Kinetic aspects of the emulsion polymerization of butadiene

Weerts, P.A., German, A.L. and Gilbert, R.G. (1991) Kinetic aspects of the emulsion polymerization of butadiene. Macromolecules, 24 7: 1622-1628. doi:10.1021/ma00007a027

Author Weerts, P.A.
German, A.L.
Gilbert, R.G.
Title Kinetic aspects of the emulsion polymerization of butadiene
Journal name Macromolecules   Check publisher's open access policy
ISSN 0024-9297
Publication date 1991-04
Sub-type Article (original research)
DOI 10.1021/ma00007a027
Volume 24
Issue 7
Start page 1622
End page 1628
Total pages 7
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract Kinetic information on particle growth is obtained for the ab initio emulsion polymerization of butadiene. It is shown that the decrease in particle number by coagulation (induced by the high ionic strength) hardly affects polymerization rate, since the average number of radicals per particle (n̄) increases with particle size. From a rate analysis of intervals II and III it follows that the system is "zero-one" (n̄ ≤ 0.5), i.e., termination is not rate-determining. Zero-one kinetics, in combination with a low initiator efficiency, explains the small effect of initiator concentration on polymerization rate. The radical loss mechanism responsible for the zero-one kinetics could not be established unambiguously, but chain transfer/desorption processes involving polybutadiene, thiol, surfactant, and the Diels-Alder dimer 4-vinyl-1-cyclohexene were all refuted on experimental grounds. Desorption of monomeric species seems a reasonable explanation, given the rather low estimate for the propagation rate coefficient.
Keyword Particle Nucleation
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
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Created: Mon, 07 Mar 2011, 15:59:25 EST