Document Type

Thesis

Date of Award

5-31-1970

Degree Name

Master of Science in Chemical Engineering - (M.S.)

Department

Chemical Engineering and Chemistry

First Advisor

Angelo J. Perna

Second Advisor

Hung T. Chen

Third Advisor

William H. Snyder

Abstract

The free radical solution polymerization of vinyl acetate in benzene was studied under simulated commercial conditions. The effects of monomer, initiator, inhibitor, and chain transfer agent concentration on the reaction rate and intrinsic viscosity were examined. The initial reaction rates with monomer concentrations from 40% to 70% and AIBN concentrations from 0.2% to 0.5% were in agreement with the kinetic equation, - d[M]/dT = K[M]2 [I]1/2. After the initial reaction there was an increase in the reaction rate apparently associated with high viscosities, which is consistent with the Trommsdorff effect. The addition of hundredths of a percent hydroquinone reduced the initial reaction rate significantly but the final reaction rate was not effected. The addition of a lower boiling solvent, hexane, reduced the reaction rate and the addition of a higher boiling diluent, heptane, increased the reaction rate. The changes of the reaction rate were apparently associated with the changes in the reaction temperature. The addition of 0.03% dodecyl mercaptan, a chain transfer agent, decreased the initial reaction rate and the polymer intrinsic viscosity by 11%.

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