CN1022189C - 长纤维增强的聚酰胺型复合材料的制法 - Google Patents

长纤维增强的聚酰胺型复合材料的制法 Download PDF

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CN1022189C
CN1022189C CN87106424A CN87106424A CN1022189C CN 1022189 C CN1022189 C CN 1022189C CN 87106424 A CN87106424 A CN 87106424A CN 87106424 A CN87106424 A CN 87106424A CN 1022189 C CN1022189 C CN 1022189C
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米歇尔·洛蒂澳
米歇尔·格兰密
吉尔·孔尼阿
孟西阿·阿兰
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Abstract

长纤维增强的聚酰胺型复合材料的制法，是于拉出之前先用聚酰胺浸渍纤维，其特征在于，由聚酰胺低聚物或预聚物浸渍过的纤维先进行热处理，以使聚合链增长，然后进行拉出成型。

Description

本发明是关于一种用长纤维增强的聚酰胺型复合材料的制法。本方法是，将长纤维用聚酰胺的预聚物或低聚物进行浸涂，再将之加热以便在拉出前进行聚合反应。
已知有人将热塑性树脂如聚酰胺，在纤维存在下挤压，以改进其机械性能。然而，所使用的这种方法有缺陷，因材料中含有很大比例的短纤维，故没有优良的机械性能，特别是优良的抗挠曲强度。
用纤维增强可塑性树脂的优良机械性能，可用长纤维增强树脂获得。为了制得这样的长纤维复合物，通常是采用拉出技术，所谓拉出技术是将预先用可塑的树脂浸渍好的长纤维通过加热的拉丝模孔而拉出。按照这种技术，可制得一些复合物型材、直线的或弯曲的，它们在主要方向上能得到高度增强，在此方向上的机械性能，在组合协调的情况下，可与某些金属相比美。
在此技术中，纤维的浸渍是重点和难点。但是，估计在使用热固性树脂，如环氧树脂或聚酯类，来浸渍纤维的情况下，困难不会太大。因为这些热固性树脂在室温下常为液体或溶液。已证明比较困难的是，用室温下为固体并有相当高的熔点的热塑性树脂来浸渍纤维。
现有的一些不同技术都不很有效并难于使用。例如用热塑性聚合物粉料在流化床中浸渍纤维，即是这种情况。也有这样的情况，使纤维在热塑性聚合物的溶液中通过，这一技术的主要缺点是需除去大量的溶剂。
在上述条件下，难于用长纤维有效地增强聚酰胺。为了得到足够大 的流动性，这些热塑性聚合物需保持于高温中，以便能够很好地浸渍纤维，或者加入溶剂作成很稀的溶液，这又存在除去溶剂的问题。
按照本发明的技术，可克服上述缺陷。本发明的技术是，用聚酰胺的预聚物或低聚物浸渍纤维，这些聚酰胺分子链的每个末端都具有一个易进行反应的活性官能团，能使低聚物或预聚物的一个分子与另一个分子进行反应，然后，在通过拉出使组合物成型前将之加热可使聚合物的分子链增长。链末端的活性官能团，通常相当于每个分子上有一个胺基和一个羧基。
这些分子量较小的低聚物和预聚物有其优点，即在熔化温度时为流动性的。聚酰胺系列的化合物通常是由己内酰胺、己二胺与己二酸、己二胺与癸二酸、十二碳内酰胺与十一碳羧酸等制备。还有聚酰胺-亚胺。作为实例，可列举出一些聚酰胺低聚物或预聚物：6，6.6，6.10，6.12，11和12。
本发明特别推荐的一些低聚物和预聚物，相当于如下的通式：
Figure 871064243_IMG2
式中m为5-11;n为10-40。
纤维，最好采用长纤维，亦即连续长丝或玻璃粗丝，一般采用玻璃纤维、碳纤维、芳香酰胺类如KEVLAR等，将纤维在粉状或熔融状态的预聚物或低聚物中循环浸渍。
当浸渍是在粉料中进行时，粉料最好处于流化形式。以流化形式进行时，可参考粉料流化的已知方法。
浸渍后的纤维进行加热处理，温度最好为190-350℃，以完善纤维的浸渍和使聚酰胺链增长。将从前边结构式中选用的低聚物或预聚物转变成n值为50-80的聚合物。
在加热进行聚合反应处理后，将用聚合物浸渍后的纤维通过成型拉 丝模予以拉伸，模的温度需保持使材料最好处于190-300℃。为了使型材保持很好的最后结构，建议将成型后的材料在第二个保持于室温的成型器中的冷却。
根据温度条件和玻璃纤维与树脂重量之比，浸渍后的纤维通常要在拉出装置中进行拉伸，速度为每分钟0.3-3米。
下面的例子是用于解释本发明，但并不限制本发明。
例1
于一个边长为500毫米的底部是多孔的立方形反应器中加入25公斤的预聚物粉料，预聚物的结构式如下：
Figure 871064243_IMG3
这些粉料的粒径分布为80-200微米。粉料的流化是在反应器底部采用超压为2巴的压缩空气。
使18根玻璃粗纤维R099    P    103    VETROTEX（2400Tex），以每分钟0.5米的速度在流化床中通过。经过浸渍的纤维在红外线隔板下面进行预热，然后通过100×200毫米并保持270℃的拉丝模。最后使材料通过50×50毫米和保持240℃的成型拉丝模，从前一个拉丝模中出来的拉伸长度大约为500毫米。将材料再通过50×100毫米和处于室温的最后一个成型拉丝模，便得到一定形状的型材。
将得到的材料制成截面为4×10毫米的棒条。将所制成的棒条材料按照ISOR-178标准进行三点法挠曲测试。
如下结果是对含65%单位重量玻璃的试件所测得的结果：
杨氏模数E＝26GPa
断裂应力＝450MPa
用如下结构式的聚合物代替预聚物，与上述情况作比较：
Figure 871064243_IMG4
在此情况下，杨氏模数E为22GPa，断裂应力为425MPa。
例2
操作条件同例1，而采用如下结构式的预聚物：
杨氏模数E＝20GPa;断裂应力＝400MPa。
例3
操作条件同例1，而是采用如下结构式的预聚物：
Figure 871064243_IMG6
前一个拉丝模的温度为300℃，而不是270℃。
杨氏模数E＝23GPa;断裂应力＝593MPa。
例4
操作条件同例1，采用例3的预聚物，但却使用KEVLAR纤维代替玻璃纤维。
如下结果是得自含30%重量KEVLAR的试件：
杨氏模数E＝24GPa;断裂应力＝358MPa。
例5
操作条件同例4，但采用如下结构式的预聚物：
Figure 871064243_IMG7
杨氏模数E＝23GPa;断裂应力＝308MPa。

Claims (8)

1、长纤维增强的聚酰胺型复合材料的制法，该方法是用聚酰胺预先浸渍纤维和拉出，其特征在于由聚酰胺低聚物或预聚物浸渍过的纤维需进行热处理，以使聚合物链增长，然后通过拉出进行成型。
2、按照权利要求1所述的制法，其特征在于低聚物或预聚物在其分子链的每个末端上具有一个易进行反应的活性官能团，能使低聚物或预聚物的一个分子与另一分子进行反应。
3、按照权利要求2所述的制法，其特征在于低聚物或预聚物在其分子链的末端具有一个胺基官能团和一个羧酸官能团。
4、按照权利要求3所述的制法，其特征在于低聚物或预聚物的结构式如下
Figure 871064243_IMG1
式中m为5-11，n为10-40。
5、按照权利要求1至4中任何一项所述的制法，其特征在于浸渍后的纤维在拉出前进行加热，温度范围为190-350℃。
6、按照权利要求4所述的制法，其特征在于浸渍后的纤维在拉出前进行加热，以使低聚物或预聚物转变成高聚物，使n值达到50-80。
7、按照权利要求1-4中任何一项所述的制法，其特征在于用低聚物或预聚物浸渍后的纤维在热处理后，在保持190-300℃的成型拉丝模中拉出。
8、按照权利要求1-4中任何一项所述的制法，其特征在于拉出的速度是每分钟0.3-3米。
CN87106424A 1986-09-17 1987-09-17 长纤维增强的聚酰胺型复合材料的制法 Expired - Lifetime CN1022189C (zh)

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KR102086309B1 (ko) 2016-07-15 2020-03-06 미츠비시 가스 가가쿠 가부시키가이샤 복합 재료의 제조 방법 및 복합 재료
FR3067640B1 (fr) 2017-06-14 2022-06-24 Arkema France Procede de fabrication d'une piece en materiau composite
WO2018229114A1 (fr) 2017-06-14 2018-12-20 Arkema France Procédé de fabrication d'une pièce en matériau composite a partir de prépolymères
FR3073857B1 (fr) 2017-11-21 2019-10-11 Arkema France Composition et procede pour materiau composite avec impregnation par composition reactive d'un prepolymere polyamide et d'un allongeur de chaine diepoxyde
FR3128154B1 (fr) 2021-10-15 2024-05-10 TDCL Investissement Matériau composite

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PT85731B (pt) 1990-08-31
JPH07115413B2 (ja) 1995-12-13
US4927583A (en) 1990-05-22
PT85731A (fr) 1987-10-01
FR2603891A1 (fr) 1988-03-18
CA1323161C (fr) 1993-10-19
FR2603891B1 (fr) 1990-12-14
DE3766678D1 (de) 1991-01-24
DK485187A (da) 1988-03-18
DK485187D0 (da) 1987-09-16
FI86736C (fi) 1992-10-12
JPS6382731A (ja) 1988-04-13
FI874046A (fi) 1988-03-18
EP0261020A1 (fr) 1988-03-23
ATE59055T1 (de) 1990-12-15
KR880004009A (ko) 1988-06-01
CN87106424A (zh) 1988-03-30
KR930002462B1 (ko) 1993-04-02
FI874046A0 (fi) 1987-09-16
EP0261020B1 (fr) 1990-12-12
DK167930B1 (da) 1994-01-03
ES2005311A6 (es) 1989-03-01
FI86736B (fi) 1992-06-30

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