Abstract: | The diad tacticity of poly(isopropyl acrylate) was measured from the β-proton absorptions of poly(isopropyl acrylate-α,β-d2) obtained with a 100 MHz NMR spectrometer, and temperature dependence of the tacticity of the polymers obtained by radical polymerization was determined. Enthalpy and entropy differences between isotactic and syndiotactic addition for poly(isopropyl acrylate) were calculated to give the following values: Δ(ΔS) = 0.7 eu; Δ(ΔH) = 0.51 kcal/mole. In the hydrolysis of poly(isopropyl acrylate-α,β-d2), it was found that the rate of hydrolysis of poly(isopropyl acrylate) was dependent on the molecular weight rather than on the tacticity. As for the rate of racemization during hydrolysis, the rate for syndiotactic polymer was much faster than that for the isotactic polymer. The exchange reaction of deuterium at α-position with hydrogen occurred in all the polymers during hydrolysis reaction. |