We present a theory of the "autoacceleration" of polymerization rates during free radical polymerization, known as the gel effect. Termination reactions between long living chains are so retarded by entanglements that "short-long" terminations provide the fastest mechanism. Consistent with several experiments, this leads to polymerization rates independent of the radical production rate Rᵢ, in contrast to the √Rᵢ dependence in the classical theory. For long chains, the instantaneous polymer product is a copy of the living population, following an exponential distribution with mean length N̄~1Rᵢ.
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O’Shaughnessy et al. (1994) studied this question.
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