Abstract
Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.
Highlights
BackgroundPolyolefin has been one of the most important commercial synthetic plastics in our daily life, and the market capacity is still increasing even in the conventional polymers such as polyethylene [HDPE (High Density Poly-How to cite this paper: Apisuk, W., Tsutsumi, K., Kim, H.J., Kim, D.H. and Nomura, K. (2014) A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers
No resonance ascribed to the cyclization of OD was observed, indicating that the polymerization proceeded with notable selectivity of OD repeated insertion, affording polymers containing terminal olefinic double bond in the side-chain, as demonstrated previously [35]
Quantitative epoxidation of the olefinic double bonds in the resultant copolymer could be achieved by using m-chloroperbenzoic acid under mild conditions; a facile, precise synthesis of functionalized polyolefin can be demonstrated by adopting this approach
Summary
BackgroundPolyolefin has been one of the most important commercial synthetic plastics in our daily life, and the market capacity is still increasing even in the conventional polymers such as polyethylene [HDPE (High Density Poly-How to cite this paper: Apisuk, W., Tsutsumi, K., Kim, H.J., Kim, D.H. and Nomura, K. (2014) A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers. For introduction of more reactive functionality (terminal olefin) into the side chain for the efficient functionalization process under mild conditions, use of nonconjugateddiene like 1,5-hexadiene (HD) for synthesis of functionalized polyolefin by the favored repeated HD insertion has been considered [33] [34], most of the reported examples using ordinary catalysts such as zirconocene (exemplified as 3 and 4, Scheme 4), titanocene, half-zirconocene, and others favored cyclopolymerization incorporating methylene-1,3-cyclopentane unit (Scheme 4, route A).
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