Organo-fn,d0-Mediated Synthesis of Amine-Capped Polyethylenes. Scope and Mechanism
作者： Smruti B. Amin , SungYong Seo , Tobin J. Marks
DOI: 10.1021/OM700831T
关键词:
摘要: Amines of varying Bronsted acidity and steric encumberance are investigated as chain-transfer agents to functionalize polyolefins via organolanthanide-mediated olefin polymerization processes. Ethylene homopolymerizations carried out with activated Cp′2LnCH(Si(CH3)3)2 (Cp′ = η5-Me5C5; Ln La, Sm, Y, Lu) precatalysts in the presence aniline, n-propylamine, N,N-bis(trimethylsilyl)amine, di-sec-butylamine, N-tert-butyl(trimethylsilyl)amine, di-isopropylamine, dicyclohexylamine. In these amines, activities up 104 g polymer/(mol Ln·atm ethylene·h) narrow product polymer polydispersities observed, consistent single-site Amine efficiency follows trend C6H5NH2 ≈ nC3H7NH2 << [Si(CH3)3]2NH secBu2NH < N-tBu[Si(CH3)3]NH iPr2NH Cy2NH yield polyethylenes structure H(CH2CH2)nNRR′, where an efficient agent is defined a reagent that both terminates chain growth facilitate...
acs.org
sci-hub.se 参考文章(89)
Berth-Jan Deelman, Willem M. Stevels, Jan H. Teuben, Miles T. Lakin, Anthony L. Spek, Insertion Chemistry of Cp*zY(2-pyridyl) and Molecular Structure of the Unexpected CO Insertion Product (Cp"2y) 2@ mq 2:q 2-oc (NC 5H4) 2) Organometallics. ,vol. 13, pp. 3881- 3891 ,(1994) , 10.1021/OM00022A025
Martin Booij, Berth Jan Deelman, Rob Duchateau, Djurre S. Postma, Auke Meetsma, Jan H. Teuben, C-H Activation of Arenes and Substituted Arenes by the Yttrium Hydride (Cp*2YH)2: Competition between Cp* Ligand Metalation, Arene Metalation, and H/D Exchange. Molecular Structures of Cp*2Y(μ-H)(μ-η1,η5-CH2C5Me4)YCp* and Cp*2Y(o-C6H4PPh2CH2) Organometallics. ,vol. 12, pp. 3531- 3540 ,(1993) , 10.1021/OM00033A027
Amber M. Kawaoka, Tobin J. Marks, Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes. Scope and mechanism. Journal of the American Chemical Society. ,vol. 127, pp. 6311- 6324 ,(2005) , 10.1021/JA044174I
Ilmar A. Koppel, Peeter Burk, Ivar Koppel, Ivo Leito, Generalized principle of designing neutral superstrong Brønsted acids. Journal of the American Chemical Society. ,vol. 124, pp. 5594- 5600 ,(2002) , 10.1021/JA0255958
Yue Yang, Valerie V. Sheares, Synthesis of disubstituted amine-functionalized diene-based polymers Polymer. ,vol. 48, pp. 105- 109 ,(2007) , 10.1016/J.POLYMER.2006.09.064
Marc Dahlmann, Gerhard Erker, Klaus Bergander, Experimental Characterization of the Alkene-Addition/-Insertion Energy Profile at Homogeneous Group 4 Metal Ziegler-Type Catalysts Journal of the American Chemical Society. ,vol. 122, pp. 7986- 7998 ,(2000) , 10.1021/JA0005338
Ilmar A. Koppel, Peeter Burk, Ivar Koppel, Ivo Leito, Takaaki Sonoda, Masaaki Mishima, Gas-Phase Acidities of Some Neutral Brønsted Superacids: A DFT and ab Initio Study Journal of the American Chemical Society. ,vol. 122, pp. 5114- 5124 ,(2000) , 10.1021/JA0000753
Denis V. Gribkov, Kai C. Hultzsch, Frank Hampel, 3,3‘-Bis(trisarylsilyl)-Substituted Binaphtholate Rare Earth Metal Catalysts for Asymmetric Hydroamination Journal of the American Chemical Society. ,vol. 128, pp. 3748- 3759 ,(2006) , 10.1021/JA058287T
B. Scott Williams, Mark D. Leatherman, Peter S. White, Maurice Brookhart, Reactions of vinyl acetate and vinyl trifluoroacetate with cationic diimine Pd(II) and Ni(II) alkyl complexes: identification of problems connected with copolymerizations of these monomers with ethylene. Journal of the American Chemical Society. ,vol. 127, pp. 5132- 5146 ,(2005) , 10.1021/JA045969S
Guoqiang Fan, Jin-Yong Dong, An examination of aluminum chain transfer reaction in rac-Me2Si[2-Me-4-Naph-Ind]2ZrCl2/MAO-catalyzed propylene polymerization and synthesis of aluminum-terminated isotactic polypropylene with controlled molecular weight Journal of Molecular Catalysis A-chemical. ,vol. 236, pp. 246- 252 ,(2005) , 10.1016/J.MOLCATA.2005.04.053