Polymerization of acrylonitrile in dimethyl carbonate: A kinetic and mechanistic study

For the first time, a new polymerization medium, dimethyl carbonate (DMC), was used for the polymerization of acrylonitrile (AN), and polyacrylonitrile (PAN) powder was obtained successfully. The effects of polymerization factors, including monomer concentrations, temperature and initiator concentrations on the structures and properties of PAN powders were investigated by nuclear magnetic resonance spectroscopy (NMR), total internal reflectance Fourier transform infrared spectrometer (FTIR), wide-angle X-ray diffractometer (WXRD) and thermal gravimetric analyzer (TGA). The polymerization kinetic and mechanistic study of PAN with DMC as the polymerization medium were discussed in details. There are three key achievements in this paper. First, the kinetic equation of PAN polymerization with DMC as a medium was established: R_p = K[ABVN]^0.92[AN]^6.78. This result shows that the R_p is highly dependent on the AN concentrations. Second, the chain transfer constant of DMC was measured to be 4.57 × 10⁻⁴ at 60 °C, and the chain transfer constant increases with polymerization temperature. Lastly, the structures and properties of PAN powders prepared with H₂O, tetrahydrofuran (THF) and DMC as media were compared. The results showed that the PAN prepared with DMC as a medium by free radical polymerization had a higher conversion, molecular weight and better crystalline property compared to THF. These findings indicate that DMC is a promising medium for manufacturing high quality PAN powder by free radical polymerization.