Polyacrylonitrile (PAN) copolymers of different molecular weights were synthesized by a suspension polymerization and precipitation polymerization method. The rheology behaviors of the synthesized PAN copolymers were investigated in relation to their molecular weight, solid content and melting temperature. The influence of "historical effects" on the spinning solution of PAN was studied by analyzing the laws of viscosity considering the diversification time and temperature. The viscosity disciplines of each spinning solution conformed well to the rheological universal laws in a comparison of the suspension polymerization product with that of precipitation polymerization. Viscosity changes in the swelling process of dissolution were gentler in the suspension polymerization product; a small amount of water will quickly debase the solution viscosity, and high-speed mixing can greatly shorten the time required by the spinning solution to reach the final viscosity.

Acrylonitrile (AN)-acrylamide (AM) copolymers were prepared by nitric acidic hydrolysis of homopolyacrylonitrile. The acrylamino group increased as a function of hydrolysis time, while crystallinity decreased. Differential scanning calorimetry and a thermal gravimetric analysis indicated that the acylamino introduced by acidic hydrolysis effectively enhanced the cyclization reaction at low temperature due to the change of the cyclization reaction mechanism. Char-yield of AN-AM copolymers also gradually increased with increasing hydrolysis time. The maximum char-yield was 49.48% when hydrolized at 23°C in 65% nitric acid solution for 18 h, which was 30% higher than that of non-acidic hydrolysis of homopolyacrylonitrile. Simulation of the practical process also showed an increase of char yields, where the char yields were 55.43% and 62.60% for homopolyacrylonitrile and copolyacrylonitrile, respectively, with a hydrolysis time of 13 h.

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.