An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity

BN 2-vinylnaphthalene
(BN2VN) is a novel precursor to vinyl alcohol
copolymers via sodium hydroperoxide oxidation. We show that the unusual
aromaticity of the BN heterocycle leads to styrene-like reactivity.
Computational data including structural parameters and nucleus independent
chemical shift (NICS) values support the aromaticity of the BN naphthalene
side chain of BN2VN. Styrene (St) and BN2VN reactivity ratios (r1(BN2VN) = 0.423; r2(St) = 2.30; r1r2 = 0.97) were determined by nonlinear least-squares (NLLS)
statistical methods. We demonstrate control of copolymer physical
properties, including glass transition temperature. This work outlines
design principles for the synthesis of tailored polymeric styrene–vinyl
alcohol architectures.