Date of Award

Spring 1984

Document Type

Dissertation

Degree Name

Doctor of Engineering Science in Chemical Engineering

Department

Chemical Engineering and Chemistry

First Advisor

Ching-Rong Huang

Second Advisor

John E. McCormick

Third Advisor

David S. Kristol

Fourth Advisor

George Y. Lei

Fifth Advisor

Richard C. Progelhof

Abstract

Mathematical modeling of unsteady state photopolymerization in an isothermal batch reactor has been investigated. An analytical solution of the distribution of active polymers as a function of reaction time has been determined. It is verified that the quasi-stationary state approximation is valid in the photopolymerization process.

The free radical polymerization of styrene is forced periodically by on-off UV light regulation to the reactor. The effect of operating condition, the ratio of light-off period to light on/off period, on the polydispersity and molecular weight distribution are theoretically and numerically investigated. Significant broadening on molecular weight distribution can be obtained during the unsteady state process.

Experimental results of polydispersity are compared to a kinetic model of a nonuniformly initiated photopolymerization, which comprises a high dose rate region and a very low dose rate region. Good agreement is obtained between the model and experiments after fitting three parameters.

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