CN105385334A - 一种双组份水性聚氨酯透明导热涂层的制备方法 - Google Patents

一种双组份水性聚氨酯透明导热涂层的制备方法 Download PDF

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CN105385334A
CN105385334A CN201510940055.5A CN201510940055A CN105385334A CN 105385334 A CN105385334 A CN 105385334A CN 201510940055 A CN201510940055 A CN 201510940055A CN 105385334 A CN105385334 A CN 105385334A
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姚伯龙
高旭瑞
李洪萍
王利魁
邓丽朵
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Abstract

本发明公开了一种双组份水性聚氨酯透明导热涂层的制备方法。本文以水性聚氨酯分散体为A组份，水性聚氨酯固化剂为B组份，氧化铝和氧化石墨作为导热填料，添加其他助剂制备室温固化的具有导热功能的双组份水性聚氨酯。通过端羟基有机硅树脂改性水性聚氨酯，合成得到硬度和耐候性、耐水性、耐磨性大幅提高的水性双组份聚氨酯树脂。该树脂可广泛用于环保、建筑、家用电器、油墨、涂料等。加入的导热粉体可以大幅度提高树脂的导热性能，可广泛应用于电子元器件等散热部位。

Description

一种双组份水性聚氨酯透明导热涂层的制备方法
技术领域
本发明涉及一种双组份水性聚氨酯透明导热涂层的制备方法。
背景介绍
近年来，随着人们对能源和环境保护的重视，世界各国对溶剂型涂料中挥发性有机物组分(VOC)的排放越来越加以限制，研制低污染环保型的水性涂料已经成为涂料开发的主要方向。水性聚氨酯是一种新型的环保型的高分子材料.由于符合国家环保法规对挥发性有机物(VOC)排放的限制，应用面越来越广泛，以显示出其强大的生命力。水性涂料以水为分散介质，具有不燃、无毒、不污染环境和节省能源等优点，双组分聚氨酯涂料具有成膜温度低、附着力强、耐磨性好、硬度大以及耐化学品、耐侯性好等优越性能，因而广泛作为工业防护、木器家具和汽车涂料。但水性聚氨酯成膜后具有一定的亲水性能，故耐水性能一般不高水性聚氨酯膜主要依靠氢键和范德华力等作用力与基材结合在一起,因此，附着力一般并不理想。将有机硅用于聚氨酯的改性是改善聚氨酯和有机硅材料单一材料性能缺陷的一条重要途径，随着研究的深入，有机硅改性聚氨酯的应用日益广泛。
近年来全球工业生产和科学技术发展迅猛，以至于人们对导热材料有了更多新的要求，不仅要求其具有优良的机械性能，如用于废水处理和化工生产中的热交换器即需要具有很高的热传导能力；又需要良好的耐化学腐蚀.在电气和电子工业中由于集成电路技术和制造工艺的革新，电路板上集成越来越多的电子元件、逻辑电路，集成电路的功能越来越强大，但由此也带来了发热量增大的问题，因此散热问题亟需由高导热性的绝缘材料来解决。
发明内容
本发明所得的一种双组份水性聚氨酯透明导热涂层，用三羟甲基丙烷作为支化点合成多羟基的双组份水性聚氨酯，提高其固化膜的耐水性、硬度及附着力用端羟基硅油改性双组份水性聚氨酯在其分子链上引入了硅氧键(-Si-o-Si-),由于硅氧键相比碳碳键(-C-C-)的键长大得多，使得链的柔顺性大大提高，也增加了聚氨酯耐水性和耐热性。在合成的水性聚氨酯中加入氧化铝和氧化石墨大幅度提高水性聚氨酯的导热性能，制得双组份水性聚氨酯透明导热涂层，得到的膜的综合性能优异。
本发明的技术方案是：
一种双组份水性聚氨酯透明导热涂层的制备方法，包括如下步骤：
(1)将聚酯二元醇、三羟甲基丙烷(TMP)、多羟基羧酸、小分子二元醇、端羟基硅油加入三口烧瓶中混合均匀，其中三羟甲基丙烷(TMP)和多羟基羧酸用一定量溶剂溶解。将温度调至50～60℃，缓慢滴加二异氰酸酯，约1～2h滴完.滴完后向体系滴加2～3滴催化剂，将温度升至70～80℃，保温反应，每1h测一次NCO值，当NCO值为零时停止加热，期间用丙酮调节粘度，降温至40～50℃，用胺中和，使pH达到8～10时左右，在高速搅拌下加入去离子水乳化，搅拌约1～3h，40～60℃下旋蒸即可得到有机硅改性的羟基型水性聚氨酯；
(2)将上述水性聚氨酯树脂按比例与氧化铝和氧化石墨充分混合，后加入水性消泡剂、分散剂、流平剂、增稠剂。按比例配置聚氨酯固化剂，充分搅拌，用滤网过滤，室温下熟化15～30min后涂膜。涂膜于常温下放置一段时间，再放入烘箱中低温烘烤20～30min，取出后于常温下固化24～48h。
步骤(1)中所述的端羟基硅油为端羟甲基硅油、端羟乙基硅油、端羟丙基硅油、端羟丁基硅油中的一种或几种的混合物，端羟基硅油的分子量在500～2000，聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的一种或几种的混合物，羟基硅油与聚酯二元醇的物质的量的比：n(羟基硅油)/n(聚酯二元醇或聚醚二元醇)＝1:(5～9)；三羟甲基丙烷的质量分数为5～10％；多羟基羧酸为2,2’-二羟甲基丙酸(DMPA)、2,2’-二羟甲基丁酸(DMBA)中的一种或几种的混合物；小分子二元醇为1,6-己二醇、1,4-丁二醇中的一种或几种的混合物，小分子二元醇的用量占总质量的1～5％；催化剂为二月桂酸二丁基锡(DBTDL)，催化剂的质量百分含量为0.1～0.3％；二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛二酮二异氰酸酯(IPDI)、己二异氰酸酯(HDI)、4,4’-二苯基甲烷二异氰酸酯中的一种或几种的混合物，二异氰酸酯与含羟基化合物的物质的量比：n(二异氰酸酯)/n(含羟基化合物)＝1:1.1～1.5；丙酮加入量的质量分数为5～20％；胺为三乙胺或二甲氨基乙醇中的一种或几种的混合物，三乙胺的物质的量与羧基的摩尔比：n(三乙胺)/n(羧基含量)＝0.6～1.1:1；去离子水的加入的质量分数为树脂的30～60％；
步骤(2)中所述的氧化铝为30～3000nm；水性聚氨酯固化剂与水性树脂的为(0.15～0.3)；1；消泡剂占3～5％；分散剂占3～5％；流平剂占3～5％；增稠剂占5～10％；氧化铝或者氧化石墨占10～20％。
本发明的有益效果是：通过以上反应，合成得到硬度和耐候性、耐水性、耐磨性大幅提高的水性双组份聚氨酯树脂。该树脂可用于提高涂料的耐候性，也可大大提高耐水耐油性，可广泛用于环保、建筑、家用电器、油墨、涂料等。加入的导热粉体可以大幅度提高树脂的导热性能，可广泛应用于电子元器件等散热部位。
具体实施方式
下面结合实施例对本发明作进一步的说明,但是实施例并不构成对本发明要求保护范围的限制：
实施方案中所有使用的甲苯二异氰酸酯、异佛尔酮二异氰酸酯、己二异氰酸酯等都是经过减压蒸馏得到的，聚醚或聚酯二元醇经过抽真空处理，催化剂和溶剂通过分子筛处理，二羟甲基丙酸在120℃烘箱烘烤2h，其他改性剂如端羟烷基硅油都是抽真空处理的。
实施例1
(1)将20g分子量2000的聚碳酸酯二元醇、3g三羟甲基丙烷(TMP)、4g2,2’-二羟甲基丙酸、2g的1,4-丁二醇、4g分子量2000的端羟基硅油加入三口烧瓶中混合均匀，其中三羟甲基丙烷(TMP)和2,2’-二羟甲基丙酸用3g的N-甲基吡咯烷酮溶解。将温度调至50℃，缓慢滴加22g异氟尔酮二异氰酸酯，约1h滴完.滴完后向体系滴加2滴二月桂酸二丁基锡，将温度升至70℃，保温反应，每1h测一次NCO值，当NCO值为零时停止加热，期间用10g丙酮调节粘度，降温至40℃，用2.4g三乙胺中和，使pH达到8时左右，在高速搅拌下加入60g去离子水乳化，搅拌约1h，40℃下旋蒸即可得到有机硅改性的羟基型水性聚氨酯；
(2)将上述10g水性聚氨酯树脂与2g氧化铝或1g氧化石墨充分混合，后加入0.36g水性消泡剂，0.36g流平剂，0.36g分散剂，0.52g增稠剂。0.13g聚氨酯固化剂，充分搅拌，用滤网过滤，室温下熟化15min后涂膜。涂膜于常温下放置一段时间，再放入烘箱中低温烘烤20min，取出后于常温下固化24h。
实施例2
(1)将10g分子量1000的聚己内酯二元醇、3g三羟甲基丙烷(TMP)、3g的2,2’-二羟甲基丙酸、2g的1,6-己二元醇、3g分子量2000的端羟基硅油加入三口烧瓶中混合均匀，其中三羟甲基丙烷(TMP)和2,2’-二羟甲基丙酸用4g的N,N-二甲基甲酰胺溶剂溶解。将温度调至60℃，缓慢滴加18g甲苯二异氰酸酯，约1h滴完.滴完后向体系滴加3d滴二月桂酸二丁基锡，将温度升至80℃，保温反应，每1h测一次NCO值，当NCO值为零时停止加热，期间用5g丙酮调节粘度，降温至50℃，用2.6g三乙胺胺中和，使pH达到10时左右，在高速搅拌下加入50g去离子水乳化，搅拌约3h，60℃下旋蒸即可得到有机硅改性的羟基型水性聚氨酯；
(2)将上述10g水性聚氨酯树脂按比例与1g氧化铝或1g氧化石墨充分混合，后加入0.36g水性消泡剂，0.36g流平剂，0.36g分散剂，0.54增稠剂。按比例配置0.3g聚氨酯固化剂，充分搅拌，用滤网过滤，室温下熟化30min后涂膜。涂膜于常温下放置一段时间，再放入烘箱中低温烘烤30min，取出后于常温下固化48h。
实施例3
(1)将20g聚碳酸酯二元醇、2g三羟甲基丙烷(TMP)、2g的2,2’-二羟甲基丙酸、2g的1,4-丁二元醇、3g分子量2000的端羟基硅油加入三口烧瓶中混合均匀，其中三羟甲基丙烷(TMP)和2,2’-二羟甲基丙酸用4g的N-甲基吡咯烷酮溶解。将温度调至50℃，缓慢滴加15g己二异氰酸酯，约2h滴完.滴完后向体系滴加3滴二月桂酸二丁基锡，将温度升至70℃，保温反应，每1h测一次NCO值，当NCO值为零时停止加热，期间用6g丙酮调节粘度，降温至40℃，用1.7g三乙胺中和，使pH达到8时左右，在高速搅拌下加入80g去离子水乳化，搅拌约1h，40℃下旋蒸即可得到有机硅改性的羟基型水性聚氨酯；
(2)将上述10g水性聚氨酯树脂按比例与1g氧化铝和0.5g氧化石墨充分混合，后加入0.24g水性消泡剂，0.24g流平剂，0.24g分散剂，0.48g增稠剂。按比例配置0.3g聚氨酯固化剂，充分搅拌，用滤网过滤，室温下熟化30min后涂膜。涂膜于常温下放置一段时间，再放入烘箱中低温烘烤30min，取出后于常温下固化24h。

Claims (1)

1.一种双组份水性聚氨酯透明导热涂层的制备方法，包括如下步骤：
(1)将聚酯二元醇、三羟甲基丙烷(TMP)、多羟基羧酸、小分子二元醇、端羟基硅油加入三口烧瓶中混合均匀，其中三羟甲基丙烷(TMP)和多羟基羧酸用一定量溶剂溶解。将温度调至50～60℃，缓慢滴加二异氰酸酯，约1～2h滴完.滴完后向体系滴加2～3滴催化剂，将温度升至70～80℃，保温反应，每1h测一次NCO值，当NCO值为零时停止加热，期间用丙酮调节粘度，降温至40～50℃，用胺中和，使pH达到8～10时左右，在高速搅拌下加入去离子水乳化，搅拌约1～3h，40～60℃下旋蒸即可得到有机硅改性的羟基型水性聚氨酯；
(2)将上述水性聚氨酯树脂按比例与氧化铝和氧化石墨充分混合，后加入水性消泡剂、分散剂、流平剂、增稠剂。按比例配置聚氨酯固化剂，充分搅拌，用滤网过滤，室温下熟化15～30min后涂膜。涂膜于常温下放置一段时间，再放入烘箱中低温烘烤20～30min，取出后于常温下固化24～48h。
步骤(1)中所述的端羟基硅油为端羟甲基硅油、端羟乙基硅油、端羟丙基硅油、端羟丁基硅油中的一种或几种的混合物，端羟基硅油的分子量在500～2000，聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的一种或几种的混合物，羟基硅油与聚酯二元醇的物质的量的比：n(羟基硅油)/n(聚酯二元醇或聚醚二元醇)＝1:(5～9)；三羟甲基丙烷的质量分数为5～10％；多羟基羧酸为2,2’-二羟甲基丙酸(DMPA)、2,2’-二羟甲基丁酸(DMBA)中的一种或几种的混合物；小分子二元醇为1,6-己二醇、1,4-丁二醇中的一种或几种的混合物，小分子二元醇的用量占总质量的1～5％；催化剂为二月桂酸二丁基锡(DBTDL)，催化剂的质量百分含量为0.1～0.3％；二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛二酮二异氰酸酯(IPDI)、己二异氰酸酯(HDI)、4,4’-二苯基甲烷二异氰酸酯中的一种或几种的混合物，二异氰酸酯与含羟基化合物的物质的量比：n(二异氰酸酯)/n(含羟基化合物)＝1:1.1～1.5；丙酮加入量的质量分数为5～20％；胺为三乙胺或二甲氨基乙醇中的一种或几种的混合物，三乙胺的物质的量与羧基的摩尔比：n(三乙胺)/n(羧基含量)＝0.6～1.1:1；去离子水的加入的质量分数为树脂的30～60％。
步骤(2)中所述的氧化铝为30～3000nm；水性聚氨酯固化剂与水性树脂的为(0.15～0.3)；1；消泡剂占3～5％；分散剂占3～5％；流平剂占3～5％；增稠剂占5～10％；氧化铝或者氧化石墨占10～20％。
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