Halide-free neodymium phosphate based catalyst for highly cis-1,4 selective polymerization of dienes

Neodymium-based Ziegler–Natta type catalytic systems are known to produce polydienes with high cis-1,4 content. It is generally believed that in Ziegler–Natta catalytic systems, a halide or pseudohalide, whether in the catalyst itself or a separate source, is required for the success of the polymerization. In this work, we have synthesized an unusual halide-free neodymium diethyl phosphate catalyst for diene polymerization. This neodymium complex combined with triisobutylaluminum (TIBA), formed a binary catalytic system and was used to polymerize β-myrcene. The catalytic system displays high stereospecificity and produces poly(β-myrcene) with 96% cis-1,4 content and a relatively narrow molecular weight distribution (M(w)/M(n) = 1.80). Also, kinetic studies indicated the catalytic system gives a pseudo-living polymerization. The block copolymer poly(β-myrcene)-b-poly(isoprene) was successfully synthesized by sequential monomer addition, further demonstrating the pseudo-living nature of polymerization with the neodymium diethyl phosphate catalyst.