Cationic rare earth metal alkyls as novel catalysts for olefin polymerization and copolymerization

Organometallic catalysts for copolymerization of cyclic olefins

Recent developments in the synthesis of functional poly(olefin)s

http://www.rsc.org/suppdata/CC/b7/b708534f/b708534f.pdf

Cationic scandium aminobenzyl complexes. Synthesis, structure and unprecedented catalysis of copolymerization of 1-hexene and dicyclopentadiene.

The copolymerization of ethylene and cycloolefins [cyclopentene (CPE), cyclohexene (CHX), cycloheptene (CHP), cyclooctene (COT), cyclododecene (CDO), norbornene (NB), and 5,6-dihydrodicyclopentadiene HDCPD] and cyclodiolefins [1,3-cyclopentadiene (CPD), 1,4-cyclohexadiene (CHD), 1,5-cyclooctadiene (COD), 2,5-norbornadiene (NBD), and dicyclopentadiene (DCPD)] was investigated with a constrained-geometry catalyst, dimethylsilylene(tetramethylcyclopentadienyl)(N-tert-butyl)titanium dichloride, with methyl isobutyl aluminoxane as a cocatalyst. In the copolymerization with cycloolefins, the olefins, except for CHX, CDO, and HDCPD, were copolymerized via the 1,2-insertion mode with the following reactivity: NB > CHP > COT > CPE. In the copolymerization with cyclodiolefins, corresponding copolymers, except for copolymerization with CHD, were obtained. A crosslinking fraction was detected in the copolymers with COD and NBD. The reactivity of the cyclodiolefins, except for COD, was higher than that of the cycloolefins. CPD was copolymerized via 1,2-insertion, 1,4-insertion or 1,2-insertion of dimerized DCPD. The copolymerization with COD showed peculiar behavior under the copolymerization condition of a high COD concentration in the feed.

Copolymerization of ethylene with cycloolefins or cyclodiolefins by a constrained-geometry catalyst

Copolymerizations of ethylene with endo-dicyclopentadiene (DCP) were performed by using Cp2ZrCl2 (Cp = Cyclopentadienyl), Et(Ind)2ZrCl2 (Ind = Indenyl), and Ph2C(Cp)(Flu)ZrCl2 (Flu = Fluorenyl) combined with MAO as cocatalyst. Among these three metallocenes, Et(Ind)2ZrCl2 showed the highest catalyst performance for the copolymerization. From 1H-NMR analysis, it was found that DCP was copolymerized through enchainment of norbornene rings. The copolymer was then epoxidated by reacting with m-chloroperbenzoic acid. 13C-NMR spectrum of the resulting copolymer indicated the quantitative conversion of olefinic to epoxy groups. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 103–108, 1999

J. Suzuki

Papers

Synthesis and functionalization of poly(ethylene‐co‐dicyclopentadiene)