A novel consecutive chain transfer reaction to p-methylstyrene and hydrogen during metallocene-mediated olefin polymerization.

This paper describes the first example of consecutive chain transfer reaction, first to p-methylstyrene (or styrene) and then to hydrogen, during metallocene-catalyzed propylene polymerization by rac-Me(2)Si2-Me-4-Ph(Ind)](2)ZrCl(2)/MAO complex. The PP molecular weight is inversely proportional to the molar ratio of p-methylstyrene]/propylene] and styrene]/propylene] with the chain transfer constants of k(tr)/k(p) = 1/6.36 and 1/7.5, respectively. Although hydrogen does not influence the polymer molecular weight, it greatly affects the catalyst activity. Each PP chain formed contains a terminal p-methylstyrene (or styrene) unit. The terminal p-MS unit can be metalated to form a stable polymeric anion for living anionic polymerization to prepare new PP diblock copolymers, such as PP-b-PS, which are very difficult to prepare by other methods. The overall process resembles a transformation reaction from metallocene to living anionic polymerization.