A Comparison of the Phase-Transfer-Catalyzed Chlorinations of Various Polymethylstyrenes by Hypochlorite

The phase-transfer-catalysed chlorinations of poly(2-methylstyrene), poly(3-methylstyrene), poly(2,4-dimethylstyrene) and poly(2,5-dimethylstyrene) using sodium hypochlorite in chloroform/dichloromethane mixtures are compared with that for poly(4-methylstyrene). Over the range of conditions employed, the chlorination of poly(2-methylstyrene) is barely detectable and the polymers with methyl substituents in the meta position show a lesser tendency to undergo chlorination than those with methyl substituents in the para position. In all cases concomitant modification of the molecular weight distributions of the polymers are minimal when the reactions are carried out at an aqueous phase pH of 8.5 and with a chloroform-rich organic phase. With a dichloromethane-rich organic phase, polymer chain scission is marked. The experimental observations are discussed both in terms of a compatible mechanism and of inductive effects involving the phenyl ring substituents.