C–H bond addition and copolymerization reactions of N-arylmaleimides: Fundamentals of coagent-assisted polymer cross-linking

Solid-state rheometry and model compound reactions are used to investigate free radical reactions of N-arylmaleimide coagents with saturated and unsaturated polymers. N,N′-m-phenylene dimaleimide (BMI) is shown to provide superior cross-link densities over diacrylate and diallyl coagents for all of the polymers studied, including linear low density polyethylene (LLDPE), poly(ethylene oxide) (PEO), cis-poly(butadiene) (PBD) and cis-poly(isoprene) (PIP). Studies of the N-phenylmaleimide (NPM) + cis-cyclooctane system show that C–H bond addition to yield N-aryl-2-alkylsuccimide grafts is the predominant reaction pathway, as opposed to maleimide homopolymerization. In contrast, peroxide-initiated reactions of cis-cyclooctene with small NPM concentrations generate highly alternating poly(cycloctene-alt-N-phenylmaleimide) in high yield, indicating that unsaturated mers in materials such as PBD engage maleimides in an efficient alternating copolymerization between electron-rich and electron-deficient monomer pairs. Factors that affect the reactivity of different polymers in these C–H bond additions and alternating copolymerizations are discussed.

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► Maleimide coagents do not homopolymerize efficiently.
► C–H addition of maleimides to alkanes yields 2-alkylsuccinimide grafts.
► Alternating copolymerization of maleimides and alkenes efficient at low [monomer].