CN107033805A - 一种聚丙烯酸酯‑玻璃纤维布的复合导热绝缘压敏胶带及其制备方法 - Google Patents

一种聚丙烯酸酯‑玻璃纤维布的复合导热绝缘压敏胶带及其制备方法 Download PDF

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CN107033805A
CN107033805A CN201710276822.6A CN201710276822A CN107033805A CN 107033805 A CN107033805 A CN 107033805A CN 201710276822 A CN201710276822 A CN 201710276822A CN 107033805 A CN107033805 A CN 107033805A
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许义彬
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Abstract

一种聚丙烯酸酯‑玻璃纤维布的复合导热绝缘压敏胶带,其特征在于,首先以乙烯基三氯硅烷水解缩合得到八乙烯基多面体倍半硅氧烷;八乙烯基多面体倍半硅氧烷的乙烯基与烯丙基缩水甘油醚的烯丙基催化聚合反应,得到环氧基多面体倍半硅氧烷;然后与二环已基甲烷二异氰酸酯反应,得到具有端‑NCO基团的多面体倍半硅氧烷;以此硅氧烷改性聚合聚丙烯酸酯,得到胶液,最后在两层玻璃纤维之间涂敷胶液并干燥,得到聚丙烯酸酯‑玻璃纤维布的复合导热绝缘压敏胶带。本发明的胶带,导热率高,粘接性能好,耐老化性能优异,同时具有优异的模切加工性能,可广泛用于各种发热器件和散热片的粘结。

Description

一种聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带及其 制备方法
技术领域
本发明属于胶带领域,具体涉及一种聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带及其制备方法。
背景技术
多面体低聚倍半硅氧烷(polyhedral oligomeric silsesquioxane,POSS)是一类特殊的倍半硅氧烷,分子为(RSiO1.5)n,其结构通常由六面体笼形的Si-O-Si无机内核和顶点的8个有机取代基R组成,其中R可以是一个或多个有机官能团,是一种真正意义上的分子纳米杂化化合物。这种新型的杂化材料不仅具备高分子材料的韧性、成本低以及良好加工性,同时又具有无机材料的强度高、不易氧化、耐高温、力学性能好等多个优点。目前,利用POSS作为纳米构件制备新型有机-无机杂化材料已经成为研究的热点,引入POSS可提高材料的热稳定性,改善机械性能和其它物理性能。
作者唐威等人在《环氧基倍半硅氧烷的合成与表征》一文中,以乙烯基三氯硅烷经水解缩合,先制备八乙烯基多面体倍半硅氧烷,然后以过氧乙酸直接氧化乙烯官能团制得环氧基多面体倍半硅氧烷。采用此种方法制备得到的环氧基多面体倍半硅氧烷,平均每个多面体倍半硅氧烷只能带有3-4个环氧基,且环氧基的相对位置不固定,得到的是带有不同个数和不同位置环氧基的多面体倍半硅氧烷。而且此种方法得到的环氧基直接连载多面体倍半硅氧烷的骨架Si上,由于位阻较大,反应活性大大降低,影响其使用性能。
发明内容
本发明的目的在于提供一种导热性能优异的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带及其制备方法。
为了实现上述目的,本发明采用了如下技术方案:
一种聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带,其特征在于,首先以乙烯基三氯硅烷水解缩合得到八乙烯基多面体倍半硅氧烷;八乙烯基多面体倍半硅氧烷的乙烯基与烯丙基缩水甘油醚的烯丙基催化聚合反应,得到环氧基多面体倍半硅氧烷;然后与二环已基甲烷二异氰酸酯反应,得到具有端-NCO基团的多面体倍半硅氧烷;以此硅氧烷改性聚合聚丙烯酸酯,得到胶液,最后在两层玻璃纤维之间涂敷胶液并干燥,得到聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带。
所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带,其特征在于,其由如下步骤制备而成:
(1)将乙烯基三氯硅烷与丙酮按质量比为1:10-12的比例加入到反应容器中,机械搅拌使其混合均匀,以30-40滴/min的速率缓慢滴加相当于丙酮重量份35-45%的去离子水,40-45℃恒温冷凝回流60-72h,抽滤,丙酮洗涤3-4次,再采用四氢呋喃与甲醇体积比为1:2-3配置的混合溶液重结晶,60-65℃真空干燥20-24h,得到八乙烯基多面体倍半硅氧烷;
(2)将步骤(1)的产物、烯丙基缩水甘油醚和甲苯按质量比1:1.2-1.3:8-10加入反应容器中,通氮气30-40min排除氧气并混合搅拌均匀,加入催化剂2,2′-偶氮二异丁腈和助催化剂乙酰基丙酮酸铬,继续混合搅拌均匀,升温至60-70℃,恒温磁力搅拌冷凝回流12-15h,旋转蒸发浓缩,60-65℃真空干燥,得到环氧基多面体倍半硅氧烷;
(3)在干燥反应器内按质量比1:8-10:0.01-0.02:12-15加入步骤(2)的产物、二环已基甲烷二异氰酸酯、二月桂酸二丁基锡和二甲基亚砜,通氮气并混合搅拌均匀,升高温度至55-65℃,恒温磁力搅拌6-8h,除去过量的二环已基甲烷二异氰酸酯,得到具有端-NCO基团的多面体倍半硅氧烷;
(4)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯按质量比为1:1.2-1.3:0.4-0.5加入到反应器中,通氮气,并控制温度为75-85℃,恒温磁力搅拌至均匀;加入偶氮二异丁腈和步骤(3)的产物,继续恒温磁力搅拌8-10h,冷却至室温,得到胶液;用涂膜器在两层玻璃纤维布之间涂布500-700μm厚的胶液,干燥,得到聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带;其中丙烯酸丁酯、偶氮二异丁腈和步骤(3)的产物的质量比为1:0.01-0.02:0.2-0.3。
所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带的制备方法,其特征在于,步骤(3)中除去过量的二环已基甲烷二异氰酸酯的方法为透析法。
所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带的制备方法,步骤(4)中干燥为以2-4℃/min的升温速率升温至85-90℃干燥20-24h。
采用上述的技术方案,本发明的有益效果为:
本发明以乙烯基三氯硅烷水解缩合得到八乙烯基多面体倍半硅氧烷;八乙烯基多面体倍半硅氧烷的乙烯基与烯丙基缩水甘油醚的烯丙基催化聚合反应,得到环氧基多面体倍半硅氧烷;此种方法得到是全部环氧基多面体倍半硅氧烷,而且环氧基与多面体倍半硅氧烷的骨架Si之间通过一定长度的柔性链相连,位阻较小,环氧基的反应活性较高。本发明所合成的环氧基多面体倍半硅氧烷含有8个环氧基团,与二环已基甲烷二异氰酸酯反应,得到具有端-NCO基团的多面体倍半硅氧烷;以此硅氧烷改性聚合聚丙烯酸酯,得到胶液;将键能较大的Si-O键和Si-C键引入聚丙烯酸酯中,同时环氧基多面体倍半硅氧烷分子中庞大的多面体刚性结构,有利于聚丙烯酸酯的定向的排布,因此,其具有更高的导热性能,能够有效提高导热绝缘压敏胶带的导热率,延长电子器件的使用寿命。本发明以玻璃纤维布作为胶带的基材,提高胶带的绝缘性,并使其适于工业大规模自动化生产,同时具有优异的模切加工性能,组装生产方便,生产效率较高。
具体实施方式
本实施例的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带,其由如下步骤制备而成:
(1)将乙烯基三氯硅烷与丙酮按质量比为1:10的比例加入到反应容器中,机械搅拌使其混合均匀,以30滴/min的速率缓慢滴加相当于丙酮重量份35%的去离子水,45℃恒温冷凝回流72h,抽滤,丙酮洗涤3次,再采用四氢呋喃与甲醇体积比为1:3配置的混合溶液重结晶,65℃真空干燥24h,得到八乙烯基多面体倍半硅氧烷;
(2)将步骤(1)的产物、烯丙基缩水甘油醚和甲苯按质量比1:1.2:10加入反应容器中,通氮气30min排除氧气并混合搅拌均匀,加入催化剂2,2′-偶氮二异丁腈和助催化剂乙酰基丙酮酸铬,继续混合搅拌均匀,升温至70℃,恒温磁力搅拌冷凝回流15h,旋转蒸发浓缩,65℃真空干燥,得到环氧基多面体倍半硅氧烷;
(3)在干燥反应器内按质量比1:10:0.01:15加入步骤(2)的产物、二环已基甲烷二异氰酸酯、二月桂酸二丁基锡和二甲基亚砜,通氮气并混合搅拌均匀,升高温度至65℃,恒温磁力搅拌8h,除去过量的二环已基甲烷二异氰酸酯,得到具有端-NCO基团的多面体倍半硅氧烷;
(4)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯按质量比为1:1.2:0.4加入到反应器中,通氮气,并控制温度为85℃,恒温磁力搅拌至均匀;加入偶氮二异丁腈和步骤(3)的产物,继续恒温磁力搅拌10h,冷却至室温,得到胶液;用涂膜器在两层玻璃纤维布之间涂布600μm厚的胶液,干燥,得到聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带;其中丙烯酸丁酯、偶氮二异丁腈和步骤(3)的产物的质量比为1:0.01:0.2。
本实施例的步骤(3)中除去过量的二环已基甲烷二异氰酸酯的方法为透析法。
本实施例的步骤(4)中干燥为以2-4℃/min的升温速率升温至85-90℃干燥20-24h。

Claims (4)

1.一种聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带,其特征在于,首先以乙烯基三氯硅烷水解缩合得到八乙烯基多面体倍半硅氧烷;八乙烯基多面体倍半硅氧烷的乙烯基与烯丙基缩水甘油醚的烯丙基催化聚合反应,得到环氧基多面体倍半硅氧烷;然后与二环已基甲烷二异氰酸酯反应,得到具有端-NCO基团的多面体倍半硅氧烷;以此硅氧烷改性聚合聚丙烯酸酯,得到胶液,最后在两层玻璃纤维之间涂敷胶液并干燥,得到聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带。
2.根据权利要求书1所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带,其特征在于,其由如下步骤制备而成:
(1)将乙烯基三氯硅烷与丙酮按质量比为1:10-12的比例加入到反应容器中,机械搅拌使其混合均匀,以30-40滴/min的速率缓慢滴加相当于丙酮重量份35-45%的去离子水,40-45℃恒温冷凝回流60-72h,抽滤,丙酮洗涤3-4次,再采用四氢呋喃与甲醇体积比为1:2-3配置的混合溶液重结晶,60-65℃真空干燥20-24h,得到八乙烯基多面体倍半硅氧烷;
(2)将步骤(1)的产物、烯丙基缩水甘油醚和甲苯按质量比1:1.2-1.3:8-10加入反应容器中,通氮气30-40min排除氧气并混合搅拌均匀,加入催化剂2,2′-偶氮二异丁腈和助催化剂乙酰基丙酮酸铬,继续混合搅拌均匀,升温至60-70℃,恒温磁力搅拌冷凝回流12-15h,旋转蒸发浓缩,60-65℃真空干燥,得到环氧基多面体倍半硅氧烷;
(3)在干燥反应器内按质量比1:8-10:0.01-0.02:12-15加入步骤(2)的产物、二环已基甲烷二异氰酸酯、二月桂酸二丁基锡和二甲基亚砜,通氮气并混合搅拌均匀,升高温度至55-65℃,恒温磁力搅拌6-8h,除去过量的二环已基甲烷二异氰酸酯,得到具有端-NCO基团的多面体倍半硅氧烷;
(4)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯按质量比为1:1.2-1.3:0.4-0.5加入到反应器中,通氮气,并控制温度为75-85℃,恒温磁力搅拌至均匀;加入偶氮二异丁腈和步骤(3)的产物,继续恒温磁力搅拌8-10h,冷却至室温,得到胶液;用涂膜器在两层玻璃纤维布之间涂布500-700μm厚的胶液,干燥,得到聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带;其中丙烯酸丁酯、偶氮二异丁腈和步骤(3)的产物的质量比为1:0.01-0.02:0.2-0.3。
3.根据权利要求书2所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带的制备方法,其特征在于,步骤(3)中除去过量的二环已基甲烷二异氰酸酯的方法为透析法。
4.根据权利要求书2所述的聚丙烯酸酯-玻璃纤维布的复合导热绝缘压敏胶带的制备方法,其特征在于,步骤(4)中干燥为以2-4℃/min的升温速率升温至85-90℃干燥20-24h。
CN201710276822.6A 2017-04-25 2017-04-25 一种聚丙烯酸酯‑玻璃纤维布的复合导热绝缘压敏胶带及其制备方法 Pending CN107033805A (zh)

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