Abstract
Abstract
The unique feature of polymers is the flexibility of their long chains, achieved by rotation about their many backbone bonds, which enable them to assume an extremely large number of different Conformations. This is the source of their unique material behaviors, such as rubber‐like elasticity and their time and processing dependencies. Polymer conformations and material properties depend upon their Configurations, among which are the mode of enchainment of diene monomers, regiosequences (directions of monomer insertion), the stereosequences (stereochemical arrangements of atoms in the polymer chain), co‐monomer sequences of vinyl polymers, branches, and cross‐links. Polymer configurations cannot be altered without breaking and reforming their covalent bonds. In this article, we describe how the conformational characteristics of polymers can be rigorously treated, with account explicitly taken of their configurations, and how various conformationally averaged chain properties can be connected to the behaviors of their materials to allow improved structure–property relations. As examples, because
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C NMR resonances depend on local polymer microstructures, the average bond conformation probabilities calculated for each microstructure can be used to assign their resonances. The applied to its dilute solution (the Kerr‐Effect) is very sensitive to the Configuration/Macrostructure of the overall polymer chain. When compared to the molar Kerr constants (mK) calculated for chains possessing the microstructures determined by
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C NMR, the Macrostructures or complete molecular architectures of polymer chains may be revealed.