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<sup>∧</sup>O}­PdMe­(L)] (P<sup>∧</sup>O = κ<sup>2</sup>-P,O–Ar<sub>2</sub><i>P</i>C<sub>6</sub>H<sub>4</sub>SO<sub>2</sub><i>O</i> with Ar = 2-MeOC<sub>6</sub>H<sub>4</sub>; L = CH<sub>3</sub>CN) (<b>3</b>) in coordination/insertion copolymerization of ethylene with difunctional olefin is investigated. In a significant development, complex <b>3</b> 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 <b>3</b> tolerates difunctional vinyl monomers and provides direct access to difunctional polyolefins that have not been attempted before.