The addition of bromotrichloromethane to vinyl acetate. Part 1.—The products of the photochemical and benzoyl-peroxide-catalyzed reactions

Bengough, W. I.; Thomson, R. A. M.

doi:10.1039/tf9605600407

Cited by 9 publications

(4 citation statements)

References 2 publications

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“…The rate-concentration relationships can therefore be summarized as follows : Again, from the results given in part l , 4 it would appear that reaction (7) and subsequent polymerization propagation reactions might contribute to the overall contraction rate and hence be indistinguishable from the reaction resulting in the formation of 1 : 1 adduct. No obvious explanation can be given for the 3/2 power dependence of the rate on the BTCM concentration obtained by previous workers 1 under conditions of excess vinyl acetate.…”

Section: Intensity Exponentsmentioning

confidence: 99%

Addition of bromotrichloromethane to vinyl acetate. Part 2.—Kinetics of the photochemical reaction

Bengough¹,

Thomson²

1961

Trans. Faraday Soc.

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Attempts have been made to measure the velocity coefficients involved in the photochemical addition of bromotrichloromethane to vinyl acetate. The system was studied using concentrations of bromotrichloromethane ranging from 0.26-9-58 mole 1.-1, and of vinyl acetate from 0.55-10.5 mole 1.-1. Conditions could not be found such that the chain-transfer reaction between a bromotrichloromethane molccule and the radical produced by the addition of a trichloromethyl radical to a vinyl acetate molecule became rate-controlling, and hence we could not measure its velocity coefficient. Rates of initiation were measured using DPPH, and the values obtained were found to be influenced to some extent by the solvent employed, and also by the technique used. These effects are reflected in the values of the velocity coefficients, which at 25°C were found to be : k2 = 795, 2410 and 1590 1. mole-1 sec-1, and k4 = 0.53 X 108, 1.61 x 108 and 1 . 0 6 ~ 108 1. mole-1 sec-1, when the rate of initiation was determined absorptiometrically in monomer, in solvent, and dilatometrically respectively. The last value in each case, is in good agreement with the results of previous workers 1 who evaluated these coefficients by substantially the same method.

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Section: Intensity Exponentsmentioning

confidence: 99%

Addition of bromotrichloromethane to vinyl acetate. Part 2.—Kinetics of the photochemical reaction

Bengough¹,

Thomson²

1961

Trans. Faraday Soc.

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“…2 1,l'-Azo-bis-isobutyronitrile (AIBN) was also obtained from Kodak Ltd. and purified by recrystallization from absolute ethanol, giving a product with m.p. 2 1,l'-Azo-bis-isobutyronitrile (AIBN) was also obtained from Kodak Ltd. and purified by recrystallization from absolute ethanol, giving a product with m.p.…”

Section: Methodsmentioning

confidence: 99%

“…They deduced that under conditions such that reaction (2) is the slow step in the propagation process (e.g., with excess TBr) termination proceeds mainly via reaction (4), and the rate of reaction is then given by -dM/d t = k2(l/k4)0* 5 [MI, (i) where I is the rate of initiation. Again when reaction (3) is rate controlling, termination occurs mainly by reaction (6) and the rate is given by -dM/dt = k3(I/k@*5[TBr].…”

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Kinetic studies on the telomerization and polymerization of vinyl chloride

Bengough¹,

Thomson²

1965

Trans. Faraday Soc.

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The photochemical reaction between brornotrichloromethane (TBr) and vinyl chloride (VC) has been studied over a wide range of reactant concentrations varying from 0.087 to 9.24 mole 1.-1 for TBr and from 1.26 to 14.4 mole 1.-1 for VC. The products of the reaction vary from the 1 : 1 adduct to low molecular weight polymer. Under the conditions studied, the reactions proceed by radical chain processes. When TBr is in excess, the addition of trichloromethyl radicals to VC is the rate-determining step, and the velocity coefficient for this reaction at 25°C was 990-1950

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“…On the other hand, even a much lower concentration of bromotrichloromethane gives halogenated styrene as the principle photoproduct (160). Chain transfer for polymer radicals to halogenated alkanes can often be very great; only telomer or low molecular weight polymer is produced (43,278).…”

Section: Halogen-containing Compoundsmentioning

confidence: 99%