Pulsed laser study of the propagation kinetics of acrylamide and its derivatives in water

Pascal, P., Winnik, M.A., Napper, D.H. and Gilbert, R.G. (1993) Pulsed laser study of the propagation kinetics of acrylamide and its derivatives in water. Macromolecules, 26 17: 4572-4576. doi:10.1021/ma00069a024

Author Pascal, P.
Winnik, M.A.
Napper, D.H.
Gilbert, R.G.
Title Pulsed laser study of the propagation kinetics of acrylamide and its derivatives in water
Journal name Macromolecules   Check publisher's open access policy
ISSN 0024-9297
Publication date 1993-08
Sub-type Article (original research)
DOI 10.1021/ma00069a024
Volume 26
Issue 17
Start page 4572
End page 4576
Total pages 5
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
The pulsed laser polymerization method has been applied to aqueous acrylamide (AAm) in the absence and presence of 3 mol dm-3 propionamide to obtain the propagation rate coefficient (kp) as a function of temperature. Below ca. 50°C in the absence of propionamide, kp decreases with increasing temperature. It is proposed that this is due to the existence of an H-bonded intermediate complex along the reaction coordinate, which at low temperatures enhances propagation but which breaks down at higher temperatures. In the presence of propionamide or above 50°C in the absence of propionamide, the temperature dependence of kp behaves normally, supporting the proposition. Assuming that the high-temperature rate represents "normal" propagation in the absence of the formation of complex, kp = 7 × 106 dm3 mol-1 s-1 exp[-(21 ± 2 kJ mol-1)/RT]. Analysis of these results suggests that the driving force behind the proposed intermediate complex could be H-bonding in nature. Studies of kp for α-methyl- and N-methyl-substituted AAm derivatives indicate that the former imposes greater constraints upon the propagation pathway than the latter.
Keyword Free-radical polymerization
Flash-initiated polymerization
Consistent values
Rate parameters
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, 15:54:36 EST