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| - Molecular Weight Distribution in Free-Radical PolymerModification with Cross-Linking: Effect ofChain-Length-Dependent Termination
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| Abstract
| - A general equation of molecular weight distribution has beenderived for free-radical polymermodification with cross-linking. The equation takes into accountchain-length-dependent diffusion-controlled radical termination. It reduces to Saito's equation whenthe termination becomes chain-lengthindependent. A simple three-parameter chain-length-dependencefunction is employed. Calculations ofmolecular weight development, gel point, and gel/sol fraction for bothpolymer and radical populationshave been made numerically with a uniform initial distribution. Ithas been shown that the chain-length-dependent termination has a strong effect on the molecular weightdevelopment and gelationbehavior. It causes significant deviation from the well-studiedrandom process of cross-linking. It delaysgel point but accelerates gel growth.
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