The termination reaction in free radical copolymerization. I. Methyl methacrylate and butyl‐ or dodecyl methacrylate

Using a spatially intermittent reactor, the absolute rate constant for the termination reaction in free radical copolymerization has been measured for the monomer pair methyl methacrylate (MMA)–butyl methacrylate (BMA). For the pair MMA–dodecyl methacrylate (DMA) the relative rate constant for termination has been measured. In both cases the termination rate constant was a monotonically changing function of the monomer feed composition. This function can be well approximated by a simple calculation of the enchained monomer units' contributions to the average segmental friction coefficient of the copolymer chain. An attempt to apply a previously derived theoretical treatment based on penultimate unit effects produced physically unrealistic results.