COPOLYMERIZATION WITH CHAIN TRANSFER MONOMER .2. MOLECULAR-WEIGHT DISTRIBUTION

The full molecular weight distribution formed in a batch free-radical copolymerization with chain transfer monomer is considered theoretical ly. A Monte Carlo simulation algorithm is proposed on the basis of the random sampling technique. Illustrative calculations are conducted fo r the cases with equal reactivity of all types of double bonds. It was found that even when the probability of possessing a branch point is the same for all units, the formed molecular weight distribution is hi ghly dependent on the chain connection rule. Bimolecular termination b y combination may contribute to form extremely large polymer molecules by forming cross-linkages between primary chains. Under the idealized conditions, homogeneously branched polymer molecules are formed, and the analytical solution for the molecular weight distribution can be o btained.