Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.13, 2549-2560, 1997
Metallocene-Catalyzed Ethene/Styrene Copolymerization and Terpolymerization with Olefinic Termonomers
Ethene was co-and terpolymerized with 1-octene and styrene using the methylalumoxane (MAO) activated halfsandwich metallocene Me2Si(Me4Cp)(N-t.-butyl)TiCl2 (Cp = cyclopentadienyl, Me = methyl) as catalyst. At temperatures of 40 and 60 degrees C styrene concentration was varied in order to investigate the influence of the comonomers. Despite decreasing the overall activity with respect to ethene/1-octene copolymerization, polymerization activity was found to exibit a relative maximum with increasing styrene concentration. An explanation is given taking two different comonomer effects into account. Low styrene concentration promoted higher 1-octene incorporation compared to ethene/1-octene copolymerization but significantly lowered the molecular weight of the terpolymers. With constant ethene and 1-octene concentration it was possible to produce ethene/1-octene/styrene terpolymers with styrene content varying from 0 to 25 mol % and 1-octene content varying from 8 to 21 mol %. All terpolymers were amorphous. With constant ethene content it was found possible to vary their glass transition temperature with 1-octene/styrene molar ratio incorporated in the terpolymer. C-13-NMR spectroscopic microstructure analysis showed that no styrene/1-octene sequences were found in the terpolymer backbone. Furthermore terpolymerizations were conducted successfully incorporating norbornene, 1,5-hexadiene and propene as monomers in terpolymertization with ethene and styrene.
Keywords:ZIEGLER-NATTA CATALYSTS;ALPHA-OLEFINS;COPOLYMERIZATION;ETHYLENE;POLYMERIZATION;1-BUTENE;STYRENE;SYSTEM