α-シアノメチルメタクリレートのラジカル重合における立体規則性生長の溶媒効果

概要

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α-Cyanomethylmetacrylate was synthesized in the reseach. This monomer was radically polymerized in 0℃, 60℃ and 120℃ temperatures and various solvents. These solvent effects on stereotactic occurence of polymeric products were done to the transformed polymethylmetacrylate by hydrolysis that they are determined by means of the nuclear magnetic resonance (NMR) spectroscopy. In this case, Diads value is converted from the obtained Triads value, i. e. the index of estimationis concerned with the difference of entropy (⊿S_s^i), as well as enthalpy (⊿H_s^i), of the activation regarding the Diads propagation. As a result, It has also turned out the compensation effect is established between both parameters, i. e, entropy (⊿S_s^i) and enthalpy (⊿H_s^i) of the activation regarding the Diads propagation. The stereotactic occurence came from the peculiarity of polymer. In addition to that, the solvent effects on streotacticity were also considered. The regularity in syndiotactic structure increased when solubility parameter (δ) value in polymerization solvent was nearly the same as those in monomer and polymer. The activation enthalpy was also found to be larger in bipolar solvents than in unipolar solvents, so the formation of polymerized compounds with syndiotactic structure was easier in bipolar solvents.
東海大学の論文