CN1037679A - 用长纤维增强的热塑性树脂的制备方法 - Google Patents

用长纤维增强的热塑性树脂的制备方法 Download PDF

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CN1037679A
CN1037679A CN89103068A CN89103068A CN1037679A CN 1037679 A CN1037679 A CN 1037679A CN 89103068 A CN89103068 A CN 89103068A CN 89103068 A CN89103068 A CN 89103068A CN 1037679 A CN1037679 A CN 1037679A
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米歇尔·格兰美特
贝纳德·戈登
米歇尔·洛蒂欧
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Arkema France SA
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Abstract

长纤维增强的热塑性树脂的制法，此方法包括用 一个在直角机头上有模具，由热塑性润湿聚合物将粗 纱浸渍，然后将所述浸过的粗纱送入第二个模中用增 强热塑性聚合物包覆。

Description

本发明关于用长纤维增强的热塑性树脂的制备方法。此方法包括在将纤维用一种可以与热塑性润湿聚合物相容的热塑性聚合物包复之前，用一种热塑性润湿聚合物充分地浸渍每根纤维。每根纤维的充分浸渍包括将粗纱用热塑性润湿聚合物在一个直角机头上进料的模具中浸渍。浸渍的粗纱在定型模的出口重新进入第二个同样是在直角机头上进料的模具中，在这里用一种可以与热塑性润湿聚合物相容的热塑性聚合物包复。
使用长纤维增强热塑性树脂是已知的。传统的方法是将纤维芯或粗纱用热塑性树脂挤压包复。但是由于某些热塑性树脂如聚烯烃对纤维的粘结不佳出现的问题在英国专利1094439已有所叙述并且得到部份解决。克服这个缺点的办法是在纤维用选定的热塑性树脂包复之前，用一种热塑性润湿聚合物，如用含烯键的不饱和多无羧酸接枝改性的聚烯烃来浸渍。然而浸渍的方法还是不太令人满意，最现实的方法是将纤维在最终覆盖之前连续通入润湿聚合物的溶液中。除了会有将微量溶剂留在材料中的危险之外，这种方法也不太可行，因为需要不适当地使用溶剂，花费大。
美国专利3，993，726中叙述了一种连续制备玻璃长纤维增强热塑性树脂制品的方法。根据所述技术，在一个通过挤塑机从在直角机头上进料的模具中，用热塑性润湿树脂和增强热塑性树脂的混合物浸渍粗纱。
纤维是这样浸渍的：将粗纱纤维在模具中膨松，并将所述纤维和热塑性混合物通过一个阻塞区，为的是更好地将材料渗入各纤维之间。这个系统并不太令人满意，因为由另一种聚合物稀释的润湿聚合物效力损失了大部份。
根据本发明方法，由于用一种简单的将所述润湿树脂通过粗纱纤维最广地分布方法，有可能使用最少量的润湿树脂使纤维能增强最大量的热塑性树脂。此法包括在第一步中将粗纱在细心地将纤维膨松之后，将其通过一个在直角机头上的模具并通入热塑性润湿树脂。在浸渍纤维之后，进入第二步，通过同样是在直角机头上的模具通入可以与热塑性润湿树脂相容的热塑性包复树脂。
在第一步中，在通入浸渍模之前，使粗纱膨松以使各粗纱纤维明显地并排展开。在这种情况下，粗纱呈布或带的形状，由一系列各自平行连续的纤维构成。为了排齐纤维，在将粗纱膨松时，在粗纱通入阻塞区的至少一段弯曲的通道之后，将粗纱通过加入熔融的热塑性润湿聚合物的浸渍模中弯曲通道能迫使构成粗纱的纤维展开。在进入定型模之前，这样形成的布或带子然后用热塑性润湿树脂浸渍并且拉长，进入由大致上与前边一段或数段弯曲通道平行的弯曲通道构成的一个新的阻塞系统中。在此系统中，浸渍了热塑性润湿树脂的布或带子通过至少两段相对或互相平行的曲折通道。在这些条件下，浸渍了热塑性润湿树脂的纤维整体在第一段曲折通道中，在它的一个面上被压碎，使树脂在熔融状态渗入纤维之间通向对面。在浸过的纤维总体与相反的曲折通道接触时，产生相反的作用。这种阻塞系统在与热塑性润湿聚合物接触之前和之后可以最少量的聚合物浸渍一根根的纤维。
浸渍的纤维最后通入定型模中使之成带子或空心草茎杆状物。
附图1表示出第一步的设备：在浸渍前阻塞系统（1），必要时可有一真空接口，（2）浸渍模与一个挤塑机（未表示出）相联，（3）浸渍纤维的阻塞系统和（4）定型模。
在定型模出口，浸渍了润湿树脂的纤维进入用增强热塑性树脂包复的第二阶段。为此，在最好超过所述润湿树脂熔融温度约40℃的温度下，用热塑性润湿树脂浸渍的连续纤维通入传统的在直角机头上的模具中，这种模具如用于包复电线或电缆的那种。在这个模具中通入要用纤维增强的热塑性树脂，并且是大体上与阻塞系统的定型模在一直线上。在这个模具出口处，带子或灯心草茎杆状物均造粒。这些长纤维粒，即其纤维长度相当于颗粒的长度，特别适于注塑，模压和挤塑传递成型。
被润湿树脂浸渍的连续纤维由定型模出来，润湿树脂呈熔融状态。润湿树脂最好在进入加入包复树脂的第瞿＞咧坝胫芪Э掌哟ダ淙础＝樟巳笫髦牧宋诮胝飧瞿＞咧巴ǔＮ?0-80℃之间。
在浸渍了热塑性润湿树脂的纤维的定型模具和包复模具之间的距离取决于使用的树脂的热性能。这一距离同样取决于挤塑物的取出速度。这一距离最好尽可能小，实践中通常为0.5-4米之间。
润湿聚合物与包复用标准聚合物重量比取决于最终要达到的纤维重量百分比。通常得到的最终物料中含20-40%纤维。在这些条件下，单浸渍润湿树脂的连续纤维通常总共含约70-75%纤维，30-25%的润湿聚合物。最终得到的物料重量组成为约20-40%纤维，8-17%润湿聚合物，72-43%标准覆盖聚合物。
用于增强热塑性塑料的连续纤维是已知的。它们是有机的或无机的。作为实例，可以是玻璃纤维、二氧化硅纤维、碳或聚芳基酰胺纤维粗纱。
如前所述，热塑性润湿聚合物应该与包复热塑性聚合物相容。这种相容性是一个特征，虽然已为技术人员熟知并且实践中非常重要，其科学的意义尚未非常令人满意地给出。并不涉及到关于所考虑的聚合物部份地相混性的非常有争议的细节，在此人们认为如能将两种聚合物相混，使得得到的物料的机械性能相近于或超过两者中较差的一个性能时，这两种聚合物就是可以相容的。
按照这个定义，有以下各对实例：
-接枝高密度聚乙烯-低密度聚乙烯
-接枝高密度聚乙烯-乙烯和醋酸乙烯的共聚物（EVA）
-接枝的乙烯和醋酸乙烯共聚物-聚氯乙烯
-接枝聚丙烯-聚丙烯
-聚（醚-酰胺）嵌段共聚物-聚酰胺
-功能聚酰胺（例如α，ω-二胺的，α，ω-二酸的，α胺ω酸的和单胺的）-聚酰胺
-改性乙烯和醋酸乙烯共聚物-乙烯和醋酸乙烯共聚物或低密度聚乙烯（PEbd）
-接枝的线型低密度聚乙烯（PEbdl）-线型低密度聚乙烯或低密度聚乙烯均可相容，而氯乙烯均聚物和苯乙烯均聚物不相容。
热塑性润湿聚合物是指一种可以增加纤维-聚合物密切接触的面，因而起到偶联剂作用的聚合物。在Polymer    Engineering    Composite（M.O.W.Richardson-Appl.Sc.Publ.1977）一文中解释了偶联剂的作用，最为人知的是有机硅烷。
热塑性润湿聚合物通常由低粘度聚合物中选择，或者在与相应的起始聚合物相比极性提高的聚合物中选择。
低粘度聚合物最好是这样一种聚合物，其熔融粘度（θf+40℃）最高等于按照美国测试标准ASTM    D1328方法，在230℃，2.16千克下，熔体指数20的聚丙烯的熔融粘度。
在低粘度聚合物中，例如有用过氧化降解改性的聚合物，如聚丙烯、聚酰胺、聚苯乙烯的情况，或者还有用一种功能性聚酰胺低聚物和一种共反应物如多环氧物或多异氰，酸酯反应或者是用一种功能性聚丙烯与一种共反应物如聚醚二酸、二羟基化的马丁二烯或α，ω-二胺的聚酰胺加聚反应而得到的聚合物。这些低粘度聚合物同样可由饱和聚酯起始制得，如聚对苯二甲酸丁二醇酯或聚对苯二甲酸乙二醇酯，其链由于控制降解断开，这样得到一种功能低聚物。在二胺，特别是十二烷二胺的存在下，将饱和聚酯热共混就生成功能低聚物。
在极性比相应的起始聚合物提高的聚合物中，最好使用能具有反应性的极性点的聚合物。具有极性点的聚合物通常是例如在聚乙烯、聚丙烯或共聚物的情况下，由顺酐、丙烯酸、醋酸乙烯起始，或者更通常是由例如提供一些酮、醛、酸、酯、氰基、胺等类型的极性点的化合物起始，经过接枝或者嵌段改性的聚合物。
在特别推荐的接枝或嵌段改性的聚合物中，例如有接枝聚丙烯，如接枝顺酐或丙烯酸的聚丙烯;聚（乙烯-醋酸乙烯）或由顺酐接枝者;接枝高密度聚乙烯如接枝丙烯酸或顺酐的高密度聚乙烯;接枝线型低密度聚乙烯如接枝丙烯酸或顺酐的线型低密度聚乙烯;聚（醚-酰胺）嵌段共聚物。
某些润湿聚合物可以通过接枝或控制降解在粗纱浸渍步骤中就地直接制得。为此，将下列组份反应：聚合物、降解剂更可能是接枝剂，它们在挤塑机中处于熔融状态通入浸渍模中。在用过氧化方法降解的情况下，最好在过氧化物中选择于反应温度（通常为180-250℃之间）下，半衰期低于或等于聚合物在挤塑机中停留时间者。相对于基础聚合物重量而言，接枝剂和/或降解剂的百分比通常为0.5-3%（重量）之间。
下列实例说明本发明，但不对其加以限制。
实例1
用一个螺杆直径30毫米的双螺杆轮转挤塑机，用带阻塞区的直角机头上的模具往浸渍模中进料，聚丙烯进行在线顺酐接枝。
制备这种顺酐接枝的聚丙烯偶联料的配方如下：
聚丙烯    3050    MN4    100份
顺酐    0.85%
过氧化物    LUPEROX    101（DHBP）0.7%
氯苯    0.2%
预先将聚丙烯与顺酐粉末混合，然后进料器加到挤塑机中达进料水平面。
用计量泵将溶于氯苯中的过氧化物在压力下注入熔融物料中。
反应物温度为180℃。
用10，500-13，500帕真空，在挤塑机上进行在线脱气。
于230℃和2.16千克下由模具测得熔体指数为350。
凝胶渗透色谱分析给出下列数值：
Mw＝85，000    Mn＝38.000    I＝2.2
测定顺酐百分比为3500ppm。
用这种聚合物往根据图1包括下列几个区的设备中加料：
-阻塞区1
长：60毫米
宽：100毫米
间隙：3毫米
漏斗形进料口和一段最高处的高度为10毫米的弯道。
-浸渍模区2
长：90毫米
宽：100毫米
两个直径为10毫米的进料道
区的出口处间隙：3毫米
-阻塞区3
长：200毫米
宽：100毫米
3峰正弦形阻塞
峰间距离：40毫米
间隙：3毫米
-定形区4
1.65毫米直径的5孔模
长：100毫米
宽：100毫米
在保持210℃的浸渍模中通入5根E2400tex.玻璃纤维粗纱。
聚合物流量为1.2千克/小时。
在4.6米/分钟速度下拉出空心草茎状物，玻纤重量含量大约70%。
然后将这些空心草茎状物通入位于第一模1米处的包复模中。
与第一模基本在同一直线上的第二个模保持210℃。第二模垂直地装在保持平均温度200℃的一个单螺杆挤塑机上，以10千克/小时速度通入在230℃、2.16千克下熔体指数为12的聚丙烯。
由这个模的一些4毫米直径的孔中拉出玻纤重量含量约为20%的空心草茎状物，然后冷却并造粒到6毫米长。
在注塑的80×10×4毫米试样上进行挠曲三点试验（ISO    178标准）。
挠曲模量：2630兆帕
最大负荷下应力：64.5兆帕
在下列条件下对100×100×2.8毫米的样品测耐落锤冲击强度：
降落高度：1米
锤直径：12.7毫米
锤重：5.14千克
速度：4.43米/秒
这样测得断裂能量为8.20焦耳。
实例2（对比例）
除了直径为4毫米的空心草茎状物是直接在装有直径4毫米的出口孔阻塞的第一模中制得之外，重复实例1。不用熔体指数12的聚丙烯牌号进行过分挤压。
得到用一种润湿聚合物浸渍的含20%（重量）玻璃纤维的空心草茎状物，切割成6毫米长。
注塑产品的机械性能如下：
挠曲模量：2050兆帕
最大负荷下应力：56.7兆帕
断裂能（落锤冲击强度）：7.6焦耳
实例3
除了润湿聚合物的阻塞模是由30毫米直径和等于22个直径长的单螺杆挤塑机出发进料之外，再用实例1的设备。在此设备上制出玻璃纤维增强的聚酰胺12的空心草茎状物和颗粒。
阻塞模保持在260℃，粗纱上覆盖了平均分子量等于5000的单NH2的聚酰胺12低聚物。制得的玻璃纤维含量约为70%的空心草茎状物，然后通入保持280℃并且通入高粘度挤塑牌号聚酰胺12的一个模。最终得到的颗粒中玻璃纤维重量百分比约20%。
得到的产品机械性能如下：
挠曲模量：3400兆帕
最大负荷下应力：110兆帕
断裂能量（落锤冲击强度）：8.75焦耳
实例4
在实例3的设备和条件下，制备用玻璃纤维增强的聚对苯二甲酸醇酯空心草茎状物和颗粒。
粗纱首先通入在260℃下并在1-5%（重量）下并通入聚对苯二甲酸丁二醇酯和十二烷二胺混合物的阻塞模中。
得到的空心草茎状物玻璃纤维重量含量约为70%，通过在270℃下并通入硬质牌号的聚对苯二甲酸丁二醇酯的模。最终得到的6毫米长的颗粒中玻璃纤维重量百分比约20%。
得到的产品机械性能如下：
挠曲模量：5230兆帕
最大负荷下应力：140兆帕
断裂能量（落锤冲击强度）：6.6焦耳

Claims (10)

1、用长纤维增强的热塑性树脂的制备方法，此方法包括经过用挤塑技术将两种热塑性聚合物连续浸渍纤维，此方法的特征在于，在直角机头上的模具中用热塑性润湿聚合物浸渍以粗纱形式的纤维之后，所述浸渍过的粗纱在高于热塑性润湿聚合物的熔融温度下，再在第二个模具中用要增强的热塑性聚合物包复。
2、根据权利要求1的方法，其特征在于在用热塑性润湿聚合物浸渍粗纱之前，将粗纱通入阻塞区使之膨松，以及在浸渍之后拉入第二阻塞区，然后定型并通过第二个包复模。
3、根据权利要求1或2任一项的方法，其特征在于由第一模具出来的用热塑性润湿聚合物浸渍的粗纱进入温度为40-80℃之间的第二个模具中，热塑性润湿聚合物呈熔融状态。
4、根据权利要求1至3任一项的方法，其特征在于在第一步将粗纱通入阻塞区使之膨松;使粗纱穿过用一个挤塑机通入热塑性润湿聚合物的浸渍模;浸渍过的粗纱通过第二阻塞区以及通过定型模，还在于在第二步中浸渍过热塑性润湿聚合物的粗纱通过与第一步中的模基本在一直线上的模具，并用第二个挤塑机通入要增强的热塑性润湿聚合物。
5、根据权利要求1至4任一项的方法，其特征在于在给浸渍模供料的挤塑机中于熔融状态下经接枝或者控制降解直接制备润湿聚合物。
6、根据权利要求5的方法，其特征在于热塑性润湿聚合物进行过氧化降解。
7、根据权利要求5的方法，其特征在于热塑性润湿聚合物是用一种二胺降解的饱和聚酯，以便制得一种功能低聚物。
8、根据权利要求1至4任一项的方法，其特征在于热塑性润湿聚合物是用一种功能化的聚酰胺低聚物和共反应物的加聚产品。
9、根据权利要求1至8任一项的方法，其特征在于在第一步中用润湿树脂浸渍连续的纤维，重量比为70-75%的纤维对30-25%聚合物。
10、根据权利要求1至9任一项的方法，其特征在于在通入要增强的热塑性润湿聚合物的模具出口处，最终产品重量组成为：20-40%纤维、8-17%润湿聚合物、72-43%要增强的标准热塑性聚合物。
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CN101538934B (zh) * 2009-03-27 2012-09-05 江苏源盛复合材料技术股份有限公司 一种热塑性复合材料建筑模板及其制备工艺和专用设备
CN101695873B (zh) * 2009-10-30 2012-05-30 广州科苑新型材料有限公司 长纤维增强塑料生产用纤维丝束熔融浸渍模头及浸渍方法
CN103802231A (zh) * 2014-01-25 2014-05-21 广州金发碳纤维新材料发展有限公司 连续纤维增强胶带的双面熔融浸渍设备及方法
CN103753831A (zh) * 2014-02-12 2014-04-30 台州市家得宝科技有限公司 一种连续纤维增强热塑性复合材料的浸渍模具及浸渍方法
CN111212714A (zh) * 2017-10-16 2020-05-29 费德玛有限责任两合公司 用聚合物熔体浸渍纤维束的装置和方法
CN111212714B (zh) * 2017-10-16 2022-05-10 费德玛有限责任两合公司 用聚合物熔体浸渍纤维束的装置和方法

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DE68901061D1 (de) 1992-04-30
CA1334327C (fr) 1995-02-14
ES2010958A6 (es) 1989-12-01
FI892205A0 (fi) 1989-05-08
KR890017056A (ko) 1989-12-14
EP0342080B1 (fr) 1992-03-25
FI892205A (fi) 1989-11-10
KR950001988B1 (ko) 1995-03-08
JPH01317751A (ja) 1989-12-22
CN1021643C (zh) 1993-07-21
FR2630967A1 (fr) 1989-11-10
PT90494B (pt) 1994-10-31
US4937028A (en) 1990-06-26
ATE74057T1 (de) 1992-04-15
FR2630967B1 (fr) 1993-12-10
PT90494A (pt) 1989-11-30
DK173608B1 (da) 2001-04-30
EP0342080A1 (fr) 1989-11-15
FI97786C (fi) 1997-02-25
FI97786B (fi) 1996-11-15
DK224289A (da) 1989-11-10
JP2954235B2 (ja) 1999-09-27

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