Synthesis and characterization of star and comb polystyrenes using isometric poly(chloroethyl vinyl ether) oligomers as reactive backbone

In the course of studies dealing with the synthesis and the characterizatio n of the properties of highly branched polymers with controlled chain param eters, the selectivity of the grafting reaction of polystyryllithium chains onto poly(chloroethyl vinyl ether) has been investigated. To that purpose, a series of isometric poly(chloroethyl vinyl ether) oligomers with precise degree of polymerization, ranging from 3 to 9, were prepared by selective fractionation of a poly(CEVE) of narrow polydispersity into its different n -mers. The latter were used as reactive backbone for grafting PSLi chains. Characterization of the graft copolymers shows that the substitution of chl oride off CEVE units is quantitative and yields comblike copolymers with a number of branches corresponding to the number of monomer units in the isom etric poly(CEVE) backbone. The poly/CEVE)-g-polystyrenes show the typical s olution behavior of star polystyrenes.