Novel Linear and Branched Poly(1,4-ketone)-b-polyalcohol Block Structures through Control of the Catalyst Initiation Mechanism

New Single-Site Palladium Catalysts for the Nonalternating Copolymerization of Ethylene and Carbon Monoxide

“…Cleavage of the Pd−O bonds by protonation and/or carbonylation of the complex would lead to a dicationic cis- (bis-phosphine) palladium(II) dicarbonyl complex ( a ). It has been shown that the carbonyl ligand may undergo nucleophilic attack by an alcohol (methanol) to form a monocationic ester complex ( b ) . No example of a cationic Pd(II) complex has ever been reported in the literature that is able to introduce extra ethylene insertions in a CO−C 2 H 4 copolymer.…”

Activation of late transition metal catalysts for olefin polymerizations and olefin/CO copolymerizations

“…The in-corporation of these alcohols into the polymer structure was demonstrated by different techniques, thus presenting a promising approach towards new block copolymer materials. 76 Although the experiments above were not aimed at the verification of the activation mechanism under the applied conditions, some interesting conclusions in this respect could be drawn. It was observed, for example, that, in case of activation by Me-EG and quenching by H 2 O, solely the polymer with keto-ester end-groups was formed and in nearly equimolar amount respective to the used catalyst, at that.…”

A Catalytic Approach to Functional Poly(1,4‐ketone)s Bearing Pendant Monosaccharide Fragments

“…The glycosylated monomers ( 2a , b ) were terpolymerized with carbon monoxide and propylene according to Scheme . Activation of the catalyst precursor was performed by addition of a defined amount of diethylene glycol 20,21…”

“…The GPC analyses of the products show relatively narrow molecular weight distributions (PDI ≈ 1.3). This fact led to the conclusion that no deactivation of the catalyst during the polymerization occurs and further materials with architectures like a block structure might be developed 20. The extra functionality of the monomers afforded products with reduced molecular weights.…”