Active centers in the polymerization of ethylene using titanium tetrachloride–alkylaluminum catalysts

Abstract

AbstractA method was developed to measure the active centers in a titanium tetrachloridealkylaluminum catalyst system for the polymerization of ethylene. The method depends on the assertion that the active carbon atom of the growing chain is relatively basic and will react with alcohol‐O‐t. The tritium becomes incorporated in the polymer. The relationship used is N = AG/a, where N is the corrected active center concentration, A is the radioactivity of the polyethylene in counts/min./g., G is the polymer concentration at the time of sampling and a is the specific activity of the quench methanol‐O‐t in counts/min./mole. The data were corrected for the kH/kT isotope effect of 3.7 which was measured for the alcohol‐O‐t reaction. This isotope effect was unchanged over a wide range of molecular weights and reaction conditions. The basicity of the carbon on the growing polymer chain was proved by quenching the reaction with C14‐labelled alcohol. The resulting polymer was not radioactive. The values of N could be correlated with polymerization rates. Values of the active center concentration and polymer chain lifetime were calculated as a function of molecular weight using fractionated polymer. The centers are very heterogeneous and the lifetimes of polymer chains range from 1 to 30 min. (with an average of 4 min. for the particular conditions used). Calculated values of viscosity‐ (M̄v) and number‐average molecular weights as a function of time of reaction agreed well with the experimental data. Because of the long lifetime of some chains, a steady state in M̄v is not reached, and M̄v increases throughout the course of the reaction. Catalyst efficiency was calculated from a knowledge of N. The efficiency, which can vary from 0.3 to 15% based on the titanium, is a function of how the catalyst components are brought together. The value of N in these systems is about 10−3 to 10−4 moles/liter compared to 10−7 to 10−9 for the concentration of active species in free radical systems. The value of the propagation constant, kp, is comparable in both systems. It is concluded that the very rapid polymerization rate in these heterogeneous systems is due solely to high values of N. These high values of N argue against bimolecular termination of centers. The stability of the centers when refluxed under argon support this idea and cast doubt on chain termination via hydride ion transfer or transfer to solvent. The value for the activation energy of kp is 11.8 over the range of 40 to 68°C. The value of the activation energy for initiation of centers is deduced to be 11.8 kcal./mole, also.