Abstract
As mentioned in Chap. 3, the KP model [1] may be applicable not only to stiff polymers but also to ordinary flexible polymers if the characteristic ratio C n increases monotonically to its coil-limiting value C∞ as the number of skeletal bonds n in the chain is increased. For symmetric chains such as polymethylene, polyoxymethylene, and polyoxyethylene there is indeed good agreement between values of (R 2 ) as a function of n for the KP and RIS models if the contour length L of the former is properly converted to n [2,3]. However, C n increases to C∞ more rapidly than expected from the KP model for poly(dimethylsiloxane) [4], while it decreases to C∞ with increasing n for poly-DL-alanine [5] or even exhibits a maximum in the case of, for instance, syndiotactic poly(methyl methacrylate) [6], as already seen in Fig. 2.4. Such breakdown of the KP model is probably due to the fact that these real chains with different skeletal bond angles possess locally preferred helical conformations. Further, as anticipated in Chap. 3, it is impossible to assign local vectors and tensors to the KP chain unless they are parallel to and cylindrically symmetric about its contour, respectively.
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Yamakawa, E.H. (1997). Chain Statistics — Helical Wormlike Chains. In: Helical Wormlike Chains in Polymer Solutions. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-60817-9_4
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DOI: https://doi.org/10.1007/978-3-642-60817-9_4
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