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Controlled radical polymerization of vinyl esters and vinyl amides: experimental and theoretical studies

Morin, Aurélie. Controlled radical polymerization of vinyl esters and vinyl amides: experimental and theoretical studies. PhD, Institut National Polytechnique de Toulouse, 2013

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Official URL: http://ethesis.inp-toulouse.fr/archive/00002480/

Abstract

This thesis focus on Controlled Radical Polymerization (CRP) of vinyl esters and vinyl amides. One of the possibilities to achieve this control is a dynamic reversible trapping of the growing radical chains (P•) by a controlling agent (T) to form a dormant species (P─T’). The radical concentration in the medium can be dramatically reduced so that the unwanted terminations are disfavored and polymers with controlled molecular weights and low dispersity can be obtained. A way to achieve this control is the use of metallic complexes, which can oxidize and form a metal-carbon bond, as trapping agent in the so-called Organometallic Mediated Radical Polymerization (OMRP). So far, different transition metals have been used with gretaer or smaller success. In this study, the synthesis of copper(I) complexes and their investigation for the vinyl acetate and ethylene polymerization under OMRP conditions were performed. We also used computational chemistry as a tool to better understand why the cobalt(II) acetylacetonate (Co(acac)2) has, so far, given the best results for either vinyl acetate or vinyl amides polymerization. Thanks to Density Functional Theory (DFT), the crucial role of the monomer carbonyl group coordination to cobalt was pointed out.

Item Type:PhD Thesis
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Institution:Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
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Research Director:
Poli, Rinaldo
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Deposited On:19 Dec 2013 22:58

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