CN105924660B - 一种扩散渗析用阳离子型橡塑复合膜的制备方法 - Google Patents
一种扩散渗析用阳离子型橡塑复合膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种扩散渗析用阳离子型橡塑复合膜的制备方法，通过在线聚合的方式将所有的反应物，包括功能单体甲基丙烯酸(MAA)和氯磺化聚乙烯橡胶(CSM)，都溶解在甲苯溶剂中，形成均勾的溶液，然后引发聚合、交联反应，反应结束后，加入正硅酸乙酯(TEOS)或硅烷偶联剂混合，制备出一系列不同性质的扩散渗析用杂化阳离子膜。本发明制备的扩散渗析专用阳离子膜的水含量(WR)为13.4％～20.8％，膜在2M 65℃氢氧化钠溶液中浸泡60h后的质量损失率为4.8％～9.5％，OH‑渗析系数UOH为0.008～0.019m/h，分离系数为17.5～23.2。
Description
一、技术领域
本发明涉及一种阳离子膜的制备方法，具体地说是一种扩散渗析用阳离子型橡塑复合膜的制备方法，属于膜技术领域。
二、背景技术
离子交换膜，简称离子膜，是一种含离子基团的、对溶液中的离子具有选择透过能力的高分子膜，目前广泛应用于海水和海苦咸水淡化、食品、医药、化工、生物技术、工业废水处理和生活污水、酸碱回收等过程。例如，离子膜应用于扩散渗析(Diffusion Dialysis，DD)过程，可以有效分离和回收酸性或碱性废液。然而扩散渗析回收碱的技术虽然己经有所发展和突破，其应用范围远不及扩散渗析回收酸的技术。一方面是碱性废水成分复杂，导致碱的回收效率较低；另一方面，是缺乏高性能的阳离子扩散渗析膜。目前，文献关于阳离子扩散渗析膜的研究工作并不多，而可用于扩散渗析的商品化阳离子交换膜种类也较少。高性能阳离子交换膜的缺乏大大限制了扩散渗析回收碱技术的发展。
当前回收碱所用的离子膜一般为有机无机杂化膜，这类膜多由亲水性的聚合物材料(PVA、SPPO)和多硅共聚物构成，它们的共同点是拥有良好的碱通量，然而，在耐碱性方面始终是不尽人意，高温耐碱性膜的缺失，使得扩散渗析回收碱技术难以有重大突破。
氯磺化聚乙烯橡胶(CSM)为饱和橡胶，具有耐臭氧、耐紫外线、耐酸碱和耐热等一系列宝贵性能，力学性能良好，在没有补强剂的情况下具有17.7MPa的拉伸强度。选用CSM为铸膜基质，利用它良好的耐酸碱和力学性能等性能，可以应用到高温扩散渗析回收碱方面来。
三、发明内容
本发明旨在提供一种扩散渗析用阳离子型橡塑复合膜的制备方法，通过构建一种半互穿网络(sIPN)的方法，制备出新型扩散渗析用阳离子膜，以提高阳离子膜的离子通量及耐碱性。
本发明选取CSM这种耐碱性能优异的橡胶为铸膜基质，同时选取带有功能基团(-COOH)的单体甲基丙烯酸(MAA)为离子交换基团，二者采用半互穿网络结构(sIPNs)的方式解决共混遇到的相容性问题，优化二者之间的优异性能，开发出一种耐碱性阳离子交换膜，拓宽膜材料的应用范围，突破扩散渗析膜材料的技术发展瓶颈。
本发明扩散渗析用阳离子型橡塑复合膜的制备方法，包括如下步骤：
1、有机膜液的制备：将2g CSM溶于甲苯中获得CSM的甲苯溶液，将单体甲基丙烯酸(MAA)加入CSM的甲苯溶液中，在引发剂和交联剂的存在下聚合得到以PMAA聚合物网络为骨架、CSM线型高分子链均匀分散在其中的sIPNs结构，即CSM-PMAA铸膜液；
2、有机无机杂化：将正硅酸乙酯(TEOS)或硅烷偶联剂滴加至步骤1获得的CSM-PMAA铸膜液中，于80℃下密封搅拌1小时，脱泡后获得杂化铸膜液；
3、成膜：将所述杂化铸膜液在干净的玻璃板上流延成膜，干燥后升温至130℃并保温5小时，获得扩散渗析用阳离子型橡塑复合膜。
步骤1中氯磺化聚乙烯(CSM)与甲基丙烯酸(MAA)的质量比为2:1。
步骤1中所述引发剂为偶氮二异丁腈(AIBN)，添加量为甲基丙烯酸(MAA)质量的1％；所述交联剂为二乙烯基苯(DVB)，添加量为100μL。
步骤1中聚合反应的温度为80℃，时间为5小时。
步骤1中甲苯的体积为50-60mL。
步骤2中所述脱泡是在室温下静置2-3小时。
步骤2中硅烷偶联剂为KH550。
步骤2中正硅酸乙酯或硅烷偶联剂的添加量为CSM与MAA质量之和的10％-30％。
步骤3中干燥温度为60℃。
步骤3中升温至130℃的升温速率为10℃/h。
当KH550取0.6g时，膜的分离效果最佳。
本发明以氯磺化聚乙烯橡胶为膜基质，辅以带功能基团羧基(-COOH)的聚甲基丙烯酸，二者以半互穿网络结构物理缠结一起，优于一般共混方式所得到的膜结构。通过对膜进行扩散渗析测试，发现膜的OH-渗析系数UOH为0.01-0.02mol/h左右，WO42-的渗析系数很高，致使膜的分离系数在11-13左右之间，通过对膜离子交换能力(IEC)，含水量(WR)等系列测试，得出出现这种现象的原因是CSM本身结构问题。未交联的CSM分子链之间的自由体积大，与PMAA之间有很大的间隙，导致膜的致密度不高，对WO42-水和离子的阻碍力不足。解决这种问题的方式有两种：一是可以通过对CSM橡胶进行硫化，得到三维稳定结构的CSM，但其存在弊端，如因交联度高而导致膜内离子流动性差，同时本发明是用溶液共混的方式，不适合橡胶的传统的硫化工艺。二是通过加入一些有机偶联剂，水解缩合得到无机网络结构来提高膜的致密性。
本发明通过对膜的耐碱性，含水量，扩散渗析，膜的分离系数一系列的测试，得出膜在耐碱性方面性能优异，有望应用于高温下的扩散渗析回收碱的过程。
四、具体实施方式
实施例1：
1、有机膜液的制备：将2g CSM溶于30mL甲苯中获得CSM的甲苯溶液，将1g单体MAA溶于10mL甲苯中，随后与CSM的甲苯溶液混合得混合液，通入氮气，将所述混合液升温至50℃并加入交联剂DVB和引发剂AIBN，升温至80℃搅拌反应5小时，得到CSM-PMAA铸膜液；引发剂的添加量为MAA质量的1％，交联剂的添加量为100μL。
2、有机无机杂化：将0.3g TEOS滴加至步骤1获得的CSM-PMAA铸膜液中，于80℃下密封搅拌1小时，室温下静置2-3小时脱泡后获得杂化铸膜液；
3、成膜：将所述杂化铸膜液在干净的玻璃板上流延成膜，60℃下干燥，干燥后以60℃为起始温度升温至130℃并保温5小时，升温速率为10℃/h，获得扩散渗析用阳离子型橡塑复合膜。
4、性能测试：
a、水含量(WR)测试：称量0.15-0.2g样品，记录重量为m1，室温浸泡在蒸馏水中2天，尽量不让样品浮在水面；取出样品，快速用滤纸吸干表面的水份，快速称量，记重量为m2；WR＝(m2-m1)*100％/m1平行测定两个样品，取平均值。
b、抗碱能力测试：称量0.15-0.2g样品，记录重量为m1,浸泡在65℃2M NaOH中60h，再浸泡水中，隔几个小时换水一次，约12h/4次，以洗去膜上残留的碱液；取出样品，用滤纸快速吸干样品表面的水分，快速称重，记为m2,再将样品45-65℃烘干，称重，重量记为m3。
损失率＝(m1-m3)*100％/m1平行测定两个样品，取平均值。
c、扩散渗析过程测试：扩散渗析池是由左右两半室组成，测试时，把膜固定在扩散渗析池中间，然后在扩散渗析池两侧各加100ml废液和100ml蒸馏水，同时通电搅拌以减小浓差极化的影响，1h后停止搅拌，分别取出渗析液和水侧液进行测定。测试及计算方法见《膜科学杂志》(Journal of Membrane Science 356(2010)96–104)。
经测试，本实施例所获得的扩散渗析用阳离子型橡塑复合膜的性能参数为：膜的水含量(WR)为16.54％，膜的损失率为4.85％，-渗析系数UOH为0.019m/h，分离系数S为21.38。
实施例2：
本实施例的制备方法同实施例1，不同的是本实施例中CSM与甲基丙烯酸(MAA)质量之和与正硅酸乙酯质量比为1:0.3(即CSM添加量2g，MAA添加量1g，TEOS添加量0.9g)。
经测试，本实施例所获得的扩散渗析用阳离子型橡塑复合膜的性能参数为：膜的水含量(WR)为20.83％，膜的损失率为4.78％，渗析系数UOH为0.016m/h，分离系数为23.18。
实施例3：
1、有机膜液的制备：将2g CSM溶于30mL甲苯中获得CSM的甲苯溶液，将1g单体MAA溶于10mL甲苯中，随后与CSM的甲苯溶液混合得混合液，通入氮气，将所述混合液升温至50℃并加入交联剂DVB和引发剂AIBN，升温至80℃搅拌反应5小时，得到CSM-PMAA铸膜液；引发剂的添加量为MAA质量的1％，交联剂的添加量为100μL。
2、有机无机杂化：将0.3g KH550滴加至步骤1获得的CSM-PMAA铸膜液中，于80℃下密封搅拌1小时，室温下静置2-3小时脱泡后获得杂化铸膜液；
3、成膜：将所述杂化铸膜液在干净的玻璃板上流延成膜，60℃下干燥，干燥后以60℃为起始温度升温至130℃并保温5小时，升温速率为10℃/h，获得扩散渗析用阳离子型橡塑复合膜。
经测试，本实施例所获得的扩散渗析用阳离子型橡塑复合膜的性能参数为：膜的水含量(WR)为13.43％，膜的损失率为8.176％，渗析系数UOH为0.018m/h，分离系数为22.59。
实施例4：
本实施例的制备方法同实施例3，不同的是KH550的添加量为0.6g。
经测试，本实施例所获得的扩散渗析用阳离子型橡塑复合膜的性能参数为：膜的水含量(WR)为20.3％，膜的损失率为8.139％，渗析系数UOH为0.011m/h，分离系数为23.87。
实施例5：
本实施例的制备方法同实施例3，不同的是KH550的添加量为0.9g。
经测试，本实施例所获得的扩散渗析用阳离子型橡塑复合膜的性能参数为：膜的水含量(WR)为15.36％，膜的损失率为9.547％，渗析系数UOH为0.008m/h，分离系数为17.54。
Claims (9)
1.一种扩散渗析用阳离子型橡塑复合膜的制备方法，其特征在于包括如下步骤：
(1)有机膜液的制备：将2g CSM溶于甲苯中获得CSM的甲苯溶液，将单体MAA加入CSM的甲苯溶液中，在引发剂和交联剂的存在下聚合得到以PMAA聚合物网络为骨架、CSM线型高分子链均匀分散在其中的sIPNs结构，即CSM-PMAA铸膜液；CSM与MAA的质量比为2:1；
(2)有机无机杂化：将正硅酸乙酯或硅烷偶联剂滴加至步骤(1)获得的CSM-PMAA铸膜液中，于80℃下密封搅拌1小时，脱泡后获得杂化铸膜液；
(3)成膜：将所述杂化铸膜液在干净的玻璃板上流延成膜，干燥后升温至130℃并保温5小时，获得扩散渗析用阳离子型橡塑复合膜。
2.根据权利要求1所述的制备方法，其特征在于：
步骤(1)中所述引发剂为偶氮二异丁腈，添加量为MAA质量的1％；所述交联剂为二乙烯基苯，添加量为100μL。
3.根据权利要求1所述的制备方法，其特征在于：
步骤(1)中聚合反应的温度为80℃，时间为5小时。
4.根据权利要求1所述的制备方法，其特征在于：
步骤(1)中甲苯的体积为50-60mL。
5.根据权利要求1所述的制备方法，其特征在于：
步骤(2)中所述脱泡是在室温下静置2-3小时。
6.根据权利要求1所述的制备方法，其特征在于：
步骤(2)中硅烷偶联剂为KH550。
7.根据权利要求1所述的制备方法，其特征在于：
步骤(2)中正硅酸乙酯或硅烷偶联剂的添加量为CSM与MAA质量之和的10％-30％。
8.根据权利要求1所述的制备方法，其特征在于：
步骤(3)中干燥温度为60℃。
9.根据权利要求1所述的制备方法，其特征在于：
步骤(3)中升温至130℃的升温速率为10℃/h。
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