Abstract
An effect of the surrounding polymers of a polymer radical on its termination rate has been studied in the radical polymerization of methyl methacrylate. The surrounding polymers were prepared by prepolymerization at a temperature T during time t. After t, the temperature was changed to T* and the polymerization was continued to obtain the kinetic data. When the chain length n̄ of the surrounding polymers was smaller than that n̄* of the polymer radical, termination rate was found to be k̄t∝1/n̄ at n̄≤n̄c and k̄t=const. at n̄>n̄c where n̄c≃300 c−2 (c, polymer concentration). When n̄>n̄*, k̄ is independent of n̄. On the basis of the above results, the onset of the gel effect is defined to be the point at which k̄t changes abruptly at n̄c. This point was found explicitly to be the critical conversion at which n̄–x curve (x, conversion) and n̄c cross each other.
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Ito, K. Effect of the Surrounding Polymers of a Polymer Radical on Its Termination Rate. Polym J 14, 101–106 (1982). https://doi.org/10.1295/polymj.14.101
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DOI: https://doi.org/10.1295/polymj.14.101