芳香族系メタクリル酸エステルの立体規則性 : ラジカル重合における立体規則性生長の溶媒と温度効果
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概要
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Three types of monomeric aryl methacrylate esters were synthesized. Each monomer was radically polymerized in various solvents and differential temperatures. These solvent effects on stereotactic occurence of polymeric products were done to the transformed polymethyl methacrylate samples by hydrolysis that they are determined by means of the nuclear magnetic resonance (NMR) spectroscopy. In this case, the index of estimation is concerned with the difference of entropy (⊿S_s^i), as well as enthalpy (⊿H_s^i) of the activation regarding the diads propagation from conversion of triads propagation. On stereotactic occurence in radical polymerization of aryl methacrylate esters, the syndiotacticity became higher than other at the point where the solubility parameter of monomer or polymer neighbour with that of solvent, and lower temperature. The influence of stereotactic occurence is examined about relying on steric effect in the end of monomer, the result was, however, liable to show lower syndiotacticity by the bulky steric effect in its end. It has also turned out that the compensation effect is established between both parameter, i. e., entropy (⊿S_s^i) and enthalpy (⊿H_s^i) of the activation regarding the diads propagation. The obtained "Tactically Isokinetical Tempereture (TIT)" is a peculiar temperature that there are not any relations between both stereotacticity and solvent types. It was indicated that the TIT is related to the glass transition temperature and the thermodynamics second-order transition temperature of its polymer in here. Therefore, the stereotactic occurence came from the peculiarity of polymer. In addition to that, the solvent effects on stereotacticity were also considered.
- 東海大学の論文
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