Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by 13C NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and 280℃. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter CNF=I2240cm-1/ (I1595cm-1+f*I1595cm-1) was defined to evaluate residual nitrile groups. Crystallinity and crystal size were calculated with X-ray diffraction dates. The results indicated that the nitrile groups had partly converted into a ladder structure as stabilization proceeded. The rate of reaction increased with treatment temperature; crystallinity and crystal size decreased proportionally to pyrolysis temperature. The iso-conversional method coupled with the Kissinger and Flynn-Wall-Ozawa methods were used to determine kinetic parameters via differential scanning calorimetry analysis with different heating rates. The active energy of the reaction was 171.1 and 169.1 kJ/mol, calculated with the two methods respectively and implied the sensitivity of the reaction with temperature.

The precipitation polymerization of acrylonitrile (AN) was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at 50~65℃ using α,α'-azobisisobutyronitrile (AIBN) as an initiator. The increased molecular weight polyacrylonitrile (PAN) was prepared with increasing the H2O/DMSO ratio from 10/90 to 80/20. The viscosity average molecular weight of H2O/DMSO solvent was 4.4 times larger than that of H2O/DMF solvent, and precipitation polymerization was accelerlated due to the far decreased chain transfer effect of DMSO. Based on the experimental results, the increased PAN molecular weight was regarded as the summation of two mechanisms: i) particle-particle aggregation and ii) particle-radical attachment. The theoretical equation derived from the mechanisms was well coincided with the experimental results showing the linear relationship between the viscosity average molecular weight and the H2O/DMSO ratio.