HIGH-CONVERSION POLYMERIZATION .7. A DEFINITION OF THE EXPLOSIVE REGION AND THE INFLUENCE OF FREE-VOLUME ON IT

The easily observed autoacceleration of free radical polymerization is defined as the explosive region and an arbitrary but quantitative definition of it is made. Using this definition it is shown that the explosive regions of solution polymerizations of methyl methacrylate occur at constant values of the product of polymer concentration times (molecular weight)** one-half . This upholds the concept that polymer entanglements control the termination reaction in this region. It is also shown that this region does not, as previously suggested, occur at a constant value of free volume, but that free volume does play a role in determining the rate of termination at a given level of chain entanglements.