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 [{PO}PdMe(L)] (PO = κ-P,O-ArCHSO with Ar = 2-MeOCH; L = CHCN) () in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex 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 tolerates difunctional vinyl monomers and provides direct access to difunctional polyolefins that have not been attempted before.