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Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts

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Topics in Organometallic Chemistry

Part of the book series: Topics in Organometallic Chemistry

Abstract

This chapter describes the brief history of iron or cobalt catalysts for olefin polymerisation and oligomerisation. Since the discovery in 1998 that 2,6-bis(imino)pyridine iron and cobalt halides, on activation with MAO, can convert ethylene to highly linear polyethylene, numerous reports have been concerned with ligand modification, mechanisms for precatalyst activation, identifying the active species and understanding the mode of propagation/chain transfer. In addition, heterogenisation of this class of catalysts, their incorporation into macrocycles/polymers and their use in reactor blending/tandem catalysis has seen some important developments; alternative ligand architectures that can support active iron and cobalt catalysts are also discussed as are different types of olefinic monomer.

1 Introduction

2 Synthesis of 2,6-Bis(imino)pyridine Iron(II) and Cobalt(II) Halides

2.1 Ligand Preparation

2.2 Complexation with MX2 (M = Fe, Co)

3 2,6-Bis(imino)pyridine Iron Halide/MAO and Cobalt Halide/MAO Catalysts

3.1 Catalytic Evaluation

3.2 MAO-Generated “Active Species”

3.3 Propagation and Chain Transfer Pathways/Theoretical Studies

3.4 Other Co-catalysts/Activators

3.5 Well-Defined Iron and Cobalt Alkyls

4 Supported Catalysts

5 Macrocyclic and Polymeric Derivatives

6 Tandem Catalysis

7 Alternative Iron and Cobalt Catalysts

8 Conclusions

References

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Abbreviations

Acac:

Acetylacetonate

Ar:

Aryl

Bn:

Benzyl

Cy:

Cyclohexyl

DEAC:

Diethylaluminium chloride

DFT:

Density functional theory

DRIFT:

Diffuse reflectance infrared fourier transform

EPR:

Electron paramagnetic resonance

ESI-MS:

Electrospray ionisation tandem mass spectrometry

Et:

Ethyl

Et2O:

Diethyl ether

Fc:

Ferrocenyl

g (mmol h bar)–1 :

Grams per millimole (of precatalyst) per hour per bar

HDPE:

High density polyethylene

i-Bu:

iso-Butyl

i-Pr:

Isopropyl

IR:

Infra red

LLDPE:

Linear low density polyethylene

MAO:

Methylaluminoxane

Me:

Methyl

MeCN:

Acetonitrile

Mesityl or Mes:

2,4,6-Trimethylphenyl

MMAO:

Modified methylaluminoxane, AlMeO:Al-i-BuO = 3:1

NMR:

Nuclear magnetic resonance

Ph:

Phenyl

PS:

Polystyrene

Py:

Pyridine

t-Bu:

tert-Butyl

TEA:

Triethylaluminium

THF:

Tetrahydrofuran

ULDPE:

Ultra low density polyethylene

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Authors and Affiliations

  1. Department of Chemistry, Imperial College, South Kensington Campus, London, SW7 2AZ, UK

    Vernon C. Gibson

  2. Department of Chemistry, University of Leicester, University Road, Leicester, LE1 7RH, UK

    Gregory A. Solan

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Gibson, V., Solan, G. (2008). Iron-Based and Cobalt-Based Olefin Polymerisation Catalysts. In: Topics in Organometallic Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2008_10

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  • DOI: https://doi.org/10.1007/3418_2008_10

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