Abstract
Polyacrylonitrile (referred to as γ-PAN) was prepared by γ-ray irradiation on an acrylonitrile–urea canal complex at −78°C. The pentad tacticity was evaluated from 13C NMR spectra according to a method proposed by Kamide et al. The content of a mmmm sequence (m; meso) for γ-PAN was 0.37±0.02 over a wide range of molecular weight, which was about 4.4 times larger than that for PAN, prepared by conventional redox polymerization (R-PAN). Light scattering and solution viscosity were measured in dimethyl sulfoxide (DMSO), 57—67 wt% aq nitric acid at 25°C. By extrapolation of the second virial coefficient A2 to zero 56.5 wt% aq nitric acid was expected to be a Flory theta solvent at 25°C. Mark–Houwink–Sakurada equations and empirical relations between the radius of gyration ‹S2›z1/2 and Mw were determined in various solvents. The unperturbed chain dimension A was determined by four methods. In DMSO γ-PAN has larger A than R-PAN. The conformation parameter σ was 2.6—2.8 for γ-PAN, which is some 35% larger than the expected value when simple steric hindrance due to the side chain group is considered. Unexpectedly larger conformation parameters σ for γ- and R-PAN were interpreted by considering the rigidity of the chain due to intra-interactions between neighbouring CN groups in meso-sequence.
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Kamide, K., Yamazaki, H. & Miyazaki, Y. Effects of Stereoregularity on Molecular Parameters of Polyacrylonitrile Polymerized by Gamma-Ray Irradiation. Polym J 18, 819–836 (1986). https://doi.org/10.1295/polymj.18.819
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DOI: https://doi.org/10.1295/polymj.18.819