Synthesis of polyolefins with unique properties by using metallocene-type catalysts |
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Authors: | Yukio Imanishi Naofumi Naga Michiyo Tsubooka |
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Affiliation: | Graduate School of Materials Science, Nara Institute of Science and Technology 8916-5, Takayama-cho, Ikoma, Nara, Japan 630-0101, Fax: +81-774-53-8207 |
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Abstract: | Copolymerization of ethylene and 1,5-hexadiene (HD) by zirconocene catalysts proceeded via cyclization-addition mechanism to form 1,3-didsubstituted cyclopentane structure in the polyethylene chain. The 1,3-cyclopentane structure was found to be taken in the crystalline structure of polyethylene (isomorphism) by partially chainging the trans zigzag chain into gauche conformation, thereby, inducing a transformation of orthorhombic crystal to pseudohexagonal crystal. Copolymerization of ethylene and cyclopentene (CPE) by zirconocene catalysts yielded copolymers having 1,2-disubstituted cyclopentane structure in the polyethylene chain. The 1,2-cyclopentane structure was not taken into the crystalline structure of polyethylene. The melting point (Tm) and the crystallinity (Xc) of polyethylene decreased by copolymerization of HD or CPE, and the Tm- and Xc-decreasing effect of CPE was stronger than HD. For copolymers of propylene and HD or CPE obtained with isospecific zirconocene catalyst, the isomorphism was not ovserved. |
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Keywords: | copolymerization ethylene 1,5-hexadiene isomorphism: zirconocene catalyst |
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