Determination of the optical anisotropy of atactic polystyrene using a grating monochromator

• Published in: Macromolecular chemistry and physics 1996-06, Vol.197 (6), p.1945-1957
• Main Authors: da Silveira, Nádya Pesce, Samios, Dimitrios, Strehle, Frank, Dorfmüller, Thomas
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Properties and characterization; Solution and gel properties
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.1996.021970614

To extract the intrinsic molecular scattering from unwanted collision‐induced contributions as much as possible we propose a simple useful method recording the depolarized Rayleigh spectra using a double grating monochromator and correcting the spectra for the high‐frequency wings. For this purpose we tested the system polystyrene/CCl4 for which an asymptotic value of the optical anisotropy 〈γ2〉/x ≅ 30 Å6 with degree of polymerization x > 20 was found. The depolarized Rayleigh intensity of 2,4‐diphenylpentane and anionically polymerized atactic polystyrene standards was also measured in dilute solutions in the θ‐solvent bicyclohexyl (θ = 61°C). From the absolute depolarized Rayleigh ratio we obtained the configurational average optical anisotropy per number of monomer units, 〈γ2〉/x. We have chosen cumene as a model compound estimating that its optical anisotropy is similar to that of a quasi monomer unit. No significant temperature dependence of 〈γ2〉/x and of the static internal pair correlation in the temperature range from 25°C up to 80°C was found.