CN116141785B - 具有超高效耐洗性的非对称分离纤维膜及其制备方法 - Google Patents

具有超高效耐洗性的非对称分离纤维膜及其制备方法 Download PDF

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CN116141785B
CN116141785B CN202310023731.7A CN202310023731A CN116141785B CN 116141785 B CN116141785 B CN 116141785B CN 202310023731 A CN202310023731 A CN 202310023731A CN 116141785 B CN116141785 B CN 116141785B
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CN116141785A (zh
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殷先泽
程冰冰
郑龙
晏松
李钰山
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Wuhan Textile University
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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Abstract

本发明涉及一种具有超高效耐洗性的非对称分离纤维膜及其制备方法，本发明通过静电纺丝法制备聚偏氟乙烯(PVDF)纤维膜，然后再利用羧甲基壳聚糖流体(CMCfs)与聚偏氟乙烯(PVDF)混合纺丝溶液在PVDF纤维膜的一侧纺制CMCfs/PVDF膜，制备得到一种超高效耐洗，非对称分离纤维膜。通过本发明制备方法得到的非对称分离纤维膜，其具有较好的重复利用性、超高的分离效率(99.5‑99.99％)和耐洗性强，可应用于油水分离领域。本发明制备过程简单且环保，原材料价格低廉，来源广泛，可大规模生产。

Description

具有超高效耐洗性的非对称分离纤维膜及其制备方法
技术领域
本发明涉及功能性膜的制备方法领域，具体涉及一种具有超高效耐洗性的非对称分离纤维膜及其制备方法。
背景技术
随着工业和生活废水的迅速增加，含油废水的回收和分离已成为全世界面临的挑战。开发各种方法和分离膜以有效分离各种油/水混合物仍然是一个挑战。目前，已有许多物理方法被用于处理各种含油废水，包括撇油法、浮选法、沉降法和沉淀法。然而，在实践中，我们面对的是复杂苛刻条件下的油水混合物，特别是表面活性剂稳定的油水乳液。在大多数情况下，表面活性剂稳定的乳剂是非常小的分散液滴，表现出良好的乳剂稳定性，这使得在使用过程中很难分离这种乳剂。此外，大多数分离材料主要集中在单一的选择性润湿性，不能提高分离效率。分离膜分离过程中循环性能，润湿性下降以及分离效率达不到99.5％以上，然而，获得具有这种特性的Janus膜是一个挑战。受到荷叶和沙漠甲虫背壳的启发，因此，迫切需要设计两侧润湿性极相反的Janus膜。采用静电纺丝法制备纤维膜具有孔径可控、孔结构相互连接、比表面积体积比大、孔隙率高等优点，在油水乳状液分离中具有潜在的应用价值。目前文献所报道大多数用静电纺丝方法构建的Janus纤维膜主要包括表面涂层亲水性/疏水性层、表面接枝亲水性/疏水性聚合物和表面组装过程。然而，由于相邻纤维之间的空间有限，纤维表面的有机或无机涂层会不规则地聚集在孔隙通道中，破坏孔隙的连通性。此外，由于纤维分布在膜上的不同位置，控制这种涂层的厚度是非常麻烦的。另一方面，表面改性会影响纤维的固有性能。在使用过程中，表面涂层可能被溶剂洗掉或被机械力去除。
发明内容
本发明要解决的技术问题是针对以上问题和要求，提供一种具有超高效耐洗性的非对称分离纤维膜及其制备方法。
为解决以上技术问题，本发明采用以下技术方案：
具有超高效耐洗性的非对称分离纤维膜的制备方法，包括以下步骤：
步骤1、制备羧甲基壳聚糖流体；
步骤2、制备聚偏氟乙烯溶液；
步骤3、将羧甲基壳聚糖流体添加到聚偏氟乙烯溶液中，其中羧甲基壳聚糖流体的质量分数为5-15wt％,在60-70℃下反应24h，得到PVDF/CMCFs纺丝溶液；
步骤4、利用聚偏氟乙烯溶液进行静电纺丝得到聚偏氟乙烯纤维膜；
步骤5、采用PVDF/CMCFs纺丝溶液，利用静电纺丝方式在聚偏氟乙烯纤维膜的一侧上纺制纤维膜，干燥后得到具有超高效耐洗性的非对称分离纤维膜。
进一步的，所述羧甲基壳聚糖分子量为10kDa-30kDa,脱乙酰度为90％，取代度≥80％。
进一步的，所述羧甲基壳聚糖流体通过羧甲基壳聚糖溶液与聚乙二醇取代的十八叔胺溶液共混，通过扩散-静电自组装法将反应后的混合溶液透析之后烘干后制备得到。
进一步的，所述羧甲基壳聚糖流体与聚偏氟乙烯溶液的质量分数之和为20wt％。
具有超高效耐洗性的非对称分离纤维膜，由上述的方法制备得到。
本发明采用以上技术方案后，与现有技术相比，具有以下优点：
由于分离纤维膜分离99.5％以上效率是一个挑战，而且分离过程膜的循环性能和润湿性下降。本发明直接将羧甲基壳聚糖流体和聚偏氟乙烯混合在
一起配成纺丝液，采用静电纺丝的方法，使其羧甲基壳聚糖流体嵌入到纤维5表面，通过热处理过程原位生长锚定在纤维的内表面，避免表面涂覆脱落的问题。
本发明突破常规外涂亲水改性涂层制备方法，受无溶剂纳米类流体概念启发，将天然高分子多糖流体嵌入到纤维里面，解决表面涂覆容易脱落的问
题。基于这一独特思路，以多糖流体可以降低PVDF纺丝粘度为目标，通过0调节多糖流体和PVDF的质量分数比，采用静电纺丝技术，引入具有两亲性的多糖流体做成双成膜，多糖流体热处理过程中会锚定在纤维膜内表面，解决表面涂层可能被溶剂洗掉的关键问题。
而且申请人对采用不同质量分数的CMCFs进行了试验发现，只有CMCfs的质量分数在5wt％-15wt％之间，且CMCfs与PVDF的质量分数5之和为20wt％时，最终才能得到Janus纤维膜，采用质量分数等于其他数值的CMCFs和PVDF得不到非对称分离纤维膜。
同传统方法相比，本发明的新方法具有以下优势：1)工艺简单，高效，高速；2)多糖流体可以降低PVDF纺丝的粘度；3)多糖流体锚定在纤维膜内
表面，避免表面涂覆容易脱落；4)本发明的纤维膜具有超高效耐洗性；5)，0本发明的分离膜具有超高的分离效率(99-99.99％)。
综上，本发明的方法以多糖流体迁移到纤维膜内表面为主要手段，通过静电纺丝技术发展环保型，避免涂覆容易脱落和降低PVDF纺丝黏度的制备工艺，得到了具有较好的重复利用性、超高的分离效率(99-99.99％)和耐洗性强的分离纤维膜。
5下面结合附图和实施例对本发明进行详细说明。
附图说明
图1为Janus膜的制备流程图；
图2为在25℃条件下，纯PVDF和含不同质量分数CMCFs的PVDF/CMCFs膜纺丝溶液的黏度随剪切速率的变化规律示意图；
图3为纯PVDF和含不同质量分数CMCFs的PVDF/CMCFs膜水处理后的实物图；
图4含不同质量分数CMCFs的Janus PVDF杂化膜的润湿性行为示意图；
图5为纯PVDF和含不同质量分数CMCFs的PVDF/CMCFs膜的循环性。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌，制备混合均匀的纺丝溶液(PVDF)。将PVDF纺丝溶液装入不锈钢针的注射器中进行静电纺丝。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
实施例2
首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌。然后将CMCFs添加到上述溶液中，制备混合均匀的纺丝溶液(PVDF/CMCfs)，其中CMCfs的质量分数为7.5wt％。将PVDF/CMCfs纺丝溶液装入不锈钢针的注射器中进行静电纺丝。之后，将PVDF纺丝溶液静电纺丝到PVDF/CMCfs一侧上。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
实施例3
首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌。然后将CMCfs添加到上述溶液中，制备混合均匀的纺丝溶液(PVDF/CMCfs)，其中CMCfs的质量分数为7.5wt％。将PVDF/CMCfs纺丝溶液装入不锈钢针的注射器中进行静电纺丝。之后，将PVDF纺丝溶液静电纺丝到PVDF/CMCfs一侧上。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
实施例4
首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌。然后将CMCfs添加到上述溶液中，制备混合均匀的纺丝溶液(PVDF/CMCfs)，其中CMCfs的质量分数为7.5wt％。为12.5wt％。将PVDF/CMCfs纺丝溶液装入不锈钢针的注射器中进行静电纺丝。之后，将PVDF纺丝溶液静电纺丝到PVDF/CMCfs一侧上。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
实施例5
首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌。然后将CMCfs添加到上述溶液中，制备混合均匀的纺丝溶液(PVDF/CMCfs)，其中CMCfs的质量分数为15wt％。将PVDF/CMCfs纺丝溶液装入不锈钢针的注射器中进行静电纺丝。之后，将PVDF纺丝溶液静电纺丝到PVDF/CMCfs一侧上。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
通过五种实例表明，不同质量分数的羧甲基壳聚糖纳米类流体和PVDF表明，只有使用质量分数比不能小于5wt％且不能大于15wt％的CMCfs,最终才能得到Janus膜。CMCfs流体含量在低于5wt％时，膜正反两面都是疏水性。相反，CMCfs流体含量在高于15wt％时，膜正反两面都是亲水性。说明低含量和高含量的羧甲基壳聚糖纳米类流体对Janus膜有一定的亲水改性的作用。因此，天然多糖流体引入纤维膜内表面，通过干燥过程中原位生长锚定在纤维膜内表面，大大提高了Janus膜耐洗性，比外涂亲水改性涂层要有优势，使实际大规模应用成为可能。
如图1所示，为本发明的Janus膜的制备流程图。首先，将PVDF粉末溶于DMF溶剂中并在65℃的油浴温度下搅拌。然后将CMCFs添加到上述溶液中，制备混合均匀的纺丝溶液(PVDF/CMCFs)。以同样的方式，制备PVDF溶液另一个纺丝溶液，其中CMCfs的质量分数分别为0、7.5、10、12.5、15wt％。将PVDF/CMCFs纺丝溶液装入不锈钢针的注射器中进行静电纺丝。之后，将PVDF纺丝溶液静电纺丝到PVDF/CMCFs一侧上。静电纺丝参数设置如下：高压功率为20kV，推注速率为0.16mm/min，针尖集电极距离为15cm。将收集的静电纺丝纤维用真空干燥箱在60℃下干燥5小时，以去除残留溶剂,可得到具有超高效耐洗，非对称分离纤维膜。
在常规溶液静电纺丝中，聚合物溶液中加入颗粒通常会增加溶液粘度。而我们研究了不同CMCFs浓度下PVDF/CMCFs溶液的稳态粘度，如图2所示。在剪切速率范围内，添加不同质量分数的CMCFs既不显著增加稳定粘度，也不显著改变流动曲线的形态。
如图3所示，众所周知，纤维膜的表面润湿性对油水分离性能有很大影响。在这里，一个水滴被用于观察Janus膜的润湿行为。结果5表明，在PVDF/CMCFs侧，水滴迅速润湿PVDF/CMCFs表面，并完全被膜吸附，表现出良好的亲水性。而另一侧的水滴则在90s后稳定地停留在PVDF膜表面。
如图4所示，通过把Janus膜放入水中，然后搅拌一段时间，再拿出来
干燥，观察处理之后膜的亲水性。并与未处理之前过的膜进行了比较，观察0发现处理之后膜仍然具有亲水性。这些结果表明，天然多糖流体热处理过程
中会锚定在纤维膜内表面，避免表面涂覆容易脱落的问题。
如图5所示，研究了分离表面活性剂稳定乳液的Janus膜的循环性能。结果显示，经过12次循环，得到的Janus膜对水包油和油包水的分离效率都达到99-99.99％，表明具有较好的重复利用性和超高的分离效率。
5由图2-5中不同含不同质量分数CMCFs的Janus膜的效果对比，可以看出含15wt％CMCFs的Janus膜的效果最佳。
以上所述为本发明最佳实施方式的举例，其中未详细述及的部分均为本领域普通技术人员的公知常识。本发明的保护范围以权利要求的内容为准，任何基于本发明的技术启示而进行的等效变换，也在本发明的保护范围之内。

Claims (3)

1.具有超高效耐洗性的非对称分离纤维膜的制备方法，其特征在于，包括以下步骤：
步骤1、制备羧甲基壳聚糖流体；
步骤2、制备聚偏氟乙烯溶液；
步骤3、将羧甲基壳聚糖流体添加到聚偏氟乙烯溶液中，其中羧甲基壳聚糖流体的质量分数为5-15wt%,且羧甲基壳聚糖流体与聚偏氟乙烯溶液的质量分数之和为20wt%，在60-70℃下反应24 h，得到PVDF/CMCFs纺丝溶液；所述羧甲基壳聚糖流体通过羧甲基壳聚糖溶液与聚乙二醇取代的十八叔胺溶液共混，通过扩散-静电自组装法将反应后的混合溶液透析之后烘干后制备得到；
步骤4、利用聚偏氟乙烯溶液进行静电纺丝得到聚偏氟乙烯纤维膜；
步骤5、采用PVDF/CMCFs纺丝溶液，利用静电纺丝方式在聚偏氟乙烯纤维膜的一侧上纺制纤维膜，干燥后得到具有超高效耐洗性的非对称分离纤维膜。
2.根据权利要求1所述的具有超高效耐洗性的非对称分离纤维膜的制备方法，其特征在于，所述羧甲基壳聚糖分子量为10 kDa-30 kDa,脱乙酰度为90%，取代度≥80%。
3.具有超高效耐洗性的非对称分离纤维膜，其特征在于，由所述权利要求1-2中任一项的方法制备得到。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030012223A (ko) * 2001-07-31 2003-02-12 한국화학연구원 분리막 접촉기용 비대칭 미세다공성 폴리비닐리덴디플루오라이드 중공사막 제조방법
CN110039863A (zh) * 2019-05-24 2019-07-23 浙江理工大学 单面超疏水单面亲水的Janus型微纳米复合纤维膜及其制备方法
CN110053334A (zh) * 2018-01-19 2019-07-26 中国石油化工股份有限公司 一种纳米纤维复合膜及其制备方法和应用
AU2020103787A4 (en) * 2020-11-30 2021-02-11 Junada (qingdao) Technology Co., Ltd. SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101539608B1 (ko) * 2013-03-14 2015-08-17 에치투엘 주식회사 폴리비닐리덴플루오라이드 중공사 분리막과 그 제조방법
KR101483740B1 (ko) * 2013-06-04 2015-01-16 주식회사 에코니티 비대칭성 폴리비닐리덴플루오라이드 중공사막의 제조방법 및 이로부터 제조된 중공사막
US10722847B2 (en) * 2017-06-01 2020-07-28 Vanderbilt University Composite membranes and methods of making and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030012223A (ko) * 2001-07-31 2003-02-12 한국화학연구원 분리막 접촉기용 비대칭 미세다공성 폴리비닐리덴디플루오라이드 중공사막 제조방법
CN110053334A (zh) * 2018-01-19 2019-07-26 中国石油化工股份有限公司 一种纳米纤维复合膜及其制备方法和应用
CN110039863A (zh) * 2019-05-24 2019-07-23 浙江理工大学 单面超疏水单面亲水的Janus型微纳米复合纤维膜及其制备方法
AU2020103787A4 (en) * 2020-11-30 2021-02-11 Junada (qingdao) Technology Co., Ltd. SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
In-situ growth of robust and superhydrophilic nano-skin on electrospun Janus nanofibrous membrane for oil/water emulsions separation;Bingbing Cheng .etc;《Separation and Purification Technology》;20230329;全文 *
表面喷涂壳聚糖溶液对聚偏氟乙烯多孔膜的结构和性能的影响;成世杰等;《材料研究学报》;20200630;第34卷(第6期);全文 *

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