Polymerization initiated by an electron donor–acceptor complex. Part IV. Kinetic study of polymerization of methyl methacrylate initiated by the charge‐transfer complex consisting of poly‐2‐vinylpyridine and liquid sulfur dioxide

Abstract

A kinetic study has been made of the polymerization of methyl methacrylate (MMA) initiated by a charge‐transfer complex of poly‐2‐vinylpyridine (electron donor) and liquid sulfur dioxide (acceptor) in the presence of carbon tetrachloride. It is concluded that the polymerization proceeds through free‐radical intermediates, as with the pyridine‐liquid sulfur dioxide complex system. The association constants K of acceptor and polymer electron donors which range widely in their molecular weight were determined spectrophotometrically, and it has been found that both K and overall rate of polymerization Rp of MMA decrease with increasing molecular weight of polymer donor; contrary to this, molecular weight of PMMA formed increases with increasing molecular weight of the polymer donor. Other kinetic behaviors was essentially the same as in the pyridine–liquid sulfur dioxide system, i.e., Rp is proportional to the square root of the concentration of the complex and to the 3/2‐order of the monomer concentration; Rp is clearly sensitive to the carbon tetrachloride concentration at low concentration of carbon tetrachloride, but for a higher concentration it is practically independent of the carbon tetrachloride concentration. It has been deduced from a kinetic mechanism for the initiation that a primary radical may be produced from the reduction of carbon tetrachloride by an associated complex consisting of liquid sulfur dioxide–polymer donor and the monomer.

Kinetics and modeling of charge transfer polymerization of methyl methacrylate

“…The value obtained is 3.75 kcal/mol, which is much less than 6.7 kcal/mol as reported in literature [1] for a system similar to that of the present study but accelerated by metal complex. This confirms the advantage of charge transfer polymerization over other methods.…”

“…E-mail: psts@iitm.ac.in charge transfer polymerization of MMA are summarized in Table 1. Matsuda and Ishiroshi [1] investigated kinetics initiated by transfer complex of poly-2-vinyl pyridine and liquid sulfur dioxide in the presence of carbon tetrachloride (CCl 4 ). They studied the effect of concentrations of complex, monomer and CCl 4 on the rate of polymerization and reported that both equilibrium constant and overall rate of polymerization decreased with increasing molecular weight of polymer donor.…”

Effect of ferric cyanide ions on the polymerization of methyl methacrylate

“…There has been increasing interest in the initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and vinyl chloride by the charge transfer mechanism (1)(2)(3)(4)(5). The polymerization of MMA by a compound containing a donor nitrogen atom in the presence of carbon tetrachloride (CC14) is now well established (6).…”

Polymerization of methylmethacrylate initiated by charge‐transfer complex

“…A charge-transfer mechanism for the initiation of MMA has been proposed. polymerization by charge-transfer complexes (2,3). It was observed that polymerization could be initiated by a charge-transfer complex I in the presence of carbon tetrachloride in a solvent like N, Ndimethyl formamide (DMF), dimethyl sulphoxide (DMSO), or chloroform at 30°C.…”