CN1046119A - 聚四氟乙烯单轴向拉伸成型制品 - Google Patents

聚四氟乙烯单轴向拉伸成型制品 Download PDF

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CN1046119A
CN1046119A CN90101999A CN90101999A CN1046119A CN 1046119 A CN1046119 A CN 1046119A CN 90101999 A CN90101999 A CN 90101999A CN 90101999 A CN90101999 A CN 90101999A CN 1046119 A CN1046119 A CN 1046119A
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ptfe
roller
article
film
shaped
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CN1028160C (zh
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弗朗茨·萨斯霍弗
赖恩哈德·赖恩梅勒
克里斯蒂安·H·F·施洛斯尼克
阿达尔贝特·格奥尔格·温默
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Lianjinge
Lenzing AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • External Artificial Organs (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Noodles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

为了制备聚四氟乙烯(PTFE)单轴向拉伸成型制品，将含有PTFE粉末的糊料物连续成型为成型物，它送经多组辊或辊，加热并拉伸。在进行拉伸前，成型物加热至327～450℃，同时烧结，然后拉伸。该方法制成的PTFE单轴向拉伸成型制品在拉伸方向强度至少为500N/mm2，密度为1.80～2.30g/cm3。

Description

本发明是关于聚四氟乙烯（PTFE）的单轴向拉伸制品，及其它们的制备方法。
由于聚四氟乙烯的热稳定剂和它的化学惰性，它是一种受赞赏的材料。但是，在某些领域它的应用有局限性，因为人们还不能成功地制成具有高机械强度和同时有高密度的PTFE成型制品。
例如，如果将这种材料加工成纺织纱，它可以加工成特别耐磨的PTFE织物。优异的强度和高密度的综合性能也有利于用做包裹导电体，介电击穿强度随着密度而提高。
目前，市场上可购得具有强度至多250N/mm2的PTFE成型制品，但它们的密度低于1g/cm3。这类成型制品是用拉伸没有烧结的PTFE而制成的。另一方面，至今已知烧结后PTFE成型制品的密度约为2g/cm3，但是强度不超过约50N/mm2。
从AT-B 370 674可知烧结的PTFE单轴拉伸膜，拉伸方向的强度为50N/mm2～140N/mm2。这类膜的制备是首先将PTFE粉末压成圆柱状成型制品，然后，烧结成型制品，再从上剥离成薄膜，至少加热到327℃并拉伸。
GB-A-2    025    835公开了按照糊料挤塑方法制备多孔PTFE成型制品的方法，该方法包括将基本上含有PTFE粉末和润滑剂的糊料物加压通过喷丝器，然后干燥除去润滑剂。其后，将成型制品加热至PTFE结晶熔点（327℃）以上并在加热过程中拉伸。拉伸比越大，所得成型制品的强度越大。但是，随之成型制品的密度降低了，例如拉伸率为550%时，强度升至约为42N/mm2，而密度降为约0.4g/cm3。
本发明的目的是提供一种PTFE成型制品，它没有上述的缺点，但具有高的机械强度和高密度。
本发明的PTFE制品是单轴向拉伸的，拉伸方向的强度至少为500N/mm2，最好至少为700N/mm2，密度为1.80～2.30g/cm3，最好为2.00～2.20g/cm3，成型制品较好为薄膜、带材、纺织纱或缝纫纱。在指出的强度值，纱的伸长率为3%～50%。
本发明的单轴向拉伸PTFE成型制品的制备是将含有PTFE粉末的糊料物连续制成成型物，将成型物送经多辊或辊，加热并拉伸成型物，在拉伸之前加热成型物至327～450℃，最好为350～390℃，这样烧结，然后拉伸。
本发明方法的较好实施方案是在加热为327～450℃，最好为350～390℃的辊或一对辊与未加热的引出装置间拉伸成型物。
它具有的拉伸比为1∶5～1∶30，最好为1∶10～1∶20。当拉伸比为1∶30时，得到的强度大约为1150N/mm2。
本发明方法的实施方案将由附图来更详细地说明。
首先，以已知的方法将PTFE粉末与润滑剂混合，并在20～50℃下贮存几小时，再在压力为10～50巴下加工成型物。然后用已知方法将制成的成型物通过单孔喷丝器挤成棒状，并滚压成薄膜，干燥除去润滑剂。
然后，这种干燥的薄膜连续地送入附图所示的烧结和拉伸设备中。该设备的基本组成是送料器1，两个加热辊3′、3″和未加热的引出装置4，在附图的箭头是加热辊3′、3″的转动方向和薄膜的拉动方向。
经送料器1输入的薄膜连续地经过加热的辊3′、3″，并在此烧结。为此，为了能使薄膜从两面加热，薄膜最好是像“S”形包卷在辊上。辊子已经加热到至少327℃。烧结后，薄膜立即拉伸。薄膜由附图上标示的由几个卷滚组成的未加热引出装置4拉出。最后，拉伸过的料缠绕在合适的卷料筒上。
为了生产带材，干燥的薄膜较好是当通过送料器1时，已经用切刀杆装置切开。
本发明将用下列实例更详细地说明。
实例1
将100份PTFE乳液粉末和23份汽油（沸点为186～214℃）压成圆柱棒，压延成厚度为0.1mm薄膜并干燥。然后，将该薄膜送入送料器1，切成6mm宽的带子，经已加热至380℃的辊3′、3″，同时被烧结，并用这组辊以1∶15的拉伸比拉伸。所得的带材在伸长率为5.6%时的强度为835N/mm2，密度为2.12g/cm3。
初始厚度降为0.0236mm，宽度为1.4mm。
所得PTFE带材可加工成纺织纱（加拈的或不加拈的）和缝纫纱（双拈的）。
实例2
将按照实例1压成棒的PTFE，辊压成0.114mm厚的薄膜并干燥。该薄膜经已加热到375℃的辊3′、3″，宽度为200mm，同时被烧结。烧结时立即以拉伸比为1∶15进行拉伸。在伸长率为7.5%时，所得薄膜的强度为692N/mm2，密度为2.17g/cm3，介电击穿强度为190KV/mm。薄膜的宽度为46.6mm，厚度为0.024mm。
该薄膜无孔，具有较好的滑动特性和优异的电绝缘性，它特别适用于包裹导电体。
实例3
将如实例1所述方法压成棒状的PTFE再辊成0.05mm厚的薄膜并干燥。将该薄膜切成宽为25mm的带子，经已加热到385℃的辊，同时烧结。接着，以1∶15的拉伸比拉伸，可是得到伸长率为5.6%时的薄膜强度为703N/mm2，密度为1.93g/cm3。该薄膜的宽度为5.8mm，厚度为0.013mm。

Claims (5)

1、一种聚四氟乙烯(PTFE)单相向拉伸的成型制品，该制品在拉伸方向的强度至少为500N/mm2，最好至少为700N/mm2，密度为1.80～2.30g/cm3，最好为2.00～2.20g/cm3。
2、如权利要求1的单轴向拉伸的成型制品，将它制成薄膜、带材、纺织纱成缝纫纱。
3、一种制备如权利要求1的单轴拉伸成型制品的方法，该方法包括将含PTFE粉末的糊料物连续制成成型物，将成型物送经多组辊或辊，加热并拉伸成型物，其特征在于在拉伸之前将成型物加热至327～450℃，最好为350～390℃，因此被烧结，然后拉伸。
4、如权利要求3的方法，其特征在于成型物是在加热到327～450℃，最好为350～390℃的辊或一对辊（3′、3″）与未加热的引出装置（4）间被拉伸。
5、如权利要求3或4的方法，其特征在于成型物的拉伸率为1∶5～1∶30，最好为1∶10～1∶20。
CN90101999A 1989-04-06 1990-04-06 聚四氟乙烯单轴向拉伸成型制品的制备方法 Expired - Lifetime CN1028160C (zh)

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AT0081389A AT391473B (de) 1989-04-06 1989-04-06 Monoaxial verstreckter formkoerper aus polytetrafluoraethylen und verfahren zu seiner herstellung
ATA813/89 1989-04-06

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US (1) US5167890A (zh)
EP (1) EP0391887B1 (zh)
JP (1) JP2913062B2 (zh)
KR (1) KR0178032B1 (zh)
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AT (2) AT391473B (zh)
AU (1) AU639912B2 (zh)
BR (1) BR9001696A (zh)
CA (1) CA2013122A1 (zh)
DD (1) DD293305A5 (zh)
DE (1) DE59009267D1 (zh)
ES (1) ES2075192T3 (zh)
FI (1) FI98349C (zh)
HU (1) HU212430B (zh)
IE (1) IE62562B1 (zh)
IL (1) IL93836A (zh)
RU (1) RU1839674C (zh)
UA (1) UA11068A (zh)
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CN1055431C (zh) * 1993-07-30 2000-08-16 连津格股份公司 聚四氟乙烯模塑制品及其制备方法
CN1065929C (zh) * 1993-11-03 2001-05-16 连津格股份公司 由聚四氟乙烯制成的单轴拉伸模制品
CN1082103C (zh) * 1994-06-30 2002-04-03 大金工业株式会社 膨松聚四氟乙烯长纤维及裂膜丝、其制造方法、使用其制造棉状物的方法及集尘用滤布
CN1961030B (zh) * 2004-04-23 2010-05-26 戈尔企业控股股份有限公司 含氟聚合物屏障材料
CN103770351A (zh) * 2014-02-25 2014-05-07 韩玉新 一种聚四氟乙烯薄膜带加工工艺
CN105648556A (zh) * 2014-10-31 2016-06-08 陈路 一种用于制造ptfe缝纫线的拉丝机
CN105887221A (zh) * 2014-10-31 2016-08-24 陈路 一种用于制造ptfe缝纫线的多辊牵伸装置
CN108728978A (zh) * 2018-05-05 2018-11-02 灵氟隆新材料科技江苏有限公司 一种荧光聚四氟乙烯缝纫线的制备方法
CN109203525A (zh) * 2018-08-29 2019-01-15 山东东岳高分子材料有限公司 一种高强度聚四氟乙烯薄膜的制造工艺
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CN113195187A (zh) * 2018-11-15 2021-07-30 山勝实验室有限公司 未烧结聚四氟乙烯薄膜及其多孔膜的制备方法

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CN1065929C (zh) * 1993-11-03 2001-05-16 连津格股份公司 由聚四氟乙烯制成的单轴拉伸模制品
CN1082103C (zh) * 1994-06-30 2002-04-03 大金工业株式会社 膨松聚四氟乙烯长纤维及裂膜丝、其制造方法、使用其制造棉状物的方法及集尘用滤布
CN1961030B (zh) * 2004-04-23 2010-05-26 戈尔企业控股股份有限公司 含氟聚合物屏障材料
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CN108728978A (zh) * 2018-05-05 2018-11-02 灵氟隆新材料科技江苏有限公司 一种荧光聚四氟乙烯缝纫线的制备方法
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CN113195187A (zh) * 2018-11-15 2021-07-30 山勝实验室有限公司 未烧结聚四氟乙烯薄膜及其多孔膜的制备方法
CN113195187B (zh) * 2018-11-15 2022-11-15 重庆宝曼新材料有限公司 未烧结聚四氟乙烯薄膜及其多孔膜的制备方法
CN110528131A (zh) * 2019-09-20 2019-12-03 常州华福环境科技股份有限公司 一种高强度低摩擦聚四氟乙烯缝纫线的制造工艺
CN110629303A (zh) * 2019-09-20 2019-12-31 常州华福环境科技股份有限公司 一种高强度低伸长聚四氟乙烯超细长丝的制造工艺
CN110629303B (zh) * 2019-09-20 2021-07-20 常州华福环境科技股份有限公司 一种高强度低伸长聚四氟乙烯超细长丝的制造工艺
CN110528131B (zh) * 2019-09-20 2021-07-23 常州华福环境科技股份有限公司 一种高强度低摩擦聚四氟乙烯缝纫线的制造工艺

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IE62562B1 (en) 1995-02-08
IE901099L (en) 1990-10-06
CA2013122A1 (en) 1990-10-06
US5167890A (en) 1992-12-01
IL93836A (en) 1993-04-04
JPH02286220A (ja) 1990-11-26
FI901689A0 (fi) 1990-04-03
CN1028160C (zh) 1995-04-12
HU212430B (en) 1996-06-28
HUT62232A (en) 1993-04-28
UA11068A (uk) 1996-12-25
EP0391887B1 (de) 1995-06-21
BR9001696A (pt) 1991-05-14
ES2075192T3 (es) 1995-10-01
JP2913062B2 (ja) 1999-06-28
IL93836A0 (en) 1990-12-23
KR0178032B1 (ko) 1999-05-15
AU5240290A (en) 1990-10-11
FI98349B (fi) 1997-02-28
EP0391887A2 (de) 1990-10-10
AT391473B (de) 1990-10-10
KR900016326A (ko) 1990-11-13
AU639912B2 (en) 1993-08-12
DD293305A5 (de) 1991-08-29
EP0391887A3 (de) 1992-03-18
FI98349C (fi) 1997-06-10
ATE123993T1 (de) 1995-07-15
YU67490A (en) 1991-10-31
RU1839674C (ru) 1993-12-30
HU901892D0 (en) 1990-07-28
DE59009267D1 (de) 1995-07-27
ZA902390B (en) 1990-12-28
ATA81389A (de) 1990-04-15

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