Living copolymerization of ethylene with norbornene catalyzed by bis(pyrrolide-imine) titanium complexes with MAO

Journal of the American Chemical Society
Yasunori YoshidaTerunori Fujita

Abstract

Bis(pyrrolide-imine) Ti complexes in conjunction with methylalumoxane (MAO) were found to work as efficient catalysts for the copolymerization of ethylene and norbornene to afford unique copolymers via an addition-type polymerization mechanism. The catalysts exhibited very high norbornene incorporation, superior to that obtained with Me(2)Si(Me(4)Cp)(N-tert-Bu)TiCl(2) (CGC). The sterically open and highly electrophilic nature of the catalysts is probably responsible for the excellent norbornene incorporation. The catalysts displayed a marked tendency to produce alternating copolymers, which have stereoirregular structures despite the C(2) symmetric nature of the catalysts. The norbornene/ethylene molar ratio in the polymerization medium had a profound influence on the molecular weight distribution of the resulting copolymer. At norbornene/ethylene ratios larger than ca. 1, the catalysts mediated room-temperature living copolymerization of ethylene and norbornene to form high molecular weight monodisperse copolymers (M(n) > 500,000, M(w)/M(n) < 1.20). (13)C NMR spectroscopic analysis of a copolymer, produced under conditions that gave low molecular weight, demonstrated that the copolymerization is initiated by norbornene inserti...Continue Reading

References

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Citations

May 24, 2008·Chemical Society Reviews·Tomoaki Matsugi, Terunori Fujita
Aug 3, 2014·The Journal of Chemical Physics·P Gaspard, D Andrieux
Oct 5, 2016·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Pierre Gaspard
Oct 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·D SureshPedro T Gomes
Sep 7, 2018·Organic & Biomolecular Chemistry·Wanqing WuHuanfeng Jiang
Aug 11, 2006·Chemistry : a European Journal·Yasushi NakayamaTerunori Fujita
Oct 1, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Lewis M BroomfieldManfred Bochmann
Oct 15, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Kotohiro Nomura
Oct 15, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Marina LambertiClaudio Pellecchia
Jan 13, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Clara S B GomesM Conceição Oliveira
Jun 5, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Giorgia ZanchinGiuseppe Leone
Mar 8, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Christine J CooperDavid R Allan
Jul 11, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ruiguo ZhaoHaiyan Ma
Dec 14, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Takahiro YasumotoKazushi Mashima
Jan 22, 2011·Chemical Reviews·Haruyuki MakioTerunori Fujita
Oct 26, 2013·ACS Macro Letters·Joy RomulusNicole S Sampson
Mar 3, 2015·Organic Letters·Tom van DijkKoop Lammertsma

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