Anan Shizuka, Mochizuki Yumi, Kokado Kenta, Sada Kazuki
Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-Ku, Sapporo, Hokkaido, 060-0810, Japan.
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 10, Nishi 8, Kita-Ku, Sapporo, Hokkaido, 060-0810, Japan.
Angew Chem Int Ed Engl. 2019 Jun 11;58(24):8018-8023. doi: 10.1002/anie.201901308. Epub 2019 May 8.
The A-A/B-B step-growth copolymerization between a monomer immobilized in the crystalline state and a monomer mobile in the solution state is demonstrated. One of the two monomers was immobilized as organic ligands of the metal-organic framework (MOF) and polymerized with the mobile guest monomer, resulting in the formation of linear polymers. The polymerization behavior was completely different from that of the solution polymerizations. In particular, the degrees of polymerization (DP) converged to a specific value depending on the MOF structures. The inevitable termination is caused not by imperfectness of the polymerization reaction, but by the selection of the two polymerization partners among the several adjacent immobilized monomers. This is fully supported by the Monte Carlo simulation on the basis of the polymerization mechanism. Precise immobilization of monomers in the supramolecular assemblies is a promising way for the controlled A-A/B-B step-growth polymerization.
本文展示了固定在结晶态的单体与溶液态可移动单体之间的A-A/B-B逐步增长共聚反应。两种单体中的一种作为金属有机框架（MOF）的有机配体被固定，并与可移动的客体单体聚合，从而形成线性聚合物。这种聚合行为与溶液聚合完全不同。特别地，聚合度（DP）根据MOF结构收敛到一个特定值。不可避免的终止不是由聚合反应的不完美引起的，而是由几个相邻固定单体中两种聚合伙伴的选择导致的。基于聚合机理的蒙特卡洛模拟充分支持了这一点。在超分子组装体中精确固定单体是实现可控A-A/B-B逐步增长聚合的一种有前途的方法。
