耐温、耐溶剂聚萘酰亚胺分离膜材料的制备与性质

Novel membrane materials with good thermal stability, resistance to solvent, acid and base is developed by preparing polynapthylimides and studying their properties. a series of bis(chloro)naphthylimide monomers are prepared by the reaction of chloronaphthyl anhydride and aromatic diamines. Poly ether naphthlymides are prepared by the condensation polymerization of the bis(chloro)naphthylimide monomer and bisphenol-A. Polynaphthylimides are prepared using Ni(0) catalyzed coupling polymerization of bis(chloro)naphthylimide monomers. The effect of structure on thermal, hydrolysis and solvent resistance of polyimide is investigated. Novel gas separation, ultrafiltration and nanofiltration membranes are prepared and the relationship between the structure and membrane performance are studied. This project will build up the synthetic method and fabrication conditions for gas separation and nanofiltration membrane. The effect of the structure of chemical and membrane on membrane properties will be figure out. Novel high performance polynaphthylimide membrane will be obtained.

针对有机膜材料对耐温、耐酸碱、耐溶剂等性能的要求，解决聚酰亚胺耐溶剂及耐水解问题，开展新型聚酰亚胺膜材料制备及性质研究。采用商品化的氯代萘酐与各种芳香二胺反应，制备系列双氯代酞酰亚胺。通过双酚-A与双氯代单体反应，制备聚醚萘酰亚胺。采用双氯代酞酰亚胺单体，通过Ni(0)催化的偶联聚合反应，合成聚萘酰亚胺。系统研究聚合物结构与热氧化、水解、耐溶剂等性能的关系。研究聚萘酰亚胺的气体分离、耐溶剂超滤、纳滤膜的制备方法及条件。研究膜的结构与分离性能的关系。理论上，建立聚萘酰亚胺膜材料的分子设计、制备、成膜方法，揭示微结构对膜性能的影响规律。研究发展出基于聚萘酰亚胺材料的气体分离膜、纳滤膜。

针对有机膜材料对耐温、耐酸碱、耐有机溶剂等性能要求，本项目研究了聚萘酰亚胺的制备与性能。研究了分别由Ni(0)催化偶联聚合二氯萘酰亚胺、二酚与二氯萘酰亚胺缩聚、萘二酐与二胺缩聚反应制备聚萘酰亚胺的合成方法。采用邻位含取代基的二胺与萘二酐，制备了可溶解加工的聚萘酰亚胺。揭示了聚合的最佳反应条件是先加入酸催化剂，形成反式的异酰亚胺，然后，加入碱催化剂，反式异酰亚胺重排形成聚萘酰亚胺。聚萘酰亚胺的结构及取代基赋予了聚萘酰亚胺高的热稳定性、良好溶解与成膜性、改进的水解稳定性及良好的气体分离性能。所制备的六元环聚萘酰亚胺的CO2透过性在37.2-151 barrer范围内，O2透过性在7.16-24.9 barrer范围内，O2/N2选择性在3.91-4.97之间，CO2/CH4选择性在20.9-31.7之间。气体的透过性能高于商品化聚酰亚胺Matrimid 5218 (PO2=1.46 barrer，PCO2=8.7 barrer)。采用6FDA-DAM 聚酰亚胺作为母体聚合物，有机笼状化合物Noria和它的衍生物Noria-COtBu 作为填料，制备了混合基质气体分离膜。气体分离性能显示，引入Noria增加了CO2/CH4 分离选择性，引入Noria-COtBu 增加了聚合物膜的自由体积，同时，增加了气体通量。以含有羧基的双酚单体酚酞啉 (PPH-COOH)和二氟二苯酮为原料，制备了主链含有羧基的聚芳醚酮(PAEK-COOH)。用非溶剂诱导的相转化法制备了致密超滤膜。由于聚合物PAEK-COOH含有羧基，所得超滤膜的水接触角为61.5°，说明膜具有良好的亲水性。PAEK-COOH 致密超滤膜具有水通量120 L m−2 h−1 和对刚果红染料 99.8% 的截流。膜的截流分子量为9260 Da ，而对NaCl有高的透过性。因此，PAEK-COOH 有潜力作为耐高温膜材料，用于废水处理、溶液脱色及染料回收。