Functional polymers from (vinyl)polystyrene. Short routes to binding functional groups to polystyrene resin through a dimethylene spacer: Bromine, sulfur, phosphorus, silicon, hydrogen, boron, and oxygen

Many spacer-containing functional polymers were produced by modifying beads of (vinyl)polystyrene, as obtained by free-radical suspension: polymerization of a commercial 55:45 divinylbenzene: ethylstyrene mixture, or from commercial sources. Thus, in the presence of free-radical initiators, compounds HBr, HPR(2), HP(OR)(2), and HSR (R = various alkyl, aryl or acyl, some also containing further COOH/R, OH/R, SH/R, N(H/R)(2) groups) underwent anti-Markovnikov addition to the residual vinyl groups. Similar free-radical functionalization with various HSiR(3) also proved feasible but more difficult. Other products corresponding to formal anti-Markovnikov addition of H(2)S, HSO(3)(-), HP(OH)(2), H(2), HBR(2), HOH, and HOSO(2)R were obtained by other mechanisms, or after further modifications. FTIR spectra of the resulting functional polymers often showed complete or near-complete disappearance of initial vinyl groups and their replacement by the expected spacer-supported functionalities. The polymer products were also characterized by elemental analysis and solid-state NMR. Many of these functionalized beads, or their further derivatives upon functional group modification, could act as stable and effective solid-phase reagents, catalysts, sequestering agents, or protecting groups for solid-phase synthesis.