CN1065929C - 由聚四氟乙烯制成的单轴拉伸模制品 - Google Patents

由聚四氟乙烯制成的单轴拉伸模制品 Download PDF

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CN1065929C
CN1065929C CN94191089A CN94191089A CN1065929C CN 1065929 C CN1065929 C CN 1065929C CN 94191089 A CN94191089 A CN 94191089A CN 94191089 A CN94191089 A CN 94191089A CN 1065929 C CN1065929 C CN 1065929C
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I·马里尼
A·维默
J·巴赫麦耶
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    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Abstract

一种聚四氟乙烯单轴拉伸模制品，含有滑石、云母和/或耐高温酰亚胺和/或研细白粉作为填料，其拉伸方向的强度至少为10/tex。如果本发明的模制品含有研细白粉作为填料，则该模制品适用于生产牙线。

Description

由聚四氟乙烯制成的单轴拉伸模制品
本发明涉及由聚四氟乙烯(PTFE)制成的、可成形为薄膜、带、丝或纤维形式的单轴拉伸模制品，并涉及其生产方法。
PTFE因其热稳定性和化学惰性而成为一种有价值的材料。AT-B370，674公开了一种由烧结PTFE制成的单轴拉伸薄膜，其拉伸方向的强度为50-140N／mm2。生产这种薄膜时首先要把PTFE粉末压制成园筒模制品。随后将该模制品烧结，在薄膜剥离时将其加热到至少327℃的温度，并进行拉伸。
GB-A-2 025 835叙述了用糊料挤塑工艺生产多孔PTFE模制品的方法，其中迫使主要含有PTFE粉末和润滑剂(烃类)的糊状组合物通过模头，此时通过干燥除去润滑剂。然后将该模制品加热到PTFE晶粒熔点以上的温度(327℃)，并在加热过程中进行拉伸。
AT-B 391，473公开了一种生产单轴拉伸PTFE模制品的方法，其中将糊状PTFE组合物连续加工成模制件，让其通过许多辊筒或压辊，并进行加热和拉伸，在进行拉伸之前要将模制件加热到327-450℃的温度，并进行烧结。该方法可以从PTFE生产出拉伸方向强度至少为22CN／tex(500N／mm2)的单轴拉伸模制品。
已经知道，用US-A-2，893，105和UA-A-2，933，154的天星型复合纺(Matrix Spinning)生产的PTFE复丝和AT-B-340，561的间隙剥离法(gap peel process)生产的这种丝可用于生产密封套用的盘卷塞绳。从AT-B-347，003还知道，如何用PTFE和石墨来涂布这种丝以改善其滑动性。
也已经知道，由糊料挤塑法生产的取向但不烧结的薄膜带，用PTFE分散剂浸渍并用石蜡油润滑后可用来生产填函料。含有石墨填料的这种薄膜带也可从市场购得。
所有填有石墨的产品都有一个缺点，即用于增加滑动性的石墨填料是黑色的，因而这种产品无法用于某些工业领域。此外，这种产品具有高的流动倾向(冷流)，这自然就增加了磨损。这种产品的另一个缺点是，单轴拉伸并填有石墨的模制品只具有小于10CN／tex(厘牛顿／特)的强度。
本发明旨在消除这些缺点，扩大PTFE材料的实用性，并提供一种与填充石墨的PTFE模制品相比，具有颜色浅、强度较高和冷流倾向较低的单轴拉伸模制品。此外，生产具有不同滑动性的所述PTFE模制品也是可行的。
按照本发明的方法由聚四氟乙烯(PTFE)制成的单轴拉伸模制品的特征在于：它含有滑石和／或云母和／或耐高温聚酰亚胺和／或作为填料的白粉，且其强度至少为10CN／tex，较好是超过16CN／tex。如EP-A-0 119 185和US-A-3，985，934中所公开的那些耐高温聚酰亚胺是特别适用的。
现已令人惊奇地用糊料挤塑法成功地将PTFE粉末与所述填料混合，并将其加工成例如薄膜，将这种薄膜烧结，并随后进行拉伸，从而尽管存在填料也达到了很高的强度值。例如不含填料的PTFE丝(按AT-B-370，674方法生产的)的强度为5-15CN／tex，而按本发明方法生产的含填料的丝的强度可高达25CN／tex。按照本发明的模制品可含有高达40％(重量)的填料。减小断裂拉伸强度伴随着断裂伸长的减小和抗蠕变的增加，这是用这种丝作为密封套密封材料的一个重要特点。
按照本发明的模制品可含有高达40％(重量)的填料，而拉伸强度不会小于所指出的最小值，即不小于10CN／tex。
按照本发明的模制品的一个优选实例的特征在于该模制品含有20-30％(重量)的滑石和／或云母和或耐高温聚酰亚胺作为填料。这样的一种模制品具有良好的滑动性。按照DIN533 75方法所做的测定揭示由纯PTFE制成丝的动摩擦值(μp)约为150(110-200)，以石墨为填料的丝的动摩擦值在50-100之间，而按照本发明以滑石为填料的丝，其动摩擦值在30-70之间。
如果按照本发明的模制品还有利地具有不超过30％的伸长率，则这种模制品非常适于用作例如在泵中用于密封轴(在密封套壳内)的材料。迄今为止一直使用含有石墨填充剂的PTFE模制品作为这种材料。这种已知模制品的抗蠕变性能不够，且磨损大，因而在石墨填料的情况下磨损的黑色物质会从密封套壳内漏出，从而使被密封的浅色液体变色或被污染。本发明实例的模制品没有这些缺点中的任何一个缺点。
如果按照本发明的模制品以丝的形式成形，则这种丝可方便地用于生产盘卷密封材料。
按照本发明的模制品的另一优选实例的特征在于该模制品含有至少5％(重量)的白粉作为填料。现已证实白粉可使动摩擦μp增加到至少200，因此这种材料很适合要求高动摩擦的场合的一切用途。
按照本发明的模制品的又一个优选实例的特征在于该模制品只含白粉作为填料，而且呈牙线形式。现已表明使用本发明的牙线与使用先有技术的牙线相比，可以保持更多的胶质。调节白粉的用量可以改变牙线的动摩擦。实验已经揭示，含有0．1-15 ％(重量)白粉的牙线是特别适用的。
本发明还涉及生产本发明模制品的方法，所述方法的特征在于组合了下列特点：
a)使聚四氟乙烯粉末与滑石和／或云母和／或一种耐高温聚酰亚胺和／或白粉和一种烃混合，
b)使所得到混合物成形为预成形制品并脱除所述的烃，
c)将脱除烃的预成形制品烧结，随后在烧结状态进行拉伸。
填料的用量最好不超过模制品重量的40％。
预成形制品加热到至少327℃的温度，较好380-400℃，以备烧结。
为了使本发明模制品达到指出的强度值，烧结后的预成形制品较好以1∶5-1∶20的拉伸比，更好以1∶5-1∶15的拉伸比进行拉伸。
在按照本发明方法的一个具体实例中，预成形制品是一种薄膜，这种薄膜在烧结和拉伸之后裁成带条，这种带可很方便地用针轧机进行原纤维化处理。
本发明较好的实施方案可由下列实例详细说明。本发明的模制品是用AT-B 391，473所公开的烧结和拉伸设备生产的。
实例1
将100重量份Hchst AG公司生产的市售PTFE粉末Hostaflon TF2029与25重量份滑石(Naintsch A-30)和30重量份糊料挤塑中常用的润滑剂(沸点为186-214℃的一种烃)混合，并压成园筒形模制品。随后将这些园筒形制品压制成线，并进一步轧制成薄膜，再通过干燥脱除润滑剂。干燥后的薄膜在385℃进行烧结，然后以1∶7的拉伸比进行拉伸，就可制得一种具有良好滑动性、在6．5％伸长时强度为21．3CN／tex的非常柔软的薄膜(邵尔D30-38)。
实例2
将70份Hostaflon TF 2029型PTFE粉末与30份A-30滑石和30份润滑剂混合并按实例1方法轧制成薄膜、干燥、烧结和拉伸。在5．5％伸长时强度为19．5CN／tex。
实例3
按实例1的同样方法将实例1中所述的混合物加工成薄膜，所不同的是在395℃进行烧结，然后以1∶8．5的拉伸比进行拉伸。5％伸长时的强度为24．5CN／tex。然后将该薄膜进行原纤维化处理并用22％石蜡油浸泡。
最终产品为复丝纱线形式，可直接加工成盘卷塞绳。石蜡油起着润滑剂的作用。
实例4
将100份Algoflon DF 200型PTFE粉末(生产厂家：Ausimont S．P．A．)与47份A-60滑石和30份润滑剂混合，并加工成薄膜。所述薄膜在390℃烧结，并以1∶6拉伸比拉伸。所得薄膜在8％伸长时的强度为16CN／tex。
实例5
以相同方法将实例4所述混合物加工成薄膜，所不同的是在395℃烧结，以1∶7拉伸比拉伸。5％伸长时的强度为17．5CN／tex。拉伸后将薄膜进行原纤维化处理，然后用20％石蜡油浸泡。
实例6
将75份牌号为Hostaflon TF 209的PTFE粉末与25份云母和27份润滑剂混合，并按实例1所述同样的方法加工成薄膜，并进行拉伸。伸长率为8．5％时的强度是16．5CN／tex。
实例7
100份牌号为Algoflon DF 200的PTFE粉末与10份白粉和25份润滑剂混合，并加工成薄膜。所述薄膜在390℃进行烧结，以1∶13．5拉伸比进行拉伸，并裁成带条。所得带条在伸长率为4．5％时其强度为26CN／tex。掺入白粉后产品的动摩擦增加。该产品可用作牙线。

Claims (15)

1．由聚四氟乙烯制成的单轴拉伸模制品，该模制品含有滑石和／或云母和／或耐高温聚酰亚胺和／或白粉作为填料，其拉伸方向的强度至少为10CN／tex(厘牛顿／特)。
2．按照权利要求1的模制品，其特征在于该模制品含有不超过40％重量的填料。
3．按照权利要求2的模制品，其特征在于该模制品含有20-30％重量的滑石和／或云母和／或耐高温聚酰亚胺作为填料。
4．按照权利要求2的模制品，其特征在于它含有至少5％重量的白粉作为填料。
5．按照权利要求1-4中任一项的模制品，其特征在于其伸长率不大于30％。
6．按照权利要求2的模制品，其特征在于它只含有白粉作为填料，且呈牙线形式。
7．按照权利要求6的模制品，其特征在于它含有0．1-15％重量的白粉。
8．按照权利要求1-7任何一项的模制品的生产方法，其特征在于组合了下列特点：
a)使聚四氟乙烯粉末与滑石和／或云母和／或一种耐高温聚酰亚胺和／或白粉和一种烃混合，
b)使所得到混合物成形为预成形制品并脱除所述的烃，
c)将脱除烃的预成形制品烧结，随后在烧结状态进行拉伸；
其中，所述步骤a)、b)和c)是依次进行的。
9．按照权利要求8的方法，其特征在于填料的用量不超过模制品重量的40％。
10．按照权利要求8或9的方法，其特征在于将预成形制品加热到至少327℃的温度以备烧结。
11．按照权利要求10的方法，其特征在于将预成形制品加热到380-400℃的温度以备烧结。
12．按照权利要求8或9的方法，其特征在于将烧结后的预成形制品以1∶5-1∶20的拉伸比进行拉伸。
13．按照权利要求12的方法，其特征在于将烧结后的预成形制品以1∶5-1∶15的拉伸比进行拉伸。
14．按照权利要求8或9的方法，其特征在于所述预成形制品是一种薄膜，该薄膜在烧结和拉伸后裁成带条。
15．按照权利要求14的方法，其特征在于使烧结和拉伸后的带条经受原纤维化处理。
CN94191089A 1993-11-03 1994-09-28 由聚四氟乙烯制成的单轴拉伸模制品 Expired - Fee Related CN1065929C (zh)

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WO1995012698A1 (de) 1995-05-11
TW323294B (zh) 1997-12-21
DE59408419D1 (de) 1999-07-22
ATA222193A (de) 1994-12-15
KR960700364A (ko) 1996-01-20
JPH08505430A (ja) 1996-06-11
BR9406468A (pt) 1996-01-23
AT399882B (de) 1995-08-25
ATE181377T1 (de) 1999-07-15
EP0677120B1 (de) 1999-06-16
EP0677120A1 (de) 1995-10-18
RU2135531C1 (ru) 1999-08-27
US5804290A (en) 1998-09-08
RU95115559A (ru) 1997-06-10
KR100330805B1 (ko) 2002-11-22
CN1117299A (zh) 1996-02-21

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