CN109486112B - 一种热塑性聚合物基复合材料及其制备方法 - Google Patents

一种热塑性聚合物基复合材料及其制备方法 Download PDF

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CN109486112B
CN109486112B CN201811322014.XA CN201811322014A CN109486112B CN 109486112 B CN109486112 B CN 109486112B CN 201811322014 A CN201811322014 A CN 201811322014A CN 109486112 B CN109486112 B CN 109486112B
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王钧
邹俊杰
杨小利
刘伟
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Bestone New Material Technology Wuhan Co ltd
Wuhan University of Technology WUT
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Abstract

本发明涉及一种热塑性聚合物基复合材料及其制备方法。所述热塑性聚合物基复合材料是由环氧树脂、双酚A/F、催化剂的混合物或低聚物浸渍增强材料并原位聚合制成。所述热塑性聚合物基复合材料具有优异的浸渍性能、优良的二次加工性能、较高的耐热性能及力学性能，综合性能优异。

Description

一种热塑性聚合物基复合材料及其制备方法
技术领域
本发明涉及一种热塑性聚合物基复合材料及其制备方法，属于聚合物基复合材料技术领域。
背景技术
聚合物基复合材料已广泛应用到航空航天、船舶、汽车等领域，根据其树脂基体的不同可分为热固性和热塑性复合材料。在过去的半个世纪中，热固性树脂基复合材料作为一种新型材料早已获得工程界的普遍承认，已经进入工业化生产阶段，并以相当高的速率保持快速增长。但是，热固性复合材料仍然存在着某些不足，如固化时间长、VOC排放大、抗冲击和抗损伤能力低等。当今时代，全世界都在极度关注废弃物和有害气体对环境造成的日益严重的污染问题，欧美等发达国家已经开始要求复合材料制造商对热固性复合材料废弃物进行回收处理，并限制热固性复合材料成型过程中有害气体的排放。热塑性复合材料成型时间短、废料可以回收再利用等独特优点，受到复合材料界广泛关注。
目前，热塑性复合材料的制造方法主要为热熔法或溶剂法。热熔法主要是通过加热的方法将热塑性树脂熔融变成粘稠状液体然后再浸渍纤维。但是，热塑性聚合物熔体均具有较高的熔体黏度，较高的熔融温度，给热塑性复合材料的纤维浸渍和加工成型带来了一定的困难。溶剂法是通过适当的溶剂将树脂溶解变成溶液然后再浸渍纤维，而后再将溶剂加热蒸发除去。但是这种方法成本高，VOC排放大，且残留的溶剂会影响复合材料的性能。因此，原位聚合法制备热塑性聚合物基复合材料越来越得到关注。
中国专利CN 200510110969公开了一种原位聚合法制备纤维增强ABS的方法。中国专利CN 201610382346公开了一种原位聚合法制备纤维增强聚烯烃及PMMA的方法。中国专利CN 200610040172公开了一种热塑性聚氨酯(TPU)/尼龙6复合材料的原位缩聚的制备方法。上述方法主要是针对现有常用热塑性基体，通过原位聚合的方法制备热塑性复合材料，可以克服传统熔融法及溶剂法的部分缺点，但是其制备的复合材料的界面性能未能得到关注。
中国专利CN 106117514 A公开了一种热塑性复合材料及制备的方法，是采用单官能基一级胺或双官能基二基胺和环氧树脂的混合物浸渍纤维后，通过原位聚合的方法制成复合材料。这种方法虽然解决了界面问题，但是使用通用环氧树脂制备的复合材料耐热性能较低，玻璃化转变温度为50-65℃，实用价值不高。
因此，传统热固性复合材料虽然具有耐热高、强度高等优点，但也存在环境友好性不足、生产工艺受限、不可回收等缺点，热塑性复合材料具有成型速率高、无VOC排放、环境友好、可回收利用等优势，但传统热塑性复合材料也存在树脂对纤维的浸润不足，耐热不足等劣势，热塑性复合材料主流的热熔法浸渍效果差，所需温度高；溶剂法将会消耗大量的有机溶剂，易造成环境污染；新兴的原位聚合法在界面、原料选用、耐热性能方面存在不足的问题。因此，需要开发一种综合性能优良的热塑性复合材料。
发明内容
针对上述问题，本发明提供了一种热塑性聚合物基复合材料及其制备方法，制备的热塑性聚合物基复合材料具有优良的二次加工性能、较高的耐热性能及力学性能，综合性能优异。
为了实现上述目的，本发明采用的技术方案为：
一种热塑性聚合物基复合材料，由环氧树脂、双酚A/F、催化剂的混合物或低聚物浸渍增强材料后进行原位聚合反应而制成，其中，双酚A/F的摩尔数为环氧官能团摩尔数的0.3-0.6，催化剂在混合物中的重量百分比为0.1％-5％。
优选地，所述环氧树脂为以下结构通式所示的一种或多种：
Figure BDA0001857332470000021
其中，R代表C2-C18烷基或芳香基或环烷基、双酚A结构、双酚F结构、双酚S结构、卤代双酚A结构、卤代双酚F结构、卤代双酚S结构、氢化双酚A结构、氢化双酚F结构、氢化双酚S结构；n为0-20。
更优选地，所述环氧树脂为双酚A型环氧树脂。
优选地，所述催化剂为季胺盐、叔膦、季鏻盐及其组合物。
优选地，所述的增强材料包括但不限于玻璃纤维、碳纤维、芳纶纤维、凯芙拉纤维、玄武岩纤维、PBO纤维、尼龙纤维、超高分子量聚乙烯纤维、聚酰亚胺纤维、聚酯纤维的一种或组合。
一种热塑性聚合物基复合材料的制备方法，包括以下步骤：
(1)先将环氧树脂加热到80-150℃，再加入双酚A/F溶解并搅拌均匀制成A组分备用；
(2)将催化剂分散到环氧树脂中，制成B组分备用；
(3)将A组分和B组分混合后，迅速对增强材料进行浸渍，浸渍完成后，进行原位聚合制成热塑性聚合物基复合材料。
其中，步骤(1)和(2)中，用到的环氧树脂在A、B组分中的分配比例以方便设备进行计量混合为限度。也可添加少量多官能度环氧树脂，以形成支化或轻度交联结构聚合物，添加量以控制交联密度未达到凝胶点，聚合产物为可溶、可熔的热塑性聚合物为限度。
优选地，步骤(3)中，所述A组分与B组分的体积比为10∶1～1∶1，以便于混合操作。
优选地，步骤(3)中，浸渍时的温度为80-120℃。
优选地，步骤(3)中，进行原位聚合的温度为80-200℃。
另外，步骤(3)制成的热塑性聚合物基复合材料可二次加热软化后，进行二次加工。
与现有技术相比，本发明的有益效果是：
利用了双酚A/F在一定温度下能够溶解到环氧树脂中的特性，制成低粘度液体，可以方便的浸渍增强材料；浸渍完成后，在一定的温度下，又可以原位聚合生成线型高分子聚合物。
本发明综合利用便宜易得的原材料，使用原位聚合的方法，制得力学性能、耐热性能、界面性能都很优异的热塑性聚合物基复合材料。
具体实施方式
为了更好的理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明不仅仅局限于下面的实施例。
实施例1
1.A组分的制备
称取100g双酚A型环氧树脂(850S，EEW＝185-195，购自南通星辰合成材料有限公司)，加热到115℃后，加入80g双酚A，充分搅拌至双酚A完全溶解，上述混合物即为A组分。
测试A组分110℃的粘度为150mPa.s。
将A组分在110℃温度下保温放置3天后，测试其110℃的粘度为380mPa.s。
2.B组分的制备
称取100g双酚A型环氧树脂(850S，EEW＝185-195，购自南通星辰合成材料有限公司)，加入4g甲基三苯基溴化膦分散均匀，上述混合物为B组分。
测试B组分在80℃时的粘度为220mPa.s。
将B组分在80℃下保温存放8天，测试其在80℃时的粘度为420mPa.s。
3.A组分和B组分混合
将A、B组分按5∶1混合均匀，测试其80℃时的粘度为408mPa.s，在80℃下保温1小时后，测试其80℃时的粘度为1964mPa.s。继续保温3小时，然后升高温度到160℃保温1小时，测试产物Tg为113℃。
4.热塑性聚合物基复合材料的制备
裁剪9块15cm×15cm的玻璃纤维布，平铺于玻璃板上，将A、B组分按5∶1混合均匀并保持温度为80℃，用刷子均匀地涂覆于玻璃纤维布上，浸透玻璃纤维布。将浸透好的纤维布放入烘箱中120℃下4小时，进行原位聚合，制成9块复合材料预浸片。
将9块预浸片叠放在一起，放入热压机的模具中，模具温度160℃，热压5分钟取出，冷却，制成热塑性复合材料层合板。
从实施例1可以看出，双酚A在一定温度下，可充分溶解到环氧树脂中，形成低粘度溶液，且在较高温度下具有很长的存储期；催化剂分散到环氧树脂中以后，在较高温度下可以有很长的存储期；A、B组分混合后，可快速反应生成聚合物；使用本发明可得到低粘度液体，有效的浸渍增强材料，制备热塑性聚合物基复合材料。
实施例2
在实施例1的基础上，其他条件不变，将催化剂改为苄基三甲基氯化胺，也能制得相似的热塑性复合材料层合板。
实施例3
在实施例1的基础上，其他条件不变，将催化剂改为三苯基膦，也能制得相似的热塑性复合材料层合板。
从实施例2、3可以看出，改用不同的催化剂，也能得到相似的热塑性复合材料。
实施例4
在实施例1的基础上，其他条件不变，将双酚A型环氧树脂改成双酚F型环氧树脂(EEW＝165-175，购自南通星辰合成材料有限公司)，将双酚A改成双酚F，也能成功制得热塑性复合材料层合板，但是耐热性能略低，Tg为76℃。
从实施例4可以看出，改用双酚F及双酚F型环氧树脂，也能得到相似的热塑性复合材料。
实施例5
在实施例1的基础上，其他条件不变，将其中10％的双酚A型环氧树脂改成酚醛型环氧树脂(NPPN-631，EEW＝168-178，购自南亚环氧树脂(昆山)有限公司)，也能成功制得热塑性复合材料层合板，测试产物Tg为122℃。
将制得的复合材料层合板放入350℃烘箱内半小时，发现聚合物基体可以熔化。
从实施例5可以看出，添加少量的多官能度环氧树脂，制成得复合材料也具有热塑性，且能够提高耐热性。

Claims (6)

1.一种热塑性聚合物基复合材料的制备方法，由环氧树脂、双酚A或F、催化剂的混合物或低聚物浸渍增强材料后进行原位聚合反应，其中，双酚A或F的摩尔数为环氧官能团摩尔数的0.3-0.6，催化剂在混合物中的重量百分比为0.1％-5％，包括以下步骤：
(1)先将环氧树脂加热到80-150℃，再加入双酚A或F溶解并搅拌均匀制成A组分备用；
(2)将催化剂分散到环氧树脂中，制成B组分备用；
(3)将A组分和B组分混合后，迅速对增强材料进行浸渍，浸渍时的温度为80-120℃，浸渍完成后，进行原位聚合制成热塑性聚合物基复合材料，原位聚合的温度为80-200℃，所述A组分与B组分的重量比为10：1～1：1。
2.根据权利要求1所述的一种热塑性聚合物基复合材料的制备方法，其特征在于，所述环氧树脂为以下结构通式所示的一种或多种：
Figure FDA0003594185140000011
其中，R代表C2-C18烷基或芳香基或环烷基、双酚A结构、双酚F结构、双酚S结构、卤代双酚A结构、卤代双酚F结构、卤代双酚S结构、氢化双酚A结构、氢化双酚F结构、氢化双酚S结构；n为0-20。
3.根据权利要求1所述的一种热塑性聚合物基复合材料的制备方法，其特征在于，所述催化剂为季胺盐、叔膦、季鏻盐或其组合物。
4.根据权利要求1所述的一种热塑性聚合物基复合材料的制备方法，其特征在于，所述的增强材料选自玻璃纤维、碳纤维、玄武岩纤维、PBO纤维、尼龙纤维、超高分子量聚乙烯纤维、聚酰亚胺纤维、聚酯纤维中的一种或组合。
5.根据权利要求1所述的一种热塑性聚合物基复合材料的制备方法，其特征在于，也可添加少量多官能度环氧树脂，以形成支化或轻度交联结构聚合物，添加量以控制交联密度未达到凝胶点，聚合产物为可溶、可熔的热塑性聚合物为限度。
6.权利要求1-5任意一项所述的一种热塑性聚合物基复合材料的制备方法制成的热塑性聚合物基复合材料。
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