Fundamental studies of grafting reactions in free radical copolymerization. IV. Grafting of styrene, acrylate, and methacrylate monomers onto vinyl‐polybutadiene using benzoyl peroxide and AIBN initiators in solution polymerization.

Vinyl‐1,2 polybutadiene (vinyl‐PBD) was used as the backbone polymer for the grafting of styrene, methacrylate, and acrylate monomers using both benzoyl peroxide and AIBN initiators. Radical attack on the backbone can occur through the pendant vinyl group or at the tertiary, allylic hydrogen site. Effective graft sites are formed via double bond addition of either primary (initiator) or polymer radicals. The production of tertiary allylic radicals on the backbone chain also occurs and results in moderate to dramatic reaction rate re‐tardation in every monomer system. The type of initiator is only important when the polymer radicals are not very reactive, as in the case of styrene, and to a lesser extent for methacrylate monomer. Graft efficiencies are generally higher when using vinyl‐PBD than when using cis‐PBD.