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Captodative olefins in polymer chemistry

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Polymer Synthesis Oxidation Processes

Part of the book series: Advances in Polymer Science ((POLYMER,volume 102))

Abstract

The radical polymerization behavior of captodative olefins such as acrylonitriles, acrylates, and acrylamides α-substituted by an electron-donating substituent is reviewed, including the initiated and spontaneous radical homo- and copolymerizations and the radical polymerizations in the presence of Lewis acids. The formation of low-molecular weight products under some experimental conditions is also reviewed. The reactivity of these olefins is analyzed in the context of the captodative theory. In spite of the unusual stabilization of the captodative radical, the reactivity pattern of these olefins in polymerization does not differ significantly from the pattern observed for other 1,1-disubstituted olefins. Classical explanations such as steric effects and aggregation of monomers are sufficient to rationalize the observations described in the literature. The spontaneous polymerization of acrylates α-substituted by an ether, a thioether, or an acylamido group can be rationalized by the Bond-Forming Initiation theory.

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Abbreviations

AIBN:

Azo-bis(isobutyronitrile)

CT:

Charge transfer

DTBP:

Di-tert-butyl peroxide

DTBPO:

Di-tert-butyl peroxalate

EDA:

Electron-donor-acceptor

ESR:

Electron spin resonance (spectroscopy)

HPLC:

High-pressure liquid chromatography

IBN:

Isobutyronitrile radical

LALLS:

Low angle laser light scattering

MA:

Methyl acrylate

MMA:

Methyl methacrylate

N.A.:

Not available

NVCz:

N-Vinylcarbazole

SEC:

Size exclusion chromatography

St:

Styrene

T:

Tetramethylene

Tc :

Ceiling temperature

VA:

Vinyl acetate

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Author notes

  1. J. Penelle

    Present address: Département de Chimie, Université Catholique de Louvain, Place L. Pasteur 1, B-1348, Louvain-la-Neuve, Belgium

Authors and Affiliations

  1. C. S. Marvel Laboratories, Department of Chemistry, The University of Arizona, 85721, Tucson, Arizona, USA

    J. Penelle, A. B. Padias & H. K. Hall Jr.

  2. Department of Chemical Science and Technology, Tokushima University, Minamijosanjima, 770, Tokushima, Japan

    H. Tanaka

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Penelle, J., Padias, A.B., Hall, H.K., Tanaka, H. (1992). Captodative olefins in polymer chemistry. In: Polymer Synthesis Oxidation Processes. Advances in Polymer Science, vol 102. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-55090-9_3

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