Preparation Of Functional Polymers Based On Non-Isocyanide-Based Multi-Component Reactions

Higher efficiency has been the goal of polymer scientist for a long time,and low yields together with complex synthetic steps have always been an important obstacle to the practical application of many functional polymer materials.To solve this problem,multi-component reactions?MCRs?have been introduced into polymer chemistry as a representative of highly efficient organic reactions,and have been developed into an important tool for polymer synthesis.In this paper,we hope to apply the MCRs to the field of functional polymer synthesis,and utilize its high-efficiency,mild conditions and modularity to produce polymer materials with novel functions efficiently.Here,we mainly investigated the Biginelli reaction and the Kabachnik-Fields?K-F?reaction,which belong to Non-isocyanide-based MCRs.Compared with the conventional isonitrile-based MCRs,these reactions are environmentally friendly and easily available,which make them more suitable for functional polymer synthesis.The traditional way of functional polymer synthesis is to prepare functionalized monomers before the polymerization process.However,such methods are limited by their cumbersome steps and low yield when applied to large-scale synthesis.For this reason,synthesis methods such as post-polymerization modification?PPM?and“one-pot method”were developed.By simplifying the reaction process and purification steps,they greatly improved the synthesis efficiency of functional polymers.In this paper,the PPM and the one-pot method are both used to form a novel functional polymer synthesis system together with MCRs.Firstly,we synthesized random copolymers with active side chains,and through PPM by Biginelli reaction,we introduced functional groups into the polymer side chains,thus preparing a series of polymers with adhesive properties.Through the analysis of the post-modification products,we confirmed that the Biginelli reaction can achieve high-efficiency PPM.And by microscopic and macroscopic characterization of the adhesive performance of the polymer,we not only verified the excellent performance of the functionalized polymer,but also clarified the unique contribution of the Biginelli reaction to the improvement of the adhesive function.Secondly,we synthesized a bifunctional polymeric contrast agent which can be used in both CT and ¹⁹F Magnetic Resonance Imaging(¹⁹F MRI)by the"one pot method"system of KF reaction and reversible addition-fragmentation chain transfer?RAFT?.Through the"one-pot"system kinetics tracking,we verified that the K-F/RAFT system can maintain good compatibility when applied to the synthesis of functional polymers.we will study the practical performance of the dual-function contrast agent in our future work.As a representative of non-isocyanide-based MCRs,the Biginelli reaction and K-F reaction are characterized by high efficiency,modularity,mild conditions,etc.It is an extremely effective synthesis method in the field of functional polymer synthesis which focu on efficiency.With the exploration of more multi-component reaction systems and the continuous development of polymer synthesis methods,the potential application of multi-component reactions in the synthesis of functional polymers will be further explored.