The photolysis of n-butyl-(N,N-diethyl dithiocarbamyl)propionate (RTC), an initiator for "livingΓ free radical polymerizations, has been investigated in order to elucidate the mechanism of these polymerizations. The photolysis yields tetraethylthiuram disulphide (TED), and its degradation products,
Mechanism of the polymerization ofn-butyl acrylate initiated byN,N-diethyldithiocarbamate derivatives. Part 2. Investigation of the reaction mechanism
β Scribed by Dika Manga, J.; Tardi, M.; Polton, A.; Sigwalt, P.
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 321 KB
- Volume
- 45
- Category
- Article
- ISSN
- 0959-8103
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β¦ Synopsis
The polymerization of n-butyl acrylate (BuAc) initiated with a model compound (butyl-2-(N,N-diethyldithiocarbamyl)propionate, RTC) has been investigated. The living character of this polymerization has been assessed and compared with those of styrene and methyl methacrylate. The small variation of with yield is explained by the faster propagation than for styrene and methyl M 1 n methacrylate, which leads to slow initiation and extensive transfer to the initiator. Predominant reversible termination (or deactivation) of the growing chains by the dithiocarbamyl radicals gives, however, polymers of functionality near to unity, which are photoinitiated at the same rate as RTC and reinitiate the polymerization of BuAc with a linear growth of the up to 40% yield. This is M 1 n better than was obtained with methyl methacrylate. Side reactions also take place leading to a decrease of functionality, to the formation of tetraethylthiuram disulphide and of carbon disulphide. Possible mechanisms are proposed for the secondary reactions.
1998 SCI.
π SIMILAR VOLUMES
Conductimetry was used for monitoring the radical polymerization of a weak electrolyte (acrylic acid) in aqueous solution and for determination of the kinetic parameters of the reaction (reaction order with respect to monomer, activation energy). The results obtained were consistent with those deter