3 years ago

Synergetic Effect of Monomer Functional Group Coordination in Catalytic Insertion Polymerization

Synergetic Effect of Monomer Functional Group Coordination in Catalytic Insertion Polymerization
Inigo Göttker-Schnetmann, Stefan Mecking, Hannes Leicht
PhS- and PhNH-functionalized dienes are copolymerized efficiently with butadiene to stereoregular copolymers by [(mesitylene)Ni(allyl)][BArF4] (Ni-1). Overall polymerization rates and comonomer incorporations depend strongly on the linker length between the diene moiety and functional group, in, e.g., PhS—(CH2)xC(═CH2)—CH═CH2 (PhS-x-BD, x = 3–7), in particular for certain linker lengths high comonomer reactivity ratios stand out. This effect is related to a favorable binding of the comonomer to the active site comprising coordination of its functional group, which significantly enhances comonomer incorporation in the growing polymer chain.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b03087

DOI: 10.1021/jacs.7b03087

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