CN106751503B - 高模碳纤维预浸料用中温固化环氧树脂体系的制备方法 - Google Patents

高模碳纤维预浸料用中温固化环氧树脂体系的制备方法 Download PDF

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CN106751503B
CN106751503B CN201611121723.2A CN201611121723A CN106751503B CN 106751503 B CN106751503 B CN 106751503B CN 201611121723 A CN201611121723 A CN 201611121723A CN 106751503 B CN106751503 B CN 106751503B
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李刚
向艳丽
李强
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Shandong Guangxuan New Material Co.,Ltd.
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Abstract

本发明涉及一种高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其解决了现有中温固化预浸料的复合材料刚度与韧性不易同时满足、制备工艺复杂且使用不方便的技术问题,其包括如下步骤:(1)将芳香胺固化剂与双马来酰亚胺树脂混合反应,制备改性芳香胺固化剂;(2)将酚氧树脂溶解于液体环氧树脂中,然后加入改性芳香胺固化剂预聚,再降温加入潜伏性固化体系母料组分混合均匀,制备一种兼具高模量、高强度和高韧性的中温固化环氧预浸料树脂体系。

Description

高模碳纤维预浸料用中温固化环氧树脂体系的制备方法
技术领域
本发明涉及复合材料领域,具体地说是一种高模碳纤维预浸料用中温固化环氧树脂体系的制备方法。
背景技术
预浸料作为复合材料构件的中间产品,其质量的优劣、纤维和树脂基体的界面粘接强度直接影响了复合材料的性能。碳纤维复合材料在受到外力作用下,若树脂基体的刚性与韧性不足时,树脂基体难以与高模量碳纤维的模量和断裂形变相匹配,则树脂基体先发生屈服破坏,不能有效传递应力,限制了高模碳纤维性能的发挥,提高树脂基体的模量和韧性可以有效提高碳纤维树脂基复合材料的综合性能。中温固化体系具有成形温度低、周期短、制件尺寸稳定性好等优点,可以显著降低生产成本和能耗,提高生产效率。
申请号为201310287363.3的中国发明专利申请公开了一种韧性环氧树脂固化体系及其制备方法,该发明利用热塑性塑料聚醚酰亚胺、聚砜、聚醚砜等来增韧环氧树脂,提高了固化物的冲击强度和断裂韧性,但热塑性塑料需溶解在溶剂中方能使用。
公开号为CN102702482A的中国发明专利申请公开了高强度和高模量的热固性树脂组合物,是通过氰酸酯单体、双马来酰亚胺单体、环氧树脂、双噁唑啉化合物等组成,通过混合反应后固化物有较高的强度和模量,但是树脂体系为高温固化且固化时间较长。
专利号为US3920768的美国专利公开了一种芳基酰亚胺改性环氧树脂体系的制备方法,利用芳基酰亚胺与环氧树脂混合制备得到性能较为优良的树脂体系,但是制备的预浸料基本没有粘性、工艺性差、且需高温固化。
发明内容
本发明就是为了解决现有中温固化预浸料的复合材料刚度与韧性不易同时满足、制备工艺复杂且使用不方便的技术问题,提供一种以双马来酰亚胺改性的芳香胺固化剂提高树脂基体的模量和强度,以高分子量酚氧树脂实现树脂基体的增韧,并满足预浸料制备的工艺要求且使用方便的高模碳纤维预浸料用中温固化环氧树脂体系的制备方法。
为此,本发明提供了一种高模碳纤维中温固化环氧树脂预浸料的制备方法,其将芳香胺固化剂与双马来酰亚胺树脂按照(2~4):1的摩尔比于120~160℃下反应0.5h~5h,制备改性芳香胺固化剂。将酚氧树脂于120~150℃下溶解于液体环氧树脂中,然后加入上述改性芳香胺固化剂预聚0.5~1.5h,再降温至70~80℃加入潜伏性固化体系母料组分混合均匀,制备增强增韧的中温固化环氧预浸料用树脂体系。将上述树脂体系采用胶膜机涂膜,然后经由复合机与增强纤维或织物复合,制备耐热性和工艺性良好的同步增强增韧中温固化预浸料。酚氧树脂的数均分子量在40000~60000,相对于100份液体环氧树脂,其质量份数为5~15份。改性芳香胺固化剂,相对于100份液体环氧树脂,其质量份数为1~5份。
优选的,芳香胺固化剂为二氨基二苯基甲烷、二氨基二苯砜、二氨基二苯醚中的一种或几种。
优选的,双马来酰亚胺树脂为二苯甲烷双马来酰亚胺、二苯砜双马来酰亚胺、二苯醚双马来酰亚胺中的一种或几种。
优选的,液体环氧树脂为双酚A缩水甘油醚、双酚F缩水甘油醚、双酚AD缩水甘油醚、酚醛环氧树脂、脂环族环氧树脂中的一种或几种。
优选的,潜伏性固化体系母料组分为双氰胺、改性双氰胺、脲类衍生物、咪唑衍生物中的一种或几种,相对于100份液体环氧树脂,其质量份数为5~15份。
本发明的有益效果是:双马来酰亚胺改性的芳香胺固化剂的加入在结构上引入苯环与酰亚胺环结构,提高树脂体系的交联密度增加其模量。酚氧树脂是热塑性的环氧树脂,与基体环氧树脂完全相容,添加后树脂基体的韧性得以提升,而且可以拓宽树脂的粘度曲线,解决复合材料成型时树脂流胶严重的问题。本发明可以同步提高环氧树脂的刚度和韧性,使得树脂基体能够与碳纤维的模量和断裂应变相匹配,有利于提高复合材料中高模碳纤维强度的发挥效率。
具体实施方式
以下通过具体实施例对本发明做更详细的说明:
实施例1
将芳香胺固化剂与双马来酰亚胺树脂按照2:1的摩尔比于120℃下反应5h,制备改性芳香胺固化剂,再将5份数均分子量为40000的酚氧树脂在120℃下溶解于100份液体环氧树脂中,然后加入1份上述改性芳香胺固化剂预聚0.5h,降温至70℃加入5份潜伏性固化体系母料组分混合均匀,制备增强增韧中温固化环氧预浸料树脂体系;将上述树脂体系于130℃下固化2小时,测其拉伸模量为3050MPa、断裂伸长率为2.54、弯曲模量为3070MPa。将上述树脂体系采用胶膜机制备胶膜,然后经由复合机与增强纤维或织物复合制备预浸料。将上述预浸料在130℃下固化2小时,测其层间剪切强度为68MPa。
实施例2
将芳香胺固化剂与双马来酰亚胺树脂按照3:1的摩尔比于140℃下反应2.5h,制备改性芳香胺固化剂,再将10份数均分子量为50000的酚氧树脂在130℃下溶解于100份液体环氧树脂中,然后加入3份上述改性芳香胺固化剂预聚1h,降温至75℃加入10份潜伏性固化体系母料组分混合均匀,制备增强增韧中温固化环氧预浸料树脂体系;将上述树脂体系于130℃下固化2小时,测其拉伸模量为3210MPa、断裂伸长率为2.75、弯曲模量为3200MPa。将上述树脂体系采用胶膜机制备胶膜,然后经由复合机与增强纤维或织物复合制备预浸料。将上述预浸料在130℃下固化2小时,测其层间剪切强度为71MPa。
实施例3
将芳香胺固化剂与双马来酰亚胺树脂按照4:1的摩尔比于160℃下反应0.5h,制备改性芳香胺固化剂,再将15份数均分子量为60000的酚氧树脂在150℃下溶解于100份液体环氧树脂中,然后加入5份上述改性芳香胺固化剂预聚1.5h,降温至80℃加入15份潜伏性固化体系母料组分混合均匀,制备增强增韧中温固化环氧预浸料树脂体系;将上述树脂体系于130℃下固化2小时,测其拉伸模量为3380MPa、断裂伸长率为2.89、弯曲模量为3400MPa。将上述树脂体系采用胶膜机制备胶膜,然后经由复合机与增强纤维或织物复合制备预浸料。将上述预浸料在130℃下固化2小时,测其层间剪切强度为73MPa。
对比例1
将5份数均分子量为40000的酚氧树脂在120℃下溶解于100份液体环氧树脂中,降温至70℃加入5份潜伏性固化体系母料组分混合均匀,制备增强增韧中温固化环氧预浸料树脂体系;将上述树脂体系于130℃下固化2小时,测其拉伸模量为2830MPa、断裂伸长率为2.45、弯曲模量为2810MPa。将上述树脂体系采用胶膜机制备胶膜,然后经由复合机与增强纤维或织物复合制备预浸料。将上述预浸料在130℃下固化2小时,测其层间剪切强度为62MPa。

Claims (5)

1.一种高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其特征是包括如下步骤:
(1)将芳香胺固化剂与双马来酰亚胺树脂按照(2~4):1的摩尔比于120~160℃下预聚反应0.5h~5h,制备改性芳香胺固化剂;
(2)将酚氧树脂于120~150℃下溶解于液体环氧树脂中,然后加入所述步骤(1)中得到的改性芳香胺固化剂预聚0.5~1.5h,再降温至70~80℃加入潜伏性固化体系母料组分混合均匀,制备增强增韧中温固化环氧预浸料树脂体系;所述酚氧树脂的数均分子量在40000~60000,相对于100份液体环氧树脂,其质量份数为5~15份;所述改性芳香胺固化剂,相对于100份液体环氧树脂,其质量份数为1~5份。
2.根据权利要求1所述的高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其特征在于所述的芳香胺固化剂为二氨基二苯基甲烷、二氨基二苯砜、二氨基二苯醚中的一种或几种。
3.根据权利要求1所述的高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其特征在于所述的双马来酰亚胺树脂为二苯甲烷双马来酰亚胺、二苯砜双马来酰亚胺、二苯醚双马来酰亚胺中的一种或几种。
4.根据权利要求1所述的高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其特征在于所述的液体环氧树脂为双酚A缩水甘油醚、双酚F缩水甘油醚、双酚AD缩水甘油醚、酚醛环氧树脂、脂环族环氧树脂中的一种或几种。
5.根据权利要求1所述的高模碳纤维预浸料用中温固化环氧树脂体系的制备方法,其特征在于所述的潜伏性固化体系母料组分为双氰胺、改性双氰胺、脲类衍生物、咪唑衍生物中的一种或几种,相对于100份液体环氧树脂,其质量份数为5~15份。
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