Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride

Journal Article · Mon Mar 01 00:00:00 EST 1982 · J. Polym. Sci., Polym. Chem. Ed.; (United States)

DOI:https://doi.org/10.1002/pol.1982.170200304· OSTI ID:5620554

Zubov, V P; Lachinov, M B; Ignatova, E V; Georgiev, G S; Golubev, V B; Kabanov, V A

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), Vol. 20:3
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
COPOLYMERIZATION
CHEMICAL REACTION KINETICS
LEWIS ACIDS
METHYL METHACRYLATE
CHEMICAL RADIATION EFFECTS
STYRENE
ALUMINIUM CHLORIDES
COMPARATIVE EVALUATIONS
EXPERIMENTAL DATA
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
RADICALS
ULTRAVIOLET RADIATION
ALUMINIUM COMPOUNDS
AROMATICS
CARBOXYLIC ACID ESTERS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
DATA
ELECTROMAGNETIC RADIATION
ESTERS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
METHACRYLIC ACID ESTERS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYMERIZATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
REACTION KINETICS
SPECTRA
360401* - Polymers & Plastics- Preparation & Fabrication- (-1987)
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400600 - Radiation Chemistry