Reversible Coordinative Chain Transfer Polymerization of Butadiene Using a Neodymium Phosphonate Catalyst

Abstract

This study involves an investigation of the chain transfer reaction of butadiene (Bd) polymerization, under the neodymium tris[bis(2-ethylhexyl)phosphate] (Nd)/diisobutyl aluminum hydride (Al)/ethylaluminum sesquichloride (Cl)/Bd catalytic system. The results show that the chain transfer reaction itself is reversible. Only chain propagation and chain exchange reactions occurred during the later period of polymerization, and there was a linear relationship between the molecular weight and the conversion rate. All polymer chains showed sufficient reactivity to propagate by reacting with the monomer. The degree of the chain transfer reaction can be determined by the amount of Al, and the molecular weight in the synthetic polybutadiene can be accurately designed by the formula Mn=54·Bd/Nd/(0.67Al/Nd-7.17). The catalyst-polymerized butadiene afforded products featuring a relatively narrow molecular weight distribution and a high cis-1,4 stereospecificity. One of these products, polybutadiene rubber, showed narrow distribution in the sample, and exhibited good physical and mechanical properties, low abrasion, and low rolling resistance.