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Mechanism of emulsion polymerization of vinylidene chloride. III. Effects of stirring rate on kinetics
Author(s) -
Evans Charles P.,
Hay Peter M.,
Marker Leon,
Murray Robert W.,
Sweeting Orville J.
Publication year - 1961
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1961.070051306
Subject(s) - monomer , kinetics , polymerization , emulsion polymerization , particle (ecology) , polymer , diffusion , polymer chemistry , chemical engineering , persulfate , chloride , pulmonary surfactant , materials science , chemistry , emulsion , organic chemistry , thermodynamics , catalysis , physics , oceanography , quantum mechanics , engineering , geology
The effect of stirring speed on the rate of the persulfate‐catalyzed polymerization of vinylidene chloride has been determined. It was found that the first‐stage rate decreases with increasing stirring speed, that the second‐stage rate increases with increasing stirring speed, and that the rate of the third stage is independent of stirring speed. These results, as well as those of an earlier paper, may be explained in the following manner. The second stage slow‐down results from monomer starvation, caused by slow diffusion from coalesced droplets. Recovery is caused by transfer of monomer at the time of collision between a polymer particle and a monomer droplet. These collisions are allowed when the repulsive forces between monomer droplet and polymer particle are reduced because of surfactant deficiency.