CN103392034B - 纤网、其制备方法和包括该纤网的过滤器 - Google Patents

纤网、其制备方法和包括该纤网的过滤器 Download PDF

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CN103392034B
CN103392034B CN201180064424.9A CN201180064424A CN103392034B CN 103392034 B CN103392034 B CN 103392034B CN 201180064424 A CN201180064424 A CN 201180064424A CN 103392034 B CN103392034 B CN 103392034B
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CN103392034A (zh
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李玧应
李振揆
吴永泽
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Shenzhen Wote Advanced Materials Co Ltd
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Abstract

公开了一种纤网、其制备方法和包括该纤网的过滤器。所述公开的纤网包含全芳香族液晶聚酯树脂，该全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元。

Description

纤网、其制备方法和包括该纤网的过滤器
技术领域
本发明涉及一种纤网、其制备方法和包括该纤网的过滤器，更详细地说，涉及包含全芳香族液晶聚酯树脂的纤网、其制备方法和包括该纤网的过滤器，所述全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元。
背景技术
以往的用于家庭和工业的过滤器通过利用如熔喷法(melt-blown)或纺粘法(spun bonding)之类的熔融纺丝法对聚乙烯(PE)、聚丙烯(PP)或聚对苯二甲酸乙二醇酯(PET)进行纺丝来制备，或者通过使用湿式法来制备，该湿式法是将聚合物溶解于溶剂中而形成膜。然而，所述熔融纺丝法虽然具有制造成本低、工艺简单而生产率高这样的优点，但是具有在原材料方面有限制的缺点。并且，所述湿式法存在需要很多时间和费用以及大量的溶剂、且安全性低这样的问题。
此外，PE、PP和PET由于耐热性不充分因而包含它们的过滤器具有在高温下聚合物被劣化或熔化而丧失过滤功能的担忧，并且这些化合物在溶剂中的溶解性不足，因此难以在用于制备高性能过滤器的静电纺丝法中使用。
发明内容
技术问题
本发明一实施方案提供了一种包括全芳香族液晶聚酯树脂的纤网，所述全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元。
本发明另一方案提供了一种制备所述纤网的方法，其包括对含有全芳香族液晶聚酯树脂的溶液进行静电纺丝或对全芳香族液晶聚酯树脂进行熔融纺丝的步骤。
本发明再另一实施方案提供了一种包括所述纤网的过滤器。
解决技术方案
根据本发明的一个方面，提供了一种包含全芳香族液晶聚酯树脂的纤网，所述全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元。
所述羟基苯甲酸可以选自由对羟基苯甲酸、3-羟基苯甲酸、2-羟基苯甲酸及它们的组合组成的组。
所述羟基萘甲酸可以选自由6-羟基-2-萘甲酸、3-羟基-2-萘甲酸、2-羟基-1-萘甲酸、1-羟基-2-萘甲酸及它们的组合组成的组。
所述全芳香族液晶聚酯树脂可包含70～80摩尔份的衍生自羟基苯甲酸的重复单元和20～30摩尔份的衍生自羟基萘甲酸的重复单元。
所述纤网可以包含具有1～9,000nm范围内的平均直径的纤维。
根据本发明的另一个方面，提供了一种制备纤网的方法，其包括对含有全芳香族液晶聚酯树脂的溶液进行静电纺丝或对全芳香族液晶聚酯树脂进行熔融纺丝的步骤。
所述包含全芳香族液晶聚酯树脂的溶液可以包含选自由三氟甲磺酸、五氟苯酚、3，5-双(三氟甲基)苯酚、对氟苯酚、对氯苯酚、1，1，2，2-四氯乙烷、三氟乙酸、六氟异丙醇、氯仿、二氯甲烷、四氢呋喃、二恶烷和它们的组合组成的组中的至少一种溶剂。
根据本发明的再另一个方面，提供了一种包括所述纤网的过滤器。
所述过滤器可以是超低渗透空气(ultra low penetration air，ULPA)过滤器或高效微粒空气(high efficiency particulate air，HEPA)过滤器。
有益效果
根据本发明的一实施方案，通过包含全芳香族液晶聚酯树脂的纤网，所述全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元，从而可以提供一种耐热性和强度优异的纤网。
根据本发明的另一实施方案，通过包含所述纤网，从而可以提供一种捕获能力(capturing capacity)高、相对于相同的捕获效率具有低压力损失、能够去除纳米尺寸的污染微粒、且能够有效阻止各种微细菌的流动的过滤器。
具体实施方式
在下文中，对根据本发明的一实施方案的纤网进行详细说明。
根据本发明的一实施方案的纤网包含全芳香族液晶聚酯树脂，所述全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元。
本说明书中，“纤网”是指多个纤维排列(aligned)并相互结合而形成的网，“纤维”是指在放大观察时看起来像细、长的线的物质。
所述纤网因作为主要原料的全芳香族液晶聚酯树脂的固有特性而具有优异的耐热性和强度。
所述全芳香族液晶聚酯树脂可以包含70～80摩尔份的所述衍生自羟基苯甲酸的重复单元和20～30摩尔份的所述衍生自羟基萘甲酸的重复单元。如果所述衍生自羟基苯甲酸的重复单元和所述衍生自羟基萘甲酸的重复单元的含量在上述范围以内，则易于制备所述全芳香族液晶聚酯树脂，并且具有作为过滤器材料足够的耐热性和强度。
所述全芳香族液晶聚酯树脂可通过以下步骤来制备：
步骤(a)，通过将一种以上的单体缩聚而合成全芳香族液晶聚酯预聚物；和
步骤(b)，通过将所述预聚物固相缩聚而合成全芳香族液晶聚酯树脂。
在步骤(a)中使用的单体包含：选自由对羟基苯甲酸、3-羟基苯甲酸、2-羟基苯甲酸及它们的组合组成的组中的羟基苯甲酸；和选自由6-羟基-2-萘甲酸、3-羟基-2-萘甲酸、2-羟基-1-萘甲酸、1-羟基-2-萘甲酸及它们的组合组成的组中的羟基萘甲酸，但不包含诸如间苯二甲酸、2，6-萘二甲酸、对苯二甲酸和邻苯二甲酸之类的芳香族二羧酸。在所述步骤(a)中使用的单体可进一步包含芳香族二醇、芳香族二胺、芳香族羟基胺和/或芳香族氨基羧酸。
此外，在所述全芳香族液晶聚酯预聚物的合成步骤中，可以进一步使用金属乙酸盐作为用于促进反应的催化剂。所述金属乙酸盐催化剂可以包括选自由乙酸镁、乙酸钾、乙酸钙、乙酸锌、乙酸锰、乙酸铅、乙酸锑和乙酸钴组成的组中的至少一种。所述金属乙酸盐的用量例如以100重量份的所述单体为基准可以为0.10重量份以下。
作为所述步骤(a)的合成方法，可以使用溶液缩聚或本体缩聚(bulkcondensation polymerization)。此外，在步骤(a)中，为了促进缩聚反应，可以使用通过用例如酰化剂(特别是乙酰化剂)等化学物质进行预处理而反应性得以增强的单体(即，酰化单体)。
为了所述步骤(b)中的固相缩聚反应，需要对所述预聚物提供适当的热，作为提供这样的热的方法，包括利用加热板的方法、利用热空气的方法、利用高温流体的方法等。为了去除固相缩聚反应时所产生的副产物，可以利用惰性气体净化反应器内容物或者通过真空来去除。
此外，所述全芳香族液晶聚酯树脂在其链内包含各种重复单元，例如可以包含如下重复单元。
(1)衍生自芳香族羟基羧酸的重复单元：
-O-Ar-CO-
(2)衍生自芳香族二醇的重复单元：
-O-Ar-O-
(3)衍生自芳香族二胺的重复单元：
-HN-Ar-NH-
(4)衍生自芳香族羟基胺的重复单元：
-HN-Ar-O-
(5)衍生自芳香族氨基羧酸的重复单元：
-HN-Ar-CO-
在上述化学式中，Ar可以为亚苯基(苯撑)、亚联苯基(联苯撑)、亚萘基(萘撑)或2个亚苯基通过碳或非碳元素彼此连接的芳香族化合物，或者可以为亚苯基、亚联苯基、亚萘基或2个亚苯基通过碳或非碳元素彼此连接的芳香族化合物中的1个以上的氢被其它元素取代的芳香族化合物。
所述纤网可包含具有1-9,000nm范围内的平均直径的纤维。当所述纤维的平均直径在该范围内时，包含所述纤网的过滤器由于每单位面积中纤维所占的表面积大而过滤器的效率变高，并且所述纤网作为过滤器材料具有足够的强度。
所述纤网可进一步包含二氧化钛(TiO2)和/或炭黑等添加剂。相对于100重量份的全芳香族液晶聚酯树脂，所述添加剂的含量可以为5～10重量份。当所述添加剂的含量在该范围内时，可以提高所述纤网中的纤维之间的粘合力。
在下文中，对本发明一实施方案的纤网的制备方法进行详细的说明。
根据本发明的另一个实施方案的制备纤网的方法包括对含有全芳香族液晶聚酯树脂的溶液进行静电纺丝或对全芳香族液晶聚酯树脂进行熔融纺丝的步骤。
本说明书中，“静电纺丝(electrospinning)”是指，使聚合物溶液通过施加了高电压的喷嘴吐丝至低电势收集器并借助电场拉伸所述聚合物溶液中的聚合物，“熔融纺丝(melt spinning)”是指，将聚合物熔化后通过喷嘴挤出至空气中，并进行冷却及固化，来形成纤网。
所述含有全芳香族液晶聚酯树脂的溶液可以包含上述的全芳香族液晶聚酯树脂和溶剂，该溶剂为选自由三氟甲磺酸、五氟苯酚、3，5-双(三氟甲基)苯酚、对氟苯酚、对氯苯酚、1，1，2，2-四氯乙烷、三氟乙酸、六氟异丙醇、氯仿、二氯甲烷、四氢呋喃、二恶烷和它们的组合组成的组中的至少1种。即，所述溶剂可溶解所述全芳香族液晶聚酯树脂。
所述含有全芳香族液晶聚酯树脂的溶液的浓度可根据所使用的溶剂的类型在1％(重量/体积％)以下的低浓度到50％(重量/体积％)以上的高浓度的范围内适当选择。此外，所述含有全芳香族液晶聚酯树脂的溶液的浓度可进一步考虑静电纺丝装置的喷嘴和收集器之间的距离、喷嘴和收集器之间的电势差和从喷嘴排出的所述溶液的吐出量等来选择。
在静电纺丝中使用的喷嘴和收集器的表面可由铂、金、银、钨、铜、不锈钢、或它们的合金形成。例如，喷嘴和收集器的表面可由涂覆铂的不锈钢形成。
为了改善通过静电纺丝形成的纤网的强度，可以利用热空气、压延、针刺、水刺或化学键合等方法，将所述纤网附着于非织造布、纸或合成纤维等各种基材。
使用上述方法制备的纤网可用作二次电池的隔膜或者如汽车用滤油器或空气过滤器等过滤器。
根据本发明的另一个实施方案的过滤器包括所述纤网。例如，所述过滤器可以为通过利用压延法将所述纤网附着于非织造布而制备的超低渗透空气(ULPA)过滤器或高效微粒空气(HEPA)过滤器。本说明书中，“ULPA过滤器”是指能够过滤99.999％以上的具有120nm以上的粒子的过滤器，“HEPA过滤器”是指能够过滤99.97％以上的具有0.3μm以上的粒子的过滤器。通过所述过滤器而被过滤的粒子可以为粉尘、污染物、霉菌和/或细菌等。
以下，将举出实施例对本发明进行更详细的说明，但本发明并非限定于这些实施例。
实施例1
制备例1：全芳香族液晶聚酯树脂的制备
在可控温度的10L容量的间歇式反应器中，添加3.018kg的对羟基苯甲酸、1.300kg的6-羟基-2-萘甲酸和0.3g的乙酸钾(催化剂)，并注入氮气以使反应器内部为不活泼状态，然后在该反应器中进一步添加3.024kg的乙酸酐。然后，用30分钟将反应器的温度升高至150℃并且在该温度下将所述单体的羟基乙酰化2小时。之后，在去除乙酰化反应中所产生的乙酸的同时，用5小时20分钟将反应器的温度升高至320℃后保持20分钟，从而通过单体的缩聚反应来制备全芳香族液晶聚酯预聚物。此外，在制备上述预聚物时，还产生作为副产物的乙酸，将该乙酸也与上述乙酰化反应中所产生的乙酸一起在所述预聚物的制备过程中连续去除。然后，从反应器收集所述预聚物并进行冷却及固化。
然后，将所述全芳香族液晶聚酯预聚物粉碎至平均粒径为1mm，然后将3kg的粉碎的全芳香族液晶聚酯预聚物添加至10L容量的回转窑反应器中，并在使氮气以1Nm3/小时的流速流动的同时，用1小时将反应器的温度升高至失重起始温度、即200℃，然后用6小时将温度升高至290℃并保持5小时，由此制备全芳香族液晶聚酯树脂。接着，用1小时将反应器冷却至室温，然后从反应器收集全芳香族液晶聚酯树脂。
制备例2：全芳香族液晶聚酯树脂溶液的制备
在80℃加热板(hot plate)上，在不进行借助磁棒或机械搅拌器的搅拌的情况下，将制备例1中所制备的5g的全芳香族液晶聚酯树脂溶解于10ml的五氟苯酚中，然后将生成物再次溶解在20ml的六氟异丙醇中，由此制备全芳香族液晶聚酯树脂溶液。
制备例3：由全芳香族液晶聚酯树脂制备纤网
使用泵，将制备例2中所制备的全芳香族液晶聚酯树脂溶液提供至静电纺丝装置(自行生产的，将电压调高至50,000V)的喷嘴，然后将在所述喷嘴中的溶液喷射至配置于喷嘴之下的收集器，由此制备纤网。此时，在喷嘴和收集器之间施加50,000V，并且使溶液以0.5ml/min的速率从所述喷嘴吐出。此外，喷嘴和收集器的表面为涂覆铂的不锈钢，并且喷嘴和收集器之间的距离为40cm。为了无损坏地从收集器分离由全芳香族液晶聚酯树脂溶液制备的纤网，将特氟龙膜配置在收集器上并将所述溶液吐丝至所述特氟龙膜的表面。然后，通过使用80℃的热风机从所制备的纤网去除溶剂。
制备例4：过滤器的制备
使用压延装置(由Seoul system制造)，将制备例3中所制备的纤网(厚度：5,000nm)附着于聚丙烯纺粘非织造布(110g/m2)。此时，所述附着温度为200℃。然后，然后，使用烘箱干燥机(ASUNG PLANT产品)，在130℃下干燥4小时以上，以将水分含量降低为200wtppm以下，由此得到完成的过滤器。
比较例1
为了与制备例4中所制备的过滤器进行比较，购买一种常用的纤网(C&S公司的HPFT1S非织造布)，其是通过将具有5,000nm厚度的聚丙烯纤网附着于110g/m2的聚丙烯纺粘非织造布来制备的。
评价例
评价例1：纤维平均直径的评价
对于实施例1和比较例1的过滤器，使用光学显微镜(YS1-T Nikon)和扫描电子显微镜(Hitachi S-3500)进行分析，测量包括在上述每个过滤器的纤网中纤维的平均直径。具体地说，通过改变取样位置对每个过滤器收集200个样品，测量包括在每个样品中的纤网内的纤维的直径，然后求出它们的平均值，并将其记为纤维的平均直径。测量的纤维直径的标准偏差为±0.05％。评价结果显示在下表1中。
<表1>
平均直径
实施例1 1,000nm
比较例1 9μm
参考上表1，包括在实施例1的过滤器中的纤网的纤维的平均直径为包括在比较例的过滤器中的纤网的纤维的平均直径的1/9倍。
评价例2：过滤效率和压力损失的评价
使用自动过滤器测试仪(TSI公司，Model 8130)，对于实施例1的过滤器和比较例1的过滤器的过滤效率和压力损失进行评价。此时，使用固体NaCl(平均粒径：0.26μm)作为气溶胶生成材料(aerosol-forming material)，空气流速为30L/min，并且每个样品的尺寸为10cm x 10cm。具体地说，将20个样品在30℃储存24小时后，评价过滤效率和压力损失，另外，将其他的20个样品在150℃储存24小时后，评价过滤效率和压力损失。在每种情况下，求出20个样品的测量值的平均值，并将其记为每个过滤器的过滤效率和压力损失。评价结果显示在下表2中。
<表2>
*1：过滤效率＝(通过过滤器之前的量-通过过滤器之后的量)/通过过滤器之前的量×100
*2：压力损失是指过滤器前侧和后侧之间的压力差
参考上表2，实施例1的过滤器与比较例1的过滤器相比，在低温和高温都显示出更优异的过滤效率和更低的压力损失。此外还显示，实施例1的过滤器在高温下保持与低温下相同的过滤效率。
参照实施例对本发明进行了说明，但上述实施例只是示例性的，只要是具有本技术领域的一般知识的人员，就可能会理解到从上述实施例实现各种变形及均等的其他实施例。因此，本发明的技术保护范围由权利要求书的技术思想定义。

Claims (9)

1.一种纤网，其包含全芳香族液晶聚酯树脂，该全芳香族液晶聚酯树脂包含衍生自羟基苯甲酸的重复单元和衍生自羟基萘甲酸的重复单元，但是不包含衍生自芳香族二羧酸的重复单元；所述全芳香族液晶聚酯树脂在其链内包含如下重复单元：
(1)衍生自芳香族羟基羧酸的重复单元：-O-Ar-CO-
(2)衍生自芳香族二醇的重复单元：-O-Ar-O-
(3)衍生自芳香族二胺的重复单元：-HN-Ar-NH-
(4)衍生自芳香族羟基胺的重复单元：-HN-Ar-O-
(5)衍生自芳香族氨基羧酸的重复单元：-HN-Ar-CO-
在上述化学式中，Ar可以为亚苯基(苯撑)、亚联苯基(联苯撑)、亚萘基(萘撑)或2个亚苯基通过碳或非碳元素彼此连接的芳香族化合物，或者可以为亚苯基、亚联苯基、亚萘基或2个亚苯基通过碳或非碳元素彼此连接的芳香族化合物中的1个以上的氢被其它元素取代的芳香族化合物。
2.根据权利要求1所述的纤网，其中所述羟基苯甲酸选自由对羟基苯甲酸、3-羟基苯甲酸、2-羟基苯甲酸及它们的组合组成的组。
3.根据权利要求1所述的纤网，其中所述羟基萘甲酸选自由6-羟基-2-萘甲酸、3-羟基-2-萘甲酸、2-羟基-1-萘甲酸、1-羟基-2-萘甲酸及它们的组合组成的组。
4.根据权利要求1所述的纤网，其中所述全芳香族液晶聚酯树脂包含70-80摩尔份的衍生自羟基苯甲酸的重复单元和20-30摩尔份的衍生自羟基萘甲酸的重复单元。
5.根据权利要求1所述的纤网，其包含具有1-9,000nm范围内的平均直径的纤维。
6.一种制备纤网的方法，其包括对含有如权利要求1-5任一所述全芳香族液晶聚酯树脂的溶液进行静电纺丝或对全芳香族液晶聚酯树脂进行熔融纺丝的步骤。
7.根据权利要求6所述的方法，其中所述含有全芳香族液晶聚酯树脂的溶液包含选自由三氟甲磺酸、五氟苯酚、3,5-双(三氟甲基)苯酚、对氟苯酚、对氯苯酚，1,1,2,2-四氯乙烷、三氟乙酸、六氟异丙醇、氯仿、二氯甲烷、四氢呋喃、二恶烷和它们的组合组成的组中的至少一种溶剂。
8.一种过滤器，其包括权利要求1至5中的任一项所述的纤网。
9.根据权利要求8所述的过滤器，该过滤器为超低渗透空气(ULPA)过滤器或高效微粒空气(HEPA)过滤器。
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EP2662482A2 (en) 2013-11-13
CN103392034A (zh) 2013-11-13
EP2662482A4 (en) 2015-09-30
TW201231748A (en) 2012-08-01
KR101770826B1 (ko) 2017-08-23
JP2014508227A (ja) 2014-04-03
TWI577845B (zh) 2017-04-11
WO2012093775A3 (ko) 2012-09-07
US20130269304A1 (en) 2013-10-17

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