改性UiO-66增效聚吡咯高通量耐溶剂纳滤膜的制备与增效机制研究

To address low-solvent-permeable issue of polypyrrole (PPy) based solvent resistant nanofiltration membranes, we propose incorporation of UiO-66 with abundant intrinsic-nanopores into the PPy selective layer to construct additional solvent passageways, thereby accelerating the solvents passing through the intrinsic pores of UiO-66 and interval pores between the UiO-66 and PPy selective layer in this project. Firstly, the crosslinked polyacrylonitrile substrates and highly conjugated PPy selective layer will be synthesized to develop PPy based composite solvent resistant nanofiltration membranes with excellent solvent-resistant performance and high rejections towards active pharmaceutical molecules. Secondly, the finely control of chemical structure, pore structure and size of UiO-66 nanoparticles will be mainly investigated through adjusting the structures of the organic ligand and surface grafting conditions of UiO-66 to solve the issue that nanoparticles are hard to disperse in the polymer based selective-layer uniformly. Then, the PPy/modified-UiO-66 mixed matrix organic solvent nanofiltration membranes will be fabricated and the effects of the types and content of modified UiO-66 on the structure and separation performance of the mixed matrix membranes will be studied systematically. Finally, the relations between the structure and separation performance of the PPy/modified UiO-66 mixed matrix membranes will be investigated to reveal the mechanism behind the enhanced solvent permeances caused by the incorporation of modified UiO-66 at the molecular level, thereby providing theoretical support and technological exploration for developing high permeance solvent resistant nanofiltration membranes and frontal basic research on the application of solvent resistant nanofiltration membrane on the separation of active pharmaceutical small molecules.

针对聚吡咯基耐溶剂纳滤膜溶剂渗透通量低的难题，本项目提出在聚吡咯选择层中引入具有丰富内部孔径结构的UiO-66，利用其内部的本征孔及其与聚吡咯选择层形成的界面孔，形成额外溶剂通道，促进有机溶剂快速渗透。本项目研究交联聚丙烯腈基膜及高度共轭的聚吡咯选择层的制备方法，开发兼具优异耐溶剂性能与高截留性能的聚吡咯复合耐溶剂纳滤膜；重点研究通过改变UiO-66配体结构及表面接枝条件实现UiO-66纳米粒子化学结构、孔径结构与粒径的控制，解决纳米粒子在聚合物选择层中难以均匀分散的问题；研究聚吡咯/改性UiO-66混合基质纳滤膜的制备方法并系统研究改性UiO-66种类与添加量对其结构及性能影响规律，从分子水平上揭示该种膜结构与分离性能的构效关系，阐述改性UiO-66对聚吡咯耐溶剂纳滤膜的增效机制；为制备高通量耐溶剂纳滤膜提供理论支撑和技术探索，为耐溶剂纳滤膜在小分子活性药物分离应用提供前沿性基础研究。

针对耐溶剂纳滤膜溶剂渗透通量低的难题，本项目提出在聚吡咯选择层中引入具有丰富内部孔径结构的UiO-66，利用其内部的本征孔及其与聚吡咯选择层形成的界面孔，形成额外溶剂通道，促进有机溶剂快速渗透。本项目研究交联聚丙烯腈基膜及高度共轭的聚吡咯选择层的制备方法，开发兼具优异耐溶剂性能与高截留性能的聚吡咯复合耐溶剂纳滤膜；重点研究通过改变UiO-66配体结构及表面接枝条件实现UiO-66纳米粒子化学结构、孔径结构与粒径的控制，解决纳米粒子在聚合物选择层中难以均匀分散的问题；研究聚吡咯/改性UiO-66混合基质纳滤膜的制备方法并系统研究改性UiO-66种类与添加量对其结构及性能影响规律，从分子水平上揭示该种膜结构与分离性能的构效关系，阐述改性UiO-66对聚吡咯耐溶剂纳滤膜的增效机制；所制备的改性UiO-66增效聚吡咯耐溶剂纳滤膜对不同种类活性组分可以保持95%截留率，对不同溶剂渗透性可达20 L m-2 h-1 bar-1以上，在活性组分提纯领域展现独特分离效果。为制备高通量耐溶剂纳滤膜提供理论支撑和技术探索，为耐溶剂纳滤膜在小分子活性药物分离应用提供前沿性基础研究。发表学术文章14篇，获得授权专利4项，获得黑龙江省自然科学二等奖1项，威海市自然科学优秀学术奖二等奖1项。