,5-六甲基三硅氧烷或1,1,3,3-四甲基二硅氧烷。
6.根据权利要求1至4中任一项所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述乙烯基环氧树脂为以下任意一种：
3,4-环氧-1-丁烯、1,2-环氧基-5-己烯、1,2-环氧-7-辛烯、1,2-环氧-9-葵烯。
7.根据权利要求1至4中任一项所述的阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述多官能度环氧树脂为以下任意一种：
丙三醇三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、双间苯二酚缩甲醛四缩水甘油醚。
8.根据权利要求1至4中任一项所述阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述填料为以下任意一种：
陶瓷粉、氧化锌、凹凸棒石黏土、蒙脱土。
9. 根据权利要求1至4中任一项所述阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述活性小分子环氧树脂为以下任意一种：1,2,5,6- 二环氧己烷、1,2,7,8-二环氧辛烷、1,2,9,10-二环氧癸烷。
10.根据权利要求1至4中任一项所述阻燃环氧/有机硅杂化层压板的制备方法，其特征在于，所述氨基改性的三嗪化合物固化剂为以下任意一种：
1,3,5-三嗪-2,4,6-三胺、2-乙烯基-4,6-二氨基-1,3,5-三嗪。
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