Optical properties polymers

Photonics— Materials—Congresses. 2. Polymers—Optical properties— Congresses. 3. Optoelectronic devices— Materials—Congresses. 4. Polymers— Electric properties—Congresses. 

Polymers-Electric properties. 2. Polymers-Optical properties. I. Wise, Donald L. (Donald Lee). II. Series Plastics engineering (Marcel Dekker, Inc.) 45. 

Photochromic polymers—Congresses, 2. Polymers—Optical properties— Congresses. 

Smart materials. 2. Polymers—Optical properties. 3. Conducting polymers. 4. Photoreffactive materials. 5. Photobiochemistry. 

Simoni F 1997 Nonlinear Optical Properties of Liquid Crystals and Polymer-Dispersed Liquid Crystals (Singapore World Scientific)... 

There have been some attempts to compute nonlinear optical properties in solution. These studies have shown that very small variations in the solvent cavity can give very large deviations in the computed hyperpolarizability. The valence bond charge transfer (VB-CT) method created by Goddard and coworkers has had some success in reproducing solvent effect trends and polymer results (the VB-CT-S and VB-CTE forms, respectively). 

Ah initio calculations of polymer properties are either simulations of oligomers or band-structure calculations. Properties often computed with ah initio methods are conformational energies, polarizability, hyperpolarizability, optical properties, dielectric properties, and charge distributions. Ah initio calculations are also used as a spot check to verify the accuracy of molecular mechanics methods for the polymer of interest. Such calculations are used to parameterize molecular mechanics force fields when existing methods are insulficient, which does not happen too often. 

Computed optical properties tend not to be extremely accurate for polymers. The optical absorption spectra (UV/VIS) must be computed from semiempiri-cal or ah initio calculations. Vibrational spectra (IR) can be computed with some molecular mechanics or orbital-based methods. The refractive index is most often calculated from a group additivity technique, with a correction for density. 

CHEOPS is based on the method of atomic constants, which uses atom contributions and an anharmonic oscillator model. Unlike other similar programs, this allows the prediction of polymer network and copolymer properties. A list of 39 properties could be computed. These include permeability, solubility, thermodynamic, microscopic, physical and optical properties. It also predicts the temperature dependence of some of the properties. The program supports common organic functionality as well as halides. As, B, P, Pb, S, Si, and Sn. Files can be saved with individual structures or a database of structures. 

The polysdanes are normally electrical insulators, but on doping with AsF or SbF they exhibit electrical conductivity up to the levels of good semiconductors (qv) (98,124). Conductivities up to 0.5 (H-cm) have been measured. However, the doped polymers are sensitive to air and moisture thereby making them unattractive for practical use. In addition to semiconducting behavior, polysilanes exhibit photoconductivity and appear suitable for electrophotography (qv) (125—127). Polysdanes have also been found to exhibit nonlinear optical properties (94,128). 

Liquid crystal polymers are also used in electrooptic displays. Side-chain polymers are quite suitable for this purpose, but usually involve much larger elastic and viscous constants, which slow the response of the device (33). The chiral smectic C phase is perhaps best suited for a polymer field effect device. The abiHty to attach dichroic or fluorescent dyes as a proportion of the side groups opens the door to appHcations not easily achieved with low molecular weight Hquid crystals. Polymers with smectic phases have also been used to create laser writable devices (30). The laser can address areas a few micrometers wide, changing a clear state to a strong scattering state or vice versa. Future uses of Hquid crystal polymers may include data storage devices. Polymers with nonlinear optical properties may also become important for device appHcations. 

Optics. Good optical properties and low thermal resistance make poly(methyl methacrylate) polymers well suited for use as plastic optical fibers. The manufacturing methods and optical properties of the fibers have been reviewed (124) (see Fiber optics). Methods for the preparation of Fresnel lenses and a Fresnel lens film have been reported (125,126). Compositions and methods for the industrial production of cast plastic eyeglass lenses are available (127). 

Most Kaminsky catalysts contain only one type of active center. They produce ethylene—a-olefin copolymers with uniform compositional distributions and quite narrow MWDs which, at their limit, can be characterized by M.Jratios of about 2.0 and MFR of about 15. These features of the catalysts determine their first appHcations in the specialty resin area, to be used in the synthesis of either uniformly branched VLDPE resins or completely amorphous PE plastomers. Kaminsky catalysts have been gradually replacing Ziegler catalysts in the manufacture of certain commodity LLDPE products. They also faciUtate the copolymerization of ethylene with cycHc dienes such as cyclopentene and norhornene (33,34). These copolymers are compositionaHy uniform and can be used as LLDPE resins with special properties. Ethylene—norhornene copolymers are resistant to chemicals and heat, have high glass transitions, and very high transparency which makes them suitable for polymer optical fibers (34). 

Structure and Crystallinity. The mechanical—optical properties of polycarbonates are those common to amorphous polymers. The polymer may be crystallized to some degree by prolonged heating at elevated temperature (8 d at 180°C) (16), or by immersion ia acetone (qv). Powdered amorphous powder appears to dissolve partially ia acetone, initially becoming sticky, then hardening and becoming much less soluble as it crystallizes. Enhanced crystallization of polycarbonate can also be caused by the presence of sodium phenoxide end groups (17). 

Optical properties of cyanines can be usefiil for both chiral substituents/environments and also third-order nonlinear optical properties in polymer films. Methine-chain substituted die arbo cyanines have been prepared from a chiral dialdehyde (S)-(+)-2-j -butylmalonaldehyde [127473-57-8] (79), where the chiral properties are introduced via the chiral j -butyl group on the central methine carbon of the pentamethine (die arbo cyanine) chromophore. For a nonchiral oxadicarbocyanine, the dimeric aggregate form of the dye shows circular dichroism when trapped in y-cyclodextrin (80). Attempts to prepare polymers with carbocyanine repeat units (linked by flexible chains) gave oligomers with only two or three repeat units (81). However, these materials... 

The properties of the final polymer (melting point, solubiUty, optical properties, etc) depend on the nature of the side chain incorporated into the structure, so that judicious choice of substituent can lead to material tailorabiUty. 

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