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CN102282301B - 利用高粘度材料对ptfe进行电纺丝 - Google Patents

利用高粘度材料对ptfe进行电纺丝 Download PDF

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Publication number
CN102282301B
CN102282301B CN201080004845.8A CN201080004845A CN102282301B CN 102282301 B CN102282301 B CN 102282301B CN 201080004845 A CN201080004845 A CN 201080004845A CN 102282301 B CN102282301 B CN 102282301B
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CN
China
Prior art keywords
poly
dispersion
ptfe
pad
weight
Prior art date
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Expired - Fee Related
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CN201080004845.8A
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English (en)
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CN102282301A (zh
Inventor
布鲁斯·L·阿诺
罗伯特·巴拉德
大卫·P·加纳
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Zeus Industrial Products Inc
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Zeus Industrial Products Inc
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Priority to CN201410312160.XA priority Critical patent/CN104178926B/zh
Publication of CN102282301A publication Critical patent/CN102282301A/zh
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    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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    • 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
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    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract

本发明描述了一种制备PTFE垫的改进方法。该方法包括：提供含有PTFE、成纤聚合物和溶剂的分散体，其中所述分散体的粘度为至少50,000cP。提供一种装置，该装置包括电荷源和与该电荷源相距一定距离的靶。提供电压源，该电压源在所述电荷源处建立第一电荷，而在所述靶处建立相反的电荷。通过使所述分散体与所述电荷源接触从而使所述分散体带上静电荷。在所述靶上收集所述带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。

Description

利用高粘度材料对PTFE进行电纺丝
相关申请的交叉引用
本申请要求于2009年1月16日提交的待审的美国临时专利申请No.61/145,309、以及于2009年10月30日提交的待审的美国临时专利申请No.61/256,349的优先权，它们的全部内容以引用方式并入本文。
背景技术
本发明涉及聚四氟乙烯(PTFE)的电纺丝方法。更具体来说，本发明涉及对高粘度PTFE分散体进行电纺丝，以及利用该方法所制备的制品。
静电纺丝工艺在本技术领域内是公知的，如在美国专利No.2,158,416、No.4,043,331、No.4,143,196、No.4,287,139、No.4,432,916、No.4,689,186、No.6,641,773和No.6,743,273中所描述的工艺，它们的内容以引用方式并入本文。以引用方式并入本文的美国专利No.4,323,525、No.4,127,706和No.4,044,404提供了有关从水性分散体或者其它分散体对PTFE进行加工和静电纺丝的信息。
静电纺丝(在本技术领域中也被称为电纺丝)涉及带电聚合物向带电表面的移动。在一个实施方案中，将聚合物通过小的带电喷孔(例如针)排至靶，其中，针和靶带有相反的电荷。需要认识到的是，聚合物的性质至关重要。在本技术领域中，人们长期以来一直认为有必要保持小于约150泊的相对低的粘度，其中对于较低分子量的聚合物来说，其粘度应相对较高，而对于较高分子量的聚合物来说，其粘度应相对较低。如果过高的粘度和过高的分子量相组合，则认为不能充分成纤。
因为触变性限制(导致喷孔堵塞、成纤性差等)，因此长期以来人们一直认为使聚合物溶液的粘度提高至超过约150泊是不可取的。此外，当使用带电喷孔时，聚合物纤维在飞行过程中会发生排斥，人们长期以来认为这会限制给定喷射体积内的纤维数量。通过辛勤的研究，本发明人已经发现，与现有认知相反，将粘度大大增加至远超过以前认为可行的程度，实际上会改善所得材料，并且会提供其它以前认为不可能获得的性能和优点。
发明内容
本发明的目的在于，提供一种对PTFE进行电纺丝的改进方法。
本发明的另一个目的在于，提供一种基于电纺丝PTFE来制备优良制品的方法。
本发明的独特的特征在于，能够利用现有的电纺丝技术和设备来提供改善的制品。
一种制备PTFE垫的方法提供了这些优点，以及将会被认识到的其它优点。该方法包括提供含有PTFE、成纤聚合物和溶剂的分散体，其中，所述分散体的粘度至少为50,000cP。提供包括电荷源和与该电荷源相距一定距离的靶的装置。提供电压源，该电压源在所述电荷源处建立第一电荷，而在所述靶处建立相反的电荷。通过使所述分散体与所述电荷源接触而使分散体带上静电荷。在所述靶上收集带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。
一种制备PTFE垫的方法还提供了另外的优点。该方法包括提供含有下述成分的分散体：粒度为至少0.1微米至不大于0.8微米的PTFE；1重量％至不大于10重量％且分子量为至少50,000至不大于4,000,000的聚环氧乙烷；以及溶剂，其中，所述分散体的粘度为至少50,000cP。提供包括喷孔和与该喷孔相距一定距离的靶的装置。提供电压源以在所述喷孔处建立第一电荷，而在所述靶处建立相反的电荷。迫使所述分散体通过所述喷孔，其中，通过使所述分散体与所述喷孔接触而使分散体带上静电荷。在所述靶上收集所述带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。
附图说明
图1示意性示出电沉积。
图2示意性示出本发明的方法。
具体实施方式
本发明涉及将聚四氟乙烯(PTFE)静电纺丝成为连续纤维以用于制成无纺布片、薄膜、管状物和衣料且有潜力用于多种其它用途和形式的方法。具体来说，与以前认为可行的粘度直接相比，本发明涉及在相对于现有技术来说非常高的粘度下对PTFE进行电纺丝。
图1示意性示出静电纺丝装置。在图1中，将如本文进一步描述的高粘度分散体装入贮存器10中。输送系统11将所述分散体自所述贮存器输送至电荷源12(可以为喷孔)。相距该电荷源12一定距离布置靶15。电源16(例如直流电源)在所述电荷源和靶之间建立电荷差，从而使聚合物材料14带上与所述靶相反的电荷。所述聚合物材料被静电吸引至所述靶，并且沉积在其上。所述靶可以静止、运动，或者可以为连续的或者近似连续的材料，其可通过在传送辊17(或者类似的物体)上移动，从而移动穿过聚合物所撞击的区域。在一个实施方案中，将电荷施加到与所述靶导电接触的辊上(或者如图所示接地)。所述靶可以是连续的环状物，或者其可以起始于传送装置(例如供卷筒(supply spool))，并且收纳于收集装置(例如接收卷筒(receiver spool))。在可供选择的实施方案中，可以将所述电荷源和靶置于共同的分散体浴中。
本方法需要具有足够PTFE固体百分比的分散体或者悬浮液，以有助于将所收集的纤维垫后加工成具有一定机械完整性的形式。如果分散体中的PTFE固体含量过低，则所得材料将不具有或具有差的机械完整性。第二，必须仔细选择用于提高溶液、悬浮液或者分散体粘度的、待纺的聚合物(也称为成纤聚合物)。我们发现，加入所述PTFE中的成纤聚合物的分子量过低将导致低劣的性能和加工特性。还据信，分子量过高将导致粘度增加，使得在电纺丝和固化过程中，没有足够的聚合物将PTFE粉末真正结合到一起。此外，必须精确控制用于将所述PTFE粉末烧结到一起的工艺，从而使所得制品具有良好的机械完整性。
优选的是，所述PTFE的分子量为106至108。
优选的是，所述PTFE的粒度为至少0.1微米至不大于0.8微米。更优选的是，所述PTFE的粒度为至少0.2微米至不大于0.6微米。粒度小于0.1微米时，所述材料难以制备。粒度大于0.8微米时，该粒度接近目标纤维直径，从而在纤维中成为缺陷。对于其它用途来说，较大的粒度可能适于使用。
参照图2对制备非织造PTFE材料的方法进行说明。制备粒度分布窄的PTFE粉末的水性分散体，20。将成纤聚合物加入所述分散体中，22。所述成纤聚合物的加入量优选在1重量％至10重量％之间，更优选为约2重量％至7重量％，最优选为约4重量％至5重量％。所述成纤聚合物优选在溶剂(优选为水)中具有高溶解度，溶解度大于约0.5重量％是优选的。当在约400℃下烧结时，所述成纤聚合物的灰分优选小于约5重量％，甚至更低的灰分更为优选。
特别优选的成纤聚合物包括：葡聚糖、藻酸盐、壳聚糖、瓜尔胶化合物、淀粉、聚乙烯基吡啶化合物、纤维素化合物、纤维素醚、水解聚丙烯酰胺、聚丙烯酸酯、聚羧酸酯、聚乙烯醇、聚环氧乙烷、聚乙二醇、聚乙烯亚胺、聚乙烯吡咯烷酮、聚丙烯酸、聚(甲基丙烯酸)、聚(衣康酸)、聚(丙烯酸2-羟乙酯)、聚(甲基丙烯酸2-(二甲氨基)乙酯-co-丙烯酰胺)、聚(N-异丙基丙烯酰胺)、聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)、聚(乙烯基甲醚)、聚(乙烯醇)、12％乙酰化聚(乙烯醇)、聚(2，4-二甲基-6-三嗪基乙烯)、聚(3-吗啉基乙烯)、聚(N-1，2，4-三唑基乙烯)、聚(乙烯基亚砜)、聚(乙烯胺)、聚(N-乙烯基吡咯烷酮-co-乙酸乙烯酯)、聚(g-谷氨酸)、聚(N-丙酰亚氨基乙烯)、聚(4-氨基-磺基-苯胺)、聚[N-(对磺基苯基)氨基-3-羟甲基-1，4-亚苯基亚氨基-1，4-苯撑)]、异丙基纤维素、羟乙基、羟丙基纤维素、乙酸纤维素、硝酸纤维素、藻酸铵盐、i-卡拉胶、N-[(3’-羟基-2’，3’-二羧基)乙基]壳聚糖、魔芋葡甘聚糖、支链淀粉、黄原胶、聚(烯丙基氯化铵)、聚(烯丙基磷酸铵)、聚(二烯丙基二甲基氯化铵)、聚(苄基三甲基氯化铵)、聚(二甲基十二烷基(2-丙烯酰胺基乙基)溴化铵)、聚(4-N-丁基吡啶亚乙基碘)(poly(4-N-butylpyridiniumethylene iodine))、聚(2-N-甲基吡啶亚甲基碘)(poly(2-N-methylpridiniummethylene iodine))、聚(N-甲基吡啶-2，5-二基亚乙烯基)(poly(N methylpyridinium-2，5-diylethenylene))、聚乙二醇聚合物及共聚物、纤维素乙醚、纤维素乙基羟乙基醚、纤维素甲基羟乙基醚、聚(甲基丙烯酸1-甘油酯)、聚(2-乙基-2-唑啉)、聚(甲基丙烯酸2-羟乙酯/甲基丙烯酸)90∶10、聚(甲基丙烯酸2-羟丙酯)、聚(2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(2-乙烯基-1-甲基溴化吡啶)、聚(2-乙烯基吡啶氮氧化物)、聚(2-乙烯基吡啶)、聚(3-氯-2-羟丙基-2-甲基丙烯酰氧乙基三甲基氯化铵)、聚(4-乙烯基吡啶氮氧化物)、聚(4-乙烯基吡啶)、聚(丙烯酰胺/2-甲基丙烯酰氧乙基三甲基溴化铵)80∶20、聚(丙烯酰胺/丙烯酸)、聚(烯丙胺盐酸盐)、聚(丁二烯/马来酸)、聚(二烯丙基二甲基氯化铵)、聚(丙烯酸乙酯/丙烯酸)、聚(乙二醇)双(2-氨乙基)(poly(ethylene glycol)bis(2-aminoethyl))、聚(乙二醇)单甲醚、聚(乙二醇)-双酚A二缩水甘油醚加合物、聚(环氧乙烷-b-环氧丙烷)、聚(乙烯/丙烯酸)92∶8、聚(1-赖氨酸氢溴酸盐)、聚(1-赖氨酸氢溴酸盐)、聚(马来酸)、聚(丙烯酸正丁酯/2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(N-异丙基丙烯酰胺)、聚(N-乙烯基吡咯烷酮/甲基丙烯酸2-二甲氨基乙酯)硫酸二甲酯季铵盐(poly(N-vinylpyrrolidone/2-dimethylaminoethylmethacrylate)，dimethyl sulfatequaternary)、聚(N-乙烯吡咯烷酮/乙酸乙烯酯)、聚(氧乙烯)失水山梨醇单月桂酸酯()、聚(苯乙烯磺酸)、聚(乙烯醇)N-甲基-4(4’-甲酰苯乙烯基)吡啶甲基硫酸酯缩醛(poly(vinyl alcohol)，N-methyl-4(4′-formylstyryl)pyridinium，methosulfate acetal)、聚(乙烯基甲基醚)、聚(乙烯胺)盐酸盐、聚(乙烯基膦酸)、聚(乙烯基磺酸)钠盐和聚苯胺。
特别优选的成纤聚合物为分子量是50,000至4,000,000的聚环氧乙烷(PEO)，更优选的分子量为约250,000至350,000，并且最优选的分子量为约300,000。
进一步参照图2，在混合后，优选将PTFE与成纤聚合物的分散体均质化，24。在特别优选的方法中，允许在不搅拌的情况下缓慢形成所述聚合物分散体，之后将其转移至瓶罐转辊(jar roller)，该瓶罐转辊以恒定的速率使分散体转动若干天。优选形成在所得高粘度混合物中没有或者只有少量夹带气体的均匀分散体。一旦所述分散体具有均匀的稠度，优选将其过滤以去除任何块状物或凝胶。之后，将已经过滤的具有所需粘度的分散体装入具有固定导电元件(用作电荷源)的受控泵送装置中，26。特别优选的导电元件为喷孔，例如被切钝并且经砂磨以去除任何毛刺的16号针。将所述泵送装置的喷射量设定为预定的速率，所述预定的速率取决于所制备的形式和所需的纤维直径。优选将所述电荷源与精密直流电源的正极相连。优选将所述电源的负极与收集表面或靶相连。可以将极性反转，但这不是优选的。
所述靶的表面可以为圆筒、机件(device)或平板。该表面可以为金属、陶瓷或者聚合物材料，特别优选选自以下的材料：不锈钢、钴铬合金、镍钛(镍钛合金)、镁合金、聚交酯(polyactide)、聚乙交酯、聚羟基丁酸酯、聚羟基烷基酸酯(polyhydroxyalkynoate)、聚二烷酮(polydioxinine)、聚醚醚酮(PEEK)、聚氨酯、聚碳酸酯和聚环氧乙烷。将电源上的电压增加至所需电压，从而均匀地吸取出聚合物/PTFE分散体。
所施加的电压通常为2,000至80,000伏。通过连接电源所诱导的电荷使带电的聚合物被排斥离开电荷源，并且将其吸引至所述收集表面。
优选将所述收集靶相对于所述泵和喷孔系统垂直放置，并且使其在至少一个方向上运动，从而使吸向靶的纤维均匀地覆盖整个表面，28。一旦充分覆盖所述收集表面，优选将所述材料固化/烧结，30，可以将整个收集表面置于烘箱中而原地进行固化/烧结，也可以将片状物、管状物或者其它的形式从所述收集表面移除，而后在烘箱中进行烧结。
电纺丝得到的PTFE织物在烧结过程中发生收缩。不被任何理论所束缚，据信，所述收缩以两步骤进行。一开始，所述纤维和织物(初纺纤维和织物)包含水分和成纤聚合物(优选为聚环氧乙烷)。完成纺丝之后，将所述样品干燥并且进行低程度的纤维重整。将所述纤维和织物置于550°F至900°F的温度下持续一段时间，对所述样品进行烧结，从而消除所述水分和成纤聚合物。推断在该消除过程中发生第二次更显著的收缩。据信，在未使所述织物松弛的情况下，在所述第二次收缩中发生织物的开裂和纤维的断裂。
为了适应收缩，可以将所述纤维和织物纺在膨胀的结构上。之后可以将该结构移除或者使其收缩。这样可以使得织物在烧结过程中收缩而不发生开裂。另一种方法涉及，将所述纤维和织物纺在这样的结构上，该结构之后(在烧结之前)可以膨胀或收缩。收缩或者膨胀和收缩的程度优选大约为3％至100％，并且取决于电沉积织物垫的厚度和尺寸。
对于片状织物来说，如果将沉积方向设定为垂直于该织物平面，则必须在所述织物平面中的至少一个或更多个方向上发生收缩或者膨胀/收缩。对于沉积在圆筒形表面上的织物来说，必须使所述织物沿径向和/或纵向收缩或者收缩/膨胀。对于球形表面来说，必须使所述织物沿径向收缩或者收缩/膨胀。无论基于何种形状的表面来进行纺丝，都可以将这些收缩和/或膨胀/收缩的基本原则应用在任何电纺丝织物上。因此，基于PTFE织物的非常复杂的织物形状成为可能。
在特别优选的实施方案中，使用了高粘度材料。出乎意料地发现，通过将粘度为至少50,000cP至不大于300,000cP的材料进行电纺丝，能够观察到优越的性能。更优选的是，所述粘度为至少100,000cP至不大于250,000cP，最优选的是，所述粘度为至少150,000cP至不大于200,000cP。当粘度超过300,000cP时，则该材料会逐渐变得难以形成纤维。
在一个实施方案中，电纺丝分散体基于Daikin D210PTFE和Sigma Aldrich公司的分子量为300,000的聚环氧乙烷。Daikin D210PTFE为适于示范本发明的代表材料。Daikin D210PTFE具有约59重量％至62重量％的固体、6.0重量％至7.2重量％的表面活性剂、8.5至10.5的pH、1.5至1.53的比重、以及35cP的最大布氏粘度。
所述分散体的PTFE固体％优选为50重量％至80重量％，更优选为55重量％至65重量％，甚至更优选为59重量％至61重量％。比重优选为1.5至1.54，并且更优选为1.51。例如，1000ml分散体的重量范围应当为1500g至1530g，其中含有885g至933.3g的PTFE。
特别优选的实施方案为固体PTFE为60％，比重为1.51，每1000ml分散体中含有909gm PTFE。
在特别优选的例子中，每1000ml Daikin D210分散体中优选含有32gm至52gm成纤聚合物(最优选为PEO)，这样，成纤聚合物固体与PTFE分散体的比例(例如PEO/PTFE)为：在1000ml分散体中，PEO为0.032gm/ml至0.052gm/ml。当成纤聚合物的重量比例低于0.03gm/ml时，导致形成非常劣质的且不均一的纤维垫。劣质被定义为纤维断裂程度高(＞20％)，并且形成在本技术领域中也被称为“形成小珠(beading)”的不均一的纤维直径。断裂纤维以及/或者不均一纤维的存在会导致纤维垫中出现不均一的孔隙。由于不连续的原纤从垫中被拉出，因此断裂的原纤(尤其是短原纤)的存在会导致效率随时间而降低。
典型的PTFE分散体中含有60％的PTFE固体和介于200,000Mw至4,000,000Mw之间的PEO。特别典型的是，成纤聚合物是分子量为300,000的PEO，它与PTFE的比值为0.03至0.06。
采用布氏LV粘度计，在25℃下、在设定为2.5的恒定转速(#25转子)下测量不同的PEO/PTFE配制物的粘度，结果在表1中示出。
表1
样品 扭矩(％) 粘度(cp)
0.052gm/ml PEO 88.5 171,000
0.048gm/ml PEO 76.8 147,000
0.044gm/ml PEO 79.2 152,000
0.040gm/ml PEO 58.5 112,000
0.036gm/ml PEO 40.1 77,000
0.032gm/ml PEO 34.5 66,000
假设1000ml Diakin D210分散体中含有909gm PTFE，优选的PEO/PTFE分散体的百分比范围为0.032至0.060gm/ml。为示范本发明，特别优选为约0.048gm/ml。
对于沉积而言，除非另外指明，否则本发明在此优选并依赖带电的针和接地的靶。部分由于安全因素，这在工业领域已被认可为标准做法。也可以使用接地的针和带电的靶，但由于结果形成较差的材料，因此并不优选。
为了方便说明本文所述的样品，利用11kV、14kV或17kV的电压，相应的针尖与靶顶端(TTT)之间的距离为4.5″、5.5″和6.5″。根据所采用的试验装置来设计选择电压和距离，这对于本技术领域的技术人员来说是公知的。出于示范的目的，将样品沉积于金属箔上，干燥，并且之后在725°F下烧结5分钟，之后利用SEM进行检测。通过此方法，制备了平滑、厚重、宽幅的网状物，这表明在材料迁移效率方面得到显著改善。使用相反极性的试验结果较差。沉积得到约5″宽度的垫。
目测观察显示，在通过相反的极性而制备的样品中出现不同程度的劣化。此外，显微照片显示出纤维的断裂、以及纤维扭曲形成了纤维束。纤维直径和纤维束直径也分布广泛。所有这些纤维特征将导致形成不均一且劣质的纤维垫。这些纤维特征与我们尝试由低PEO/PTFE浓度的分散体进行电纺丝所观察到的劣等纤维垫的品质是一致的。在高压并且针尖至靶的距离为5.5″和6.5″的情况下，显示出最大程度的纤维断裂，而在TTT距离为4.5″的情况下，显示出最大程度的成束现象。
当在高放大倍率下检测“正常”的电纺PTFE时，没有明显的纤维断裂，所有纤维的直径均一，并且纤维垫能够经得住烧结过程。
代表性的结果在表2至表4中示出，括号中给出标准偏差。在这些表中，用毛细管流动孔径分析仪(型号CFP-1100-AEXL，PorousMaterials公司制造)，采用“干燥/润湿”测试类型来检测气流、孔径和泡点。使用气体比重计，采用标准ISO1183-3检测密度。在模冲的ASTM D638V型犬骨形样品几何形状下采用标准ASTM D882来检测拉伸性能、伸长率和模量。采用布氏LV粘度计，在25℃下、在所列的对于#25转子设定的恒定转速下测量不同的PEO/PTFE配制物的粘度。
本方法所提供的独特的优点在于，与现有技术的样品相比，本发明所得材料经烧结之后，具有明显减少的断裂的原纤。原纤断裂的减少会减少劣质材料，因此提高了制备生产率。这不需要损失产品特性即可实现。
已参照所述优选实施方案对本发明进行了说明，但并不仅限于此。本技术领域的技术人员可以实现本发明的目的和范围内的其它的实施方案和改进形式，这在所附的权利要求书中更加具体地阐明。
表2：PTFE膜(60％PTFE，0.048gm/ml PEO/1000ml PTFE分散体)的物理性能。
表3：PTFE膜(67％PTFE，0.015gm/ml至0.040gm/ml PEO/1000ml PTFE分散体)的物理性能。
表4：PTFE膜(72％PTFE，0.020gm/ml至0.030gm/ml PEO/1000ml PTFE分散体)的物理性能。

Claims (23)

1.一种制备PTFE垫的方法，该方法包括： 
提供分散体，该分散体包含： 
PTFE； 
成纤聚合物；以及 
溶剂，其中所述分散体的粘度为至少50,000cP； 
提供这样的装置，该装置包括电荷源和与该电荷源相距一定距离的靶； 
提供电压源，以在所述电荷源处建立第一电荷，而在所述靶处建立相反的电荷，其中，通过使所述分散体与所述电荷源接触从而使所述分散体带上静电荷； 
在所述靶上收集所述带静电荷的分散体以形成垫前体； 
以及加热所述垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。 
2.权利要求1所述的制备PTFE垫的方法，其中，所述分散体包含50重量％至80重量％的PTFE固体。 
3.权利要求2所述的制备PTFE垫的方法，其中，所述分散体包含59％重量至61重量％的PTFE固体。 
4.权利要求1所述的制备PTFE垫的方法，其中加热所述垫还包括烧结。 
5.权利要求4所述的制备PTFE垫的方法，其中，所述烧结在至少500°F至不大于900°F的温度下进行。 
6.权利要求1所述的制备PTFE垫的方法，其中，所述分散体的粘度为至少100,000cP至不大于300,000cP。 
7.权利要求1所述的制备PTFE垫的方法，该方法包括在所述电荷源和所述靶之间提供2,000至80,000伏特的电压。 
8.权利要求1所述的制备PTFE垫的方法，其中，所述分散体包含至少1重量％至不大于10重量％的所述成纤聚合物。 
9.权利要求1所述的制备PTFE垫的方法，其中，所述分散体包含的成纤聚合物与PTFE的重量比为至少3.0至不大于5.5。 
10.权利要求1所述的制备PTFE垫的方法，其中，所述成纤聚合物在所述溶剂中的溶解度大于0.5重量％。 
11.权利要求1所述的制备PTFE垫的方法，其中，所述溶剂为水。 
12.权利要求4所述的制备PTFE垫的方法，其中，在400℃下烧结之后，所述成纤聚合物的灰分小于5重量％。 
13.权利要求1所述的制备PTFE垫的方法，其中，所述成纤聚合物选自由以下物质组成的组：葡聚糖、藻酸盐、壳聚糖、瓜尔胶化合物、淀粉、聚乙烯基吡啶化合物、纤维素化合物、水解聚丙烯酰胺、聚丙烯酸酯、聚羧酸酯、聚乙烯醇、聚环氧乙烷、聚乙二醇、聚乙烯亚胺、聚乙烯吡咯烷酮、聚丙烯酸、聚(甲基丙烯酸)、聚(衣康酸)、聚(丙烯酸2-羟乙酯)、聚(甲基丙烯酸2-(二甲氨基)乙酯-co-丙烯酰胺)、聚(N-异丙基丙烯酰胺)、聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)、聚(乙烯基甲醚)、聚(乙烯醇)、12％乙酰化聚(乙烯醇)、聚(2，4-二甲基-6-三嗪基乙烯)、聚(3-吗啉基乙烯)、聚(N-1，2，4-三唑基乙烯)、聚(乙烯基亚砜)、聚(乙烯胺)、聚(N-乙烯基吡咯烷酮-co-乙酸乙烯酯)、聚(g-谷氨酸)、聚(N-丙酰亚氨基乙烯)、聚(4-氨基-磺基-苯胺)、聚[N-(对磺基苯基)氨基-3- 羟甲基-1，4-亚苯基亚氨基-1，4-苯撑)]、藻酸铵盐、i-卡拉胶、N-[(3’-羟基-2’，3’-二羧基)乙基]壳聚糖、魔芋葡甘聚糖、黄原胶、聚(烯丙基氯化铵)、聚(烯丙基磷酸铵)、聚(二烯丙基二甲基氯化铵)、聚(苄基三甲基氯化铵)、聚(二甲基十二烷基(2-丙烯酰胺基乙基)溴化铵)、聚(4-N-丁基吡啶亚乙基碘)、聚(2-N-甲基吡啶亚甲基碘)、聚(N-甲基吡啶-2,5-二基亚乙烯基)、聚乙二醇聚合物及共聚物、聚(甲基丙烯酸1-甘油酯)、聚(2-乙基-2-唑啉)、聚(甲基丙烯酸2-羟乙酯/甲基丙烯酸)90∶10、聚(甲基丙烯酸2-羟丙酯)、聚(2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(2-乙烯基-1-甲基溴化吡啶)、聚(2-乙烯基吡啶氮氧化物)、聚(2-乙烯基吡啶)、聚(3-氯-2-羟丙基-2-甲基丙烯酰氧乙基三甲基氯化铵)、聚(4-乙烯基吡啶氮氧化物)、聚(4-乙烯基吡啶)、聚(丙烯酰胺/2-甲基丙烯酰氧乙基三甲基溴化铵)80∶20、聚(丙烯酰胺/丙烯酸)、聚(烯丙胺盐酸盐)、聚(丁二烯/马来酸)、聚(二烯丙基二甲基氯化铵)、聚(丙烯酸乙酯/丙烯酸)、聚(乙二醇)双(2-氨乙基)、聚(乙二醇)单甲醚、聚(乙二醇)-双酚A二缩水甘油醚加合物、聚(环氧乙烷-b-环氧丙烷)、聚(乙烯/丙烯酸)92∶8、聚(1-赖氨酸氢溴酸盐)、聚(1-赖氨酸氢溴酸盐)、聚(马来酸)、聚(丙烯酸正丁酯/2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(N-异丙基丙烯酰胺)、聚(N-乙烯基吡咯烷酮/甲基丙烯酸2-二甲氨基乙酯)硫酸二甲酯季铵盐、聚(N-乙烯吡咯烷酮/乙酸乙烯酯)、聚(氧乙烯)失水山梨醇单月桂酸酯()、聚(苯乙烯磺酸)、聚(乙烯醇)N-甲基-4(4’-甲酰苯乙烯基)吡啶甲基硫酸酯缩醛、聚(乙烯基甲基醚)、聚(乙烯胺)盐酸盐、聚(乙烯基膦酸)、聚(乙烯基磺酸)钠盐和聚苯胺。 
14.权利要求13所述的制备PTFE垫的方法，其中，所述成纤聚合物为聚环氧乙烷。 
15.权利要求14所述的制备PTFE垫的方法，其中，所述聚环氧乙烷的分子量为至少50,000至不大于4,000,000。 
16.权利要求13所述的制备PTFE垫的方法，其中，所述淀粉 选自支链淀粉。 
17.权利要求13所述的制备PTFE垫的方法，其中，所述纤维素化合物选自异丙基纤维素、羟乙基纤维素、羟丙基纤维素、乙酸纤维素、硝酸纤维素和纤维素醚。 
18.权利要求17所述的制备PTFE垫的方法，其中，所述纤维素醚选自纤维素乙醚、纤维素乙基羟乙基醚和纤维素甲基羟乙基醚。 
19.权利要求1所述的制备PTFE垫的方法，其中，所述靶为膨胀结构。 
20.权利要求1所述的制备PTFE垫的方法，该方法还包括使所述靶膨胀或收缩。 
21.权利要求1所述的制备PTFE垫的方法，该方法还包括在所述收集之前，使所述靶膨胀或收缩。 
22.权利要求1所述的制备PTFE垫的方法，其中所述分散体的粘度为50,000cP至249，000cP。 
23.一种制备PTFE垫的方法，该方法包括： 
提供分散体，该分散体包含： 
粒度为至少0.1微米至不大于0.8微米的PTFE； 
1重量％至不大于10重量％且分子量为至少50,000至不大于4,000,000的聚环氧乙烷；以及 
溶剂，其中，所述分散体的粘度为至少50,000cP； 
提供这样的装置，该装置包括喷孔和与该喷孔相距一定距离的靶； 
提供电压源，以在所述喷孔处建立第一电荷，而在所述靶处建 立相反的电荷； 
迫使所述分散体通过所述喷孔，其中，通过使所述分散体与所述喷孔接触而使所述分散体带上静电荷； 
在所述靶上收集所述带静电荷的分散体以形成垫前体； 
以及加热所述垫前体以除去所述溶剂和所述聚环氧乙烷，从而形成所述PTFE垫。 
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