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• Maleimide copolymers bearing pendant allyl groups were obtained by radical copolymerization of maleimide and allylmaleimide with methylmethacrylate and allylmethacrylate. • Copolymerization of N-allylmaleimide with allylmethacrylate leads to the formation of crosslinked copolymers with high heat resistance. • All the copolymers are stable up to 290°C; AMI copolymers are more heat resistant. • At 450°C, depolymerization is the dominant pyrolysis mechanism of poly(АMI-МMA), but depolymerization process of poly(АMI-AMA) does not occur due to increasing the number of crosslinkages Maleimide copolymers bearing pendant allyl groups were obtained by radical copolymerization of maleimide and allylmaleimide with methylmethacrylate and allylmethacrylate in bulk and methanol solution in the presence of AIBN. The structural features of the copolymers were studied using UV, IR, and NMR spectroscopy. During the copolymerization of maleimide with allylmethacrylate and N-allylmaleimide with methylmethacrylate at high conversions, an increase in the viscosity of the system is observed, which results in cross-linking along the "allyl bonds" of side polymer chains with the formation of insoluble copolymers that swell in DMSO. Copolymerization of N-allylmaleimide with allylmethacrylate already at initial conversions leads to the formation of crosslinked copolymers with high heat resistance. The thermal degradation behavior of copolymers was studied and the volatile products were investigated. [ABSTRACT FROM AUTHOR]