Precision Synthesis of Complex Macromolecular Architectures of Gaseous Monomers and their Property Studies

The thesis work is split into five major chapters, viz. metal catalyzed polymerization of 1,3 butadiene, various protocols for synthesis of Poly(vinylidenefluoride) block copolymers, Copper (0) metal mediated iodine degenerative transfer controlled radical photo emulsion VDF homopolymerization, synthesis of 2,3,3,3 - tetrafluoropropene (TFP) homo, random and block copolymers, metal catalyzed interconversion of inactive perfluorohalides. Controlled radical polymerization of 1,3 butadiene was successfully achieved by using various group 8 and group 10 metal complexes such as the Fe,Ni, Run+1X3/(Nitrogen, Oxygen, Halide, Phosphine) ligand complexes. First instance of photo mediated polymerization of 1,3 butadiene were developed for Fe-complexes. A library of complex PVDF block copolymer architecture were synthesized by Mn2(CO)10 catalyzed quantitative activation of the PVDF-CF2-CH2-I and PVDF-CH2-CF2-I chain ends, and their properties were studied. Metal-free organo photocatalyst mediated controlled radical polymerization of the second block in PVDF block copolymers was achieved, and the kinetics of polymerization and chain end activation were studied in detail. Novel poly(TFP) homopolymer, random and block copolymer with VDF architectures were synthesized by Cu(0), Mtx(CO)y catalyzed radical polymerization. Rational selection of parameters such as the nature of the solvent, temperature, metal ligand complexes and various additives was evaluated to optimize the kinetic parameters for successful interconversion of RFCl, RFBr and RFI substrates