The Kinetics of the Polymerization of Vinyl Acetate

Abstract

perature immediately before making the observation. Isothermal distillation within the apparatus furnishes a very sensitive test for the purity of the liquid. As the result of observations made on acetic acid, bromine, benzene and carbon tetrachloride, it may be concluded that the vapor pressure of a sample of liquid rapidly elevated to the boiling point is identical with that which it exerts after remaining for several hours at the boiling point. Delay in attaining internal equilibrium is therefore not a factor of influence in the measurement of boiling point or vapor pressure of these liquids, and observations may be made as soon as temperature equilibrium is established.

Auto-oxidation.

“…No polymerization of this substance was found to occur in the dark provided oxygen was excluded, whereas either light or 11 Since the work of Heinemann, numerous other patents, taken in various countries, describe the polymerization of several organic substances in presence of oxygen, organic peroxides, ozone, and ozonides. In connection with this work the following recent contfributions are of interest : the polymerization of styrene catalyzed by benzoperacid (32); that of isoprene, under high pressures, catalyzed by organic peroxides (159); that of vinyl acetate catalyzed by benzoyl peroxide (160); that of styrene, indene, etc. catalyzed by octylene ozonides (161); and that of styrene and cyclopentadiene catalyzed by benzoyl peroxide and diphenylethylene peroxide (162).…”

Volume dilatometry

“…Mondain-Monval [26] determined the various transition temperatmes for sulfm and for selenium. Severa] investigators use d dilatometers to study volume changes dming polymerization [14,30,33] and other reactions [15] . The quantity of bound water in solids has been determined accmatf'ly by similar procedmes [2, ].…”

“…In previous papers on volume dilatometers [5,6,10,12,13,15,16,19,21,28,33,36,38,39], the emphasis has always been on the results obtained, and the descriptions of methods of operation have usually been very brief or missing completely. Standard texts on measurements in physical chemistry do not include descriptions of the construction and operation of volume dilatometers.…”

Determination of the velocity coefficients for polymerization processes. - I. The direct photopolymerization of vinyl acetate

“…This is most readily accomplished by measuring the contraction of the monomer as it polymerizes, the total volume contraction being 26*8 2 % for 100% polymerization at 25° C (Starkweather & Taylor 1930). The reaction vessel was of such dimensions that a drop of 0*01 mm.…”