Synthesis of functionalized polyolefin with transition metal catalysts

Abstract

This thesis deals with synthesis of polyolefins having functional groups by early and late transition metal catalysts. Introducing functionalities into polyolefin has been considered as a challenging subject because of high oxophilicity of conventional transition metal catalysts and their polymerization behavior. To make functional polyolefins, the following attempts have been made; Pd-diimine catalyzed copolymerization of acetate monomers with ethylene, synthesis of polyolefin elastomer with supported Ni-diimine catalyst, synthesis of hydroxy-terminated polyethylene and its block copolymer with metallocene catalyst, and synthesis of ultra high molecular weight polyethylene by living polymerization of ethylene. Low oxophilicity of Pd-diimine catalyst enables direct copolymerization of functional monomers with ethylene. ω-Undecylenyl acetate monomer was synthesized and successfully copolymerized with ethylene. ω-Undecylenyl acetate comonomer prevents dimerization of living ethylene chain and polyethylene copolymer with narrow PDI (~1.05) was obtained. Novel polyimine ligand was synthesized by step polymerization of diamine and diketone monomer. Metallation of this polyimine ligand by Ni generates unique polymer-supported heterogeneous catalyst. Elastomeric linear-branch block polyethylene was synthesized by this catalyst. Selective chain transfer reaction was observed during the ethylene polymerization with bis-pentamethylcyclopentadienyl zirconium dichloride/MAO catalyst. β-Hydride elimination or chain transfer to aluminum occurred selectively depending upon the polymerization conditions like TMA content and temperature. Aluminum-terminated polyethylene was prepared by aluminum chain transfer reaction and converted to hydroxy-terminated polyethylene through oxidation of the aluminum-carbon bond. From this hydroxy terminated polyethylene, poly(ethylene-b-caprolactone) block copolymer was synthesized by stannous octoate initiated living polymerization of ε -...