Abstract
Molecular mechanisms were proposed to account for extraordinary optical activities of polyisocyanates containing chiral moieties (chiral monomer or initiator fragment) reported by Green et al. and by Okamoto et al., where the polyisocyanate molecule was modeled by a helical chain consisting of an alternating sequence of right-handed and left-handed helices with helix reversals in between. Theoretical predictions based on this model were consistent with remarkable dependence of optical rotation on monomer composition for random copolyisocyanates of chiral and achiral monomers and enantiomorphous copolymers and chain length dependence of optical rotation for achiral polyisocyanates with a chiral initiator fragment on the chain end. The helix reversal was shown to be the key factor for all the cases and more frequent for aromatic sidechain polymer poly(m-methyl phenyl isocyanate) than for aliphatic side chain polymers such as poly(butyl and hexyl isocyanate)s.
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Gu, H., Sato, T., Teramoto, A. et al. Molecular Mechanisms for the Optical Activities of Polyisocyanates Induced by Intramolecular Chiral Perturbations. Polym J 29, 77–84 (1997). https://doi.org/10.1295/polymj.29.77
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DOI: https://doi.org/10.1295/polymj.29.77