Effects of Hydrogen and 1-Butene Concentrations on the Molecular Properties of Polyethylene Produced by Catalytic Gas-Phase Polymerization

The effects of the variations in concentrations of hydrogen (0−480 mol/m 3 ) and 1-butene (0−380 mol/m 3 ) on the gas-phase copolymerization of ethylene and 1-butene over a MgCl 2 /SiO 2 -supported Ti catalyst were investigated using a semibatch reactor operated at 70 °C. Polymers were characterized by size exclusion chromatography (SEC), melt flow index, analytical and preparative temperature-rising elution fractionation (ATREF and PTREF), and PTREF−SEC cross-fractionation. Excellent correlations were obtained between the reactor operating conditions and polymer properties; e.g., the average polymerization rate was proportional to 1/(1 + a [H 2 ] 0.5 ), the methyl group concentration in the polymer was proportional to the 1-butene concentration, and the melt flow index varied as M w - 3.4 . The most significant finding was that the hydrogen concentration dependence of the termination rate by hydrogen was different for different catalytic sites; the termination rate was first order for the catalytic sites responsible for the formation of copolymer and half-order for the sites responsible for the homopolymer component of the polymer.