According to kinetic mechanisms, liquid phase polymerization and solid phase polymerization are different in acrylonitrile (AN) polymerization, and so the relationship between the contribution ratio and molecular weight distribution (MWD) was obtained through theoretic analysis. The precipitation homopolymerization of AN was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at 50~65℃ using α,α'-azobisisobutyronitrile as an initiator. The contribution ratio decreased and approached 0; the MWD also decreased and approached 2 with the increase of the H2O/DMSO ratio from 10/90 to 90/10. The experimental data were found to coincide well with the theoretical equation derived from the mechanisms.

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.

PAN precursor fibers were produced via wet-spinning process, and effects of polymerization and spinning processes, especially the stretching process, were investigated on mechanical properties and micro-morphologies of precursor fibers. An increase in molecular weight, dope solid and densification and a decrease in surface defects were possible by controlling polymerization temperature, the number of heating rollers for densification and the jet stretch ratio, which improved the mechanical properties of precursor fibers. The curves for strength, modulus, tensile power and diameter as a function of stretch ratio can be divided into three stages: steady change area, little change area and sudden change area. With the increase of stretch ratio, the fiber diameter became smaller, the degree of crystallization increased and the structure of precursor fibers became compact and homogeneous, which resulted in the increase of strength, modulus and tensile power of precursor fibers. Empirical relationship between fiber strength and stretch ratio was studied by using the sub-cluster statistical theory. It was successfully predicted when the strengths were 0.8 GPa and 1.0 GPa under a certain technical condition, the corresponding stretch ratio of the fiber were 11.16 and 12.83 respectively.