Journal of Applied Polymer Science, Vol.74, No.7, 1851-1857, 1999
Synthesis and characterization of elastoplastic poly(styrene-co-ethylene) using novel mono(eta(5)-cyclopentadienyl) titanium and modified methylaluminoxane catalysts
Elastoplastic poly(styrene-co-ethylene) with high molecular weight was synthesized using novel mono(eta(5)-pentamethylcyclopentadienyl)tribenzyloxy titanium [Cp*Ti(OBz)(3)] complex activated with four types of modified methylaluminoxanes (mMAO) containing different amounts of residual trimethylaluminum (TMA). The ideal mMAO, used as a cocatalyst for the copolymerization of styrene with ethylene, contains TMA approaching to 17.8 wt %. The oxidation states of the titanium-active species in different Cp*Ti(OBz)(3)/mMAO catalytic systems were determined by the redox titration method. The results show that both active species may exist in the current system, where one [Ti(IV)] gives a copolymer of styrene and ethylene, and the second one [Ti(III)] only produces syndiotactic polystyrene (sPS). Catalytic activity, compositions of copolymerization products, styrene incorporation, and copolymer microstructure depend on copolymerization conditions, including polymerization temperature, Al/Ti, molar ratio, and comonomers feed ratio. The copolymerization products were fractionated by successive solvent extractions with boiling butanone and tetrahydrofuran (THF). The copolymer, chiefly existing in THF-soluble fractions, was confirmed by C-13-NMR, GPC, DSC, and WAXD to be an elastoplastic copolymer with a single glass transition temperature.
Keywords:ETHYLENE-STYRENE COPOLYMERIZATION;SYNDIOSPECIFICPOLYMERIZATION;REACTION-MECHANISM;COMPLEXES