CN1131719C - 气体可渗透纤维织物 - Google Patents

气体可渗透纤维织物 Download PDF

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CN1131719C
CN1131719C CN96191836A CN96191836A CN1131719C CN 1131719 C CN1131719 C CN 1131719C CN 96191836 A CN96191836 A CN 96191836A CN 96191836 A CN96191836 A CN 96191836A CN 1131719 C CN1131719 C CN 1131719C
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gas permeable
fabric
composition
permeable fabric
fluoropolymer
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CN1173828A (zh
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K·H·威斯
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

公开一种由多孔基质制成的气体可渗透纤维织物，该基质用含有含氟聚合物和硬化、成膜材料的组合物处理过。

Description

气体可渗透纤维织物
本发明涉及气体可渗透纤维织物，更具体地涉及可制成所要求形状并使硬化的气体可渗透纤维织物，以及涉及它们在工业环境中，如作为滤器的应用。
发明背景
可成型，可硬化的气体可渗透纤维织物在工业和环境中有许多应用。首要考虑的应用就是它们用作过滤介质。在某些应用中，这种过滤器必须能经受连续暴露于特别高的温度(高达280℃)下而不降解。
另外，希望过滤器能被制成所要求的形状，然后再硬化而成为耐用的物品。例如，常常希望过滤器所占空间体积最小而表面积最大。这样，过滤器常常被打褶成“手风琴”型式的构形。
典型过滤器的基质，尽管是耐久而且是耐热的，但却难于模制成且保持各种所要求的构型。因此，在过去，早已提出用各种聚合物浸渍过滤器基质，这样给予过滤器基质以模压加工性和形状的保留性。参见US专利3,918,943，DE4137627 C2，这些专利文献描述了用聚酰亚胺粘合剂处理的玻璃纤维纸制成的过滤器，和由含氟聚合物处理过的玻璃或石英纤维制的板。
现有技术的气体可渗透纤维织物的缺点在于聚合物处理在纤维织物上实现均匀分布是困难的，导致盲点和纤维织物不均匀的强度。另外，切口撕裂强度趋于下降。
发明概述
本发明提供由一种组合物处理过的多孔基质制成的气体可渗透纤维织物，该组合物包含含氟聚合物和一种硬化、成膜材料。更具体地说，本发明提供用含氟聚合物和聚酰胺酰亚胺混合物处理过的气体可渗透纤维织物，以提供制成所要求构型，且随后硬化的可成型、可硬化的基质，从而产生适合各种工业和环境最终使用(end-uses)的耐热、耐用的纤维织物。
最佳实施方案的详细描述
除非另有说明，本文所用的下列术语具有以下所指明的含义。
本发明纤维织物的最终使用(end-uses)可以分为两类：一类“高温最终使用”指的是那些需要抵抗在温度约为200℃-280℃下的降解一段较长时间，和抵抗在温度约为280℃-365℃下持续期间多达约10分钟的使用。
另一类“中温最终使用”指的是那些需要抵抗至多在约200℃温度下的降解一段较长时间，和抵抗在温度约200℃-280℃下持续期间多达约10分钟的使用。
对于用在本发明中的“多孔基质”可以是机织的也可以是非机织的，并且可由许多不同的纤维制成的。对于高温的最终使用，合适的纤维包括间-聚芳基酰胺、对-聚芳基酰胺、聚芳基酰胺的共聚物、聚酰胺酰亚胺、聚噁二唑、聚酰亚胺、聚醚醚酮、聚醚酮酮、聚苯并咪唑、聚四氟乙烯(PTFE)、玻璃、陶瓷、及其混合物。优选基质包括那些由间-聚芳基酰胺(例如NOMEX)、对-聚芳基酰胺(例如KEV-LAR)、PTFE(例如TEFLON)、PTFE-玻璃混合物(例如TEFAIRE)，所有这些都可从杜邦公司(DuPont Company)买到的，优选基质还有聚酰胺(例如P-84，由澳大利亚Lenzing公司买到的)。
对于中等温度的最终使用来说，制造的纤维织物可用纤维如聚酰胺、聚丙烯腈、聚酯、聚亚苯基硫醚、聚醚酰亚胺、粘胶纤维、棉花、改性纤维素及其混合物。优选制造中温抗性基质的纤维是聚丙烯腈、棉花或改性纤维素。
“含氟聚合物”就其本身是已知技术，并且在最终使用操作条件下可以得到本发明化学保护性和润滑性的纤维织物。对于高温最终使用来说，用于本发明合适的含氟聚合物是聚四氟乙烯(PTFE)和四氟乙烯(FFE)与一种或多种的1)全氟化乙烯醚，2)全氟化乙烯-丙烯，3)六氟丙烯和4)1，1-二氟乙烯的共聚物；以及其混合物(参见US专利4,252,859)。优选这种含氟聚合物是TEFLON(PTFE)、TEPLON PFA(TFE和约1.5％的全氟-丙基-乙烯基-醚的共聚物)和TEFLONFEP(TFE和约10-12％全氟化乙烯-丙烯共聚物)，所有这些都可从杜邦公司(DuPont Company)买到的。
对于中温最终使用来说，普通的从市场上可以买到的含氟聚合物在水中的分散体是合适的，例如OLEOPHOBOL(Pfersee)、ZEPEL(DuPont)和SCOTCHGUARD(3M)。优选的这类含氟聚合物是OLEOPHOBOL。
通常，提供的含氟聚合物是水分散体的形式，并且引入具有含氟聚合物组合物的水是作为组合物的载体的。然而，如有要求的话，有机液体如醇类(例如糠醇)、酮类、脂族和芳族烃(例如N-甲基吡咯烷酮)、或其混合物都可以使用。
含氟聚合物优选以1-30％(按重量计)，更好为5-20％(按重量计)的量存在于处理多孔基质的组合物中。
“硬化成膜材料”是已知技术，正如其名称的含义，它给予本发明纤维织物的尺寸的稳定性，即刚性。在或低于本发明所用含氟聚合物的熔化温度下它们能形成膜。合适的成膜材料，及其制造方法，描述于US专利4,087,394中，这种成膜材料包括适于抗中温用途的丙烯酸聚合物、硝化纤维素、聚酰胺、聚氯乙烯以及混有硝化树脂的环氧树脂(季氢氧化物聚合物)衍生物；和适于抗高温用途的聚酰胺或聚酰胺酸盐(聚酰亚胺和聚酰胺酰亚胺的前体)。
在本发明中优选硬化膜是聚酰胺酰亚胺(PAI)，它是聚酰胺酸盐，如1，2，4-苯三酸酐，和芳族二元胺如4，4′-二苯氨基甲烷或双(4-氨基苯基)甲烷的反应产物。通常，制备PAI的组合物还包括三乙胺、二乙基乙醇胺、糠醇、甲基吡咯烷酮和水。
硬化成膜材料优选以1-30％(按重量计)的量，更好的是以3-10％(按重量计)的量存在于处理多孔基质的组合物中。
“云母粒子，涂有颜料或片状金属的云母粒子；及其混合物”从市场上是可以买到的，在US专利4,123,401中有描述。它们在含氟聚合物和成膜剂的组合物中存在量高达10％(按重量计)，优选存在量范围在3-6％(按重量计)。
供本发明处理多孔基质用的组合物含有含氟聚合物和成膜剂，以及任选地含有其它的成分如前述云母基粒子，以及常规的添加剂如抗氧化剂、流动控制剂、表面活性剂、增塑剂、抗静电剂等。这些添加剂依本发明纤维织物主要的最终使用而定，可以使用常规量。
通过把适当量的适当成分简单的混合在一起就能制造本发明的组合物。
组合物中的总固体含量由涂有组合物的基质、施涂方法，固化程序以及类似因素决定。在通常情况下，把组合物制成水分散体，含固体1-80％(按重量计)。
组合物可以任何有效方式涂覆，如喷雾、滚筒涂覆、浸渍和刮刀法。
根据最终使用，通常在基质重量3-30％的比率下按干重为基础把组合物涂于基质上。再使涂覆过的基质形成所需要的形状或构型，例如打褶或回旋，所得到的制品在一定温度烤干足够的时间以使组合物的含氟聚合物和成膜材料固化。另外一种方案是，烤干和成型步骤可以颠倒。
除有另外说明，规定所有的百分比都是按重量计。
实施例1-热气过滤
作为多孔基质，把从市场上买到的NOMEX芳族聚酰胺纤维(来自杜邦(Du Pont)公司)500g/m2针刺毡切成800mm×500mm大小的条状物。使用两种等级的毡：一种(A)是织机状针刺的(下文称作基质“A”)；一种(B)是烧毛的(以40m/分明火处理)和砑光的(215℃/10kg/cm)(下文称作基质“B”)。
作为处理组合物，表1列出的分散体是按US专利4,087,394所述程序制成的。
               表1-组合物I)PAI溶液*〔18.7％固体〕，II)PAI溶液*/TEFLON FEP〔23％固体(7.7％/15.3％)水分散体〕，III)PAI溶液*/TEFLON FEP/云母〔25.5％固体(7％/14％/4.6％)水分散体〕，*聚酰胺酸(由1，2，4-苯三酸酐和4，4＇-二苯氨基甲烷制备的)、水、糠醇和正-甲基吡咯烷酮的混合物。
把针刺毡多孔基质样品在BENZ实验室衬填器(Padder)上以浸液率在150和250％之间(基于干样品重量)用组合物I、II和III来浸渍，在200℃下小型拉幅架上(BENZ)上干燥3分钟，接着于300℃下烤干3分钟。用组合物I)处理的一半样品未加烤干，因为它们不含能提供高化学保护性和润滑性的含氟聚合物。施加比率列于表2，其中“owf”代表“以纤维织物重量为基”(干基)
               表2-施加比率
组合物g/l       浸液率       基质       毡上最终量
140g/l I        155％         B       2.5％owf(2.5PAI)
150g/l II       192％         B       6.8％owf(2.3PAI)
300g/1 III      145％         B       10.8％owf(3PAI)
140g/l I        235％         A       6％owf(6PAI)
500g/1 I        244％         A       23％owf(23PAI)
300g/1 II       168％         A       11.7％owf(3.9PAI)
300g/l III      169％         A       20％owf(5.4PAI)
在手动压力下把从前面步骤得到的基质在常规的设备上于200℃-250℃温度下打褶30-60秒的时间。所有制备的样品在所有的试验温度下都可打褶，尽管在较低的温度下打褶时间长些。
组合物I、II和III中的每一种都能提供具有满足要求的空气渗透性的硬化针刺毡结构。然而，组合物I的针刺毡与未处理的针刺毡比较时倾向于切口撕裂强度下降(按DIN 53849/4测量的)，而用组合物II和III处理则可保持或改进切口撕裂强度。

Claims (10)

1.一种气体可渗透纤维织物，此织物包含用含有含氟聚合物和硬化成膜材料的组合物处理过的多孔基质。
2.权利要求1的气体可渗透纤维织物，其中成膜材料是聚酰胺酰亚胺。
3.权利要求1或2的气体可渗透纤维织物，其中组合物还含有云母粒子、涂有颜料或片状金属的云母粒子；及其混合物。
4.权利要求1-3中任一项的气体可渗透纤维织物，其中含氟聚合物是聚四氟乙烯，或四氟乙烯与一种或多种的1)全氟化乙烯醚，2)全氟化乙烯-丙烯，3)六氟丙烯和4)1，1-二氟乙烯的共聚物；以及其混合物。
5.权利要求1-4中任一项的气体可渗透纤维织物，其中纤维织物是由选自间-芳族聚酰胺、对-芳族聚酰胺、芳族聚酰胺共聚物、聚酰胺酰亚胺、聚噁二唑、聚酰亚胺、聚醚醚酮、聚醚酮酮、聚苯并咪唑、聚四氟乙烯、玻璃、陶瓷，及其混合物的纤维制成的。
6.权利要求1或2的气体可渗透纤维织物，其中纤维织物是由选自聚酰胺、聚丙烯腈、聚酯、聚亚苯基硫醚、聚醚酰亚胺、粘胶纤维、棉花或改性纤维素、及其混合物的纤维制成的。
7.权利要求6的气体可渗透纤维织物，其中含氟聚合物分散在水中。
8.按前述权利要求中任一项的气体可渗透纤维织物，其中纤维织物被制成所要求的形状。
9.权利要求8的气体可渗透纤维织物，其中纤维织物是过滤器。
10.一种制造按前述权利要求中任一项的气体可渗透纤维织物的方法，包含把含有含氟聚合物和成膜材料的组合物涂于多孔基质上，使基质形成所要求的形状，和使组合物固化。
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