CN108530874A - 一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法 - Google Patents

一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法 Download PDF

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CN108530874A
CN108530874A CN201710120191.9A CN201710120191A CN108530874A CN 108530874 A CN108530874 A CN 108530874A CN 201710120191 A CN201710120191 A CN 201710120191A CN 108530874 A CN108530874 A CN 108530874A
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李刚
罗丛叶
杨小平
李波
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Beijing University of Chemical Technology
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Abstract

本发明公开一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法。其特征在于：首先制备含有聚氨酯柔性链段和刚性五元环的高温韧性环氧树脂基体，以二异氰酸酯与多元醇合成端异氰酸酯的聚氨酯预聚体，使环氧树脂开环反应得到高温韧性环氧树脂基体；将快速固化体系与液态环氧树脂捏合制备固化剂母料组分，加入高温韧性环氧树脂中混合均匀得到预浸料用树脂体系；采用热熔法制备树脂胶膜并与碳纤维或织物复合，获得快速成型预浸料。以高温韧性环氧树脂制备的树脂体系可以实现150℃下5min固化，玻璃化转变温度高，所制备预浸料的工艺性好，断裂韧性佳，适于复合材料的快速成型，易于高温脱模，不易翘曲变形，可在碳纤维复合材料的快速成型领域规模化应用。

Description

一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备 方法
技术领域
本发明属于碳纤维复合材料的技术领域，特别地涉及一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法。
背景技术
碳纤维/热固性树脂复合材料具有高比强度、高比模量、耐高温、耐疲劳等特性，是公认的首选轻量化材料，然而其较长的生产周期大大限制了碳纤维复合材料在快速成型领域的规模化应用。预浸料模压成型是碳纤维复合材料快速成型工艺之一，实现快速成型要求与之匹配的树脂体系一方面满足固化时间短，缩短成型周期，另一方面也要进行树脂基体增韧改性，改善环氧树脂固化后质脆、与纤维界面性差的缺点。
欧洲专利（EP1279688A1）公开了一种环氧树脂组合物，既可以在低温（80℃）下固化也可以在高温（150℃）下固化，固化时间由5h降低到3min，但为了提高树脂的柔韧性和冲击强度，还需要另外加入增韧组分。美国专利（U.S. 4564651）利用过量的环氧树脂与异氰酸酯混合，共固化得到力学性能、尺寸稳定性和耐热性能良好的树脂模塑材料，但是该树脂体系无法满足预浸料模压成型的工艺要求。中国专利（CN103113604A）公开了一种聚氨酯预聚体改善中低温固化预浸料层间剪切强度的制备方法，采用聚氨酯与环氧树脂接枝反应，树脂基体增韧效果显著，预浸料操作工艺性好，但是树脂的耐热性能无法满足高温下复合材料的快速成型。
发明内容
本发明针对环氧树脂固化后质脆、与纤维界面性差及其碳纤维复合材成型周期较长等缺点，通过一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法，实现对环氧树脂基体的增韧和碳纤维复合材料的快速成型。
本发明的主要技术方案：A、以两步反应法制备高温韧性环氧树脂，将二异氰酸酯和聚醚二元醇按照-NCO:-OH摩尔比例3:1~1.2:1在40~80℃反应3~6h得到端异氰酸酯的聚氨酯预聚体；将液态环氧树脂与聚氨酯预聚体及二异氰酸酯按照质量比100:10~50:4~20，在催化剂作用下于130~200℃反应1.5~6h，得到高温韧性环氧树脂基体，其中相对于质量100份环氧树脂，催化剂的质量分数为0.05~1份；B、将快速固化体系9~20份与30~60份（以环氧树脂的最终用量为100份计算）液态环氧树脂捏合制备固化剂母料组分，加入70~40份（以环氧树脂的最终用量为100份计算）步骤A所得高温韧性环氧树脂中，得到预浸料用树脂体系；C、将步骤B所得预浸料用树脂体系采用胶膜法制得胶膜，经由复合机与碳纤维或织物复合，制备快速成型预浸料。
所述的二异氰酸酯为二苯基甲烷二异氰酸酯（MDI）、液化二苯基甲烷二异氰酸酯（L-MDI）、甲苯二异氰酸酯（TDI）、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、4,4'-二环己基甲烷异氰酸酯（HMDI）中的一种或多种组合。
所述的聚醚二元醇为聚丁二烯二醇、聚硅氧烷二醇、聚四亚甲基醚二醇（PTMG）或聚丙二醇（PPG）聚乙二醇（PEG）或聚环氧丙烷中的一种或多种组合。
所述的催化剂为N,N-二甲基卞胺、三乙胺、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、LiCl、ZnI、羧酸锌、有机锌螯合物、正丁基锂、三烷基铝、氯化锌/三甲胺络合物中的一种或多种组合。
所述的液态环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、双酚AD型环氧树脂、酚醛型环氧树脂中的一种或多种组合。
所述的快速固化体系为咪唑类、硫醇类、胺类化合物、脲类衍生物、双氰胺、三氟化硼-乙胺络合物中的一种或多种组合。
本发明具有以下几方面的优点和积极效果：
（1）本发明得到的高温韧性环氧树脂中，由异氰酸酯和多元醇的反应引入了聚氨酯柔性链段，提高了树脂基体的韧性，同时强极性基团的引入使碳纤维与树脂基体间的粘结力增强，复合材料层间断裂韧性显著提升，有利于提高碳纤维的强度发挥率。
（2）本发明得到的高温韧性环氧树脂中，由异氰酸酯和环氧基的反应引入了刚性的五元环结构，提高了树脂基体耐热性能，玻璃化转变温度在140℃以上，可以实现复合材料制件的高温脱模，且不易翘曲变形。
（3）本发明能够实现树脂体系在150℃下5min固化度达到95%以上，缩短了复合材料成型周期，提高了生产效率。
具体实施方式
下面通过具体实施例对本发明做进一步的说明，但本发明不限于以下实施例。
实施例1
将聚硅氧烷二醇（Mw=2000）与异佛尔酮二异氰酸酯按照摩尔比-NCO：-OH=3:1在40℃下反应6h，得到端异氰酸酯的聚氨酯预聚体；取10g端异氰酸酯的聚氨酯预聚体，加入双酚A型环氧100g混合均匀，升高温度后加入催化剂2-苯基咪唑0.05g，继续滴加异佛尔酮二异氰酸酯20g，滴加完成后升温至200℃反应1.5h，得到高温韧性环氧树脂，测试环氧值为0.242。
取30份（质量份数，以环氧树脂的最终用量为100份计算得到，下同）液态双酚A型环氧树脂与12份双氰胺和脲类衍生物的组合物捏合得到固化体系母料，与得到的高温韧性环氧树脂70份在适宜温度下混合均匀，得到预浸料用树脂体系，150℃×5min制备浇注体样条。DSC法测试树脂体系的玻璃化转变温度为149℃，冲击强度为20KJ/m2。采用上述树脂体系制得的胶膜与碳纤维复合制成预浸料，150℃×5min得到复合材料板材。DMA法测试复合材料的玻璃化转变温度为185℃，层间断裂韧性（GIC）为534J/m2。
实施例2
将聚乙二醇（Mw=1000）与二苯基甲烷二异氰酸酯按摩尔比-NCO：-OH=2:1在80℃下反应3h，得到端异氰酸酯的聚氨酯预聚体；取30g端异氰酸酯的聚氨酯预聚体，加入酚醛型环氧和双酚F型环氧组合物100g混合均匀，升高温度后加入催化剂三乙胺1g，继续滴加二苯基甲烷二异氰酸酯12g，滴加完成后升温至160℃反应4h，得到高温韧性环氧树脂，测试环氧值为0.278。
取45份（质量份数，以环氧树脂的最终用量为100份计算得到，下同）液态双酚A型环氧树脂与9份咪唑和改性脂肪胺捏合得到固化体系母料，与得到的高温韧性环氧树脂55份在适宜温度下混合均匀，得到预浸料用树脂体系，150℃×5min制备浇注体样条。DSC法测试树脂体系的玻璃化转变温度为145℃，冲击强度为2823KJ/m2。采用上述树脂体系制得的胶膜与碳纤维复合制成预浸料，150℃×5min得到复合材料板材。DMA法测试复合材料的玻璃化转变温度为180℃，层间断裂韧性（GIC）为607J/m2。
实施例3
将聚四亚甲基醚二醇（Mw=400）与4,4’-二环己基甲烷二异氰酸酯按摩尔比-NCO：-OH=1.2:1在60℃下反应4h，得到聚氨酯预聚体；取50g聚氨酯预聚体，加入双酚AD型环氧100g混合均匀，升高温度后加入催化剂2-乙基-4-甲基咪唑0.5g，继续滴加4,4’-二环己基甲烷二异氰酸酯4g，滴加完成后升温至130℃反应6h，得到高温韧性环氧树脂，测试环氧值为0.265。
取60份（质量份数，以环氧树脂的最终用量为100份计算得到，下同）液态双酚A型环氧树脂与20份改性胺类和咪唑类组合物捏合得到固化体系母料，与得到的高温韧性环氧树脂40份在适宜温度下混合均匀，得到预浸料用树脂体系，150℃×5min制备浇注体样条。DSC法测试树脂体系的玻璃化转变温度为137℃，冲击强度为23KJ/m2。采用上述树脂体系制得的胶膜与碳纤维复合制成预浸料，150℃×5min得到复合材料板材。DMA法测试复合材料的玻璃化转变温度为174℃，层间断裂韧性（GIC）为586J/m2。
对比例
取40份（质量份数，以环氧树脂的最终用量为100份计算得到，下同）液态双酚A型环氧树脂与20份改性胺类和咪唑类组合物捏合得到固化体系母料，与固态双酚A型环氧树脂60份在适宜的温度下混合均匀，得到预浸料环氧树脂体系，150℃×5min℃制备浇注体样条。DSC法测试树脂体系的玻璃化转变温度为127℃，冲击强度为18KJ/m2。采用上述树脂体系制得的胶膜与碳纤维复合制成预浸料，150℃×5min得到复合材料板材。DMA法测试复合材料的玻璃化转变温度为161℃，层间断裂韧性（GIC）为338J/m2。

Claims (6)

1.一种高温韧性环氧树脂及其快速成型碳纤维预浸料的制备方法，其特征在于，A、以两步反应法制备高温韧性环氧树脂，将二异氰酸酯和聚醚二元醇按照-NCO:-OH摩尔比例3:1~1.2:1在40~80℃反应3~6h得到端异氰酸酯的聚氨酯预聚体；将液态环氧树脂与端异氰酸酯的聚氨酯预聚体及二异氰酸酯按照质量比100:10~50:4~20，在催化剂作用下于130~200℃反应1.5~6h，得到高温韧性环氧树脂基体，其中相对于质量100份环氧树脂，催化剂的质量分数为0.05~1份；B、将快速固化体系9~20份与30~60份（以环氧树脂的最终用量为100份计算）液态环氧树脂捏合制备固化剂母料组分，加入70~40份（以环氧树脂的最终用量为100份计算）步骤A所得高温韧性环氧树脂中，得到预浸料用树脂体系；C、将步骤B所得预浸料用树脂体系采用胶膜法制得胶膜，经由复合机与碳纤维或织物复合，制备快速成型预浸料。
2.根据权利要求1的制备方法，其特征在于：所述的二异氰酸酯为二苯基甲烷二异氰酸酯（MDI）、液化二苯基甲烷二异氰酸酯（L-MDI）、甲苯二异氰酸酯（TDI）、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、4,4'-二环己基甲烷异氰酸酯（HMDI）中的一种或多种组合。
3.根据权利要求1的制备方法，其特征在于：所述的聚醚二元醇为聚丁二烯二醇、聚硅氧烷二醇、聚四亚甲基醚二醇（PTMG）或聚丙二醇（PPG）聚乙二醇（PEG）或聚环氧丙烷中的一种或多种组合。
4.根据权利要求1的制备方法，其特征在于：所述的催化剂为N,N-二甲基卞胺、三乙胺、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、LiCl、ZnI、羧酸锌、有机锌螯合物、正丁基锂、三烷基铝、氯化锌/三甲胺络合物中的一种或多种组合。
5.根据权利要求1的制备方法，其特征在于：所述的液态环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、双酚AD型环氧树脂、酚醛型环氧树脂中的一种或多种组合。
6.根据权利要求1的制备方法，其特征在于：所述的快速固化体系为咪唑类、硫醇类、胺类化合物、脲类衍生物、双氰胺、三氟化硼-乙胺络合物中的一种或多种组合。
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