Perfluorocyclobutyl Aryl Ether‐Based Polymethacrylates with High Heat Resistance

ABSTRACT Polymethacrylate (PMMA) has held a long‐standing interest in materials science due to its good processability, considerable optical and mechanical performance, and low price. However, the current challenge lies in maintaining high thermal stability across a wide temperature range for PMMA‐based materials. Herein, a series of perfluorocyclobutyl (PFCB) aryl ether‐containing PMMA copolymers were prepared to improve the heat resistance of PMMA‐based materials via introducing PFCB moiety and forming crosslink network structures. First, a 4‐(2‐(4‐methoxyphenoxy)perflurocyclobutoxy)‐[1,1’‐biphenyl]‐4‐ylmethyl methacrylate (PFBMA) monomer with PFCB moiety was copolymerized with methyl methacrylate (MMA) to provide PFCB‐containing PMMA copolymers with exceptional thermal stability. Subsequently, a dimethacrylate monomer containing PFCB moiety was synthesized and copolymerized with MMA, resulting in crosslinked PMMA copolymers where PFCB served as a connection point. The resulting crosslinked PMMA copolymers showed higher glass transition temperature ( T g ) and thermal decomposition temperature ( T d ) than those of PMMA, along with exceptional optical transparency. This study not only establishes an efficient synthetic route for the preparation of PFCB‐containing PMMA copolymers but expands the structural diversity of functional polymers.