Modification of polybutadienes by catalytic and photochemical decomposition of dimethyldiazomalonate

Modifications of polybutadienes via catalytic and photolytic decomposition of dimethyldiazomalonate (dmdm) are described. This method pertains to the generation of highly reactive carbenes which give rise to the formation of addition and insertion products. Chemical structures of the modified polymers were confirmed by NMR spectroscopy. It was found that carbene dimers were also formed in a significant extent depending on the molecular weight and microstructure of the initial polymers.