Abstract
In order to estimate the unperturbed chain dimensions of cellulose, amylose and their derivatives, the literature data available for fourteen polymers have been analyzed systematically. The draining parameter X defined in Kurata—Yamakawa theory was evaluated by various methods and was found to be less than 2 in most instances, regardless of the methods employed. The polymers exhibited often a significant non-gaussian nature expressed by a negative value of a2≡dln(‹S2›0/M)/dlnM, where ‹S2›01/2 is the radius of gyration of a polymer chain in the unperturbed state and M is the molecular weight. Flory’s viscosity parameter Φ always showed a positive M dependence as described by aΦ≡dlnM>0. The latter finding is compatible with low X values. Two new methods for estimating A(≡6(‹S2›0/M)1/2) in the case of a2≠0 and aΦ≠0 were proposed as generalization of the Baumann plot and the Stockmayer—Fixman (SF) plot. The same A values were obtained by thermodynamic and hydrodynamic approaches. The original SF plot proved unsuccessful and underestimated A by about 50%. Cellulose, amylose, and their derivatives have large unperturbed chain dimensions and their expansion factors are not much larger than unity even in good solvents.
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Kamide, K., Miyazaki, Y. The Partially Free Draining Effect and Unperturbed Chain Dimensions of Cellulose, Amylose, and their Derivatives. Polym J 10, 409–431 (1978). https://doi.org/10.1295/polymj.10.409
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DOI: https://doi.org/10.1295/polymj.10.409