NDLI: Synthetic and mechanistic inputs of photochemistry into the bis-acetylacetonatocobalt-mediated radical polymerization of n-butyl acrylate and vinyl acetate

Content Provider	Royal Society of Chemistry (RSC)
Author	Hurtgen, Marie Jérôme, Christine Piette, Yasmine Detrembleur, Christophe Lalevée, Jacques Debuigne, Antoine Versace, Davy-Louis
Copyright Year	2012
Abstract	The input of photochemistry to the Co(acac)2 mediated radical polymerization (CMRP) of n-butyl acrylate and vinyl acetate is investigated for the first time. Upon UV irradiation, photoinitiators are able to initiate the n-butyl acrylate polymerization that remains controlled up to very high molar masses (>4 × 106 g mol−1) with low polydispersities. The photoinitiator as well as the irradiation time must be appropriately chosen to reach acceptable initiator efficiencies while maintaining an optimal control over the polymerization. Laser flash photolysis experiments were then carried out to evidence the addition of alkyl and phosphonyl radicals onto Co(acac)2 and to determine the rate constants (kdeact) of these addition reactions that were still lacking. Finally, both kinetics of polymerization and spin-trapping experiments have evidenced that the C–Co bond at the extremity of the dormant polymer chains can be easily photocleaved. UV irradiation can therefore be considered as an additional lever for tuning the reactivity of the CMRP process mediated by Co(acac)2.
Starting Page	1856
Ending Page	1866
Page Count	11
File Format	HTM / HTML PDF
ISSN	17599954
Volume Number	3
Issue Number	7
Journal	Polymer Chemistry
DOI	10.1039/c1py00443c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Molar mass Alkyl Chemical bond Acrylate Optimal control Radical polymerization Polymerization Polymer Flash photolysis Vinyl acetate Photochemistry Photoinitiator
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Bioengineering Biomedical Engineering Polymers and Plastics

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