Ziegler-Natta type catalysts have been extensively used for the polymerization of olefins and dienes. However, these catalysts can be disadvantageous due to their poor solubility in organic solvents, easy deactivation by polar monomers and high polydispersity index (PDI) of the synthesized polymers. Thus, a neodymium-based catalyst with chloride and triisobutylphosphate ligands (NdCl3 3TIBP) is developed for the polymerization of dienes and polar vinyl monomers. Single crystals of NdCl3 3TIBP were isolated and its structure was determined using X-ray diffraction showing a discrete complex. The catalytic activity of NdCl3 3TIBP combined with triisobutylalumium (TIBA) as a co-catalyst was performed for the polymerization of isoprene and bio-based myrcene (96% 1,4-cis and ~1.6 PDI). It is active for the homopolymerization of polar vinyl monomers (butyl acrylate and methyl methacrylate - ~64% syndiotacticity) and it generates block copolymers by sequential monomer addition. A quasi-living polymerization of the catalytic system was observed based on the kinetic studies. NdCl3 3TIBP/TIBA system demonstrates good catalytic activity in the polymerization of dienes while keeping stereospecific control of the reaction.

Quasi-living polymerization of dienes and polar vinyl monomers catalyzed by a discrete neodymium phosphate complex

2019 Fall National Meeting

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