FUNCTIONALIZED POLYMERS BY NONCATALYTIC ADDITION-FRAGMENTATION CHAIN TRANSFER - MODELING AND SIMULATION OF END-GROUP FUNCTIONALITY AND MOLECULAR-WEIGHT DISTRIBUTION FOR HIGH-CONVERSION REACTIONS IN A BATCH PROCESS

Kinetic models of free radically initiated polymerizations involving c hain transfer by the noncatalytic addition-fragmentation mechanism hav e been simulated with the aim of finding the effect of conversion on t he molecular weight, molecular weight distribution, and the efficiency with which specific end-group-functionalized polymers are produced. T he specific situations explored are those where (i) the magnitude of t he chain transfer constant is varied in processes where the rate of in itiation is moderate and termination takes place exclusively by combin ation or exclusively by disproportionation and (ii) the magnitude of t he initiation rate is varied for processes where there is considerable chain transfer occurring and termination is exclusively by combinatio n. These systems have been examined in detail because they relate to l ikely practical systems for the synthesis of well-tailored telechelic polymers. The results show that there are situations where it is possi ble to produce the functionalized polymers of interest with high effic iency but not with the concurrent control of the molecular weight dist ribution of the product.