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We controlled the optical anisotropy of a solution-cast film composed of cellulose triacetate (CTA) by adding ferrocene. Owing to the molecular orientation in the film plane of solution-cast films, which results from the normal stress applied during the solvent evaporation process, the average refractive index is usually higher in the plane of the film than in the thickness direction. We found that the addition of ferrocene, which is miscible with CTA, reduced the optical anisotropy by nematic interaction; i.e., ferrocene molecules are forcibly embedded into the film plane accompanying the CTA chains. Because the direction of anisotropic polarizability of ferrocene is perpendicular to the long axis of the molecule, the refractive index in the thickness direction is reduced. Furthermore, the stress-optical coefficient in the glassy state is reduced by the addition of ferrocene.

The effect of flexible chain on orientation dynamics of a small additive molecule in cellulose acetate propionate (CAP) films is investigated during stretching by means of measurements of birefringence and polarized Fourier-transform infrared (FT-IR) spectrum. The orientation birefringence is enhanced by the additives such as ethylene 2,6-naphthalate (C_2Np) and hexamethylene 2,6-naphthalate (C_6Np) oligomers, suggesting that the additives orient parallel to the CAP chain due to an intermolecular orientation correlation called as the nematic interaction (NI). At a high drawing temperature, the orientation of C_2Np is stronger than that of C_6Np, indicating that the flexible alkyl chain reduces the intermolecular NI with CAP. In contrast, C_6Np orients to the stretching direction rather than C_2Np at a low temperature. The polarized FT-IR spectra show that the orientation of rigid part in C_6Np is delayed from that of the flexible group and matrix CAP chain. Consequently, the contribution of C_6Np to birefringence and its wavelength dependence become stronger with increasing the draw ratio.

Molecular orientation of low-mass compounds (LMCs) in a cross-linked rubber is studied in order to obtain the basic information on the dynamics of LMC molecules in a polymer beyond the glass transition temperature. A small amount of LMCs such as 4-cyano-4’-pentylbiphenyl (5CB), tricresylphosphate (TCP), and styrene-based tackifier (TF) is added into polybutadiene rubber (BR). After cross-linking reaction, the sheet samples are used to evaluate the orientation birefringence during stretching and stress relaxation. The rectangular films, cut out from the cross-linked sheets, are set in a uniaxial stretching machine equipped with an optical system to measure both birefringence and tensile stress simultaneously. It is confirmed that orientation birefringence is proportional to the stress for not only pure cross-linked BR, but also cross-linked BR containing an LMC in a wide range of strain. Even after stretching, the birefringence does not change as far as the sample is kept at a constant strain. The results suggest that the LMC molecules are forced to orient with polymer chains by the strong intermolecular orientation correlation. Because of the LMC orientation, the stress-optical coefficient CR is enhanced by the addition of 5CB and TCP, but depressed by TF. Therefore, the LMC doping can be used to control the birefringence of a retardation film.

Molecular orientation of two aromatic additives in cellulose acetate propionate (CAP) matrix was investigated from orientation birefringence data and an intermolecular orientation correlation represented by nematic interaction (NI) was evaluated. Poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) oligomers with low molecular weight (ca. 400 g mol−1) were used as the additives. The NI strengths of CAP-PET and CAP-PEN were determined to be 0.28 ± 0.05 and 0.96 ± 0.15, respectively. In particular, compared with other polymer/polymer and polymer/small additive blends, the NI value in CAP/PEN blend is much stronger and represents the perfect orientation correlation. The strong orientation correlation is possibly due to the rigid naphtalate structure in PEN. Contrary, a relation between birefringence and orientation function for CAP in bulk and blend showed the same trend, suggesting that the orientation behavior of CAP determines the orientation birefringence. As two ester groups in CAP are responsible for birefringence, the alignment of the ester groups is affected by only the main chain orientation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40570.