N-substituted maleimides polymerize in the presence of a radical initiator to give polymers with excellent thermal stabilities and transparency. In this study, we synthesized various maleimide copolymers with styrenes and acrylic monomers to control their thermal and mechanical properties by the introduction of bulky substituents and intermolecular hydrogen bonding. Three-component copolymers of N-(2-ethylhexyl)maleimide in combination with styrene, alpha-methylstyrene (MSt), or 1-methylenebenzocyclopentane (BC5) as the styrene derivatives, and n-butyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, or acrylic acid as the acrylic monomers were prepared by radical copolymerization. These copolymers were revealed to exhibit excellent heat resistance by thermogravimetric analysis. Glass transition temperatures increased by the introduction of bulky MSt and BC5 repeating units. The mechanical properties of the copolymer films were improved by the introduction of intermolecular hydrogen bonding. Optical properties, such as transmittance, refractive index, Abbe number, and birefringence, were determined for the copolymers. (c) 2019 Wiley Periodicals, Inc.