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Iron-Catalyzed Oligomerization and Polymerization Reactions

Part of the Topics in Organometallic Chemistry book series (TOPORGAN,volume 50)

Abstract

Having the tremendous industrial importance of thermoplastics and elastomers in mind, it is not surprising to see a proliferation of studies on a variety of catalytic systems for polymerization and oligomerization of unsaturated hydrocarbons. Over the last 15 years, the development of mid- to late transition metal catalysts has provided significant advances in this area. The availability of iron combined with its low environmental impact and its tolerance to heteroatom functions attracts significant interest from both academia and industry. In the late 1990s, key milestones have been the development of well-characterized bulky bis(imino)pyridine-Fe(II) precatalysts, mainly for the polymerization or oligomerization of ethylene. This chapter provides a brief overview of the key developments reported in the last 5 years in the literature in the field of iron-catalyzed olefin and diolefin polymerization and oligomerization. Emphasis has been placed on ethylene oligomerization and polymerization, with a particular interest in ligand architecture modifications. The advances in characterization and understanding of catalytically active iron species and the corresponding mechanisms are reported. Heterogenization of bis(imino)pyridine iron catalytic systems has been considered for ethylene transformation and will also be covered in this chapter. The interest of iron catalysts for multiple single-site approaches such as reactor blending and tandem catalysis is also described. Finally, iron catalyst systems also present interesting features for diene polymerization even though both activities and selectivities remain far from those observed for conventional catalysts.

Keywords

  • Diolefins
  • Iron
  • Olefins
  • Oligomerization
  • Polymerization

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Fig. 1
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Scheme 1
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Scheme 2
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Fig. 19
Scheme 3
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Scheme 4
Fig. 21
Scheme 5
Fig. 22
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Scheme 6
Fig. 24
Fig. 25

Abbreviations

DSC:

Differential scanning chromatography

EASC:

Ethylaluminum sesquichloride Et3Al2Cl3

EPR:

Electron paramagnetic resonance

GPC:

Gel permeation chromatography

HDPE:

High-density polyethylene

iPr:

Isopropyl

K:

Schulz–Flory coefficient

LAO:

Linear alpha olefin

LLDPE:

Linear low-density polyethylene

MAO:

Methylaluminoxane

MMAO:

Modified methylaluminoxane

M n :

Number-average molecular weight

M w :

Weight-average molecular weight

MW:

Molecular weight

MWD:

Molecular weight distribution

NMR:

Nuclear magnetic resonance

Oct:

Octyl

PP:

Polypropylene

SHOP:

Shell higher olefin process

TEA:

Triethylaluminum = AlEt3

THF:

Tetrahydrofuran

TIBA:

Triisobutylaluminum = Al(iBu)3

TMA:

Trimethylaluminum = AlMe3

UHMWPE:

Ultrahigh molecular weight polyethylene

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Acknowledgments

We thank Dr. Vincent Monteil and Dr. Christophe Boisson for fruitful discussions on olefin and diene polymerization.

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Correspondence to Hélène Olivier-Bourbigou .

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Burcher, B., Breuil, PA.R., Magna, L., Olivier-Bourbigou, H. (2015). Iron-Catalyzed Oligomerization and Polymerization Reactions. In: Bauer, E. (eds) Iron Catalysis II. Topics in Organometallic Chemistry, vol 50. Springer, Cham. https://doi.org/10.1007/3418_2015_101

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