Synthesis of Linear α-Olefin Distributions with Flexible Mean Molecular Weight by a Ti-Al-Ni Catalyst System

The catalytic synthesis of linear α-olefins from ethylene is a key reaction in the chemical industry and one of the most important applications of homogeneous catalysis. Thus, novel protocols or concepts for the synthesis of linear α-olefins are highly desirable. Herein, we describe a trimetallic catalyst system (Ti-Al-Ni) consisting completely of earth-abundant metals. The titanium catalyst mediates coordinative chain transfer polymerization to the chain transfer agent triethylaluminum with multiple ethylene insertions prior to chain transfer. This Ti catalyst is combined with a simultaneously operating nickel catalyst. The nickel catalyst also undergoes chain transfer, displaces the grown alkyl chains via β-hydride elimination/transfer forming linear α-olefins, and recycles the chain transfer agent. The catalyst combination permits the highly efficient synthesis of various linear α-olefin distributions with flexible mean molecular weight with one catalyst system. Activities of more than 10000 kgeth mol–...

[1]  T. Dietel,et al.  A broadly tunable synthesis of linear α-olefins , 2017, Nature Communications.

[2]  J. Shabaker,et al.  Iron-Catalyzed Chain Growth of Ethylene: In Situ Regeneration of ZnEt2 by Tandem Catalysis , 2015 .

[3]  Pierre Braunstein,et al.  Ethylene oligomerization using iron complexes: beyond the discovery of bis(imino)pyridine ligands. , 2014, Chemical communications.

[4]  P. Zinck,et al.  Coordinative chain transfer polymerization. , 2013, Chemical reviews.

[5]  S. Förster,et al.  Tailored nanostructuring of end-group-functionalized high-density polyethylene synthesized by an efficient catalytic version of Ziegler's "Aufbaureaktion". , 2012, Chemistry.

[6]  Robby A. Petros,et al.  Zirconium-catalyzed carboalumination of α-olefins and chain growth of aluminum alkyls: kinetics and mechanism. , 2011, Journal of the American Chemical Society.

[7]  D. McGuinness Olefin oligomerization via metallacycles: dimerization, trimerization, tetramerization, and beyond. , 2011, Chemical reviews.

[8]  Lawrence R Sita,et al.  Ex uno plures ("out of one, many"): new paradigms for expanding the range of polyolefins through reversible group transfers. , 2009, Angewandte Chemie.

[9]  R. Kempe How to polymerize ethylene in a highly controlled fashion? , 2007, Chemistry.

[10]  Hiroshi Terao,et al.  Phenoxycycloalkylimine Ligated Zirconium Complexes for Ethylene Polymerization: Formation of Vinyl-Terminated Low Molecular Weight Polyethylenes with High Efficiency , 2006 .

[11]  G. Britovsek,et al.  Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series. , 2005, Journal of the American Chemical Society.

[12]  G. Britovsek,et al.  Iron catalyzed polyethylene chain growth on zinc: a study of the factors delineating chain transfer versus catalyzed chain growth in zinc and related metal alkyl systems. , 2004, Journal of the American Chemical Society.

[13]  S. Kojoh,et al.  Zirconium complexes having phenoxy/cycloalkylimine chelate ligands for the polymerization of ethylene for vinyl-terminated low molecular weight polyethylenes , 2002 .

[14]  Paul J. Flory,et al.  Molecular Size Distribution in Linear Condensation Polymers1 , 1936 .

[15]  G. Schulz Über die Beziehung zwischen Reaktionsgeschwindigkeit und Zusammensetzung des Reaktionsproduktes bei Makropolymerisationsvorgängen , 1935 .