Termination Kinetics in Free-Radical Bulk Copolymerization: The Systems Dodecyl Acrylate-Dodecyl Methacrylate and Dodecyl Acrylate-Methyl Acrylate

Buback, M. & Kowollik, C. (1999) Termination Kinetics in Free-Radical Bulk Copolymerization: The Systems Dodecyl Acrylate-Dodecyl Methacrylate and Dodecyl Acrylate-Methyl Acrylate. Macromolecules, 32(5).

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Abstract

The termination kinetics in free-radical bulk copolymerization of the dodecyl acrylate (DA)-dodecyl methacrylate (DMA) and DA-methyl acrylate (MA) systems has been studied by exclusively applying laser-assisted techniques. The ratio of termination to propagation rate coefficients, kt/kp, is measured by the SP-PLP technique, and kp is deduced from PLP-SEC. kt is determined up to fairly large degrees of overall monomer conversion, at least up to 40%. The discussion of the present paper focuses on the initial plateau region of constant kt, which extends up to about 15% in MA homopolymerizations and up to 70% in DA homopolymerizations. Among the existing models for copolymerization kt, the treatment that considers penultimate units and uses the geometric mean approximation to estimate cross-termination turns out to be excellently applicable. It is particularly noteworthy that plotting log kt vs monomer mole fraction (fi) yields a linear correlation for each of the two copolymerization systems. The excellent fit of kt,copo by the penultimate unit model provides some evidence that steric effects significantly contribute to termination rate control in (meth)acrylate free-radical polymerization at low and moderate degrees of monomer conversion. The entire set of experiments has been carried out at high pressure (1000 bar, 40°C) where the signal-to-noise ratio of the SP-PLP experiments is very satisfactory. No reason is seen why the conclusions derived from these measurements should not be valid at other reaction conditions including ambient pressure.

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ID Code: 99038
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :59
Export Date: 20 September 2016
CODEN: MAMOB
Correspondence Address: Buback, M.; Inst. für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany
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Keywords: Copolymerization, Free radical polymerization, Homopolymerization, Mathematical models, Monomers, Polyacrylates, Pulsed laser applications, Reaction kinetics, Size exclusion chromatography, Penultimate unit model, Polydodecyl acrylate, Polydodecyl methacrylate, Polymethyl acrylate, Pulsed laser polymerization (PLP), Copolymers
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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