Vinyl polymerization. IV. Influence of dimethylaniline on solution polymerization of vinyl chloride catalyzed by benzoyl peroxide

Abstract

In the solution polymerization of vinyl chloride with benzoyl peroxide, it was found that the initial rate of the polymerization was remarkably increased by adding dimethylaniline, but that conversion became constant at lower conversion. It was observed that when the rate became constant the benzoyl peroxide was completely decomposed and the reaction could be reinduced by adding more benzoyl peroxide. On the basis of these results, it seems possible that the polymerization is instituted by the benzoate radical and not by the dimethylaniline radical as suggested by Horner. The benzoate radical is produced through the reaction of dimethylaniline with benzoyl peroxide. In view of such considerations, we postulate a reaction mechanism for the polymerization of vinyl chloride.

Single Electron Transfer in Radical Ion and Radical-Mediated Organic, Materials and Polymer Synthesis

“…When the reaction conversion reached a plateau, no more benzoyl peroxide was left in the reaction mixture. Addition of extra benzoyl peroxide resumed the reaction . Kinetics study of polymerization of Sty catalyzed by benzoyl peroxide and dimethylaniline led the authors to conclude that this reaction was initiated by a SET process between aniline and peroxides .…”

“…Later, the same effect was also observed by Kimura's laboratory. 805 The polymerization of vinyl chloride initiated by benzoyl peroxide was carried out in THF, ethylene dichloride, dioxane, cyclohexanone, and methyl ethyl ketone in the presence or absence of dimethylaniline (Scheme 284).…”

“…Addition of extra benzoyl peroxide resumed the reaction. 805 Kinetics study of polymerization of Sty catalyzed by benzoyl peroxide and dimethylaniline led the authors to conclude that this reaction was initiated by a SET process between aniline and peroxides. 806 However, because there was ambiguity as to whether nitrogen was found in the final polymers, the radical anion of the amine was not considered to initiate the reaction.…”

Suspension polymerization of vinyl chloride at low temperature with the use of monomer‐soluble redox initiators

“…Effect of polymerization temperature on molecular weight of polymer. 1,PO ( 1 ) 0.4, (2) 0.3, ( 3 ) 0.2, ( 4 ) 0.1, (5) 0.05, ( 6 ) 0.025 mole-% to monomer; chloroform, ( I ) 3.40, (2) 2.64,( 8 ) 1.78, ( 4 ) 0.80, (Fi) none, (6)none, mole-% to monomer. Temperature dependence of overall rate of polymerization…”