ARENE-FUNCTIONALIZED POLYISOCYANIDES - A KINETIC-STUDY OF POLYMERIZATION TO PREPARE HOMOPOLYMERS AND BLOCK-COPOLYMERS

A series of several new isocyanide monomers with substituent photosensitizers and quenchers are synthesized and characterized. The polymerization of these monomers induced by [Ni(eta3-allyl)(OC-(O)CF3)]2(I) affords homopolymers and block copolymers with controllable donor and acceptor orientation and spacing. Kinetic analyses of the polymerization of the isocyanide monomers, 2-C-10H7CH2CH2NC (5), Me5C6CH2CH2NC (6), and 4-Me2NC6H4CH2NC (10), under N2 result in first-order rate expressions. The propagation rate constants k(p) for these monomers are calculated as 1.4 x 10(-1), 6.0 x 10(-3), and 3.6 x 10(-3) L.mol-1.s-1, respectively, from a kinetic analysis of the preparative polymerization of a 5-6-10 triblock copolymer. Characterization of the newly synthesized homopolymers and di- and triblock copolymers (by gel permeation chromatography, infrared spectroscopy, intrinsic viscosity measurements, and NMR spectroscopy) is described.