Glass‐Transition Temperature (Tg) of Free‐Radically Prepared Polyacrylonitrile by Inverse Gas Chromatography, 2. Molecular‐Weight Dependence of Tg of Two Different Types of Aqueous Polymers

The molecular-weight dependence of the glass-transition temperature (Tg) of a series of atactic polyacrylonitriles (PAN)s was studied by inverse gas chromatographic (IGC) analysis. PANs having different molecular weights were prepared by either; (i) the addition of isopropyl alcohol as a chain-transfer agent, or (ii) a scission reaction induced by the addition of alkali (NaOH) to a solution (N,N-dimethylformamide solution, at 25 °C) of the resulting polymer. The intrinsic viscosity [η] was in the range of 10.9–0.1 (dl · g−1), which corresponds to a viscosity-averaged molecular weight (Mv) of 1 590 000–3 000. As part of the results, a side reaction, which saw the conversion of the nitrile (CN) groups of PAN into amide (CONH2) and/or carboxylic acids (COOH) groups by alkali, was found to occur. The typical molecular-weight dependence of the Tg in free-radically prepared PAN was discussed in connection with a chain-transfer mechanism in an aqueous medium. Molecular-weight dependence of the Tg for PAN (WA). An error bar is given by a short vertical arrow.