CN87100900A - 制造多孔延伸模制体的方法 - Google Patents
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Abstract
经浆料挤压制造的模制体是在连续流动中,第一步去除润滑剂,第二步进行拉伸并同时对材料进行烧结。
Description
本发明涉及由含氟聚合物如聚四氟乙烯制造多孔可延伸模制体,特别是制造带材、薄膜、实心型材或空心型材的模制体的方法,该方法将未经熔化加工的粉状单一聚合物或混合聚合物,在借助润滑剂条件下进行压缩并形成模制体(浆料挤压),然后去除润滑剂,将模剂体拉伸,对聚合物进行烧结。
由四氟聚合物制造多孔模制体已为公众所知(DE-PS 2417901),该项专利中所采用的方法是在去除润滑剂后,以每秒钟大于2000%的拉伸速度,通过浆料挤压制成模制体,其模制体的延伸长度比不延伸的高50倍。模制体的拉伸温度为35°-327℃,在减小密度的同时抗拉强度显著提高。为了达到这样的要求,拉伸速度与一定温度范围的结合则可视为决定因素。
除了已知方法由于每秒的拉伸值很高而提出了制造工艺问题之外,根据已知方法制造的模制体在其填料范围内是没有限制的。例如拉伸速度每秒大于2000%的带材或薄膜很少用作弹性电缆或导线的多层结构中缠绕的绝缘膜。因为适用于弹性电缆或电线的带材或薄膜必须是可弯曲的,才能适应电缆和电线的转动,但是当电缆或电线的弯曲半径很小时,带材或薄膜对缠绕状态的电缆或电线的柔曲性可以没有明显的影响,也不会产生所谓的折皱。
专门用于螺旋连接进行密封的可弯曲的带材也已为公众所知(DE-OS2028393)。这种带材或薄膜是由聚四氟乙烯制成,未经烧结,纵向延伸,这是为了使聚合物的用量足够小,但并不影响已知带材的密度。这种带材很少用于电的方面,此外,也没有给出将带缠绕在管束电缆或电线上不发生带状形变所需的抗拉强度。
基于这种技术水平,本发明的任务在于寻找一种制造多孔模制体的简单工艺方法,为含氟聚合物开辟广泛有益的应用领域。
本发明这个任务的解决方法是:在连续流动时,第一步通过干燥去除润滑剂,紧接着在第二步将温度至少上升到各聚合物的晶体溶化的温度,然后拉伸模制体,在拉伸模制体的同时烧结模制体。如果模制体的拉伸与聚合材料的烧结这两个过程实际上是同时进行的,则在拉伸率较低时也能获得以含氟聚合物为基础的模制体的高抗拉强度,本发明就是以此为基础的。但是对模制体也采用另一种方法,例如带材或薄膜在烧结过程中沿模制体的流动方向或垂直方向通过机械处理形成不同的性质。
实施本发明时,如果在模制体烧结时沿拉伸方向拉伸,则特别有利。这样制造的薄膜或带材主要适用于缠绕柔韧的延伸制品,如电缆和电线,因为他们与衬垫紧贴毫无问题,并且由于横向稳定性良好,如果确实如此,则成品的柔韧性不会受显着影响。由于带边的重叠或折褶造成的损坏则可避免。
如果不是应用于这个实施例而是主要取决于带材的横向稳定性,并且抗拉强度在模制体纵向不起主要作用时,则其优点可能在于由含氟聚合物制成的带材在加热超过该物质晶体熔化温度时沿拉力方向横向拉伸,甚至根据另一个发明构思形成双轴向拉伸,即纵向拉伸和横向拉伸。在拉伸率较低的情况下,本发明的这样简单的方法使模制体在电和机械方面都具有很高的价值,能充分满足各种不同的应用领域所提出的种种要求。
在低于342℃即低于未烧结聚合材料的熔点时,与已知急骤加热技术相反,本发明也必须进行烧结。因此,实施本发明构思时,温度范围要高于342℃,优先柔用380℃-1000℃。
根据本发明对由浆料挤压制造的模制体进行干燥时,在整个流动过程中总是与紧接着的拉伸并同时烧结的步骤分开。实施本发明的干燥温度为150°-320°,优先柔用200°-300℃。从而与目前通用的润滑剂的自燃点350°-400℃保持足够的距离。
尤其是当本发明的模制体为带状或薄膜状制品时,那么根据另一个发明构思,模制体沿拉力方向的拉伸可达2000%,100-1000%则较佳。由此得到的带材特别适用于柔韧可延伸的制品。这种带材或薄膜在拉伸和烧结时的比重为0.2-1.3克/厘米3。当然,相应的拉伸比也适用于模制体在烧结过程中垂直于纵向或流动方向的机械处理,如果所需产品的性质必须如此。
如上所述,对于一定的产品,大致为柔韧可延伸的产品,取决于带材的缠绕状态,不管其用途如何都是如此,带材或薄膜在纵向和横向上的强度并不相同。因为根据本发明的带材或薄膜的拉伸方向和横向的抗拉强度之比为10-50∶1,所以这种带材或薄膜对于特殊用途和类似情况就已知制造方法的各个方面都已作了考虑。关于“已知制造方法”不仅应该理解为以含氟聚合物为基础的已知可拉伸的薄膜,而且也应该理解为其他正在应用的以聚合物为基础的带材或薄膜。因此,在电气工业方面最近以来用于各个不同目的的例如有将以线型聚脂为基础的带状薄膜用作绝缘材料,他们的商品名称可能就是为大家所熟知的“Hostaphan”。但是这种薄膜在电缆或电线工业中也用于各层之间的隔离,可能是为了抑制挥发性成份(增塑剂)的挥发,或是为了保证电缆线电线结构中各层相互间的机械位移,当缠放电缆或电线时,缠拉的作用力对这种机械位移影响很大。这种已知薄膜的缺点是在缠绕时可弯曲性很差,并且用这种薄膜包缠的电缆由于薄膜材料的刚性较高而影响其柔韧性。
如果将带材或薄膜进行打孔,则在特别柔韧的可延伸的物品中可专门用作滑动薄膜,这是在进一步实施本发明所具有的一个优点。例如借助一个刀辊,将纵向转动并以一定距离配置的刀口插入带材或薄膜中,许多这样的刀口排列可以互相转动。在交变弯曲应力很大时,在一个或多个位置上缠绕的带材料或薄膜被打孔,制品的柔韧性仍保持着,带材料或薄膜起着润滑剂的作用。
由互相可以分离但弯曲时又毫无问题应该能够互相移动的多层结构组成的可延伸的柔韧制品,可以是已经提及的用于传输能量和传递信息的电缆和电线,也可以是采用气动或液动方法用于传送测控数据的并且是由各个管组合成一束的所谓管束电缆。用作传送液体或气体介质的管道或软管也是本发明的应用领域,这里不仅是带材或薄膜得到应用,而且也可以把已经提及的一个或多个小管制成为多孔模制件,用作监测挥发性气体的所谓气体自动排放管。
在用于电缆或电线方面,本发明的带材或薄膜也可以用作滑动层或隔离层,绝缘材料可以由这些带材或薄膜构成,但是也可以根据本发明由拉伸并同时烧结多孔薄膜或带材制成同轴高频电缆的绝缘材料。多孔材料中空气含量较高,其纵向强度很高,与之相比,横向强度较低,对实现这个领域提出的要求尤为明显。
为了实施本发明的方法,提供一种有用的装置,它是由一个沿着经浆料挤压成形的模制体的流动方向配置的加热干燥装置和一个紧连着的空间隔开的连续加热炉,加热炉的出口连接缠绕装置,与其相对的在加热炉的入口连接转速较高的导辊和/或进料辊。有意识地将第一步中模制体的干燥和第二步中综合拉伸与实际上同时进行的烧结区分开来,但是在模制体流动中两者导致合理安全地操作。
根据附图所示实施例,详细说明本发明。
经浆料挤压成形的模制体是由聚四氟乙烯制成的带材1,它由备用带盘2开卷并通过导向辊3与干燥炉4连接。带材1通过温度约为280℃的该干燥炉时,去除浆料挤压所需的润滑剂。经干燥但还未拉伸和烧结的带材1立即进入炉温为430℃的烧结炉5。装于烧结炉5出口处的导辊6开始驱动,但其转速大于导向辊的转速。于是经烧结炉5中烧结温度处理的带材1开始拉伸。实际上同时进行拉伸和烧结的带材立即成为多孔模制体,通过导向辊7缠绕在附加带盘8上。
缠绕在附加带盘2上的带材的原料是聚合物粉末,加压与已知润滑剂混合,首先压缩成型坯,然后如众所周知,在本实施例中将这种型坯在活塞挤压机中挤压成圆形软线,再滚压成带材。
如果压缩比为40∶1(型坯∶圆形软线),滚压成带材后,拉伸比为1∶5,根据本发明制造的多孔烧结和拉伸的带材,达到的纵向抗拉强度为360公斤力/厘米2,横向抗拉强度为30公斤力/厘米2。
如果在同样的工作条件下,选用压缩比为50∶1,则达到的纵向抗拉强度280公斤力/厘米2,横向抗拉强度为20公斤力/厘米2。不管哪种情况,量的差异都是很显著的,或者带材的纵向抗拉强度很大,或者横向抗拉强度很大。因此,这样制造的模制体除了耐热性高和对腐蚀性介质不敏感外,主要还在于弯曲比。
与比不同当然也是可能的,即将模制体(主要是带材或薄膜)垂直于拉伸的拉力方向与聚合材料同时进行烧结。适用于这种加工的设备则是带有沿流动方向移动的拉伸构件,该拉伸构件作用于带边或薄膜边并且在烧结炉5内所需终端位置分开的同时,将薄膜温度提高到薄膜材料的晶体熔化温度,从而达到所需的拉伸度。
然而在其他情况下,例如在工业滤器或外科领域里,则与电缆技术相反,往往不是取决于模制体纵向抗拉强度的差异。
在这种情况下,根据本发明例如可以按附图所示进行操作,将已干燥但尚未拉伸和烧结的带材1送入烧结炉5,并将烧结炉温调至500℃的烧结温度。由于导辊6和导向辊3的转速不同,烧结时不断地借助这两个部件就可实现纵向拉伸,拉伸比为200-600%。同时,拉伸构件作用在带材的两边(本文未予介绍,但已在EP-PS 0075306中公开),这两个边借助适宜的导轨在带材流动时与流动方向互成直角运动,使带材也沿这个方向拉伸。这样就导致双轴向拉伸并在拉伸的同时烧结的带材在两个方向上具有较高的抗拉强度。通过本发明所达到的一个方向或两个方向上拉伸的模制体的抗拉强度超过其他已知方法所能达到的极高的拉伸度。
Claims (14)
1、由含氟聚合物如聚四氟乙烯制造多孔可延伸模制体,特别是制造带材、薄膜、实心型材或空心型材的模制体的方法,该方法将未经熔化加工的粉状单一聚合物或混合聚合物,在借助润滑剂的条件下进行压缩并形成模制体(浆料挤压),然后去除润滑剂,将模制体拉伸,对聚合物进行烧结,其特征在于模制体在连续流动时第一步通过干燥去除润滑剂,紧接着第二步将温度至少升高到各该聚合物的晶体熔化温度才进行拉伸,在与模制体拉伸的同时对聚合物进行烧结。
2、根据权利要求1的方法,其特征在于模制体沿拉力方向拉伸。
3、根据权利要求1的方法,其特征在于模制体横向于拉力方向拉伸。
4、根据权利要求1的方法,其特征在于模制体先后或同时纵向和横向拉伸,拉伸的温度范围都超过制造模制体所用聚合物的晶体熔化温度。
5、根据权利要求1或1以下权利要求之一所述的方法,其特征在于温度范围超过342℃,优先采用的温度范围为380°-1000℃。
6、根据权利要求1或1以下权利要求之一所述的方法,其特征在于第一步中模制体的干燥温度为150°-320℃,优先采用200°-300℃。
7、根据权利要求1或1以下权利要求之一所述的方法,其特征在于模制体纵向延伸可至2000%,最佳为100-1000%。
8、根据权利要求1或1以下权利要求之一所述的方法制造的带材或薄膜,其特征在于带材料或薄膜在拉伸和烧结时的比重为0.2-1.3克/厘米3。
9、根据权利要求8所述的带材或薄膜,其特征在于带材或薄膜的纵向与横向的抗拉强度比为10~50∶1。
10、根据权利要求8或9的带材或薄膜,其特征为打孔。
11、根据权利要求8或10的带材或薄膜,可用于延展制品的多层结构,如电缆和电线,管道或管束线。
12、根据权利要求11所述的电缆或电线延展制品,其特征在于电缆或电线的绝缘材料是由经拉伸并同时烧结的带材或薄膜制成。
13、根据权利要求11所述的具有在多层结构中的一层或多层的滑动薄膜或隔离薄膜的电缆或电线的延展制品,其特征在于滑动薄膜或隔离薄膜由径拉伸并同时烧结的带或薄膜制成。
14、实施权利要求1或1以下权要求之一所述方法的装置,其特征在于在由浆料挤压成形的模制体的流动位置中装有加热干燥装置和连接一个空间与之隔开的连续加热炉,加热炉的出口连接缠绕装置,与其相对的在加热炉的入口连接速较高的导辊和/或进料辊,以及(或者)在模制体两侧装有沿流动方向与其一切转动并在连续加热炉的范围内可移动的夹紧构件或拉伸构件。
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DE3605588 | 1986-02-21 | ||
DEP3605588.3 | 1986-02-21 |
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CN198787100900A Pending CN87100900A (zh) | 1986-02-21 | 1987-02-20 | 制造多孔延伸模制体的方法 |
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JP (1) | JPS62205136A (zh) |
CN (1) | CN87100900A (zh) |
AU (2) | AU6910087A (zh) |
BE (1) | BE1001311A3 (zh) |
BR (1) | BR8700796A (zh) |
CA (1) | CA1316312C (zh) |
CH (1) | CH672094A5 (zh) |
FR (1) | FR2594744B1 (zh) |
GB (1) | GB2187460B (zh) |
IT (1) | IT1202444B (zh) |
NL (1) | NL8700379A (zh) |
SE (1) | SE8700684L (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1107747C (zh) * | 1999-08-10 | 2003-05-07 | 四川大学 | 高压烧结合成聚合物大尺寸晶体的方法 |
CN102151493A (zh) * | 2011-03-18 | 2011-08-17 | 上腾新材料科技(苏州)有限公司 | 一种纳米级聚四氟乙烯微孔膜的制备方法 |
CN101580598B (zh) * | 2008-05-12 | 2013-08-21 | 日东电工株式会社 | 聚四氟乙烯多孔膜、其制造方法及过滤材料 |
CN112023715A (zh) * | 2020-08-26 | 2020-12-04 | 北京中科沃特膜科技有限公司 | 一种高孔隙率的聚四氟乙烯中空纤维膜制备方法 |
CN112088041A (zh) * | 2018-05-15 | 2020-12-15 | 住友电气工业株式会社 | 中空纤维膜和制造中空纤维膜的方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2074349C (en) * | 1991-07-23 | 2004-04-20 | Shinji Tamaru | Polytetrafluoroethylene porous film and preparation and use thereof |
US5466509A (en) * | 1993-01-15 | 1995-11-14 | Impra, Inc. | Textured, porous, expanded PTFE |
JPH08506777A (ja) * | 1993-02-18 | 1996-07-23 | ダブリュ.エル.ゴア アンド アソシエイツ,インコーポレイティド | 巨視的に穿孔された多孔質ポリテトラフルオロエチレン材料 |
DE4309779A1 (de) * | 1993-03-25 | 1994-09-29 | Herding Entstaubung | Festbett-Bioreaktor zur Reinigung von Fluiden mit Hilfe von Mikroorganismen, Trägerkörper für Festbett-Bioreaktoren sowie Verfahren zu deren Herstellung |
US11410800B2 (en) | 2018-07-31 | 2022-08-09 | Commscope Technologies Llc | Low cost extrudable isolator from slit-tape |
WO2020027962A1 (en) | 2018-07-31 | 2020-02-06 | Commscope Technologies Llc | High strength dielectric member for a communications cable |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049589A (en) * | 1973-03-19 | 1977-09-20 | Sumitomo Electric Industries, Ltd. | Porous films of polytetrafluoroethylene and process for producing said films |
US4234535A (en) * | 1976-04-29 | 1980-11-18 | Sumitomo Electric Industries, Ltd. | Process for producing porous polytetrafluoroethylene tubings |
GB2025835B (en) * | 1978-05-31 | 1982-10-27 | Nitto Electric Ind Co | Producing a porous polytetrafluorethylene article |
JPS5825368B2 (ja) * | 1979-02-14 | 1983-05-27 | 日東電工株式会社 | 多孔質ポリテトラフルオロエチレンフィルムの製造法 |
DE3020622C2 (de) * | 1980-05-30 | 1985-05-15 | W.L. Gore & Associates, Inc., Newark, Del. | Bandkabel und Verfahren zu seiner Herstellung |
JPS58119834A (ja) * | 1982-01-11 | 1983-07-16 | Nitto Electric Ind Co Ltd | 多孔質ポリテトラフルオロエチレンフイルムの製造法 |
JPS59109506A (ja) * | 1982-12-14 | 1984-06-25 | Daikin Ind Ltd | 新規なポリテトラフルオロエチレン・フアインパウダ− |
JPS59109534A (ja) * | 1982-12-14 | 1984-06-25 | Nitto Electric Ind Co Ltd | ポリテトラフルオロエチレン多孔質体 |
CA1277474C (en) * | 1985-04-02 | 1990-12-11 | Norman Ralph Harlow | Manufacture of low density, sintered polytetrafluoroethylene articles |
-
1987
- 1987-01-29 IT IT19195/87A patent/IT1202444B/it active
- 1987-02-11 CH CH508/87A patent/CH672094A5/de not_active IP Right Cessation
- 1987-02-13 BE BE8700119A patent/BE1001311A3/fr not_active IP Right Cessation
- 1987-02-16 NL NL8700379A patent/NL8700379A/nl not_active Application Discontinuation
- 1987-02-19 SE SE8700684A patent/SE8700684L/xx not_active Application Discontinuation
- 1987-02-20 FR FR878702230A patent/FR2594744B1/fr not_active Expired - Lifetime
- 1987-02-20 CA CA000530184A patent/CA1316312C/en not_active Expired - Fee Related
- 1987-02-20 AU AU69100/87A patent/AU6910087A/en not_active Abandoned
- 1987-02-20 CN CN198787100900A patent/CN87100900A/zh active Pending
- 1987-02-20 BR BR8700796A patent/BR8700796A/pt unknown
- 1987-02-20 GB GB8704045A patent/GB2187460B/en not_active Expired - Lifetime
- 1987-02-20 JP JP62035976A patent/JPS62205136A/ja active Pending
-
1990
- 1990-11-13 AU AU66596/90A patent/AU6659690A/en not_active Abandoned
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1107747C (zh) * | 1999-08-10 | 2003-05-07 | 四川大学 | 高压烧结合成聚合物大尺寸晶体的方法 |
CN101580598B (zh) * | 2008-05-12 | 2013-08-21 | 日东电工株式会社 | 聚四氟乙烯多孔膜、其制造方法及过滤材料 |
CN102151493A (zh) * | 2011-03-18 | 2011-08-17 | 上腾新材料科技(苏州)有限公司 | 一种纳米级聚四氟乙烯微孔膜的制备方法 |
CN112088041A (zh) * | 2018-05-15 | 2020-12-15 | 住友电气工业株式会社 | 中空纤维膜和制造中空纤维膜的方法 |
CN112023715A (zh) * | 2020-08-26 | 2020-12-04 | 北京中科沃特膜科技有限公司 | 一种高孔隙率的聚四氟乙烯中空纤维膜制备方法 |
Also Published As
Publication number | Publication date |
---|---|
IT8719195A0 (it) | 1987-01-29 |
SE8700684D0 (sv) | 1987-02-19 |
GB2187460B (en) | 1990-09-12 |
AU6659690A (en) | 1991-02-21 |
GB8704045D0 (en) | 1987-03-25 |
FR2594744B1 (fr) | 1990-06-08 |
FR2594744A1 (fr) | 1987-08-28 |
CA1316312C (en) | 1993-04-20 |
SE8700684L (sv) | 1987-08-22 |
CH672094A5 (zh) | 1989-10-31 |
BE1001311A3 (fr) | 1989-09-26 |
BR8700796A (pt) | 1987-12-15 |
NL8700379A (nl) | 1987-09-16 |
GB2187460A (en) | 1987-09-09 |
IT1202444B (it) | 1989-02-09 |
JPS62205136A (ja) | 1987-09-09 |
AU6910087A (en) | 1987-08-27 |
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