Article (Scientific journals)
Diffusive radical entry as the rate-determining step in amphiphilic block polyelectrolyte mediated emulsion polymerization
Leemans, Luc; Jérôme, Robert; Teyssié, Philippe
1998In Macromolecules, 31 (17), p. 5565-5571
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Keywords :
radical polymerization; emulsion polymerization
Abstract :
[en] The amphiphilic water soluble block polyelectrolytes PMMA-b-SPGMA and PMMA-b-QPDMAEMA are efficient surfactants for the radical emulsion polymerization. Negatively charged, neutral, and positively charged entering radicals were used in combination with polyanionically and polycationically tailored PMMA latex particles. It was shown that the rate of polymerization was very high for systems wherein the entering radical species had an electrical charge sign identical with that of the polyelectrolyte corona around the latex particle. PMMA-b-SPGMA turned out to be 4 times as efficient as compared to SDS emulsified MMA polymerization at 0.6 wt %. Systems wherein polyelectrolyte block and entering radical were of opposite sign displayed strongly reduced polymerization rates. When the polyelectrolyte barrier became thick enough, as in the case of a Mn = 26 000 PMMA-b-QPDMAEMA, no more polymerization was observed. The observed polymerization rate effects are discussed in terms of repulsion of equal charge radicals, leading to enhanced mobility and counterion mobility restriction of the radicals of opposite sign to the polyelectrolyte block. In the latter case, this slowed counterion diffusion of radicals of opposite sign leads to premature aqueous phase termination of free radicals and consequently low flux of entering radicals with low rates of polymerization. The experimental results obtained are consistent with the theoretically predicted case, where the “control by aqueous phase growth” theory for the entry of free radicals in latex particles is invalid.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering
Chemistry
Author, co-author :
Leemans, Luc;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Diffusive radical entry as the rate-determining step in amphiphilic block polyelectrolyte mediated emulsion polymerization
Publication date :
25 August 1998
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Volume :
31
Issue :
17
Pages :
5565-5571
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
Agfa-Gevaert [BE]
Available on ORBi :
since 23 June 2009

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