Journal of Polymer Science Part A: Polymer Chemistry, Vol.36, No.6, 1017-1029, 1998
Kinetic and microstructure studies of poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts with constrained ligand geometry
This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)(2)ZrCl2 and [C5Me4((SiMe2NBu)-Bu-t)]TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and C-13-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-cop -methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethyl ene-co-p -methylstyrene) copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol % of p-methylstyrene, the crystallinity of copolymer almost completely disappears.
Keywords:ETHYLENE-STYRENE COPOLYMERIZATION;OLEFIN POLYMERIZATION CATALYSTS;ZIEGLER-NATTA POLYMERIZATION;RUBBER GRAFT-COPOLYMERS;PROPYLENE POLYMERIZATIONS;METHACRYLATE) COPOLYMERS;BORANE APPROACH;POLYPROPYLENE;FUNCTIONALIZATION;ZIRCONOCENE