We report a novel approach for the synthesis of a readily curable and degradable resin by the radical alternating copolymerization of 1,3-diene monomers with maleic anhydride. 2,4-Dimethyl-1,3-pentadiene predominantly produced an alternating copolymer rather than a Diels–Alder adduct during the reaction with maleic anhydride. We revealed the most stable conformation as a twisted diene structure of 2,4-dimethyl-1,3-pentadiene and the other methyl-substituted dienes by DFT calculations, while a completely planar structure was preferred for the s-cis and s-trans conformers of the nonsubstituted butadiene. The highly alternating repeating structure of the produced copolymers was revealed based on the NMR analysis and copolymerization reactivity ratios. The alternating copolymers including an anhydride moiety and a carbon-to-carbon double bond in each repeating unit was conveniently used for the thermosetting, subsequent degradation, and polymer–surface modification by postpolymerization reactions such as epoxy curing and oxidative ozonolysis.

We report the synthesis of a readily curable and degradable resin using an alternating copolymer of maleic anhydride and 2,4-dimethyl-1,3-pentadiene. The anhydride moiety of the alternating copolymer reacted with difunctional compounds, such as diepoxy, diol, and diamine derivatives as the crosslinkers, to produce network polymers by thermal curing. The subsequent ozone degradation of these thermosetting resins induced the cleavage of a carbon-to-carbon double bond in the polymer main chains, leading to the re-solubilization and surface modification of the crosslinked polymer materials.

Radical copolymerization of N‐substituted maleimides (RMIs) and maleic anhydride (MAn) in combination with 2,4‐dimethyl‐1,3‐pentadiene (DMPD) and 1,3‐pentadiene (PD) provides alternating copolymers with excellent thermal stability. Onset temperatures of decomposition are 280–331 and 336–371 °C for the copolymers with DMPD and PD, respectively. Glass transition temperatures of RMI copolymers are in a wide range of 54–138 °C depending on the bulkiness of N‐substituents. MAn copolymers are transformed to the corresponding RMI copolymers by postpolymerization reactions, which consist of quantitative addition of an alkylamine to an anhydride moiety of MAn copolymers and the subsequent heating. The copolymers synthesized in this study include ozone‐degradable carbon‐to‐carbon double bonds in their main chain. Molecular weight of the copolymers rapidly decreases by ozone degradation. Surface modification of casted polymer films is also performed by exposure to ozone‐containing air.