CN113578062B - 持久亲水均孔超滤膜的制备方法 - Google Patents

持久亲水均孔超滤膜的制备方法 Download PDF

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CN113578062B
CN113578062B CN202110843413.6A CN202110843413A CN113578062B CN 113578062 B CN113578062 B CN 113578062B CN 202110843413 A CN202110843413 A CN 202110843413A CN 113578062 B CN113578062 B CN 113578062B
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CN113578062A (zh
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武春瑞
厍景国
高海富
陈小乐
宋姿萍
吕晓龙
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Tianjin Polytechnic University
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Abstract

本发明提出一种持久亲水均孔超滤膜的制备方法，首先，在聚合物膜材料的常规溶解条件下，引发、完成亲水链在聚合物链上的接枝反应，即溶解同步亲水化；进而，在该聚合物溶液(初生态膜)进入凝固浴后，利用凝固浴引发该亲水链间的交联反应，同步调控相分离成膜进程，即亲水链交联协同相分离。通过交联结构干涉聚合物分子链运动、相分离固化成膜进程，形成较均匀、规整的聚合物网络结构，实现超滤膜孔结构均一化。该方法反应条件温和，制备方法简单，在制膜过程中实现超滤膜亲水化及孔径均一化，促进超滤膜渗透通量、分离性能与抗污染能力同步提升。

Description

持久亲水均孔超滤膜的制备方法
技术领域
本发明属于过滤膜领域，涉及超滤膜，尤其是一种持久亲水均孔超滤膜的制备方法。
背景技术
聚氯乙烯，聚偏氟乙烯，聚偏氟乙烯-三氟氯乙烯等是超滤过程中被广泛采用的膜材料，具有优良的耐酸碱性、化学稳定性、机械稳定性以及耐候性等特点。但是，由于自身存在的疏水性，使其在使用过程中，易出现污染和通量低等问题，限制了它们的应用，因此，通常会通过共混的方法引入亲水材料来增加超滤膜的亲水性。但是，亲水材料的引入，增加了聚合物的亲水性，使分子链与凝固剂的亲和性增强，亲水分子链向凝固浴形成外延式生长，在膜表面形成开放孔；同时，由于亲水分子与膜材料间无稳定的化学键，亲水分子在使用过程中容易流失，造成膜性能的下降。
发明内容
本发明目的在于提供一种持久亲水均孔超滤膜的制备方法，通过溶解接枝亲水化-交联协同相分离的方法在制膜过程中同步实现膜材料亲水化和孔径均一化，促进超滤膜渗透通量、分离性能与抗污染能力同步提升。
为实现上述目的，本发明持久亲水均孔超滤膜的制备方法的具体技术方案如下：
本发明持久亲水均孔超滤膜的制备方法，包括以下步骤：
将具备反应位点的聚合物膜材料、反应性活性亲水分子、成膜致孔剂和溶剂，恒温搅拌，在聚合物膜材料常规溶解条件下完成亲水链接枝，形成铸膜液；然后，利用干-湿相分离法制备超滤膜，利用凝固浴引发亲水链间交联反应且固化成膜，即为成品超滤膜。
前述的持久亲水均孔超滤膜的制备方法，其中，所述铸膜液各组分的比例为：聚合物膜材料占铸膜液的重量百分比为13wt％～20wt％，溶剂占铸膜液的重量百分比为86wt％～75wt％，致孔剂占铸膜液重量百分比为0.1wt％～20wt％，反应活性分子占铸膜液的重量百分比为0.1wt％-20wt％，总量为100％。
该聚合物膜材料为聚氯乙烯、氯化聚氯乙烯、聚偏氟乙烯、聚偏氟乙烯-三氟氯乙烯共聚物中的一种或多种混合物；该致孔剂为分子量200～20000的聚乙二醇和聚乙烯吡咯烷酮中的一种或多种混合物；该溶剂为二甲基甲酰胺，二甲基亚砜和二甲基乙酰胺中的一种或多种混合物；所述成聚合物膜材料、致孔剂、溶剂和反应性活性亲水分子的恒温混合搅拌温度为40～80℃，恒温混合搅拌时间为2h～48h；所述的反应性活性亲水分子是指可以接枝在聚合物分子链上并且可以二次交联的亲水分子如：氨基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、氨基丙基甲基二甲氧基硅烷、氨基丙基甲基二乙氧基硅烷，二乙烯三胺丙基甲基二甲氧基硅烷、N-2-氨乙基-3-氨丙基三甲氧基硅烷、N-2-氨乙基-3-氨丙基二甲氧基硅烷、巯基丙基三乙氧基硅烷、巯基丙基三甲氧基硅烷、3-哌嗪基丙基二甲氧基硅烷等中的一种或两种以上的混合物；所述凝固浴是指氢氧化钠或者盐酸的水溶液，浓度保持在1wt％～30wt％，凝固浴温度控制在25℃～80℃。所述的超滤膜是指平板膜或者中空纤维膜中的一种。
超滤膜主要是通过孔径筛分作用去除水中的杂质，由于相分离过程的随机性，大部分超滤膜孔径分布相对较宽，限制分离膜的分离效率。从超滤膜形成的相分离原理分析，超滤膜分离孔径及分布主要受相分离过程中聚合物分子链在铸膜液中的迁移与固化进程，即聚合物胶束的形成、生长与固化等影响。如果能够在膜材料聚合物分子链/亲水接枝链中设置可被凝固剂体系激发的“锚点”，在相分离进程中，通过激发“锚点”，形成聚合物分子链间稳定的相互作用，从而将相对随机的聚合物胶束成核、成长过程转变为可控的聚合物网络形成与固化，实现聚合物链迁移、反应-交联网络形成与固化的较精确调节，将使超滤膜孔径均一化调控成为可能。
本发明基于聚氯乙烯、聚偏氟乙烯，聚偏氟乙烯-三氟氯乙烯等分子中含有C-X(X指F或者Cl等)键，可以作为原位接枝的反应位点，利用功能基团和膜材料分子链活性键的化学反应，在聚合物膜材料的常规溶解条件下，引发、完成亲水链在聚合物链上的接枝，即溶解同步亲水化实现膜材料持久亲水化；进而，在该聚合物溶液(初生态膜)进入凝固浴后，利用凝固浴引发该亲水链间的交联反应，同步调控相分离成膜进程，即亲水链交联协同相分离。通过交联结构干涉聚合物分子链运动、相分离固化成膜进程，形成较均匀、规整的聚合物网络结构，获得均匀孔结构。该方法在制膜过程中同步实现膜材料亲水化和孔径均一化，促进超滤膜渗透通量、分离性能与抗污染能力同步提升。
本发明的优点和有益效果：
1、本发明在聚合物膜材料溶解条件下实现了聚合物膜材料的持久亲水化；
2、本发明在相分离过程中利用凝固浴引发该亲水链间的交联反应，通过交联结构干涉聚合物膜材料分子链运动、相分离固化成膜进程，在超滤膜中形成较均匀、规整的聚合物网络结构，实现超滤膜孔结构均一化调控；
3、本发明通过使用溶解接枝亲水化-交联协同相分离的方法实现了超滤膜渗透通量、分离性能与抗污染能力同步提升。
附图说明
图1为本发明方法的原理图；
图2为不同活性亲水分子添加量超滤膜在溶剂中的溶解情况对比图；
图3为不同活性亲水分子添加量超滤膜孔径及孔径分布的对比图；
图4为不同活性分子添加量超滤膜抗污染性能对比图。
具体实施方式
为了更好地了解本发明的目的、结构及功能，下面对本发明一种高性能超滤膜制备方法做进一步详细的描述。
实施例1至11：
称取13wt％聚氯乙烯树脂(聚合物膜材料)，5wt％聚乙二醇200(致孔剂)，75wt％二甲基甲酰胺(溶剂)，并加入7wt％的反应性活性亲水分子，在40℃恒温搅拌48h至完全溶解形成均匀溶液，刮膜后放入具有交联因子的凝固浴中利用相转化的方法制备平板超滤膜。反应性活性亲水分子种类和凝固浴组成如表1所示，凝固浴温度为25℃。
表1添加不同反应活性分子对聚氯乙烯平板膜性能的影响
Figure BDA0003179692060000031
表1为铸膜液中添加不同反应活性分子对PVC超滤膜亲疏水性及抗污染性能的影响。其中实施例1为对照组，实施例2至11是通过在铸膜液中添加氨基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、氨基丙基甲基二甲氧基硅烷、氨基丙基甲基二乙氧基硅烷，二乙烯三胺丙基甲基二甲氧基硅烷、N-2-氨乙基-3-氨丙基三甲氧基硅烷、N-2-氨乙基-3-氨丙基二甲氧基硅烷、巯基丙基三乙氧基硅烷、巯基丙基三甲氧基硅烷、3-哌嗪基丙基二甲氧基硅烷在不同pH的去离子水中相转化制备的聚氯乙烯超滤膜。与对照组实施例1相比较，超滤膜的水接触角更低，在纯水运行300小时后水接触角保持稳定，并且超滤膜的通量恢复率与对照组相比较也有明显的提升，由此可证明通过在铸膜液中引入反应活性氨分子后超滤膜亲水性提升，并获得持久亲水性，提升了超滤膜的抗污染性能。
实施例12至16
称取20wt％的聚偏二氟乙烯树脂(聚合物膜材料)，3wt％的聚乙烯吡咯烷酮(致孔剂)和一定量的二甲基甲酰胺(溶剂)，最后加入一定量的氨基丙级三甲氧基硅烷(反应性活性亲水分子)，维持铸膜液总量为100％，在80℃恒温搅拌24h至完全溶解形成均匀溶液，刮膜后放入具有交联因子的凝固浴中利用相转化的方法制备平板超滤膜。
氨基丙级三甲氧基硅烷的添加量如表2所示，凝固浴为PH＝8.5的去离子水，凝固浴温度为80℃。
表2反应性活性分子添加量对聚偏二氟乙烯中空纤维膜性能的影响
Figure BDA0003179692060000041
表2为反应活性分子添加量对聚偏二氟乙烯中空纤维超滤膜性能的影响。实施例12至16是通过在铸膜液中添加不同量的反应性活性分子制备超滤膜，与对照组实施例1相比较，随着反应活性分子添加量的增加，超滤膜通量呈现递增趋势，并且保持稳定的BSA分子的截留率，水接触角明显降低，通量恢复率增加，归一化通量结果如图4所示，其中M0为对照组即未添加反应活性分子的超滤膜，M1、M2为实施例12和13，与M0相比较，超滤膜在添加反应活性分子后抗污染性能提升，并且随着添加量的增加而增加，由此可证明增加反应性活性分子添加量有助于提升超滤膜亲水性，抗污染性能及过滤性能；实施例12至16所得超滤膜在溶剂二甲基乙酰胺中的溶解情况如图2所示，M0为对照组即未添加反应活性分子的超滤膜，M1、M2、M3、M4分别对应实施例12、13、14、15，与对照组M0相比较，随着反应性活性分子添加量的增加，超滤膜逐渐变得不溶解，交联度增加，由此证明在添加反应活性分子后超滤膜分子链成功交联；实施例12至15所得超滤膜的孔径及孔径分布如图3所示，其中M0为对照组实施例1，M1、M2、M3、M4分别对应实施例12、13、14、15，与对照组M0相比较，在添加反应活性分子后，超滤膜的孔径由M0较宽的分布，变得更加均一，并且随着反应活性分子添加量的增加，超滤膜在最大孔径保持一致的条件下，平均孔径变大，有助于提升超滤膜分离效率，由此可证明添加反应活性分子后超滤膜孔径实现均一化。
可以理解，本发明是通过一些实施例进行描述的，本领域技术人员知悉的，在不脱离本发明的精神和范围的情况下，可以对这些特征和实施例进行各种改变或等效替换。另外，在本发明的教导下，可以对这些特征和实施例进行修改以适应具体的情况及材料而不会脱离本发明的精神和范围。因此，本发明不受此处所公开的具体实施例的限制，所有落入本申请的权利要求范围内的实施例都属于本发明所保护的范围内。

Claims (5)

1.一种持久亲水均孔超滤膜的制备方法，其特征在于：包括以下步骤：
1）溶解同步亲水化：将具备反应位点的聚合物膜材料、反应性活性亲水分子、成膜致孔剂和溶剂，恒温搅拌，在聚合物膜材料常规溶解条件下完成亲水链接枝，即溶解同步亲水化；
2）交联协同相分离：完成溶解同步亲水化的聚合物溶液，利用干-湿相分离法制备超滤膜，利用凝固浴引发亲水链间交联反应，通过形成的交联网络协同调控相分离进程，限制聚合物链运动、胶束形成生长，形成较均匀的聚合物网络结构，获得较均一的膜孔结构的超滤膜，即长效亲水均孔超滤膜；
所述聚合物膜材料为聚氯乙烯、氯化聚氯乙烯、聚偏氟乙烯、聚偏氟乙烯-三氟氯乙烯共聚物中的一种或两种以上的混合物；
所述反应性活性亲水分子为氨基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、氨基丙基甲基二甲氧基硅烷、氨基丙基甲基二乙氧基硅烷，二乙烯三胺丙基甲基二甲氧基硅烷、N-2-氨乙基-3-氨丙基三甲氧基硅烷、巯基丙基三乙氧基硅烷、巯基丙基三甲氧基硅烷中的一种或两种以上的混合物；
所述凝固浴是氢氧化钠或者盐酸的水溶液，浓度在1wt%~30wt%，凝固浴温度控制在25℃~80℃。
2.根据权利要求1所述的持久亲水均孔超滤膜的制备方法，其特征在于：所述具备反应位点的聚合物膜材料占铸膜液的重量百分比为13wt%~20wt%，溶剂占铸膜液的重量百分比为86wt%~75wt%，反应性活性亲水分子占铸膜液的重量百分比为0.1wt%~20wt%，成膜致孔剂占铸膜液的重量百分比为0.1wt%~20wt%，总量为100%。
3.根据权利要求1所述的持久亲水均孔超滤膜的制备方法，其特征在于：所述致孔剂为分子量200~20000的聚乙二醇或聚乙烯吡咯烷酮中的一种或两种以上的混合物。
4.根据权利要求1所述的持久亲水均孔超滤膜的制备方法，其特征在于：所述溶剂为二甲基甲酰胺、二甲基亚砜、二甲基乙酰胺中的一种或两种以上的混合物。
5.根据权利要求1所述的持久亲水均孔超滤膜的制备方法，其特征在于：所述恒温搅拌的温度为40~80℃，搅拌时间为2h~48 h。
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