No abstract

Kinetic models of free radically initiated polymerizations involving chain transfer by the noncatalytic addition−fragmentation mechanism have been simulated with the aim of finding the effect of conversion on the molecular weight, molecular weight distribution, and the efficiency with which specific end-group-functionalized polymers are produced. The specific situations explored are those where (i) the magnitude of the chain transfer constant is varied in processes where the rate of initiation is moderate and termination takes place exclusively by combination or exclusively by disproportionation and (ii) the magnitude of the initiation rate is varied for processes where there is considerable chain transfer occurring and termination is exclusively by combination. These systems have been examined in detail because they relate to likely practical systems for the synthesis of well-tailored telechelic polymers. The results show that there are situations where it is possible to produce the functionalized polymers of interest with high efficiency but not with the concurrent control of the molecular weight distribution of the product.