Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

Article, Other literature type English OPEN
Michiue, Kenji ; Mitani, Makoto ; Fujita, Terunori (2015)
  • Publisher: Multidisciplinary Digital Publishing Institute
  • Journal: Catalysts (issn: 2073-4344)
  • Related identifiers: doi: 10.3390/catal5042001
  • Subject: Chemistry | C2-symmetric zirconocene | TP1-1185 | QD1-999 | insertion mode | vinylenes | Chemical technology | vinyl groups | <i>C</i><sub>2</sub>-symmetric zirconocene | 1,3-butadiene | internal olefins

In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’)2]ZrCl2 (Indenyl’ = generic substituted indenyl), after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenyl)zirconium dichloride (1), rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl)] zirconium dichloride (2), rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl)]zirconium dichloride (3), rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl) zirconium dichloride (4), rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthyl)indenyl)]zirconium dichloride (5), rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenyl)indenyl))][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenyl)indenyl))]zirconium dichloride (6), rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride (7), and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride (8). We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 &gt; 7 &gt; 6 &gt; 5 &gt; 4 &gt; 3 &gt; 2 &gt; 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.
  • References (19)
    19 references, page 1 of 2

    1. Franssen, N.M.G.; Reek, J.N.H.; de Bruin, B. Synthesis of functional “polyolefins”: State of the art and remaining challenges. Chem. Soc. Rev. 2013, 42, 5809-5832.

    2. Welborn, H.C., Jr. Copolymers of Ethylene and 1,3-butadiene. EP0275676, 27 July 1988.

    3. Galimberti, M.; Albizzati, E.; Abis, L.; Bacchilega, G. 13C-NMR analysis of α-olefins copolymers with 1,3-butadiene obtained with zirconocenes/methylalumoxane catalysts. Makromol. Chem. 1991, 192, 2591-2601.

    4. Morizono, K.; Okada, K.; Yamaguchi, M. Unsaturated Copolymers, Processes for Preparing the Same, and Compositions Containing the Same. US6310164, 30 October 2001.

    5. Morizono, K.; Okada, K.; Yamaguchi, M. Unsaturated Copolymer, Preparation Thereof and Composition Containing Said Copolymer. Patent JPH1180269, 26 March 1999.

    6. Pragliola, S.; Milano, G.; Guerra, G.; Longo, P. Stereoselective Cyclopropanation by Cyclocopolymerization of Butadiene. J. Am. Chem. Soc. 2002, 124, 3502-3503.

    7. Longo, P.; Pragliola, S.; Milano, G.; Guerra, G. E Stereoregular 1,1 and 1,3 Constitutional Units from 1,3-Butadiene in Copolymerizations Catalyzed by a Highly Hindered C2 Symmetric Metallocene. J. Am. Chem. Soc. 2003, 125, 4799-4803.

    8. Longo, P.; Napoli, M.; Pragliola, S.; Costabile, C.; Milano, G.; Guerra, G. Butadiene Insertion and Constitutional Units in Ethene Copolymerizations by C2-Symmetric Metallocenes. Macromolecules 2003, 36, 9067-9074.

    9. Pragliola, S.; Costabile, C.; Magrino, M.; Napoli, M.; Longo, P. Ethene/1,3-Butadiene Copolymerization in the Presence of rac-(CH2-(3-tert-butyl-1-indenyl)2)ZrCl2/MAO Catalytic System: Study of the Polymerization Mechanism by Using 13C-Labeled 1,3-Butadiene. Macromolecules 2004, 37, 238-240.

    10. Ishihara, T.; Shiono, T. Hydrogenated 1,4-Insertion of Butadiene in the Copolymerization with Propylene Using an Isospecific Zirconocene Catalyst. J. Am. Chem. Soc. 2005, 127, 5774-5775.

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