Abstract:Model polybutadiene (PB) with low molecular weight, narrow molecular weight distribution and different contents of 1,2- structure was synthesized by living anionic polymerization of butadiene, using n-butyl lithium as initiator and tetrahydrofuran as modifier. The radical grafting reaction of model PB was carried out by using benzoyl peroxide (BPO) as radical initiator and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as radical trapper. The contents of microstructure, BPO residue and TEMPO of grafted PB products were characterized by 1H-NMR. The results show that the abstracting hydrogen reaction dominates the radical grafting reaction of PB and the contents of 1,2-structure of PB play very important roles on the radical grafting reaction of PB. The larger the content of 1,2-structure of PB is, the bigger ratio the abstracting hydrogen reaction has. When the content of 1,2-structure of PB reaches 53.6%, the radical grafting reaction of PB is all attributed to the abstracting hydrogen reaction and no double bond addition reaction exists.