CN104480636B - 一种聚偏氟乙烯纳米纤维膜材料及其制备方法与应用 - Google Patents

一种聚偏氟乙烯纳米纤维膜材料及其制备方法与应用 Download PDF

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CN104480636B
CN104480636B CN201410698087.4A CN201410698087A CN104480636B CN 104480636 B CN104480636 B CN 104480636B CN 201410698087 A CN201410698087 A CN 201410698087A CN 104480636 B CN104480636 B CN 104480636B
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polyvinylidene fluoride
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魏取福
王静
王清清
李国辉
黄机质
黄锋林
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SUZHOU BOHAN HOUSEHOLD PRODUCTS Co.,Ltd.
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    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—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
    • 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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Abstract

一种聚偏氟乙烯纤维膜材料及其制备方法与应用，涉及材料化工领域，纤维膜材料中聚偏氟乙烯纤维直径为400‑5000nm，平均分子量为30‑60万，纤维膜的孔径分布在1.34‑5.32μm范围内。一种聚偏氟乙烯纤维膜材料的制备方法，包括（1）聚合物纺丝液制备和（2）静电纺丝。一种聚偏氟乙烯纤维膜材料作为吸油材料的应用。本发明提供的聚偏氟乙烯纤维膜材料是采用静电纺丝的方法制备得到的聚偏氟乙烯/改性蒙脱土复合纤维膜材料，纤维膜材料具有优良疏水吸油效果，可作为吸油材料的实用，用于海上或水面溢油的处理、含油废水的处理、过滤材料和石油化工污染控制等领域。

Description

一种聚偏氟乙烯纳米纤维膜材料及其制备方法与应用
技术领域
本发明属于材料化工领域，特别是一种吸油材料及其制备方法，具体涉及一种聚偏氟乙烯吸油材料及其制备和应用。
背景技术
石油泄漏常常发生在石油开发，运输，存储过程中，导致严重的环境污染。随着人类保护环境的意识日益显著，研究人员已经开发大量的吸附材料用于运输、吸附溢油，理想的吸附剂要求疏水亲油，高度吸油量，成本低廉，最近，超疏水超亲油材料引起了广泛的关注。目前石油吸附材料主要分为三大类：无机矿物材料、天然有机材料、合成有机材料。在石油泄漏清理中，合成有机材料由于其可调的疏水亲油性，相对较低的成本，可被大规模使用。但是每克的吸附剂只能吸附几十克油，在实际使用中有待提高。无机矿物材料具有疏松多孔，价格便宜，吸油速度快等优点，但是部分材料再生困难，饱和吸油能力低等缺点。
传统的含油污水处理方法有重力法、离心法、吸附法、浮选法、膜分离法等，但是许多方法在实际应用中制作步骤繁杂。静电纺丝是目前制备纳米纤维膜最简单最直接的方法，所制备纤维的直径一般在数十到几千纳米，而传统的熔融纺丝、干法纺丝、湿法纺丝制备纤维的直径一般在几十到几百微米，通过静电纺丝制备的纤维材料具有更大的比表面积和孔隙率，因此具有更高的吸附能力。聚偏氟乙烯是一种低表面能的疏水材料，具有优良的柔韧性，耐化学腐蚀性、优良的耐高温色变性和耐氧化等特性，是被公认的优异的膜材料。中国专利CN102764597A采用热致相分离的方法制备了高强度，高孔隙率，高通量，高分离精度的聚偏氟乙烯超滤膜。专利CN101362057A采用热致相分离的方法制备了孔隙率高，孔径分布均匀且强度高的多孔膜。专利CN103469488A采用静电纺制备了一种强度高，兼具高孔隙率，良好浸润性能的聚偏氟乙烯锂离子电池隔膜。专利CN 103801274 A制备了吸油中空多孔的纤维膜，以石墨烯为表面吸附层，聚偏氟乙烯中空纤维多孔膜为基质层，制成膜组件用来进行油水分离，该方法步骤繁杂，效率并不高。本发明采用静电纺丝的方法制备聚偏氟乙烯纳米纤维膜用于吸油材料的研究未见报道。
发明内容
本发明解决的技术问题：针对现有技术的不足，本发明要解决的技术问题是制备一种对不同种类的油都具有较好的吸附性能且具有良好的疏水亲油效果的聚偏氟乙烯纳米纤维膜材料及其制备方法。
本发明的技术方案：一种聚偏氟乙烯纤维膜材料，聚偏氟乙烯纤维直径为400-5000nm，平均分子量为30-60万，纤维膜的孔径分布在1.34-5.32μm范围内。
一种聚偏氟乙烯纤维膜材料的制备方法，制备步骤如下：
（1）聚合物纺丝液制备：将聚偏氟乙烯溶于有机溶剂中，在35℃水浴加热溶解，待溶液澄清后，将蒙脱土超声分散于溶液中得到聚合物纺丝溶液；
其中，有机改性蒙脱土质量为纺丝溶液总质量的1-3%；
（2）静电纺丝：将聚偏氟乙烯/改性蒙脱土纺丝液进行静电纺丝，制得聚偏氟乙烯/改性蒙脱土复合纳米纤维薄膜；
其中，静电纺丝过程中滚筒转速200r/min，纺丝电压10-12kv，纺丝速度0.5-1ml/h，接收距离为11-15cm。
作为优选，步骤（1）中有机溶剂为丙酮和二甲基乙酰胺，丙酮和二甲基乙酰胺的质量比为2：3。
作为优选，步骤（2）静电纺丝的电压为10kv，纺丝速度1ml/h，接收距离为10cm。
一种聚偏氟乙烯纤维膜材料作为吸油材料的应用。
有效效果：本发明提供的聚偏氟乙烯纤维膜材料是采用静电纺丝的方法，首先将聚偏氟乙烯溶于有机溶剂得到纺丝溶液，然后将一定量改性蒙脱土超声分散在纺丝液中，进行静电纺丝制得聚偏氟乙烯纤维膜材料。制备的聚偏氟乙烯/改性蒙脱土复合纤维膜材料具有优良疏水吸油效果，可作为吸油材料的实用，用于海上或水面溢油的处理、含油废水的处理、过滤材料和石油化工污染控制等领域。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
实施例1
根据本发明提供的制备方法制备聚偏氟乙烯纤维膜材料：
（1）聚合物纺丝溶液的制备：将2gPVDF加入到10.8gDMAC和7.2g丙酮溶液中，35℃水浴加热4h，制得聚偏氟乙烯纺丝液；
（2）静电纺丝：纺丝条件，滚筒转速200r/min，纺丝电压11kv，纺丝速度1ml/h，接收距离11cm，制备得到无改性蒙脱土的聚偏氟乙烯纤维膜，纤维平均直径为251nm，纤维膜的平均孔径在5.30um。
复合纳米纤维膜对二甲基硅油的吸油量为15.945mg/mm2，对大豆油吸油量为19.377mg/mm2，对汽油吸油量为10.198mg/mm2。
实施例2
根据本发明提供的制备方法制备聚偏氟乙烯纤维膜材料：
（1）聚合物纺丝溶液的制备：将2gPVDF加入到10.8gDMAC和7.2g丙酮溶液中，35℃水浴加热4h，称取0.2g改性蒙脱土加入溶液中超声分散机械搅拌12h，制得1%改性蒙脱土的混合纺丝液；
（2）静电纺丝：纺丝条件，滚筒转速200r/min，纺丝电压10kv，纺丝速度0.5ml/h，接收距离10cm，制备得到聚偏氟乙烯/改性蒙脱土复合纳米纤维膜，纤维平均直径为428nm，纤维膜的平均孔径为4.25um。
该聚偏氟乙烯/改性蒙脱土复合纤维膜材料对二甲基硅油吸油量为19.671mg/mm2，对大豆油吸油量为20.660mg/mm2，对汽油吸油量为14.721mg/mm2。
实施例3
根据本发明提供的制备方法制备聚偏氟乙烯纤维膜材料：
（1）聚合物纺丝溶液的制备：将2gPVDF加入到10.8gDMAC和7.2g丙酮溶液中，35℃水浴加热4h，称取0.4g改性蒙脱土加入溶液中超声分散机械搅拌12h，制得2%改性蒙脱土的混合纺丝液；
（2）静电纺丝：纺丝条件，滚筒转速200r/min，纺丝电压12kv，纺丝速度0.6ml/h，接收距离12cm，制备得到聚偏氟乙烯/改性蒙脱土复合纳米纤维膜，纤维平均直径为367nm，纤维膜的平均孔径为2.56um。
该聚偏氟乙烯/改性蒙脱土复合纤维膜材料对二甲基硅油吸油量为23.322mg/mm2，对大豆油吸油量为20.803mg/mm2，对汽油吸油量为15.273mg/mm2。
实施例4
根据本发明提供的制备方法制备聚偏氟乙烯纤维膜材料：
（1）聚合物纺丝溶液的制备：将2gPVDF加入到10.8gDMAC和7.2g丙酮溶液中，35℃水浴加热4h，称取0.6g改性蒙脱土加入溶液中超声分散机械搅拌12h，制得3%改性蒙脱土的混合纺丝液；
（2）静电纺丝：纺丝条件，滚筒转速200r/min，纺丝电压10kv，纺丝速度1ml/h，接收距离10cm，制备得到聚偏氟乙烯/改性蒙脱土复合纳米纤维膜，纤维平均直径为549nm，纤维膜的平均孔径为1.34um。
该聚偏氟乙烯/改性蒙脱土复合纤维膜材料对二甲基硅油单位面积吸油量为23.752mg，对大豆油吸油量为20.983mg/mm2，对汽油吸油量为15.580mg/mm2。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (3)

1.一种聚偏氟乙烯纤维膜材料的制备方法，其特征在于，制备步骤如下：
（1）聚合物纺丝液制备：将聚偏氟乙烯溶于有机溶剂中，在35℃水浴加热溶解，待溶液澄清后，将有机改性蒙脱土超声分散于溶液中得到聚合物纺丝溶液；
其中，有机改性蒙脱土质量为纺丝溶液总质量的1-3%；
（2）静电纺丝：将聚偏氟乙烯/有机改性蒙脱土纺丝液进行静电纺丝，制得聚偏氟乙烯/有机改性蒙脱土复合纳米纤维薄膜；
其中，静电纺丝过程中滚筒转速200r/min，纺丝电压10-12kV ，纺丝速度0.5-1ml/h，接收距离为11-15cm；
制备得到的聚偏氟乙烯纤维直径为400-5000nm，平均分子量为30-60万，纤维膜的孔径分布在1.34-5.32μm范围内。
2.根据权利要求1所述的聚偏氟乙烯纤维膜材料的制备方法，其特征在于：步骤（1）中有机溶剂为丙酮和二甲基乙酰胺，丙酮和二甲基乙酰胺的质量比为2：3。
3.根据权利要求1所述的聚偏氟乙烯纤维膜材料的制备方法，其特征在于：步骤（2）静电纺丝的电压为10kV ，纺丝速度1ml/h，接收距离为10cm。
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