Di- and tri-block copolymers from the sequential living anionic copolymerization a phosphaalkene with styrene

Abstract

The living anionic polymerization of the phosphaalkene, MesP=CPh 2 ( PA ), affords a series of poly(methylenephosphine) (PMP) homo- and block co-polymers with styrene (S). Specifically, PMP m ( m = 30, 40, 50, 50), PS n – b –PMP m ( n , m = 100,29; 100,50; 50,30; 51, 62) and PMP m – b –PS 2 n – b –PMP m (2 n , m = 100,4; 200,8; 400,16; 400,24) have been prepared and characterized. Analysis by GPC-MALS-V showed that all samples were monodisperse, displayed narrow dispersities ( Đ = 1.03–1.29), and generally had molecular weights within ±(2–26%) of those targeted from the monomer-to-initiator ratios. All homo- and co-polymers displayed a single T g in their DSC chromatograms with the transition temperature for the copolymers being in between those of the corresponding homopolymers. These transitions appear to be dependent on both the copolymer composition and the corresponding chain lengths. • Living anionic copolymerization of a phosphaalkene with styrene is accomplished. • Diblock and triblock copolymers contain functional phosphine groups. • Phosphine homopolymers have high glass transition temperatures (ca. 150 °C).