Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride
A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and uv-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated.
- Research Organization:
- Lomonosov State Univ., Moscow, USSR
- OSTI ID:
- 5620554
- Journal Information:
- J. Polym. Sci., Polym. Chem. Ed.; (United States), Journal Name: J. Polym. Sci., Polym. Chem. Ed.; (United States) Vol. 20:3; ISSN JPLCA
- Country of Publication:
- United States
- Language:
- English
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ALUMINIUM CHLORIDES
ALUMINIUM COMPOUNDS
AROMATICS
CARBOXYLIC ACID ESTERS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPARATIVE EVALUATIONS
COPOLYMERIZATION
DATA
ELECTROMAGNETIC RADIATION
ESTERS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
LEWIS ACIDS
METHACRYLIC ACID ESTERS
METHYL METHACRYLATE
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYMERIZATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
REACTION KINETICS
SPECTRA
STYRENE
ULTRAVIOLET RADIATION