CN108384188B - 一种基于工程塑料非织造布的预浸料及其应用 - Google Patents

一种基于工程塑料非织造布的预浸料及其应用 Download PDF

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CN108384188B
CN108384188B CN201810074053.6A CN201810074053A CN108384188B CN 108384188 B CN108384188 B CN 108384188B CN 201810074053 A CN201810074053 A CN 201810074053A CN 108384188 B CN108384188 B CN 108384188B
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engineering plastic
woven fabric
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resin
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CN108384188A (zh
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刘万双
魏毅
蒋秋冉
张辉
徐元琛
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ZHEJIANG BAIHE ADVANCED COMPOSITES Co.,Ltd.
Donghua University
Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
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Donghua University
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Abstract

本发明涉及一种基于工程塑料非织造布的预浸料及其应用，预浸料是将工程塑料非织造布含浸在树脂组分中制得；预浸料应用于层合板、复合层合板和夹芯板中。本发明预浸料原料来源广泛、成本低、工艺简单，并可利用回收非织造布产品，使用该预浸料制造的层合板、复合层合板和夹芯板轻质且具有优良的力学性能。

Description

一种基于工程塑料非织造布的预浸料及其应用
技术领域
本发明属于高分子材料及其应用领域，特别涉及一种基于工程塑料非织造布的预浸料及其应用。
背景技术
预浸料是利用基体树脂组分在一定工艺条件控制下浸渍的连续纤维或织物，是纤维增强复合材料设计与制造的重要中间材料。采用预浸料制造复合材料具有结构设计灵活、使用方便、成型过程清洁、产品孔隙率低、制品外形多样等优点。在过去的60多年里，预浸料工艺技术和预浸料品种在欧、美等发达国家得到了快速发展，对推动先进复合材料产业的发展具有深远的影响。近年来，随着航空、轨道交通、汽车等交通工具向着轻量化方向发展，采用高性能纤维增强聚合物复合材料代替传统金属材料是目前公认的一个发展趋势。在这一背景下，开发低成本、轻质、力学性能和界面性能优良的新型预浸料，以及在其基础上设计各种轻质复合材料有着广阔的应用前景。目前商品化的预浸料主要基于碳纤维、芳纶纤维、玻璃纤维及玄武岩纤维等，其中碳纤维和芳纶纤维预浸料虽然具有轻质、高强的优点，但其成本较高，而玻璃纤维和玄武岩纤维预浸料虽然成本较低，但存在密度较大，减重效果不佳的问题。
工程塑料非织造布在环保治理、汽车工业、土木工程、医疗卫生、农业技术等诸多领域被广泛应用。工程塑料非织造布制备工艺成熟、原材料种类丰富、面密度低，其中一些特种工程塑料非织造布还具有优良的力学性能和阻燃性。每年工业界产生大量废弃的工程塑料非织造布，回收和利用这些废弃非织造布，不仅具有可观的经济价值，还具有重要的环保意义。因此，利用工程塑料非织造布制造预浸料及复合材料值得研究。
发明内容
本发明所要解决的技术问题是提供一种基于工程塑料非织造布的预浸料及其应用，预浸料原料来源广泛、成本低、工艺简单，并可利用回收非织造布产品，使用该预浸料制造的层合板和夹芯板轻质且具有优良的力学性能。
本发明的一种基于工程塑料非织造布的预浸料，所述预浸料是将工程塑料非织造布含浸在树脂组分中制得，其中预浸料中树脂组分的重量百分含量为20-70％，树脂组分溶液按重量百分比包括：基体树脂40％-100％、固化剂0％-40％、促进剂0％-10％和增韧剂0％-20％。
所述工程塑料非织造布的面密度为200-1200gsm；工程塑料非织造布的制备原料为聚醚砜、聚醚酰亚胺、聚苯硫醚、聚酰胺、聚四氟乙烯、聚偏氟乙烯中的一种或几种；工程塑料非织造布的形状为毡状、布状、网状、纸状中的一种或几种。
所述树脂为环氧树脂、酚醛树脂、聚乙烯醇缩丁醛树脂、氰酸酯树脂中的一种或几种。
所述固化剂为胺类物质、改性胺物质、咪唑物质、鎓盐物质、线性酚醛聚合物中的一种或几种。
所述促进剂为咪唑类化合物、叔胺类化合物、含磷化合物类、金属盐化合物类、脲类化合物中的一种或几种。
所述增韧剂为纳米二氧化硅、核壳结构橡胶粒子、有机硅橡胶、丙烯酸橡胶、液体丁腈橡胶、液体端胺基丁腈橡胶、液体端羧基丁腈橡胶、聚醚酮、聚醚胺、聚砜、聚醚砜、聚醚醚酮中的一种或几种。
所述树脂组分按重量百分比还包括：溶剂0％-60％，并且不为0％。
所述溶剂为丙酮、丁酮、乙醇、四氢呋喃、乙酸乙酯、二氯甲烷、氯仿中的一种或几种。
本发明的一种基于工程塑料非织造布的预浸料应用于层合板、复合层合板和夹芯板中。
所述应用于层合板中具体为：将至少一层基于工程塑料非织造布的预浸料固化得到层合板。
所述固化的温度为25-200℃，固化的压力为0.1-0.8MPa，固化的时间为10-300min。
所述应用于复合层合板中具体为：将至少一层基于工程塑料非织造布的预浸料与至少一层碳纤维预浸料、玻璃纤维预浸料、芳纶纤维预浸料或玄武岩纤维预浸料进行任意组合顺序的叠放，固化，得到复合层合板。
所述固化的温度为25-200℃，固化的压力为0.1-0.8MPa，固化的时间为10-300min。
所述应用于夹芯板中具体为：在泡沫或蜂窝芯材两侧压覆至少一层基于工程塑料非织造布的预浸料，固化，得到夹芯板；
或在泡沫或蜂窝芯材两侧压覆至少一层基于工程塑料非织造布的预浸料与至少一层碳纤维预浸料、玻璃纤维预浸料、芳纶纤维预浸料或玄武岩纤维预浸料的任意组合，固化，得到夹芯板。
所述固化的温度为25-200℃，固化的压力为0.1-0.8MPa，固化的时间为10-300min。
本发明预浸料是将工程塑料非织造布通过热熔法或溶剂法含浸在树脂组分中制得。
有益效果
本发明预浸料原料来源广泛、成本低、工艺简单、树脂浸润性好，并可利用回收非织造布产品，使用该预浸料制造的层合板、复合层合板和夹芯板轻质且具有优良的力学性能。
附图说明
图1是实施例1中复合层合板的示意图，其中1、3为碳纤维预浸料MT300/802，2为聚苯硫醚针刺毡预浸料；
图2是实施例2中夹芯板的示意图，其中1、5为碳纤维预浸料BAC 300，2、4为聚苯硫醚针刺毡预浸料，3为芳纶蜂窝。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
首先在一容器内进行树脂组分复配，按重量含量计算，加入22％双酚A型环氧树脂SM828(三木集团)，39％四官能环氧树脂AG-80(上海华谊树脂有限公司)，3％氰乙基-2-甲基咪唑，6％硅橡胶核壳粒子增韧剂ALBIDUR@EP-2240A(德国赢创工业)，再加入30％丙酮，得到树脂组分。将聚苯硫醚针刺毡(面密度为600gsm)浸入上述树脂组分中，随后在一定间距的辊中拉出，在烘箱中烘干除去溶剂，得到预浸料。将两层该预浸料叠放在一起，放入热压机中进行固化成型，固化压力为0.5Mpa，固化温度为130℃，固化时间为15min，得到层合板。将上述两层预浸料叠放在一起，在上下表面各自再叠放一层碳纤维预浸料MT300/802(航天长征睿特科技有限公司)，放入热压机中进行固化成型，固化压力为0.5Mpa，经130℃固化30min，再经170℃后固化30min，制得复合层合板。本实施例中非织造布、预浸料、层合板和复合层合板的性能参数如表1所示。
表1
Figure BDA0001558976180000031
实施例2
首先在一容器内进行树脂组分复配，加入68％酚醛树脂445D05(可隆化工苏州有限公司)，20％聚乙烯醇缩丁醛树脂
Figure BDA0001558976180000032
乙醇溶液(浓度为15％)，12％丙酮，得到树脂组分。将回收清理后的旧聚苯硫醚针刺毡(面密度为250gsm)浸入上述树脂组分中，随后在一定间距的辊中拉出，在烘箱中烘干除去溶剂，得到预浸料。将该预浸料与碳纤维预浸料BAC300(浙江百合航太复合材料有限公司)和芳纶蜂窝(上海特一新材)按下面铺层方法铺层：BAC 300-本实施例得到的预浸料-芳纶蜂窝-本实施例得到的预浸料-BAC 300。将上述铺层叠放在一起，放入热压机中进行固化成型，在固化压力为0.5MPa，固化温度为130℃，固化时间为30min条件下，制得夹芯板。本实施例中非织造布、预浸料、夹芯板的性能参数如表2中所示。
表2
测试项目 实施例2
非织造布强度(MPa) 13.7
预浸料树脂含量(％) 57.2
夹芯板树脂含量(％) 35.4
夹芯板滚筒剥离平均扭矩(N) 22.7
夹芯板三点弯曲极限载荷(kN) 1.6
夹芯板压缩极限载荷(kN) 8.5
实施例3
首先在一容器内进行树脂组分复配，按重量含量计算，加入90％双酚A型氰酸酯(郑州阿尔法化工有限公司)，加热到140℃并搅拌至双酚A型氰酸酯完全熔融，随后加入9.2％酚醛环氧树脂F-51(蓝星无锡石化)在140℃下预聚6小时，最后，加入0.8％乙酰丙酮锌(南京化学试剂股份有限公司)，搅拌均匀，待用。将所得氰酸酯树脂组合物倒入100℃的预浸料槽中，此时树脂组合物黏度约为1800mPa.s，将聚四氟乙烯增强聚苯硫醚针刺毡(面密度为500gsm)浸入上述树脂组分熔体中，随后在一定间距的辊中拉出，自然冷却到室温，得到预浸料。将两层该预浸料叠放在一起，放入热压机中进行固化成型，固化压力为0.5Mpa，经160℃固化120min，再经190℃后固化180min，制得层合板。本实施例中非织造布、预浸料、层合板的性能参数如表3所示。
表3
Figure BDA0001558976180000041
实施例4
首先在一容器内进行树脂组分复配，按重量含量计算，加入52％双酚A型环氧树脂SM828(三木集团)，12％酚醛型环氧树脂0235(蓝星无锡石化)，5％双氰胺固化剂(南通润丰石油化工有限公司)，2％有机脲促进剂QJ-10A(长沙青迅剑高分子材料有限公司)，9％液体端羧基丁腈橡胶(山东嘉颖化工有限公司)，再加入20％丙酮，得到树脂组分。将聚四氟乙烯增强聚苯硫醚针刺毡(面密度为1000gsm)浸入上述树脂组分中，随后在一定间距的辊中拉出，在烘箱中烘干除去溶剂，得到预浸料。将该预浸料与碳纤维预浸料BAC 300(浙江百合航太复合材料有限公司)和酚醛泡沫(廊坊声益建材有限公司)按下面铺层方法铺层：BAC300-本实施例得到的预浸料-泡沫芯材-本实施例得到的预浸料-BAC 300。将上述铺层叠放在一起，放入热压机中进行固化成型，在固化压力为0.3MPa，固化温度为120℃，固化时间为180min条件下，制得夹芯板。本实施例中非织造布、预浸料、夹芯板的性能参数如表4中所示。
表4
测试项目 实施例2
非织造布强度(MPa) 16.8
预浸料树脂含量(％) 49.2
夹芯板树脂含量(％) 33.8
弯曲强度(MPa) 125.5
弯曲模量(GPa) 3.6
压缩强度(MPa) 0.9

Claims (10)

1.一种基于工程塑料非织造布的预浸料，其特征在于，所述预浸料是将工程塑料非织造布含浸在树脂组分中制得，其中预浸料中树脂组分的重量百分含量为20-70％，树脂组分按重量百分比包括：基体树脂40％-100％、固化剂0％-40％、促进剂0％-10％和增韧剂0％-20％；所述工程塑料非织造布的面密度为200-1200gsm。
2.按照权利要求1所述的一种基于工程塑料非织造布的预浸料，其特征在于，所述工程塑料非织造布的制备原料为聚醚砜、聚醚酰亚胺、聚苯硫醚、聚酰胺、聚四氟乙烯、聚偏氟乙烯中的一种或几种；工程塑料非织造布的形状为毡状、布状、网状、纸状中的一种或几种。
3.按照权利要求1所述的一种基于工程塑料非织造布的预浸料，其特征在于，所述基体树脂为环氧树脂、酚醛树脂、聚乙烯醇缩丁醛树脂、氰酸酯树脂中的一种或几种；固化剂为胺物质、改性胺物质、咪唑物质、鎓盐物质、线性酚醛聚合物中的一种或几种。
4.按照权利要求1所述的一种基于工程塑料非织造布的预浸料，其特征在于，所述促进剂为咪唑化合物、叔胺化合物、含磷化合物、金属盐化合物、脲化合物一种或几种。
5.按照权利要求1所述的一种基于工程塑料非织造布的预浸料，其特征在于，所述增韧剂为纳米二氧化硅、核壳结构橡胶粒子、有机硅橡胶、丙烯酸橡胶、液体丁腈橡胶、液体端胺基丁腈橡胶、液体端羧基丁腈橡胶、聚醚酮、聚醚胺、聚砜、聚醚砜中的一种或几种。
6.按照权利要求1所述的一种基于工程塑料非织造布的预浸料，其特征在于，所述树脂组分按重量百分比还包括：溶剂0％-60％，并且不为0％；所述溶剂为丙酮、丁酮、乙醇、四氢呋喃、乙酸乙酯、二氯甲烷、氯仿中的一种或几种。
7.一种如权利要求1所述的基于工程塑料非织造布的预浸料的应用，其特征在于，应用于层合板、复合层合板和夹芯板中。
8.按照权利要求7所述的一种基于工程塑料非织造布的预浸料的应用，其特征在于，所述应用于层合板中具体为：将至少一层基于工程塑料非织造布的预浸料固化得到层合板。
9.按照权利要求7所述的一种基于工程塑料非织造布的预浸料的应用，其特征在于，所述应用于复合层合板中具体为：将至少一层基于工程塑料非织造布的预浸料与至少一层碳纤维预浸料、玻璃纤维预浸料、芳纶纤维预浸料或玄武岩纤维预浸料进行任意组合顺序的叠放，固化，得到复合层合板。
10.按照权利要求7所述的一种基于工程塑料非织造布的预浸料的应用，其特征在于，所述应用于夹芯板中具体为：在泡沫或蜂窝芯材两侧压覆至少一层基于工程塑料非织造布的预浸料，固化，得到夹芯板；
或在泡沫或蜂窝芯材两侧压覆至少一层基于工程塑料非织造布的预浸料与至少一层碳纤维预浸料、玻璃纤维预浸料、芳纶纤维预浸料或玄武岩纤维预浸料的任意组合，固化，得到夹芯板。
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