Abstract
The polymerization of acrylic acid in bulk proceeds with a very high rate and gives rise to a syndiotactic polymer. This result is attributed to the association of monomer molecules by hydrogen bonds into linear aggregates in which a stereospecific propagation is favoured. In order to verify this assumption the polymerization of acrylic acid was investigated in various solvents. It was found that the addition of methanol, dioxane and water did not significantly affect the reaction rates nor the tacticity of the polymer. In these solvents the viscosity of the monomer remains high, suggesting that the linear aggregates are not dissociated. In contrast, the addition of toluene or n-hexane sharply reduces the polymerization rate and the fraction of syndiotactic polymer. The viscosity of acrylic acid also drops in the presence of these solvents. These results are in agreement with the assumption that the polymerization of acrylic acid is strongly controlled by linear monomer aggregates.
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