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Recent Developments in Catalytic Activation of Renewable Resources for Polymer Synthesis

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Organometallics and Renewables

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 39))

Abstract

This review describes the application of organometallic and inorganic complexes as initiators and catalysts for polymerizations using renewable resources. It focuses on the ring-opening polymerization of lactide and the alternating copolymerization of carbon dioxide and epoxides. For lactide ring-opening polymerization, a general background to the reaction mechanism, kinetics, stereochemical control and polymerization control is presented. This is followed by reviews of the use of groups 3 and 13 complexes as initiators. Group 3 complexes show excellent rates, amongst the fastest reported for this polymerization, and in some cases stereocontrol. The group 13 complexes have good precedent for stereocontrol; recent advances using heavier group 13 elements, In and Ga, are highlighted. For the alternating copolymerization, an overview of the reaction kinetics, mechanism and control is presented. Recent advances in the use of catalyst operating at low pressure and dinuclear catalysts are presented.

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Abbreviations

[PPN]Cl:

Bis(triphenylphosphoranylidene)ammonium chloride

BDI:

β-Diiminate

CHC:

Cyclohexene carbonate

CHO:

Cyclohexene oxide

DMAP:

4-Dimethylaminopyridine

DNP:

2,4-Dinitrophenolate

FT-IR:

Fourier transform infrared

GPC:

Gel permeation chromatography

MALDI-ToF:

Matrix-assisted laser desorption ionization – time of flight (detection)

N-MeIm:

N-Methylimidazole

PCHC:

Poly(cyclohexene carbonate)

PDI:

Polydispersity index

PO:

Propylene oxide

PPC:

Poly(propylene carbonate)

P s :

Probability of forming a new syndio-dyad

P i :

Probability of isotactic diad formation

rac-LA:

rac-Lactide

T g :

Glass transition temperature

TOF:

Turnover frequency

TON:

Turnover number

TPP:

Tetraphenylporphyrin

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Authors and Affiliations

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

    Antoine Buchard, Clare M. Bakewell, Jonathan Weiner & Charlotte K. Williams

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  1. Antoine Buchard
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  2. Clare M. Bakewell
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  3. Jonathan Weiner
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  4. Charlotte K. Williams
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Correspondence to Charlotte K. Williams .

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Editors and Affiliations

  1. , Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, Karlsruhe, 76131, Germany

    Michael A.R. Meier

  2. , Debye Institute of Nanomaterials Science, Utrecht University, Universiteitsweg 99, Utrecht, 3584, Netherlands

    Bert M. Weckhuysen

  3. , Debye Institute of Nanomaterials Science, Utrecht University, Universiteitsweg 99, Utrecht, 3584, Netherlands

    Pieter C. A. Bruijnincx

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© 2012 Springer-Verlag Berlin Heidelberg

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Buchard, A., Bakewell, C.M., Weiner, J., Williams, C.K. (2012). Recent Developments in Catalytic Activation of Renewable Resources for Polymer Synthesis. In: Meier, M., Weckhuysen, B., Bruijnincx, P. (eds) Organometallics and Renewables. Topics in Organometallic Chemistry, vol 39. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-28288-1_5

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