Synthesis of polypropylene-co-p-methylstyrene copolymers by metallocene and Ziegler–Natta catalysts

This paper discusses the copolymerization reaction of propylene and p-methylstyrene (p-MS) via four of the best-known isospecific catalysts, including two homogeneous metallocene catalysts, namely, {SiMe₂[2-Me-4-Ph(Ind)]₂}ZrCl₂ and Et(Ind)₂ZrCl₂, and two heterogeneous Ziegler–Natta catalysts, namely, MgCl₂/TiCl₄/electron donor (ED)/AlEt₃ and TiCl₃. AA/Et₂AlCl. By comparing the experimental results, metallocene catalysts show no advantage over Ziegler–Natta catalysts. The combination of steric jamming during the consective insertion of 2,1-inserted p-MS and 1,2-inserted propylene (k₂₁ reaction) and the lack of p-MS homopolymerization (k₂₂ reaction) in the metallocene coordination mechanism drastically reduces catalyst activity and polymer molecular weight. On the other hand, the Ziegler–Natta heterogeneous catalyst proceeding with 1,2-specific insertion manner for both monomers shows no retardation because of the p-MS comonomer. Specifically, the supported MgCl₂/TiCl₄/ED/AlEt₃ catalyst, which contains an internal ED, produces copolymers with high molecular weight, high melting point, and no p-MS homopolymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2795–2802, 1999