By use of carbon black that contained alkali metal carboxylate (COOM; MLi, Na, K, Rb, or Cs) group as catalyst the anionic polymerization of β‐propiolactone (PL) was carried out at 50°C and the grafting of polyester onto the carbon black surface was investigated. Carbon black that contained COOM group was prepared by the reaction of carboxyl group on the surface with corresponding alkali metal hydroxide and was able to initiate the anionic ring‐opening polymerization of PL. The carbon black obtained from the reaction gave a stable colloidal dispersion in an organic solvent. It was confirmed that the polyester formed was grafted effectively onto the surface; for instance, by using carbon black that contained COOK group as catalyst the grafting ratio was increased to 145% (viz., 1.45 g of polyester was grafted/1 g of carbon black) with an increase in conversion. Furthermore, the effect of alkali metal countercation (M+) on the polymerization was studied. The initiating activity of COOM group on the surface increased in the following order: COOLi < COONa < COOK < COORb < COOCs. This order was in agreement with that of increasing electropositivity of these alkali metals.
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