Distinguishing Chain Growth Mechanisms in Metal-catalyzed Olefin Oligomerization and Polymerization Systems: C2H4/C2D4 Co-oligomerization/Polymerization Experiments Using Chromium, Iron, and Cobalt Catalysts | Zendy

A.K. Tomov | Zendy; V.C. Gibson | Zendy; George J. P. Britovsek | Zendy; Richard J. Long | Zendy; Martin van Meurs | Zendy; David J. Jones | Zendy; K.P. Tellmann | Zendy; Juan Chirinos | Zendy

Open Access

Distinguishing Chain Growth Mechanisms in Metal-catalyzed Olefin Oligomerization and Polymerization Systems: C₂H₄/C₂D₄ Co-oligomerization/Polymerization Experiments Using Chromium, Iron, and Cobalt Catalysts

Author(s) -

A.K. Tomov,

V.C. Gibson,

George J. P. Britovsek,

Richard J. Long,

Martin van Meurs,

David J. Jones,

K.P. Tellmann,

Juan Chirinos

Publication year - 2009

Publication title -

organometallics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.231

H-Index - 172

eISSN - 1520-6041

pISSN - 0276-7333

DOI - 10.1021/om900792x

Subject(s) - chemistry , chain propagation , olefin fiber , polymerization , catalysis , copolymer , chain (unit) , chain termination , scrambling , polymer chemistry , polymer , nuclear magnetic resonance spectroscopy , hydrocarbon , stereochemistry , radical polymerization , organic chemistry , linguistics , philosophy , physics , astronomy

A series of co-oligomerization and copolymerization reactions of C2H4/C2D4 (1:1) mixtures have been carried out using various transition metal catalysts based on Cr, Co, and Fe in combination with MAO. The oligomeric α-olefin products have been analyzed by GC and GC/MS, and the experimental results have been compared with the theoretical mass spectra derived from mathematical models. Solid polymer samples have been analyzed by 13C{1H} and 13C DEPT-135 NMR spectroscopy. C2H4/C2D4 co-oligomerization can be used as a method to differentiate between a metallacyclic or a Cossee-type chain growth mechanism in oligomerization systems. In the case of a metallacyclic mechanism, no H/D scrambling is observed, whereas for a Cossee-type mechanism, similar rates of chain propagation and chain termination (β-H elimination) result in rapid H/D scrambling of the C2H4/C2D4 feed. This method is therefore limited to oligomerization systems and cannot be applied in polymerization systems, where the rate of chain propagation ...

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