Insertion Copolymerization of Difunctional Polar Vinyl Monomers with Ethylene.

A single-step synthesis, structural characterization and application of a neutral, acetonitrile ligated, palladium-phosphinesulfonate complex [{P ^∧ O}PdMe(L)] (P ^∧ O = κ ² -P,O-Ar ₂ P C ₆ H ₄ SO ₂ O with Ar = 2-MeOC ₆ H ₄ ; L = CH ₃ CN) ( 3 ) in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex 3 was found to catalyze insertion copolymerization of industrially relevant 1,1-disubstituted difunctional vinyl monomers for the first time. Thus, insertion copolymerization of ethyl-2-cyanoacrylate (ECA or super glue) and trifluoromethyl acrylic acid (TFMAA) with ethylene produced the corresponding copolymers with 6.5% ECA and 3% TFMAA incorporation. Increasing the concentration of difunctional olefins led to higher incorporation but at the expense of lower activities. These observations indicate that complex 3 tolerates difunctional vinyl monomers and provides direct access to difunctional polyolefins that have not been attempted before.