Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined...Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined branched block copolymer assemblies.Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization,and subsequently utilized in RAFT dispersion polymerization.It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies.Reaction conditions including monomer concentration,degree of polymerization (DP) of the core-forming block,and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail.Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents.This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.展开更多
基金support from the National Natural Science Foundation of China(Grant 52222301,21971047,and 22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(Grant 2022B1515020078)the Science and Technology Program of Guangzhou(Grant 202102020631).
文摘Here,we demonstrate the use of branched macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents in RAFT dispersion polymerization,to access branched block copolymers as well as well-defined branched block copolymer assemblies.Two types of branched macro-RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization,and subsequently utilized in RAFT dispersion polymerization.It was found that only branched macro-RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well-defined morphologies.Reaction conditions including monomer concentration,degree of polymerization (DP) of the core-forming block,and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail.Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro-RAFT agents.This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well-defined structures.
