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Korean Carbon Society (한국탄소학회)
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Structural evolution and kinetic study of high isotacticity poly(acrylonitrile) during isothermal pre-oxidation

  • Zhang, Li (State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology) ;
  • Dai, Yongqiang (State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology) ;
  • Kai, Yi (State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology) ;
  • Jin, Ri-Guang (State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology)
  • Received : 2011.10.22
  • Accepted : 20111131
  • Published : 2011.12.30
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Abstract

Isotactic polyacrylonitrile (PAN) with triad isotacticity of 0.53, which was determined by $^{13}C$ NMR, using dialkylmagnesium as an initiator, was successfully synthesized. Isothermal treatment of iso-PAN was conducted in air at 200, 220, 250 and $280^{\circ}C$. Structural evolutions and chemical changes were studied with Fourier transformation infrared and wide-angle X-ray diffraction during stabilization. A new parameter $CNF={I_{2240cm}}^{-1}/ ({I_{1595cm}}^{-1}+f^*{I_{1595cm}}^{-1})$ 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.

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