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 -...