Entry rate coefficients in emulsion polymerization systems

Penboss, I. A., Gilbert, R. G. and Napper, D. H. (1986) Entry rate coefficients in emulsion polymerization systems. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 82 2247-2268. doi:10.1039/f19868202247


Author Penboss, I. A.
Gilbert, R. G.
Napper, D. H.
Title Entry rate coefficients in emulsion polymerization systems
Journal name Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases   Check publisher's open access policy
ISSN 0300-9599
Publication date 1986-01-01
Sub-type Article (original research)
DOI 10.1039/f19868202247
Volume 82
Start page 2247
End page 2268
Total pages 22
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
A detailed theory is presented for the rate coefficient for entry of free radicals into latex particles in emulsion polymerization systems; this yields an expression for the radical capture efficiency. The first-order rate coefficient for entry into a latex particle (ρ) can be accurately represented as ρ = ρA + αknĚ„, where ρA is the rate coefficient for entry of free radicals arising directly from initiator, α is a 'fate parameter' giving the relative importance of re-entry and heterotermination of desorbed free radicals, k is the exit rate coefficient and n is the average number of free radicals per latex particle. Expressions for ρA and α in terms of the rate coefficients for the component aqueous-phase mechanisms are also presented, including the dependence on the concentration of initiator and number density of latex particles. This theory is applied to extensive data on the seeded emulsion polymerization of styrene: this is a typical non-polar monomer, for which capture efficiencies are commonly low. The data fitting includes an extensive sensitivity analysis. An excellent fit to the data is obtained, whence rate coefficients for the individual aqueous phase processes may be deduced. It is concluded for this system either that entering free radicals are colloidal in nature and/or that the entering oligomeric free radical must displace a surfactant molecule from the surface of the particle. Expressions enabling one to calculate ρ (and thus the capture efficiency) for use in modelling studies of non-polar monomers are presented.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: Centre for Nutrition and Food Sciences Publications
 
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Created: Tue, 08 Mar 2011, 01:54:54 EST