CN114130210A - 一种层层自组装抗菌水凝胶过滤膜的制备方法 - Google Patents
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Abstract
本发明报道一种层层自组装抗菌水凝胶过滤膜的制备方法。用铜氨溶液溶解海藻酸钠得到混合水溶液A，同时配制酸性的阳离子聚电解质水溶液B。将基膜浸泡到水溶液B中使膜表面涂覆一层阳离子聚电解质，然后将其浸泡到混合水溶液A中，海藻酸钠与水溶液B中的聚电解质自组装成络合物，铜氨溶液遇酸释放出铜离子，交联海藻酸钠，得到铜离子交联的大分子络合物水凝胶膜；接下来将膜浸泡到水溶液B中，然后再次将膜浸泡到水溶液A中，如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。大分子自组装和铜离子交联的共同作用提高了膜的稳定性，铜离子使膜具有良好的抗菌性。该膜在污水处理、染料脱盐、抗生素去除等领域有广泛的应用前景。
Description
技术领域
本发明涉及一种层层自组装抗菌水凝胶过滤膜的制备方法，属于功能材料和膜分离领域。
本发明涉及废旧铜氨溶液、过滤膜、水凝胶等技术领域。具体涉及一种层层自组装抗菌水凝胶过滤膜的制备方法。
背景技术
膜分离技术无相态变化、工艺简单、效率高、节能环保，因其独特的优势和广泛的适用性，逐渐发展成为解决全球性水资源短缺以及水环境污染的最具前景的水处理技术之一，产生了巨大的社会和经济效益。随着膜分离技术的不断优化和改进，膜材料的需求也在不断增加，越来越多的膜材料被大量投入使用，是膜分离技术处理工艺的核心，对于污水处理效果、工艺经济性能等具有重要影响。因此，寻找一种性能优越、制备简便的过滤膜是膜分离技术需要攻关的重点方向，也成为推动膜分离技术的可持续发展的重要因素之一。
水凝胶是由亲水聚合物网络组成的材料，可以在保持其结构的同时保持大量水分，由于其具有柔软、弹性、设计灵活、良好的亲水性等特点，因此应用广泛，是制备过滤膜的理想材料。海藻酸钠(SA)是一种从褐藻类物质中提取的线性多糖，其水溶液具有较高的粘性。海藻酸钠作为一种天然存在的生物聚合物，由于其形成凝胶条件温和、无毒、可生物降解、成本低，成为在吸附水中污染物应用领域中颇有前景的物质。根据海藻酸钠可以凝胶、成膜的特性，海藻酸钠与钙离子可通过离子交联形成水凝胶。赵孔银等制备了一系列的海藻酸钙基水凝胶过滤膜【发明专利ZL201310424398.7，ZL201310424399.1，ZL201310424397.2】。另外，还可以将其与其他金属离子反应来制备凝胶，铜类化合物就是成胶的常用交联剂。
层层自组装是指分子与分子之间或分子中的某一结构与另一结构的识别，在非共价键(氢键、范德华力、静电力、疏水作用力等)的作用下自发组装成具有特殊结构的分子薄膜的过程。层层自组装制备方法简单，制备过程不需要复杂的设备；成膜物质丰富，聚电解质材料既可以是天然蛋白质、纤维素、多糖类组织，也可以是人工合成的高分子聚合物。另外，其条件可控，组装过程不受基材大小和材料的控制，可在分子水平控制组装体系的结构和性质。基于以上种种优点，层层自组装方法成为制备复合膜越来越热门的技术之一。秦威利用一种简便的方法，结合层层自组装技术，以水解聚丙烯腈为基膜，将带有正电荷的壳聚糖作为聚电解质阳离子，带有负电荷的海藻酸钠作为聚电解质阴离子，以氯化钙为离子交联剂，制备了复合膜进行染料脱盐【天津工业大学硕士毕业论文，基于壳聚糖/海藻酸钠层层自组装复合膜的制备及其性能研究，2021】。
铜氨溶液是一种古老的纤维素溶剂，可用于制备人造纤维、中空纤维、无纺布等再生纤维素制品，但利用纤维素铜氨溶液制备其它功能性新材料的研究却鲜有报道。纤维素铜氨溶液中含有大量的铜，在制备铜复合材料方面具有巨大的成本和应用优势。
本发明报道一种层层自组装抗菌水凝胶过滤膜的制备方法。用铜氨溶液溶解海藻酸钠得到混合水溶液A，同时配制酸性的阳离子聚电解质水溶液B。将基膜浸泡到水溶液B中使膜表面涂覆一层阳离子聚电解质，然后将其浸泡到混合水溶液A中，海藻酸钠与水溶液B中的聚电解质自组装成络合物，铜氨溶液遇酸释放出铜离子，交联海藻酸钠，得到铜离子交联的大分子络合物水凝胶膜；接下来将膜浸泡到水溶液B中，然后再次将膜浸泡到水溶液A中，如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。大分子自组装和铜离子交联的共同作用提高了膜的稳定性，铜离子使膜具有良好的抗菌性。该膜在污水处理、染料脱盐、抗生素去除等领域有广泛的应用前景。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是海藻酸钙水凝胶不抗菌、稳定性差、水凝胶膜厚度大、通量低等问题。
本发明解决所述海藻酸钙水凝胶不抗菌、稳定性差、水凝胶膜厚度大、通量低等问题的技术方案是提供一种层层自组装抗菌水凝胶过滤膜的制备方法。
本发明提供了一种层层自组装抗菌水凝胶过滤膜的制备方法，其特征是包括以下步骤：
a)首先配制铜氨溶液，在铜氨溶液中加入增强剂和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为0.05％-5％，增强剂的质量百分比浓度为0.01％-5％的混合物水溶液A，消泡后备用；
b)配制pH值为酸性，质量百分比浓度为0.05％-5％的阳离子聚电解质水溶液B；
c)以水解后表面带羧基的高分子膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层阳离子聚电解质，将涂覆阳离子聚电解质的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与阳离子聚电解质发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层阳离子聚电解质，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
本发明所述的增强剂为二氧化钛、羧化多壁碳纳米管、氧化石墨烯、埃洛石中的任意一种或两种及以上混合物；所述的阳离子聚电解质为壳聚糖、聚乙烯亚胺、聚乙烯基咪唑、聚二甲基二烯丙基氯化铵中的任意一种或两种及以上混合物；所述的高分子膜为聚丙烯腈膜、聚砜膜、聚偏氟乙烯膜中的任意一种。
本发明获得的膜在污水处理、染料脱盐、染料截留、抗生素去除等领域有广泛的应用前景。
具体实施方式
下面介绍本发明的具体实施例，但本发明不受实施例的限制。
实施例1.
d)首先配制铜氨溶液，在铜氨溶液中加入二氧化钛和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为0.05％，二氧化钛的质量百分比浓度为0.01％的混合物水溶液A，消泡后备用；
e)配制pH值为酸性，质量百分比浓度为0.05％的壳聚糖水溶液B；
f)以水解后表面带羧基的聚丙烯腈膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层壳聚糖，将涂覆壳聚糖的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与壳聚糖发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层壳聚糖，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
实施例2.
d)首先配制铜氨溶液，在铜氨溶液中加入羧化多壁碳纳米管和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为1.00％，羧化多壁碳纳米管的质量百分比浓度为0.50％的混合物水溶液A，消泡后备用；
e)配制pH值为酸性，质量百分比浓度为1.00％的聚乙烯亚胺水溶液B；
f)以水解后表面带羧基的聚丙烯腈膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚乙烯亚胺，将涂覆聚乙烯亚胺的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与聚乙烯亚胺发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚乙烯亚胺，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
实施例3.
d)首先配制铜氨溶液，在铜氨溶液中加入氧化石墨烯和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为2.00％，氧化石墨烯的质量百分比浓度为1.00％的混合物水溶液A，消泡后备用；
e)配制pH值为酸性，质量百分比浓度为2.00％的聚乙烯基咪唑水溶液B；
f)以水解后表面带羧基的聚砜膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚乙烯基咪唑，将涂覆聚乙烯基咪唑的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与聚乙烯基咪唑发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚乙烯基咪唑，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
实施例4.
d)首先配制铜氨溶液，在铜氨溶液中加入埃洛石和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为5.00％，埃洛石的质量百分比浓度为5.00％的混合物水溶液A，消泡后备用；
e)配制pH值为酸性，质量百分比浓度为5.00％的聚二甲基二烯丙基氯化铵水溶液B；
f)以水解后表面带羧基的聚偏氟乙烯膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚二甲基二烯丙基氯化铵，将涂覆聚二甲基二烯丙基氯化铵的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与聚二甲基二烯丙基氯化铵发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层聚二甲基二烯丙基氯化铵，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
Claims (5)
1.一种层层自组装抗菌水凝胶过滤膜的制备方法，其特征是包括以下步骤：
a)首先配制铜氨溶液，在铜氨溶液中加入增强剂和海藻酸钠，混合溶解分散均匀，得到海藻酸钠的质量百分比浓度为0.05％-5％，增强剂的质量百分比浓度为0.01％-5％的混合物水溶液A，消泡后备用；
b)配制pH值为酸性，质量百分比浓度为0.05％-5％的阳离子聚电解质水溶液B；
c)以水解后表面带羧基的高分子膜为基膜，将基膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层阳离子聚电解质，将涂覆阳离子聚电解质的基膜浸泡到步骤a)得到的混合物水溶液A中，海藻酸钠与阳离子聚电解质发生自组装形成薄膜，同时，铜氨溶液遇到酸释放出铜离子，铜离子与海藻酸钠交联生成海藻酸铜水凝胶，提高了自组装薄膜的稳定性；将膜取出用去离子水漂洗，去除膜表面未反应的海藻酸钠和铜氨溶液，再次将膜浸泡到步骤b)得到的混合物水溶液B中，使基膜表面涂覆一层阳离子聚电解质，然后再将膜浸泡到混合物水溶液A中，将膜取出用去离子水漂洗；如此重复多次，得到一种层层自组装抗菌水凝胶过滤膜。
2.如权利要求1所述一种层层自组装抗菌水凝胶过滤膜的制备方法，其特征是所述的增强剂为二氧化钛、羧化多壁碳纳米管、氧化石墨烯、埃洛石中的任意一种或两种及以上混合物。
3.如权利要求1所述一种层层自组装抗菌水凝胶过滤膜的制备方法，其特征是所述的阳离子聚电解质为壳聚糖、聚乙烯亚胺、聚乙烯基咪唑、聚二甲基二烯丙基氯化铵中的任意一种或两种及以上混合物。
4.如权利要求1所述一种层层自组装抗菌水凝胶过滤膜的制备方法，其特征是所述的高分子膜为聚丙烯腈膜、聚砜膜、聚偏氟乙烯膜中的任意一种。
5.根据权利要求1所述的制备方法获得的膜在污水处理、染料脱盐、抗生素去除中的应用。
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| CN110960992A (zh) * | 2019-12-23 | 2020-04-07 | 济南大学 | 一种含银纳米粒子的海藻酸钙抗菌过滤膜的制备方法 |
| CN111100321A (zh) * | 2019-12-31 | 2020-05-05 | 西安建筑科技大学 | 一种对聚氨酯表面改性促进挂膜效果的方法 |
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| CN110960992A (zh) * | 2019-12-23 | 2020-04-07 | 济南大学 | 一种含银纳米粒子的海藻酸钙抗菌过滤膜的制备方法 |
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