One‐Pot Synthesis of Dual Supramolecular Associative PMMA‐Based Copolymers and the Precise Thermal Property Tuning

Dual supramolecular associative polymers have attracted attention for efficient physical property modification. Herein, a one‐pot synthesis of dual supramolecular associative poly(methyl methacrylate)‐based copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization using a novel methacrylate‐type monomer (coded as UP‐MA) bearing a urea bond and a pendant pyridine group is demonstrated. UP‐MA is synthesized by reacting 4‐picolylamine and 2‐isocyanatoethyl methacrylate. The subsequent RAFT copolymerization of UP‐MA and methyl methacrylate (MMA) can be performed by directly adding MMA, a chain transfer agent, and a radical initiator into the reaction solution of UP‐MA. The estimated values of radical reactivity ratio (r) for UP‐MA and MMA are close to unity, attaining a nearly ideal random sequence of the dual supramolecular associative units in the copolymer chain. By blending a metal salt into the random copolymer, coordination bonds between the salt and the pyridine groups are formed, and the urea groups simultaneously form hydrogen bonds, generating a dual supramolecular associative network. Precise tuning of the thermal property is realized by changing the fraction of the metal salt and associative groups in the copolymers. A one‐pot synthesis of dual supramolecular associative poly(methyl methacrylate)‐based copolymers is demonstrated by using a novel methacrylate‐type monomer bearing a urea linkage and a pyridine pendant group. Blending metal salt forms a coordination bond with the pyridine group, whereas the urea linkage forms a hydrogen bond, generating a dual supramolecular network with easy‐tunable thermal properties.