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 = κ²-P,O-Ar₂PC₆H₄SO₂O with Ar = 2-MeOC₆H₄; L = CH₃CN) (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.