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• W2105317465 abstract "Abstract In this brief report, we demonstrate that Kerr effect measurements, which determine the excess birefringence contributed by polymer solutes in dilute solutions observed under a strong electric field, are highly sensitive to and capable of determining their microstructures, as well as their locations along the macromolecular backbone. Specifically, using atactic triblock copolymers with the same overall composition of styrene (S) and p ‐bromostyrene ( p BrS) units, but with two different block arrangements, that is, p BrS 90 ‐ b ‐S 120 ‐ b ‐ p BrS 90 (I) and S 60 ‐ b ‐ p BrS 180 ‐ b ‐S 60 (II), which are indistinguishable by NMR, we detected a dramatic difference in their molar Kerr constants ( m K ), in agreement with those previously estimated. Although similar in magnitude, their Kerr constants differ in sign, with m K (II) positive and m K (I) negative. In addition, S/ p BrS random and gradient copolymers synthesized by reversible addition‐fragmentation chain‐transfer (RAFT) polymerization exhibit a heretofore unexpected enhanced enchainment of racemic ( r ) p BrS‐ p BrS diads. Comparison of their observed and calculated m K s suggests that the gradient S/ p BrS copolymers possess an unanticipated additional gradient in stereosequence that parallels their comonomer gradient, that is, as the concentration of p Brs units decreases from one end of the copolymer chain to the other, so does the content of r diads. This conclusion could only be reached by comparison of observed and calculated Kerr effects, which access the global properties of macromolecules, and not NMR, which is only sensitive to local polymer structural environments, but not to their locations on the copolymer chains. Molar Kerr constants are characteristic of entire polymer chains and are highly sensitive to their constituent microstructures and their distribution along the chain. They may be used to both identify constituent microstructures and locate them along the polymer chain, thereby enabling, for the first time, characterization of their complete macrostructures. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013" @default.
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• W2105317465 date "2013-01-29" @default.
• W2105317465 modified "2023-10-18" @default.
• W2105317465 title "Characterizing polymer macrostructures by identifying and locating microstructures along their chains with the kerr effect" @default.
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• W2105317465 doi "https://doi.org/10.1002/polb.23248" @default.
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