CN112962310A - 一种多功能pvdf多级孔洞纤维薄膜及其制备方法 - Google Patents
一种多功能pvdf多级孔洞纤维薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种多功能PVDF多级孔洞纤维薄膜及其制备方法，属于膜材料技术领域，该方法通过将PVDF/PVP溶于溶剂中，以静电纺丝工艺制得PVDF/PVP复合纤维薄膜，烘干干燥后再放置于水中震荡，以去除掉其中的PVP相，得到PVDF多级孔洞纤维薄膜，最后将PVDF多级孔洞纤维薄膜浸泡于不同负载相溶液中，以实现PVDF多级孔洞纤维薄膜功能的不同；整个制备方法反应条件温和、设备通用，制备成本低，制得的PVDF多级孔洞纤维薄膜为类海绵状结构的纳米级多级孔洞纤维薄膜，纤维的直径可达300nm左右，同时具有双亲性。
Description
技术领域
本发明涉及膜材料技术领域，具体涉及到一种多功能PVDF多级孔洞纤维薄膜及其制备方法。
背景技术
随着工业的发展，水环境的污染越来越严重，特别是冶金，化工，电子等工业生产过程中产生大量的含重金属离子的废水对人类健康产生极大危害。常见的重金属废水处理方法包括化学沉淀法，电解法等，但这些方法都存在着能耗高，二次污染等问题。膜分离技术具有耗能低，占地面积小，设备集成化程度高，能够连续运作等优点，能够满足现代工业对节能、提高生产效率、低品种原材料再利用和减少环境污染的要求，成为实现经济可持续发展战略的重要组成部分。
聚偏氟乙烯(PVDF)是一种结晶性聚合物，相对密度为1.75～1.78，玻璃化温度约39℃，结晶熔点约为170℃，热分解温度在316℃以上，机械性能优良，具有良好的耐冲击性、耐磨性、耐候性和化学稳定性。因此，PVDF是一种比较受欢迎的膜材料，商业PVDF膜在微滤和超滤水处理中具有普遍的应用，已成功地应用于饮用水、气体过滤、污染物去除、溶剂精制和膜蒸馏等领域。但现有PVDF膜存在孔隙率和比表面积低、结构参数不可调控和制备工艺复杂的问题。鉴于此，提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法也就显得十分的有意义。
发明内容
针对上述的不足或缺陷，本发明的目的是提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，可有效解决现有PVDF膜存在孔隙率和比表面积低、结构参数不可调控和制备工艺复杂的问题。
为达上述目的，本发明采取如下的技术方案：
本发明提供一种多功能PVDF多级孔洞纤维薄膜的制备方法，具体包括以下步骤：
步骤(1)：将聚偏氟乙烯(PVDF)和聚乙烯吡咯烷酮(PVP)同时加入溶剂中，搅拌均匀，得到静电纺丝前驱液；
步骤(2)：将步骤(1)所得的静电纺丝前驱液进行静电纺丝，制备得到PVDF/PVP复合纤维薄膜；
步骤(3)：将步骤(2)所得的PVDF/PVP复合纤维薄膜烘干干燥后浸泡于水中，然后经恒温震荡，超声清洗，冷冻干燥，制得PVDF多级孔洞纤维薄膜；
步骤(4)：将步骤(3)所得的PVDF多级孔洞纤维薄膜浸泡于负载相溶液中，恒温震荡，制得多功能PVDF多级孔洞纤维薄膜。
进一步地，步骤(1)中聚偏氟乙烯和聚乙烯吡咯烷酮的质量比为1:1～5。
进一步地，步骤(1)中溶剂为二甲基甲酰胺、四氢呋喃、二甲亚砜和二甲基乙酰胺中的一种或两种以上。
进一步地，步骤(1)中搅拌时温度为50℃-80℃，搅拌时间为6-8小时。
进一步地，步骤(2)中静电纺丝工艺参数为电压12-18kv，收集距离12-17cm，注射速度25～35μl/min，环境温度20℃～30℃，环境湿度40％～60％。
进一步地，步骤(3)中恒温温度为70～90℃。
进一步地，步骤(3)中震荡时间为3～7天，间隔24小时换水一次。
进一步地，步骤(4)中负载相溶液为γ-Fe2O3与甘氨酸混合物水溶液、多巴胺Tris溶液、AgNO3溶液和CuSO4溶液中的一种或几种。
进一步地，γ-Fe2O3与甘氨酸混合物水溶液中γ-Fe2O3与甘氨酸的质量浓度分别为0.06～0.84g/ml和0.5～2mg/ml。
进一步地，多巴胺Tris溶液中多巴胺的质量浓度为0.5～2mg/ml，Tris溶液pH为8～9。
进一步地，AgNO3溶液中AgNO3浓度为40～60mM，优选为50mM。
进一步地，CuSO4溶液中CuSO4浓度为40～60mM，优选为50mM。
本发明还提供上述制备方法制得的多功能PVDF多级孔洞纤维薄膜。
本发明具有以下优点：
1、本发明提供一种多功能PVDF多级孔洞纤维薄膜的制备方法，该方法通过将PVDF/PVP溶于溶剂中，以静电纺丝工艺制得PVDF/PVP复合纤维薄膜，烘干干燥后再放置于水中震荡，以去除掉其中的PVP相，得到PVDF多级孔洞纤维薄膜，最后将PVDF多级孔洞纤维薄膜浸泡于不同负载相溶液中，以实现PVDF多级孔洞纤维薄膜功能的不同；整个制备方法反应条件温和、设备通用，制备成本低；
2、本发明提供一种多功能PVDF多级孔洞纤维薄膜的制备方法，先采用静电纺丝技术作为薄膜制备工艺，静电纤维出丝、相互搭接形成大量孔洞，得到多孔的PVDF/PVP复合纤维薄膜；进一步，通过去除PVP相后，使得单根纤维上具有纳米级小孔，从而得到具有多级孔洞结构的PVDF薄膜，相比于现有的商业PVDF膜，增大了材料的孔隙率和比表面积；该PVDF多级孔洞纤维薄膜为类海绵状结构的PVDF纳米多级孔洞纤维薄膜，且具有双亲性(亲水/亲油)，在此基础上对其进行表面改性，通过在PVDF薄膜的纤维上黏附不同的负载相，实现了PVDF多级孔洞纤维薄膜的多功能化；如负载相溶液为γ-Fe2O3与甘氨酸混合物水溶液，可使得PVDF多级孔洞纤维薄膜具有油水分离和油吸附功能；负载相溶液为多巴胺Tris溶液，均匀地负载了聚多巴胺纳米颗粒，可使其具有染料吸附、重金属吸附功能；负载相溶液为多巴胺Tris溶液和AgNO3溶液两种或多巴胺Tris溶液和CuSO4溶液两种时，可使其具有抗菌功能；
3、本发明采用静电纺丝技术作为PVDF多级孔洞纤维薄膜制备工艺，能通过调控电压等外场作用调控纤维结构参数，如纤维直径，纤维间空隙大小，薄膜孔隙率等；
4、本发明提供的多功能PVDF多级孔洞纤维薄膜为类海绵状结构的纳米级多级孔洞纤维薄膜，纤维表面粗糙多级孔洞且有许多纳米级别的凸起，纤维的直径可达300nm左右，同时具有双亲性。
附图说明
图1为本发明实施例1所制得的多功能PVDF多级孔洞纤维薄膜SEM图一；
图2为本发明实施例1所制得的多功能PVDF多级孔洞纤维薄膜SEM图二；
图3为本发明实施例1所制得的多功能PVDF多级孔洞纤维薄膜SEM图三；
图4为本发明对比例1所制得的多功能PVDF多级孔洞纤维薄膜SEM图；
图5为本发明对比例2所制得的多功能PVDF多级孔洞纤维薄膜SEM图；
图6为本发明实施例1所制得的多功能PVDF多级孔洞纤维薄膜对亚甲基蓝的吸附量结果图；
图7为本发明实施例1所制得的多功能PVDF多级孔洞纤维薄膜对Cr6+重金属的吸附量结果图。
具体实施方式
下面通过具体实施例对本发明作进一步说明，应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
本实施例1提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，具体过程为：将1.8g PVDF和1.8g PVP同时溶解在5ml N,N-二甲基甲酰胺(DMF)和5ml四氢呋喃(THF)的混合溶剂中(混合溶剂共计10ml)，在55℃的水浴锅中搅拌6小时，得到均匀澄清的静电纺丝前驱液；将静电纺丝前驱液放入注射器中，在电压为13kv，收集距离为15cm，注射泵的注射速度为30μl/min，环境温度为25℃，环境湿度为40％的条件下，进行静电纺丝，得到PVDF/PVP复合纤维薄膜；再将PVDF/PVP复合纤维薄膜在60℃烘箱中干燥6小时后，放入装有蒸馏水的500ml烧杯中，将烧杯放入恒温震荡中，在温度为80℃，转速为180rpm的条件下，恒温震荡4天，在这四天中，每天换水，并把膜放在超声机中超声30min，四天后，将膜取出，放入冷冻干燥机中干燥12小时，得到PVDF多级孔洞纤维薄膜；取40ml的pH＝8.5的Tris缓冲液，往其中加入20mg多巴胺(DA)，搅拌1min，得到均匀的浓度为0.5mg/ml的多巴胺Tris溶液，再取上述制得的10mg PVDF多级孔洞纤维膜放入质量浓度为0.5mg/ml的多巴胺Tris溶液中，在温度为25℃，转速为180rpm的条件下恒温震荡24小时，取出膜后，超声清洗10min，将膜放入冷冻干燥机中干燥，制得具有染料吸附、重金属吸附功能的PVDF多级孔洞纤维薄膜(PVDF/PDA多级孔洞纤维薄膜)。
实施例2
本实施例2提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，与实施例1的区别仅在于：将实施例1中0.5mg/ml的多巴胺Tris溶液替换为γ-Fe3O4与甘氨酸混合物水溶液制得具有油水分离和油吸附功能的PVDF多级孔洞纤维薄膜，其余步骤及参数均相同，其中γ-Fe2O3与甘氨酸的质量浓度分别为0.15g/ml和1mg/ml。
实施例3
本实施例3提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，与实施例1的区别仅在于：将实施例1中0.5mg/ml的多巴胺Tris溶液替换为0.5mg/ml的多巴胺Tris溶液和AgNO3(50mM)溶液，即将PVDF多级孔洞纤维膜放入多巴胺Tris溶液中，在温度为25℃，转速为180rpm的条件下恒温震荡24小时，取出膜后，再将PVDF多级孔洞纤维膜放入AgNO3(50mM)溶液中，在避光条件下，温度为25℃，转速为180rpm的条件下恒温震荡4小时，制得具有抗菌功能的PVDF多级孔洞纤维薄膜(PVDF/PDA-Ag多级孔洞纤维薄膜)，其余步骤及参数均相同。
对比例1
本对比例1提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，与实施例1的区别仅在于：多巴胺Tris溶液中多巴胺的质量浓度为1mg/ml，其余步骤及参数均相同。
对比例2
本对比例2提供一种多功能PVDF多级孔洞纤维薄膜及其制备方法，与实施例1的区别仅在于：多巴胺Tris溶液中多巴胺的质量浓度为0.2mg/ml，其余步骤及参数均相同。
实验例1
为了考察本发明制得的多功能PVDF多级孔洞纤维薄膜的膜形态和结构特征，本实验例1对实施例1和对比例1-2所得的PVDF多级孔洞纤维薄膜进行扫描电子显微镜(SEM)观察并测试，结果如1-5所示。
由图1-3可知，实施例1所制得的PVDF多级孔洞纤维薄膜上聚多巴胺(PDA)均匀地负载在PVDF多级孔洞纤维表面，纤维的直径是可达300nm左右，且具有大量多级孔洞结构，增大了材料的孔隙率和比表面积，聚多巴胺并且没有堵塞电纺纤维与纤维之间搭接形成的孔洞，也没有堵塞单根PVDF多级孔洞纤维表面的孔洞，且纤维表面粗糙多级孔洞且有许多纳米级别的凸起；由图4可知，对比例1所制得的PVDF多级孔洞纤维薄膜上PDA将PVDF多级孔洞纤维薄膜几乎完全包裹住，严重降低了膜的孔隙率，导致纤维膜失去亲油性能；由图5可知，PVDF多级孔洞纤维薄膜上几乎没有负载上聚多巴胺颗粒。
实验例2
为了考察本发明制得的多功能PVDF多级孔洞纤维薄膜的染料吸附性能和重金属吸附性能，将实施例1所制得的PVDF/PDA多级孔洞纤维薄膜分别单独浸泡在不同浓度的亚甲基蓝溶液和不同PH值的Cr6+溶液中(Cr6+溶液浓度为200mg/L)，恒温震荡仪中震荡24h后，测得PVDF/PDA多级孔洞纤维薄膜对亚甲基蓝和Cr6+重金属的吸附量，实验结果如图6-7所示。由图6可知，本实施例1所制得的PVDF/PDA多级孔洞纤维薄膜对20mg/L的亚甲基蓝溶液中亚甲基蓝的吸附量可达48.1mg/g；由图7可知，当PH＝2时，PVDF/PDA多级孔洞纤维薄膜对Cr6+重金属的吸附量约为43mg/g。说明本发明制得的PVDF/PDA多级孔洞纤维薄膜具有优异的染料吸附、重金属吸附功能。
实验例3
本实验例3考察了静电纺丝工艺参数的变化，对本发明所制得的PVDF多级孔洞纤维薄膜的影响。在实施例1的基础上，具体的静电纺丝工艺参数如表1所示。
表1静电纺丝工艺参数表
实验结果表明，当只改变电压时，电压低于12kv，由静电纺丝制备得到的PVDF多级孔洞纤维薄膜是串珠状纤维间空隙变小；电压高于18kv，由静电纺丝制备得到的PVDF多级孔洞纤维薄膜的直径很细，远小于300nm，纤维间空隙变大；当只改变注射速度时，注射速度小于25μl/min，由静电纺丝制备得到的PVDF多级孔洞纤维薄膜的纤维直径很细，注射速度继续减小时，甚至出现喷射不连续纤维的现象，无法得到直径均匀的纤维，纤维间空隙变大；注射速度大于35μl/min，也无法得到直径均匀的纤维，当注射速度逐渐增加，会得到微米级的纤维，纤维间空隙变小；当只改变收集距离时，减小收集距离，溶剂挥发的路程和时间变短，小于12cm时，会导致纤维间粘结，所制备得到的纤维直径也会增加，纤维间空隙变小；增大收集距离，所制备得到的纤维直径变细，纤维间空隙变大，当大于17cm时，无法得到连续的纤维。
以上内容仅仅是对本发明结构所作的举例和说明，所属本领域的技术人员不经创造性劳动即对所描述的具体实施例做的修改或补充或采用类似的方式替代仍属本专利的保护范围。
Claims (9)
1.一种多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，具体包括以下步骤：
步骤(1)：将聚偏氟乙烯和聚乙烯吡咯烷酮同时加入溶剂中，搅拌均匀，得到静电纺丝前驱液；
步骤(2)：将步骤(1)所得的静电纺丝前驱液进行静电纺丝，制备得到PVDF/PVP复合纤维薄膜；
步骤(3)：将步骤(2)所得的PVDF/PVP复合纤维薄膜烘干干燥后浸泡于水中，然后经恒温震荡，超声清洗，冷冻干燥，制得PVDF多级孔洞纤维薄膜；
步骤(4)：将步骤(3)所得的PVDF多级孔洞纤维薄膜浸泡于负载相溶液中，恒温震荡，制得多功能PVDF多级孔洞纤维薄膜。
2.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(1)中聚偏氟乙烯和聚乙烯吡咯烷酮的质量比为1:1～5。
3.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(1)中溶剂为二甲基甲酰胺、四氢呋喃、二甲亚砜和二甲基乙酰胺中的一种或两种以上。
4.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(1)中搅拌时温度为50℃-80℃，搅拌时间为6-8小时。
5.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(2)中静电纺丝工艺参数为电压12-18kv，收集距离12-17cm，注射速度25～35μl/min，环境温度20℃～30℃，环境湿度40％～60％。
6.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(3)中恒温温度为70～90℃；震荡时间为3～7天，间隔24小时换水一次。
7.如权利要求1所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述步骤(4)中负载相溶液为γ-Fe2O3与甘氨酸混合物水溶液、多巴胺Tris溶液、AgNO3溶液和CuSO4溶液中的一种或几种。
8.如权利要求7所述的多功能PVDF多级孔洞纤维薄膜的制备方法，其特征在于，所述γ-Fe2O3与甘氨酸混合物水溶液中γ-Fe2O3与甘氨酸的质量浓度分别为0.06～0.84g/ml和0.5～2mg/ml；所述多巴胺Tris溶液中多巴胺的质量浓度为0.5～2mg/ml，Tris溶液pH为8～9；所述AgNO3溶液中AgNO3浓度为40～60mM；所述CuSO4溶液中CuSO4浓度为40～60mM。
9.权利要求1-8任一项所述的多功能PVDF多级孔洞纤维薄膜的制备方法制得的多功能PVDF多级孔洞纤维薄膜。
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