Novel Binary/Ternary Multi-component Polymerization System And Polymer Synthesis

The concept of multicomponent reactions (MCRs) has been introduced topolymer chemistry by combining transformation of monomers with polymerization toconstruct a one-pot multicomponent polymerization (MCP) system. This strategy isable to achieve functional polymers synthesis directly. The orthogonality of bothpolymerization method and compatible organic reactions for monomers synthesis mustbe taken into consideration with care. The exploited polymerization method shouldpossess properties such as controllable reaction rate, mild reaction condition and goodcompatibility while the organic reaction must be fast, efficient and harmless to thepolymerization.Atom transfer radical polymerization (ATRP) provides an excellent platform forthe one-pot MCP system. Click chemistry reactions (for example, the CuI-catalyzedalkyne-azide cycloaddition, CuAAC) are highly efficient coupling reaction. Meanwhile,CuAAC shares catalytic system with ATRP, which is one of the prerequisites forcombination. Enzymatic reactions are also fast, efficient and highly selective. Theenzyme reactions proceeding simultaneously with ATRP has been fully demonstratedin previous literatures. Based on previous work, it is possible to develop a one-potsynthetic strategy in polymer science by combining multi-type reactions in acooperative fashion. Consistency and compatibility is expected within the threeabove-mentioned reactions by controlling reaction conditions to achieve rate matching.In this thesis, we propose two novel strategies for polymer synthesis through thecombination of orthogonal reaction(s) with controlled radical polymerization.Firstly, CuAAC and ATRP were combined to build up a CuAACcondensation-ATRP binary polymerization system for the preparation of brush-/star-like polymers. Through adjusting reacting conditions, multi-armed star polymers weresuccessfully prepared by performing CuAAC condensation and ATRP in one pot,streching in orthogonal directions.Secondly, ATRP, enzymatic transesterification and CuAAC were combined toconstruct a ternary one-pot system of multicomponent polymerization. Polymers withdesigned molecular weight, composition and narrow polydispersity index were successfully synthesized by this ternary system. Through adjusting different reactingconditions, three reactions were conducted in matching rates and without interfere toeach other and kept their respective advantages in the complex chemical environment.Furthermore, the enzymes in this system maintained high activity after use.One-pot strategy is now gaining more and more attention in polymer chemistry.Exploring the one-pot synthesis methodology, in order to prepare functional polymersfacilely and smartly, is now being one of the hottest topics in polymer synthesischemistry. It is believed that this integrated one-pot synthetic strategy will bring newvigor to the area of polymer science.