CN107921379A - 非溶剂致相分离法用制膜原液、和使用其的多孔质中空纤维膜的制造方法 - Google Patents
非溶剂致相分离法用制膜原液、和使用其的多孔质中空纤维膜的制造方法 Download PDFInfo
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Abstract
非溶剂致相分离法用制膜原液，在制膜原液中，在水溶性有机溶剂溶液中溶解15~40重量%的聚砜系树脂、5~60重量%的聚乙烯基吡咯烷酮和0.1~10重量%的聚氧乙烯脱水山梨糖醇脂肪酸酯类而得到。使用该制膜原液，以水性液体作为芯液，通过非溶剂致相分离法进行纺丝，制造多孔质中空纤维膜。所得高功能的多孔质中空纤维膜在例如100~120℃之类的高温环境下使用后，也未观察到在水蒸气透过性能方面大幅降低，因此适合用作燃料电池的水蒸气透过膜。
Description
技术领域
本发明涉及非溶剂致相分离法用制膜原液、和使用其的多孔质中空纤维膜的制造方法。进一步详细而言，涉及在用作燃料电池用加湿膜等水蒸气透过膜的多孔质中空纤维膜的制造中使用的非溶剂致相分离法用制膜原液、和使用其的多孔质中空纤维膜的制造方法。
背景技术
多孔质中空纤维膜具有能够分离气体的尺寸的孔，在各种无机膜之中，示出优异的气体分离性，在要求耐热性、耐化学试剂性的环境下也能够使用。据此，近年来，在使用多孔质中空纤维膜进行燃料电池堆叠的隔膜的加湿之类的水蒸气透过膜等中的用途得到扩展。
作为进行燃料电池堆叠的隔膜的加湿的水蒸气透过膜，如例如专利文献1中公开那样，提出了中空纤维膜，其由包含聚苯砜树脂和亲水性聚乙烯基吡咯烷酮的水溶性有机溶剂溶液的纺丝原液制作。所述中空纤维膜即使在95℃之类的温水中浸渍280小时后，拉伸率也没有大幅降低，因此在膜强度和耐久性方面是优异的。
在此，燃料电池一般而言存在高温时效率变好的倾向，因此要求在100~120℃之类的高温环境下维持性能。因此，对并入燃料电池系统中的水蒸气透过膜，要求在所述温度条件下表现出其性能。
然而，以往提出的水蒸气透过膜在暴露于120℃的高温水蒸气的环境下，随着使用进行，存在作为水蒸气透过膜的性能降低的倾向。可以认为所述倾向的原因在于，例如作为制膜原液的一个成分而使用的聚乙烯基吡咯烷酮在高温环境下其亲水性降低。因此，要求进一步改良，以使得在高温环境下持续使用后，也能够维持性能。
现有技术文献
专利文献
专利文献1：日本专利4,100,215号公报
专利文献2：日本特开2005-193194号公报
专利文献3：日本特开2012-143749号公报
专利文献4：日本特开2005-270707号公报。
发明内容
发明要解决的课题
本发明的目的在于，提供在例如100~120℃之类的高温环境下使用后、水蒸气透过性能方面也不会观察到大幅降低的高功能多孔质中空纤维膜的制造中使用的非溶剂致相分离法用制膜原液、和使用其的水蒸气透过膜。
用于解决课题的手段
所述本发明的目的通过下述内容而实现：非溶剂致相分离法用制膜原液，在制膜原液中，在水溶性有机溶剂溶液中溶解15~40重量%的聚砜系树脂、5~60重量%的聚乙烯基吡咯烷酮和0.1~10重量%的聚氧乙烯脱水山梨糖醇脂肪酸酯类而得到；
和使用该制膜原液，以水性液体作为芯液，通过非溶剂致相分离法进行纺丝，制造多孔质中空纤维膜。
发明的效果
使用本发明所述的制膜原液而制造的多孔质中空纤维膜即使在高温环境下，也能够将膜的细孔内部的亲水性保持为高，因此在120℃之类的高温环境下使用时，也能够实现作为水蒸气透过膜的性能降低小之类的优异效果。
具体实施方式
作为聚砜系树脂，可以举出例如聚砜树脂、聚苯砜树脂、聚醚砜树脂、聚芳基醚砜树脂、双酚A型聚砜树脂等，优选使用聚苯砜树脂。
聚苯砜树脂是指在主链内具有苯基砜基和醚键的物质，具有下述示出的重复单元：
即，具有亚联苯基、且不具有异丙叉基，实际中能够直接使用市售品、例如Amoco产品RADEL R系列等。
作为聚醚砜树脂，可以使用市售品、例如Solvay Advanced Polymers公司制产品Redel系列、BASF公司产品Ultrason系列、住友化学工业产品Sumikaexcel PES系列等。
这些聚砜系树脂以在制膜原液中占约15~40重量%、优选占约15~30重量%那样的浓度使用。聚砜系树脂的浓度高于上述时，制膜原液的粘度极端上升从而纺丝的作业性降低、或者膜的密度过高从而水蒸气透过性能降低，另一方面，所述浓度低于上述时，膜的强度变小，无法耐受实用，或者膜的孔径变得过大，从而除了水蒸气之外的气体透过，有可能无法表现出作为水蒸气透过膜的性能。
以聚砜系树脂作为制膜成分的制膜原液通过向其中添加亲水性聚乙烯基吡咯烷酮、聚氧乙烯脱水山梨糖醇脂肪酸酯类和水溶性有机溶剂而制备。
作为以亲水性高分子物质形式添加的聚乙烯基吡咯烷酮，可以以在制膜原液中占约5~60重量%、优选占约15~40重量%那样的浓度使用分子量为约1000(K-15)~1200000(K-90)、优选为约10000(K-30)~1200000(K-90)的物质。亲水性高分子物质的浓度高于上述时，制膜原液的粘度极端上升，从而作业性降低。
以这样的比例添加聚乙烯基吡咯烷酮在控制多孔质膜的表面孔径等结构方面可以观察到一定的影响，但以所述影响以上的程度，实现了降低多孔质膜的空气透过速度、即提高气体阻隔性、提高水蒸气透过速度这一效果。
作为聚氧乙烯脱水山梨糖醇脂肪酸酯类，可以使用聚氧乙烯脱水山梨糖醇单月桂酸酯、聚氧乙烯脱水山梨糖醇单棕榈酸酯、聚氧乙烯脱水山梨糖醇单硬脂酸酯、聚氧乙烯脱水山梨糖醇单油酸酯等，可以优选使用亲水性高的聚氧乙烯脱水山梨糖醇单月桂酸酯。聚氧乙烯脱水山梨糖醇脂肪酸酯类以在制膜原液中占约0.1~10重量%、优选占约0.5~5重量%那样的浓度使用。聚氧乙烯脱水山梨糖醇脂肪酸酯类的比例低于上述时，在水蒸气透过膜的高温环境下使用时，作为水蒸气透过膜的性能大幅降低，另一方面，所述比例高于上述时，制膜原液的相状态变得不稳定，膜的尺寸、性能不稳定，纺丝的作业性降低。
专利文献2中记载了通过聚苯砜和溶剂的热致相分离法而得到的聚苯砜多孔质膜，此时，也记载了使用作为无机颗粒和凝集剂的聚氧乙烯脱水山梨糖醇脂肪酸酯的方式，但据记载，凝集剂为了控制无机颗粒的凝集状态、使体系整体的熔融状态稳定化而使用。
专利文献3中，记载了通过抑制了所使用的洗涤液的量的高效率的膜的洗涤方法而使透水性、分离特性、低污脏性优异的分离膜，作为此时的开孔剂，也记载了使用聚氧乙烯脱水山梨糖醇脂肪酸酯的方式，但据记载，该开孔剂表面活性剂具有的特征在于，即使残留于多孔质层中并干燥，透水性、阻隔性也不会降低。同样的记载也见于专利文献4中。
这些专利文献2~4决没有教导或者暗示在100~120℃之类的高温环境下使用后、也观察不到在水蒸气透过性能方面的大幅降低这样的本发明的效果。
作为水溶性有机溶剂，可以使用甲醇、乙醇、四氢呋喃或者二甲基甲酰胺、二甲基乙酰胺、N-甲基-2-吡咯烷酮等非质子性极性溶剂，可以优选使用二甲基乙酰胺、N-甲基-2-吡咯烷酮。
非溶剂致相分离法中，不含无机颗粒的包含聚合物和溶剂的均匀的聚合物溶液通过因非溶剂的进入、溶剂向外部氛围的蒸发而导致的浓度变化从而引发相分离，在凝固浴中表现出非溶剂致相分离，由此能够制造分离膜，具体而言，可以使用干湿式纺丝法或湿式纺丝法。
使用这样的制膜原液的干湿式纺丝以水性液体、一般而言以水作为芯液而进行，使在水或水性凝固浴中凝固的多孔质中空纤维膜水洗后干燥。水洗通过常温或者温水、利用压热釜得到的加压水(例如121℃)等进行。
实施例
接着，针对实施例说明本发明。
实施例
在室温下，制备包含聚苯砜树脂(Solvay Specialty Polymers公司制产品RADELR-5000)20重量份、聚乙烯基吡咯烷酮(纯正化学产品K-30)15重量份、聚氧乙烯脱水山梨糖醇单月桂酸酯(关东化学产品Tween 20)1重量份和二甲基乙酰胺64重量份的均匀的制膜原液。
对所制备的制膜原液，使用二重环状结构的纺丝喷嘴，以水作为芯液，挤出至水凝固浴中，进行干湿式纺丝。其后，在121℃的加压水中洗涤1小时后，在60℃的烘箱中干燥，得到外径为1,000μm、内径为700μm的多孔质聚苯砜树脂中空纤维膜。
针对所得多孔质聚苯砜树脂中空纤维膜，进行水蒸气透过速度、纯水透过速度、空气透过速度的测定。
水蒸气透过速度：使用3根有效长度为17cm的中空纤维膜，制作两端开放型中空纤维膜模块，分别从膜的外侧流通RH 90%的加湿空气、此外在膜的内侧流通干燥空气，测定平均时间的水蒸气透过量，算出换算为单位膜面积、单位时间、膜的外侧与膜内侧的水蒸气分压差、平均1MPa的空气透过量的数值。
纯水透过速度：使用有效长度为15cm的两端开放型中空纤维膜模块，在温度为25℃、压力为1 MPa的条件下，以纯水作为原水，从中空纤维膜的内侧向外侧过滤(内压过滤)，测定平均时间的透水量，以换算为单位膜面积、单位时间、平均1 MPa的透水量的数值算出。
空气透过速度：将有效长度为15cm的中空纤维膜制成环状，将环两端固定于玻璃管上而得到模块，使用所得模块，从膜的内侧向外侧施加温度为25℃、压力为50kPa的空气，测定平均时间的空气透过量，算出换算为单位膜面积、单位时间、平均1MPa的空气透过量的数值た
比较例1
实施例中，不使用聚氧乙烯脱水山梨糖醇单月桂酸酯，此外将二甲基乙酰胺量变更为65重量份而使用。
比较例2
实施例中，不使用聚乙烯基吡咯烷酮，此外分别将聚氧乙烯脱水山梨糖醇单月桂酸酯量变更为15重量份、将二甲基乙酰胺量变更为65重量份而使用。
上述实施例和各比较例中得到的结果示于下表。
。
工业实用性
本发明所述的多孔质中空纤维膜在100~120℃之类的高温环境下使用后，也未观察到在水蒸气透过性能方面大幅降低，因此能够有效地用作燃料电池中使用的水蒸气透过膜等。
权利要求书(按照条约第19条的修改)
1.非溶剂致相分离法用制膜原液，在制膜原液中，在水溶性有机溶剂溶液中溶解15~30重量%的聚苯砜树脂、15~40重量%的聚乙烯基吡咯烷酮和0.5~5重量%的聚氧乙烯脱水山梨糖醇脂肪酸酯类而得到。
2.根据权利要求1所述的非溶剂致相分离法用制膜原液，其中，聚氧乙烯脱水山梨糖醇脂肪酸酯类为聚氧乙烯脱水山梨糖醇单月桂酸酯。
3.根据权利要求1或2所述的非溶剂致相分离法用制膜原液，其不含无机颗粒。
4.多孔质中空纤维膜的制造方法，其特征在于，对权利要求1或2所述的非溶剂致相分离法用制膜原液，使用二重环状喷嘴，以水性液体作为芯液，通过非溶剂致相分离法进行纺丝。
5.水蒸气透过膜，其通过权利要求4所述的制造方法制造。
6.根据权利要求5所述的水蒸气透过膜，其用作燃料电池用加湿膜。
7.根据权利要求6所述的水蒸气透过膜，其在100~120℃的高温环境下使用。
Claims (9)
1.非溶剂致相分离法用制膜原液，在制膜原液中，在水溶性有机溶剂溶液中溶解15~40重量%的聚砜系树脂、5~60重量%的聚乙烯基吡咯烷酮和0.1~10重量%的聚氧乙烯脱水山梨糖醇脂肪酸酯类而得到。
2.根据权利要求1所述的非溶剂致相分离法用制膜原液，其中，聚砜系树脂为聚苯砜树脂。
3.根据权利要求1所述的非溶剂致相分离法用制膜原液，其中，聚氧乙烯脱水山梨糖醇脂肪酸酯类为聚氧乙烯脱水山梨糖醇单月桂酸酯。
4.根据权利要求1或3所述的非溶剂致相分离法用制膜原液，其中，使用0.5~5重量%的聚氧乙烯脱水山梨糖醇脂肪酸酯类。
5.根据权利要求1、2或3所述的非溶剂致相分离法用制膜原液，其不含无机颗粒。
6.多孔质中空纤维膜的制造方法，其特征在于，对权利要求1、2或3所述的非溶剂致相分离法用制膜原液，使用二重环状喷嘴，以水性液体作为芯液，通过非溶剂致相分离法进行纺丝。
7.水蒸气透过膜，其通过权利要求6所述的制造方法制造。
8.根据权利要求7所述的水蒸气透过膜，其用作燃料电池用加湿膜。
9.根据权利要求8所述的水蒸气透过膜，其在100~120℃的高温环境下使用。
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| JP2015175353A JP2017051880A (ja) | 2015-09-07 | 2015-09-07 | 非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 |
| JP2015-175353 | 2015-09-07 | ||
| PCT/JP2016/073134 WO2017043233A1 (ja) | 2015-09-07 | 2016-08-05 | 非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 |
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| CN110975641A (zh) * | 2018-10-03 | 2020-04-10 | Nok株式会社 | 聚砜多孔中空纤维膜的制造方法 |
| CN112351832A (zh) * | 2018-06-26 | 2021-02-09 | Nok株式会社 | 加湿用多孔质中空纤维膜的制造方法 |
| CN113905808A (zh) * | 2019-06-06 | 2022-01-07 | 尤尼吉可株式会社 | 中空纤维膜、该中空纤维膜组件、加湿单元、空气干燥器、该中空纤维膜的制膜原液及该中空纤维膜的制造方法 |
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| US11465103B2 (en) | 2017-05-08 | 2022-10-11 | Universiteit Twente | Aqueous phase separation method |
| JP6964680B2 (ja) * | 2017-10-27 | 2021-11-10 | Nok株式会社 | 加湿膜用ポリフェニルスルホン中空糸膜の製造法 |
| CN109989126A (zh) * | 2017-12-29 | 2019-07-09 | 财团法人工业技术研究院 | 导电弹性纤维及其制造方法 |
| EP3877077B1 (en) | 2018-11-07 | 2024-08-07 | NX Filtration N.V. | Method for creating a porous film through aqueous phase separation |
| JP7383851B2 (ja) | 2021-04-06 | 2023-11-20 | Nok株式会社 | 中空糸膜の製造方法 |
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| CN113905808A (zh) * | 2019-06-06 | 2022-01-07 | 尤尼吉可株式会社 | 中空纤维膜、该中空纤维膜组件、加湿单元、空气干燥器、该中空纤维膜的制膜原液及该中空纤维膜的制造方法 |
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| KR20180048692A (ko) | 2018-05-10 |
| JP2017051880A (ja) | 2017-03-16 |
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