Pulsed Laser Polymerization of Alkyl Acrylates: Potential Effects of the Oxygen Presence and High Laser Power

Castignolles, Patrice, Nikitin, Anatoly N., Couvreur, Laurence, Mouraret, Guillaume, Charleux, Bernadette and Vairon, Jean-Pierre (2006) Pulsed Laser Polymerization of Alkyl Acrylates: Potential Effects of the Oxygen Presence and High Laser Power. Macromolecular Chemistry and Physics, 207 1: 81-89. doi:10.1002/macp.200500402


Author Castignolles, Patrice
Nikitin, Anatoly N.
Couvreur, Laurence
Mouraret, Guillaume
Charleux, Bernadette
Vairon, Jean-Pierre
Title Pulsed Laser Polymerization of Alkyl Acrylates: Potential Effects of the Oxygen Presence and High Laser Power
Journal name Macromolecular Chemistry and Physics   Check publisher's open access policy
ISSN 1521-3935
1022-1352
Publication date 2006-01-03
Sub-type Article (original research)
DOI 10.1002/macp.200500402
Open Access Status
Volume 207
Issue 1
Start page 81
End page 89
Total pages 9
Place of publication Zug
Publisher Wiley-VCH
Language eng
Subject 0303 Macromolecular and Materials Chemistry
Formatted abstract
Summary:  Unexpected difficulties are encountered in the determination of propagation rate coefficients (kp) in free radical polymerization of alkyl acrylates by pulsed laser polymerization (PLP), mainly due to intramolecular transfer to polymer.[1] This article is focused on the role played by the high laser power in these difficulties and the possible reactions of mid-chain radical with residual oxygen. Removing the oxygen by simple bubbling of nitrogen is sufficient to avoid alteration of the polymerization kinetics of acrylates by residual oxygen under PLP conditions. Moreover, no degradation of polymer (or solvent) has been detected after irradiation with the high laser power typically used in PLP experiments. However, it has been shown that this high laser power completely prevents from having a temporally and spatially homogeneous radical concentration in the PLP cell. A model is proposed here to simulate the pulsed laser polymerization taking initiator consumption and laser energy absorption into account. According to our simulation results, this non-negligible initiator consumption and laser power absorption can indeed have a positive influence, i.e., it favors the obtainment of a bimodal molar mass distribution fulfilling the IUPAC consistency criteria. This observation may contradict the idea that PLP-SEC is not suitable to determine accurate kp values for acrylates above 20-30 °C.
Keyword acrylates
degradation
free radical polymerization
kinetics (polymerization)
photoinitiation
pulsed laser polymerization (PLP)
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collections: Excellence in Research Australia (ERA) - Collection
Centre for Nutrition and Food Sciences Publications
 
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Created: Tue, 31 Mar 2009, 23:57:38 EST by Ms Julie Schofield on behalf of Centre for Nutrition and Food Sciences