金属功能化亚胺基纳米孔有机聚合物骨架的合成及催化乙烯齐聚研究

In current，ethylene oligomerization is the most broad and advanced technology for the α-olefin in the world. However，the homogeneous catalytic systems for ethylene oligomerization exists some shortcomings such as difficulty in separation or reuse of catalyst catalyst and consume large amounts of organic solvents. Immobilization of a homogeneous catalyst can resolve these difficulties in principle, and therefore is of considerable interest to academia and industry. A large number of the research results of supported catalyst system show that the choice of the supports has a decisive influence on the catalytic performance of ethylene oligomerization. Utilizing the existing supports, such as organic macromolecules, inorganic porous materials, inorganic-organic hybrid materials, a lot of the excellent heterogeneous catalytic systems have successful developed, but more reported results reflect that these supports have their limitations in heterogenerous catalysis. In this project, the applicant hope to synthesize a kind of metalfunctional imine-based nanoporous organic polymer frameworks and research their catalytic performance of ethylene oligomerization. We are interested in the exploration of covalently metal built-in chiral catalysis systems based on organic polymer frameworks. If catalytic center could be integrated into the skeleton, one would have a chance to create a novel porous polymer in which the skeleton itself serves as the heterogeneous catalysts and pores provide spaces for the transformation. Novel metalfunctional porous polymer frameworks maintain the catalytic active centers in the whole skeleton, and possess large specific surface area, pore structure, highly thermal and chemical stability, overcome some defects of previous reported supports in heterogeneous catalysts. Therefore, it is important to explore the synthesis of metalfunctional imine-based nanoporous organic polymer frameworks and have important academic significance and good prospects in practical application.

乙烯齐聚是当今世界应用最广泛、工艺最先进的α-烯烃生产方法之一，但均相乙烯齐聚催化体系仍存在催化剂分离、回收困难，有机溶剂用量大等缺点。均相催化剂负载化是解决上述困难的有效方法。大量负载催化体系的研究结果表明载体的选择对催化性能有着决定性影响。虽然对于现有载体如有机大分子、无机多孔材料、无机-有机杂化材料等都有比较优秀的非均相催化体系开发成功，但更多报道结果却显示出这些催化体系都有着自身局限性。在本项目中，申请人拟合成一类新型金属功能化亚胺基纳米孔有机聚合物骨架，并作为非均相催化剂催化乙烯齐聚。通过新的合成策略构筑的金属功能化聚合物骨架，保持催化活性中心均匀分布在共价连接骨架上，使骨架具有大比表面积、良好孔结构和高稳定性，克服了现有非均相催化剂各种缺陷，有望成为一类优秀的乙烯齐聚多相催化剂。因此，探索金属功能化亚胺基纳米孔有机聚合物骨架合成及催化乙烯齐聚具有重要的学术意义和良好的应用前景。

乙烯齐聚是当今世界应用最广泛、工艺最先进的α-烯烃生产方法之一，但均相乙烯齐聚催化体系仍存在催化剂分离、回收困难，有机溶剂用量大等缺点。均相催化剂负载化是解决上述困难的有效方法。大量负载催化体系的研究结果表明载体的选择对催化性能有着决定性影响。本项目中合成了一系列金属功能化亚胺基纳米孔有机聚合物骨架，利用多种表征手段确定了它们的结构特征、探索了其作为非均相催化剂催化乙烯齐聚的研究。初步的研究结果表明所合成的金属功能化亚胺基纳米孔有机聚合物骨架在助催化剂的作用下能够表现出较好的乙烯催化活性，取得了一系列有价值的研究数据。在开展功能性亚胺多孔有机聚合物骨架的合成中，我们仍然探索了亚胺基多孔有机聚合物骨架在气体吸附、离子传感、可见光催化等方面应用。所合成的共价有机骨架COF-JLU2是COF类材料当时对CO2吸附能力最高的；COF-JLU5是首次利用结晶性共价有机骨架材料作为可见光催化剂催化有机反应的例子；我们仍然提出利用交联优秀小分子催化剂的策略构筑非均相催化剂等；通过本项目的研究为多孔有机聚合物材料的设计合成及功能开发积累了大量经验、为有机多孔材料开辟了新的研究方向。