CN1055431C - 聚四氟乙烯模塑制品及其制备方法 - Google Patents

聚四氟乙烯模塑制品及其制备方法 Download PDF

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CN1055431C
CN1055431C CN93118451A CN93118451A CN1055431C CN 1055431 C CN1055431 C CN 1055431C CN 93118451 A CN93118451 A CN 93118451A CN 93118451 A CN93118451 A CN 93118451A CN 1055431 C CN1055431 C CN 1055431C
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A·韦默
J·巴哈迈耶
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Abstract

一种由聚四氟乙烯(PTFE)制成的双组份模塑制品，是按照并列排列的形式由两种PTFE组份构成的。这两种组份可在受热时收缩并且其热空气收缩率至少有1%的差别。一个优选的实施例是得到一种在热处理下可弯曲的纤维。

Description

聚四氟乙烯模塑制品及其制备方法
本发明涉及聚四氟乙烯(PTFE)模塑制品，将其加工成膜、带或纤维状及所述制品的制备方法。
PTFE由于其热稳定性和化学惰性，使其成为一种很有价值的材料。AT-B370,674公开了用烧结PTFE制成的单轴拉伸膜，这些膜在拉伸方向其拉伸强度值为50N/mm2至140N/mm2。在制造它们时首先将PTFE粉末压成圆柱形的模塑制品，然后将其烧结，当膜脱落后，将其加热到至少327℃再拉伸。
GB-A-2,025,835描述了用糊挤压法生产多孔PTFE模塑制品的方法。糊组合物，主要包括PTFE粉末和润滑剂，被强制通过模，其中润滑剂经干燥除去。然后将模塑制品加热到PTFE的晶粒熔点之上(327℃)，并在加热过程中进行拉伸。
AT-B391,473公开了用PTFE制备单轴拉伸模塑制品的方法，即将含PTFE粉末的糊状组合物连续加工成膜，由一系列辊或辗滚传输送进行加热和拉伸。在拉伸之前，将模塑先加热到327-450℃之间，优选的温度为350-390℃，在此温度范围内烧结后拉伸。此方法可生产出PTFE单轴拉伸模塑制品，该制品在拉伸方向上的拉伸强度至少为500N/mm2，其密度为1.80-2.30g/cm3。为了扩展PTFE的应用范围，需要得到用PTFE生产的弯曲纤维，本发明的主要目的就在于制造出具有稳定永久弯曲性能的PTFE纤维。
本发明的此目的是通过制造一种聚四氟乙烯(PTFE)的双组份模塑制品实现的，即该制品由两种PTFE组份按照并列排列的形式组成。这两种组份在受热时会收缩，其热空气收缩率至少有1％的差别。例如，这种纤维如果加热到200℃以上就会弯曲甚至在热处理过程中任意弯曲。
Ullmann出版的“化工技术百科全书”第四版，第十一章，第283-284页中Verlag指出尼龙纤维经双组份纺丝后可以弯曲。按照这种方法，两种性质不同的聚合物熔体同时从一个模口喷丝。上述纤维中的两种聚合物基本上有两种可能的排列方式：芯-外壳排列和并列排列。在第一种排列方式中，一种聚合物包围着另一种聚合物形如外壳而第二种排列方式中纤维可想象为是由两个半圆柱相互通过截面连接在一起的。然而，用这种方法，不可能生产稳定卷曲的PTFE纤维。
本发明基于认识到能够用简单方法制备由两层或多层收缩性质不同的PTFE层组成的双组份膜以形成粗双组份纤维。该纤维加热到200℃以上时能够稳定收缩。
因此本发明的双组份模塑制品的优选实施例是按照膜，带或纤维的形式设计的。这种纤维有利于原纤维化。
本发明涉及用上述双组份模塑制品经热处理得到的PTFE模塑制品。
模塑制品的一个优选实施例，其特征在于，得到一种弯曲纤维。这种纤维可用常规方法加工成仅含PTFE的针形毛毡，这种弯曲纤维的强度值至少为300N/mm2。
已经发现，按照本发明的纤维的梳通性能特别好，并且如果所使用的纤维是弯曲的和原纤维化的，则这种纤维非常适于制造无纺织织物和毛毡。用经原纤维化分岔的这些纤维，不需其它辅助方法就可生产出纯PTFE毛毡。这些毛毡在作为过滤器使用时，其优越性在于压力差增加小于用基质纺丝纤维制成的毛毡。本发明生产的毛毡还可用于医药技术。
本发明进一步涉及用PTFE生产双组份膜的方法，包括两种含PTFE粉末的组份模塑为并列形式，经轧平制成板状双组份模塑制品，经烧结后拉伸，前题条件是所用的PTFE粉被加工成膜后，其受热的收缩程度不同，且其热空气收缩率至少有1％的差别。将多于两种含PTFE粉末的组份加工成并列的模塑件也是可能的。
按照本发明，一个优选的改进方法包括将板状双组份模塑制品切割成带经烧结后拉伸，必要时还要进行原纤维化处理。
本发明通过附图进行详细说明。图1表示并列形式的板状双组份模塑制品的形成和构造。图2表示PTFE弯曲纤维的生产过程。
根据图1，将两种具有不同热空气收缩率的PTFE聚合物A和B与润滑剂混和形成模塑件(圆柱体)。然后将这些圆柱体沿长度方向轴向分割成两半(A和B)，然后A半部分与B半部分一同在挤压机中挤压成一股，所以股的一半含PTFE A另一半含PTFE B，在下一步，将股通过压延机轧平成膜，在这个工艺中，必须注意股位于滚子中间，这可假想为这两种材料半部分的分割线与滚距相平行。只有用这种方法才能生产出真正的双组份膜。压制后，膜可以象通常一样得以干燥并且不含润滑剂。
根据图2所示可将干燥的膜连续地送入烧结和拉伸系统。它主要包括传递单元1，一个刀杆2，二个加热滚3′，3″和一个不加热的脱离单元4，图示中箭头所指方向为加热滚3′，3″的旋转方向和膜脱离方向。
为了生产出带和纤维，干燥膜通过传递单元1就被刀杆2切割是有利的。
将进入传递单元1中的膜用刀杆2连续切成带，再将带绕到加热滚3′，3″上，烧结，最后带在滚上绕成S形以便能从两边加热。滚子至少要加热到327℃，烧结，然后直接拉伸。脱离过程是在不加热的脱离单元4上进行。图2可看出单元4上有许多轮子。为了生产纤维，带子再放在针形滚上面，然后原纤维化。为了再活化弯曲，不需加压纤维直接加热到至少200℃，就可以收缩。
本项发明可用以下实施例更详细地说明。
                      实施例1
PTFE粉末，其一为“Algoflon”DF 200(生产商Ausimont SpA)，热空气收缩值为4.5％；其二为“Telfon”3579(生产商Dupont)热空气收缩值为3.0％；将这两种粉末分别用20％的润滑剂处理(润滑剂的沸点范围在186℃至214℃之间)，分别压成圆柱体制品，然后将这些圆柱体制品沿其轴方向在中心严格地分开，再把这两种不同聚合物的二分之一部分用于主压园柱体压制成园股，然后利用一个两个辊的压延机将园股压出，形成0.1mm厚的膜，按这种方式形成的膜整个宽度上，一半厚的膜是由“Algoflon”DF 200组成，另一半是由“Teflon”3579组成。将此膜干燥，在380℃下烧结，并在此温度下以1∶11的比例拉伸，这样得到的膜厚度为20μm，用原纤维化辊可将其分裂成丝，用一个切割机可将其切割成80mm长的短纤维。再将这种短纤维放在250℃的炉子中加热30分钟，这两种PTFE聚合物在8％时，强度可达495N/mm2。
                      实施例2
将厚50μm的膜用实施例1的方法生产，拉伸，接着原纤维化。拉伸比为1∶12，膜厚度为9.5μm。在300℃时发生收缩和弯曲现象，弯曲可达到65％，当拉伸6.5％时强度可达到530N/mm2。
                      实施例3
根据实施例1，将“Teflon”3579和热空气收缩率为5.5％的“Polyflon”104 UF(生产商Daikin)与润滑剂混合形成厚度为75μm的膜。在365℃按1∶10拉伸。将得到的15μm厚的膜在一个塔中加热到300℃进行原纤维化及收缩，最后弯曲，弯曲后将股切成纤维，弯曲度为60％，在拉伸9％时，强度为427N/mm2。
                      实施例4
根据实施例3，将PTFE粉末混合后压制成圆柱体，其中压模的一半用一种粉末填充，另一半用等量的另一种粉末填充。把这种方式制造的双组份圆柱体，按实施例3中的方法加工成纤维。在310℃收缩，有62％发生弯曲，当拉伸10％时弯曲纤维强度为450N/mm2。
                      实施例5
如实施例4所描述，将“Algoflon”DF 200和具有热空气收缩率2.5％的“Hostaflon”TF 2029(生产商：Hoechst)同时填入模，压成股，然后进一步制成膜，并按照实施例1所述的条件，拉伸，原纤维化和热收缩，得到的纤维在拉伸8％时强度为480N/mm2，弯曲度为50％。

Claims (6)

1.一种聚四氟乙烯(PTFE)制成的拉伸的双组分模塑制品，以并列形式排列，由两种PTFE组分构成，加热时收缩，且其在温度200℃以上的热空气收缩率至少有1％的差别。
2.根据权利要求1所述的拉伸的双组分模塑制品，其特征在于，将其设计成膜，带或者纤维。
3.根据权利要求2所述的拉伸的双组分模塑制品，设计为纤维时，其特征在于，纤维是原纤维化的。
4.根据权利要求1，2或3所述的模塑制品，其特征在于它是弯曲纤维的形式。
5.一种生产权利要求2所述的PTFE双组分膜的方法，其特征在于，将两种含PTFE粉末的组分模塑为并列排列形式轧制成板状双组分模塑制品，经绕结然后拉伸，其前提条件是，所用的PIFE粉末被加工成膜后，其受热的收缩程度不同，并且其在温度200℃以上的热空气收缩率至少有1％的差别。
6.一种生产权利要求2的所述的PTFE双组分纤维的方法，其特征在于，将两种含PIFE粉末的组分模塑为并列排列形式轧制成板状双组分模塑制品，再将板状双组分模塑制品切割成带经烧结后进行拉伸，必要时还可以进行原纤维化处理，其前提条件是，所用的PIFE粉末被加工成膜后，其受热的收缩程度不同，并且其在温度200℃以上的热空气收缩率至少有1％的差别。
CN93118451A 1993-07-30 1993-09-30 聚四氟乙烯模塑制品及其制备方法 Expired - Fee Related CN1055431C (zh)

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WO1995004172A1 (de) 1995-02-09
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DE59305289D1 (de) 1997-03-06
BR9307124A (pt) 1999-03-30
EP0663025A1 (de) 1995-07-19
TW266183B (zh) 1995-12-21
ATE148180T1 (de) 1997-02-15
DK0663025T3 (da) 1997-07-28
EP0663025B1 (de) 1997-01-22
ATA151993A (de) 1994-10-15
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RU2119978C1 (ru) 1998-10-10

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