核壳型两亲有机多孔聚合物催化剂的设计合成及其水相催化性能和选择性催化机制研究

The development of new catalytic materials and catalytic process with enzyme characteristics is vitally important for green organic chemical industry. By referring to the characteristic of hydrophobic domains in enzymes, and taking advantage of open pore structure and excellent designability of porous organic polymer, this project proposal is to design and synthesize hydrophobic core-hydrophilic shell amphiphilic porous organic polymer supported catalysts. Based on hydrophobic effects between hydrophobic core and hydrophobic substrates, enzyme-like selectivity and activity are expected to be achieved for catalytic organic reactions in water. First, a series of random and core-shell amphiphilic porous polymers will be prepared via different synthesis methods, the regulation of composition, structure and amphiphilicity will be investigated. Then, the selective catalysis performances of the prepared catalysts for aqueous organic reactions will be studied, and the optimization of the catalytic performance will be carried out. Finally, based on the experimental results, such as the results of absorption/desorption dynamics experiments and the catalytic reactions, the mechanisms of enzyme-like selectivity and activity of core-shell amphiphilic porous polymer catalysts will be summarized. In view of the combined advantages of porous catalysis and enzyme catalysis in this new catalytic model, the result of this research is expected to provide valuable reference, information, and guidance for designing new heterogeneous catalysis, as well as widen the application fields of porous polymers.

开展具有拟酶特色的新型催化材料和催化过程研究，对发展绿色有机化工具有重要意义。本课题借鉴生物酶疏水间隔的结构特点，利用有机多孔聚合物开放的孔结构和优异的可设计性，设计合成疏水核亲水壳(核壳)型两亲有机多孔聚合物催化剂，并设想基于疏水核对水溶液中有机底物的富集作用和疏水相互作用，实现水相有机反应类似酶的高活性和底物选择性催化转化。首先，课题采用不同合成方法，制备系列无规型和核壳型两亲含膦有机多孔聚合物负载型催化剂，并探讨其组成、结构和两亲性能的调控规律；然后，考察催化剂在水相有机反应中的选择性催化性能，探讨出催化剂的性能优化规律；最后，利用吸脱附动力学等实验技术，结合催化活性结果，探讨核壳型两亲多孔聚合物催化剂的催化活性增效机制和底物选择性催化机制。鉴于该新型催化模型结合了多孔催化与仿酶催化的优点，本项目的顺利实施将为发展新型多相催化体系、拓宽有机多孔聚合物的应用范围提供实验基础和科学参考。

发展高效水-有机多相催化体系，实现两相反应高活性和高选择性进行，对有机化工的发展具有重要意义。本课题着眼于有机多孔聚合物组成/结构可设计性强的特点，基于有机多孔聚合物表面浸润性调控策略，设计合成两亲性有机多孔聚合物催化剂，特别是具有高活性、高选择性、可回收特点的两亲性水相多相催化剂。为实现两相反应高效催化转化的研究目标，我们首先采用自由基共聚法，通过调控单体的种类、比例等，制备了系列无规两亲性膦基有机多孔聚合物负载金属催化剂、两亲性有机多孔聚合物酸碱催化剂；探讨了单体种类及结构等对催化剂表面浸润性、孔径分布、比表面积的影响，实现了有机多孔聚合物表面浸润性可控调节；并基于催化剂表面浸润性调控，实现了多种重要水-有机两相反应、有机-有机两相反应的高效转化。在此基础上，采用活性自由基聚合法，制备了具有亲水壳-疏水核结构的核壳两亲含膦有机多孔聚合物负载金属催化剂，考察了其水相选择性催化性能及其影响规律，基于疏水性核对疏水性底物的选择性富集作用，提升了催化剂的底物选择性催化转化性能。本项目在执行过程中一共发表SCI收录论文12篇，授权中国发明专利1项，申请中国发明专利4件。上述的结果在发表后得到了国际同行的关注，其中，1篇论文成果被Synfacts杂志亮点评述。本项目培养在读硕士研究生2人，项目负责人2021年入选贵州省高层次创新型人才。