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CN102470559A - 由聚酰胺6以及由聚酰胺6与聚酰胺12制备的共聚酰胺生产纤维增强复合材料的方法 - Google Patents

由聚酰胺6以及由聚酰胺6与聚酰胺12制备的共聚酰胺生产纤维增强复合材料的方法 Download PDF

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CN102470559A
CN102470559A CN2010800302069A CN201080030206A CN102470559A CN 102470559 A CN102470559 A CN 102470559A CN 2010800302069 A CN2010800302069 A CN 2010800302069A CN 201080030206 A CN201080030206 A CN 201080030206A CN 102470559 A CN102470559 A CN 102470559A
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D·舍尔策
G·科里
M·韦伯
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Abstract

一种生产纤维增强复合材料的方法，其中将多股连续长丝或机织物任选与包含己内酰胺和聚酰胺6用其他原料或己内酰胺共聚物用其他原料的增强材料一起浸渍，使材料在70-100℃的温度下通过，使其在100-190℃的温度下阴离子聚合并且任选使其在90-170℃的温度下再聚合。

Description

由聚酰胺6以及由聚酰胺6与聚酰胺12制备的共聚酰胺生产纤维增强复合材料的方法
本发明涉及一种由聚酰胺6以及聚酰胺6与聚酰胺12的共聚酰胺生产纤维增强复合材料的方法。
EP-A-56 703和EP-A-579 047已经分别公开了由纤维增强热塑性塑料制备的组件和颗粒，及其拉制(pultrusion)生产方法，其中一股纤维用熔融聚合物润湿。
DE-A-10 2007 031 467公开了一种如下生产纤维增强复合材料的方法：使多股连续长丝通过包含己内酰胺和聚酰胺6用其他原料的浴并润湿它们，将被润湿连续长丝引入烘箱中，在烘箱中己内酰胺在230℃下阴离子聚合而形成附着于连续长丝上的聚酰胺6。
上述方法的缺点为纤维润湿令人不满意且残余单体和低聚物水平高。
因此已经发现一种生产纤维增强复合材料的新型改进方法，其中将多股连续长丝或机织物任选与包含己内酰胺和聚酰胺6或其他共聚酰胺用其他原料的增强材料一起浸渍，在70-100℃的温度下通过，在100-190℃的温度下阴离子聚合并且任选在90-170℃的温度下再聚合。
已经发现另一生产纤维增强复合材料的改进方法，其中将多股连续长丝或机织物任选与包含己内酰胺和聚酰胺6或其他共聚酰胺用其他原料的增强材料一起浸渍，在高于体系的熔融温度下在70-100℃的温度下通过且在低于体系的熔融温度的温度下在低于70℃下以板条形式或以缠绕形式的预浸渍体冷却。这些预浸渍体可以随后在压模中或在另一合适工具中在100-190℃的温度下阴离子聚合并且任选在90-170℃的温度下再聚合。
本发明方法可以按如下实施：
本发明方法可以开放或密闭方法，优选以开放方法实施。
在开放方法下，可将纤维或机织物任选与增强材料一起经由浸渍辊由其架(纤维支撑经轴架)通过浴或通入浸渍槽。可以任选使用粗梳栅(cardinggrid)以确保纤维在随后复合材料中所需的分布。在该情况下，增强材料可以任选引入粗梳栅之后。纤维任选与增强材料一起可以在浸渍槽中用己内酰胺和聚酰胺6用其他原料的混合物在低于聚合温度且高于混合物熔点的温度下，换言之在70-100℃，优选70-95℃，更优选70-90℃下浸渍，在100-190℃，优选100-160℃，更优选100-150℃，更特别为100-130℃的温度下阴离子聚合并且任选在100-170℃，优选100-160℃，更优选100-150℃，更特别为100-130℃的温度下再聚合，然后可以移动通过多个预成形位置，其使纤维/树脂混合物越来越接近最终所需形状。
在密闭方法下，在用己内酰胺和聚酰胺6或其他共聚酰胺用其他原料的混合物浸渍之后，整个纤维或机织物任选与增强材料一起随后在成型模中但在1.1-800巴，优选1.5-10巴，更特别为2-5巴的升高压力下—例如在浸渍槽中或在浴中在70-100℃的温度下接触，在100-190℃，优选100-160℃，更优选100-150℃，更特别为100-130℃的温度下阴离子聚合并且任选在100-170℃，优选100-160℃，更优选100-150℃，更特别为100-130℃的温度下再聚合，然后可以移动通过多个预成形位置，其使纤维/树脂混合物越来越接近最终所需形状。
在大体积复合材料下，应确保恒定或接近恒定的热分布以防止裂缝。由此固化的复合材料可以随后锯成任何所需部件。
整个方法借助例如呈连续带取出或缠绕形式的牵引工具或通过反向液压夹具保持运转；该工具将最终复合材料或预浸渍体以及由此纤维与聚合物一起和存在的话增强材料牵引出固化工具。
用聚酰胺润湿的连续线股可随后缠绕或切断成所需长度或造粒。
合适的己内酰胺优选为ε-己内酰胺。
至多20重量％，即0-20重量％，优选0-17重量％，更优选0-15重量％的己内酰胺可以由来自具有至少4个碳原子的内酰胺，特别优选ω-月桂内酰胺的共聚单体使用。
在一个优选实施方案中，可以使用ε-己内酰胺和ω-月桂内酰胺的混合物。混合比通常为1000∶1，优选100∶1，更优选10∶1，更特别为2∶1。
聚酰胺6用其他合适原料包括活化剂，其可通过使异氰酸酯如HDI(六亚甲基二异氰酸酯)与内酰胺如ε-己内酰胺反应而制备，以及封端异氰酸酯，间苯二甲酰二己内酰胺，对苯二甲酰二己内酰胺，酯如邻苯二甲酸二甲酯-聚乙二醇，与酰基氯组合的多元醇或聚二烯，羰基二己内酰胺，六亚甲基二异氰酸酯或酰基内酰胺(acyllactamate)，优选异氰酸酯，六亚甲基二异氰酸酯或酰基内酰胺，更优选六亚甲基二异氰酸酯或酰基内酰胺以及碱催化剂如卤代内酰胺镁，碱金属己内酰胺，内酰胺铝或内酰胺镁，己内酰胺钠或溴化内酰胺镁(magnesium bromide lactamate)，优选碱金属己内酰胺，内酰胺铝或内酰胺镁，己内酰胺钠或溴化内酰胺镁，更优选己内酰胺钠或溴化内酰胺镁。
所用活化剂可以为用于活化的阴离子聚合的所有活化剂，实例由此为N-酰基内酰胺如N-乙酰基己内酰胺，取代三嗪，碳二亚胺，氨腈，单-和多异氰酸酯以及相应的封端异氰酸酯化合物。活化剂优选以基于内酰胺量为0.1-1mol％的浓度使用。可以使用本发明催化剂聚合具有至少5个环成员的内酰胺如己内酰胺、月桂内酰胺、辛内酰胺、庚内酰胺、相应的C-取代内酰胺或所述内酰胺的混合物。
碱催化剂可以通过使聚醚与相应碱金属或碱土金属化合物如醇盐、酰胺、氢化物、格利雅化合物以及碱金属或碱土金属反应而制备。催化剂的加入量基于内酰胺熔体通常为0.1-40重量％，优选0.2-15重量％。
高度适合聚合的催化剂为内酰胺钾或钠。尤其合适的为己内酰胺钠，其可以容易地由NaH和ε-己内酰胺制备。
己内酰胺、活化剂和碱催化剂的混合比可以在宽范围内变化；己内酰胺/活化剂/碱催化剂的摩尔比通常为1000∶1∶1-1000∶200∶50。
合适的纤维包括无机材料如高模量碳纤维、各种类型的硅化(silicatic)和非硅化(nonsilicatic)玻璃、碳、硼、碳化硅、金属、金属合金、金属氧化物、金属氮化物、金属碳化物和硅酸盐，以及有机材料如天然和合成聚合物如聚丙烯腈、聚酯、超拉伸(ultrastretched)聚烯烃纤维、聚酰胺、聚酰亚胺、芳族聚酰胺、液晶聚合物、聚苯硫醚、聚醚酮、聚醚醚酮、聚醚酰亚胺、棉、纤维素和其他天然纤维如亚麻、剑麻、南非槿麻、大麻和蕉麻；优选高熔点材料如玻璃、碳、芳族聚酰胺、液晶聚合物、聚苯硫醚、聚醚酮、聚醚醚酮和聚醚酰亚胺，更优选玻璃、碳、芳族聚酰胺、钢、陶瓷和/或其他充分耐温的聚合物纤维或长丝。
合适的增强材料包括上述纤维的粗纱，优选非线状和线状的，更优选线状模制品如纤维、纱线、紧捻纱线织物(twists)、绳，以及纺织结构如机织物、针织物或编织物和非织造织物，优选纤维、纱线和机织物，更优选纤维和纱线。
最终复合材料中的纤维量通常为20-85体积％，优选40-70体积％；在具有纯单向增强的型材情况下，其为30-90体积％，优选40-80体积％。
增强材料可以各种方式引入浸渍槽中。例如，它可以通过具有窄缝的模被牵引。增强材料优选通过狭缝引入熔融室中而不与壁接触。
增强材料在本发明复合材料内的分布可以是均匀的；或者增强材料还可以在复合材料某些部分如在边缘区和/或尤其是增强区以高于复合材料其他部分的比例存在。
模的几何形状和尺寸可在宽范围内变化，使得所生产的复合材料(型材、片材或条材)具有不同形状和尺寸。优选直径至多为500mm，更特别为200mm的条形型材，宽度至多为2500mm且厚度至多为10mm的长方形型材和圆形型材。特别优选厚度为至多1mm的细条。
此外，弯曲型材或其形状变化的型材(例如锤柄)可借助特定方法生产。
术语“复合材料”包括由相互结合的两种或更多种物质制备的材料，例如颗粒状复合材料(分散体材料、纤维复合材料、层状复合材料(层压材料))和互穿复合材料，优选纤维复合材料和层状复合材料(层压材料)，更优选纤维复合材料。
术语“拉制”包括以间歇或连续程序，优选连续程序生产型材形式的复合材料如纤维增强塑料的技术。
型材形状多种多样，例如垫，片，管，支撑物如T和双T支撑物，U、W和UW型材，模制品，例如用于汽车工业，用于房屋，夹具，以及工具和运动装备如桨或网球拍用手柄。
纤维增强复合材料，更特别为纤维增强聚酰胺用于许多应用，包括用于纤维增强或织物增强塑料粒、型材或片材，以及用于汽车工业和其他工业用注塑模制品中。纤维在聚合物基质中使用，目的在于改进机械性能如强度、劲度和冲击韧性。可实现的性能高度取决于纤维性质及其在组件中的长度以及聚合物基质中纤维的分散质量。就机械性能而言，优选使用长的取向纤维，更特别为玻璃纤维和碳纤维。
实施例
实施例1(在两个温度阶段下的试验)
将30g(265mmol)的ε-己内酰胺在氮气气氛下熔融并在温度T1(RT1)下搅拌，同时氮气通过熔体。然后将熔体加热到温度T2，加入1.8g(13.25mmol＝5mol％)己内酰胺钠(20重量％浓度，在己内酰胺中)(作为催化剂)并且在激烈搅拌下加入0.376ml(2.42mmol＝0.9mol％)的N-乙酰基己内酰胺(作为活化剂)，根据下表继续搅拌RT2。对所得聚酰胺评价、脱模、粉碎和分析。
结果整理于下表1中。
表1
Figure BDA0000128811060000051
实施例2(在三个温度阶段下的试验)
将30g(265mmol)的ε-己内酰胺在氮气气氛下熔融并在温度T1(RT1)下搅拌，同时氮气通过熔体，在温度T2下加入1.8g(13.25mmol＝5mol％)己内酰胺钠(20重量％浓度，在己内酰胺中)，在激烈搅拌下加入0.376ml(2.42mmol＝0.9mol％)的N-乙酰基己内酰胺，并且根据下表继续搅拌RT2。对所得聚酰胺在温度T3下热处理时间RT3，并且随后取出、评价、粉碎和分析。
结果整理于下表2中。
表2
Figure BDA0000128811060000052
实施例3(拉制试验)
在N2(干燥氮气)惰性气体下，在加热金属槽中，在85℃的温度和1巴的压力(惰性气体)下将碳、玻璃或天然纤维机织物在1分钟内缓慢牵引通过含有5mol％己内酰胺钠和1mol％N-乙酰基己内酰胺的熔融己内酰胺。在1分钟浸渍之后，将浸渍织物在温度T4下引入干燥箱中，在那里停留3分钟。然后使干燥的织物束在另一干燥箱中在T5下进行随后热处理20分钟。
结果整理于下表3中。
  实施例   T4[℃]   T5[℃]  织物   外观   残余单体[重量％]
  3a   150   120  亚麻绳   良好   2.7
  3b   150   120  玻璃纤维垫*   良好   2.65
  对比3c   190   120  玻璃纤维垫*   变色，浸渍差   3.6
  对比3d   200   120  碳纤维垫   浸渍差
  3e   130   120  碳纤维垫   良好   2.5
*胶料通过燃烧除去

Claims (10)

1.一种生产纤维增强复合材料的方法，其中将多股连续长丝或机织物任选与包含己内酰胺和聚酰胺6用其他原料的增强材料一起浸渍，在70-100℃的温度下通过，在100-190℃的温度下阴离子聚合并且任选在90-170℃的温度下再聚合。
2.一种生产纤维增强复合材料的方法，其中将多股连续长丝或机织物任选与增强材料一起在70-100℃的温度下通过包含己内酰胺和聚酰胺6用其他原料的浴并且在100-190℃的温度下阴离子聚合。
3.根据权利要求1或2的生产纤维增强复合材料的方法，其中使用玻璃、碳、芳族聚酰胺、钢、陶瓷和/或其他充分耐温的聚合物纤维或长丝的连续长丝。
4.根据权利要求1-3中任一项的生产纤维增强复合材料的方法，其中阴离子聚合在100-160℃的温度下进行。
5.根据权利要求1-4中任一项的生产纤维增强复合材料的方法，其中再聚合在100-160℃的温度下进行。
6.根据权利要求1-5中任一项的生产纤维增强复合材料的方法，其中所述连续长丝以一股纤维通过浴。
7.根据权利要求1-6中任一项的生产纤维增强复合材料的方法，其中至多20重量％己内酰胺被共聚单体替代。
8.根据权利要求1-7中任一项的生产纤维增强复合材料的方法，其中使用ε-己内酰胺和ω-月桂内酰胺的混合物。
9.根据权利要求1-8中任一项的生产纤维增强复合材料的方法，其中所述长丝或机织物的浸渍在70-100℃的温度下进行。
10.一种生产纤维增强复合材料的方法，其中将多股连续长丝任选与包含己内酰胺和聚酰胺6用其他原料的增强材料一起浸渍，在70-100℃的温度(高于体系的熔融温度)下通过，然后作为预浸渍体在低于70℃的熔融温度下冷却，随后在100-190℃的温度下阴离子聚合并且任选在90-170℃的温度下再聚合。
CN2010800302069A 2009-07-08 2010-07-06 由聚酰胺6以及由聚酰胺6与聚酰胺12制备的共聚酰胺生产纤维增强复合材料的方法 Pending CN102470559A (zh)

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