Emulsifier-Free Polymerization of Methyl Methacrylate
with a Carboxyl-Containing Initiator¹

A. Yu. Men’shikova*², T. G. Evseeva*, M. V. Peretolchin*,
N. A. Chekina*, and S. S. Ivanchev**

* Institute of Macromolecular Compounds, Russian Academy of Sciences,
Bol’shoi pr. 31, St. Petersburg, 199004 Russia

** Boreskov Institute of Catalysis (St. Petersburg Branch), Siberian Division, Russian Academy of Sciences,
pr. Dobrolyubova 14, St. Petersburg, 197198 Russia

Received June 21, 2000;
Revised Manuscript Received September 28, 2000

Abstract—It was shown that the emulsifier-free polymerization of methyl methacrylate initiated by 4,4'-azo-
bis(4-cyanovaleric acid) at high initial pH values differs from the polymerization of styrene carried out under
analogous conditions. It was demonstrated that the hydrolysis of the monomer in an alkaline medium with the
formation of methacrylic acid leads to a decrease in the rate of polymerization and to a reduction in the diameter
of microspheres; nevertheless, the extent of carboxylation of the particle surface drops as pH increases. Varying
the initial pH value enables one to control the diameter of the monodisperse microspheres of PMAA in a sub-
micron range.

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