Polyacetylenes characterization

A second type of soHd ionic conductors based around polyether compounds such as poly(ethylene oxide) [25322-68-3] (PEO) has been discovered (24) and characterized. These materials foUow equations 23—31 as opposed to the electronically conducting polyacetylene [26571-64-2] and polyaniline type materials. The polyethers can complex and stabilize lithium ions in organic media. They also dissolve salts such as LiClO to produce conducting soHd solutions. The use of these materials in rechargeable lithium batteries has been proposed (25). 

Besides synthesis, current basic research on conducting polymers is concentrated on structural analysis. Structural parameters — e.g. regularity and homogeneity of chain structures, but also chain length — play an important role in our understanding of the properties of such materials. Research on electropolymerized polymers has concentrated on polypyrrole and polythiophene in particular and, more recently, on polyaniline as well, while of the chemically produced materials polyacetylene stih attracts greatest interest. Spectroscopic methods have proved particularly suitable for characterizing structural properties These comprise surface techniques such as XPS, AES or ATR, on the one hand, and the usual methods of structural analysis, such as NMR, ESR and X-ray diffraction techniques, on the other hand. 

All cyclic compounds of types 83-88 have been characterized by their diagnostically simple and C-NMR spectra. Some general regularities can be observed, namely, a small but steady upfield shift in the C-NMR spectra of the carbon signals of the polyacetylenic macrocycle with increasing ring sizes. 

The electronic band structure of a neutral polyacetylene is characterized by an empty band gap, like in other intrinsic semiconductors. Defect sites (solitons, polarons, bipolarons) can be regarded as electronic states within the band gap. The conduction in low-doped poly acetylene is attributed mainly to the transport of solitons within and between chains, as described by the intersoliton-hopping model (IHM) . Polarons and bipolarons are important charge carriers at higher doping levels and with polymers other than polyacetylene. 

Hydroxy-terminated polyester (HTPS) is made from diethylene glycol and adipic acid, and hydroxy-terminated polyether (HTPE) is made from propylene glycol. Hydroxy-terminated polyacetylene (HTPA) is synthesized from butynediol and paraformaldehyde and is characterized by acetylenic triple bonds. The terminal OH groups of these polymers are cured with isophorone diisocyanate. Table 4.3 shows the chemical properties of typical polymers and prepolymers used in composite propellants and explosives.E4 All of these polymers are inert, but, with the exception of HTPB, contain relatively high oxygen contents in their molecular structures. 

Langsdorf BL, Zhou X, Adler DH, Lonergan MC. Synthesis and characterization of soluble, ionically functionalized polyacetylenes. Macromolecules 1999 32 2796-2798. 

The aromatic residue may be any of a large number of such units but the favourite for academic study has been the perfluoromethylxylene derivative shown, which smoothly eliminates at around room temperature to give a polyacetylene containing 25 % of trans- and 75 % of m-units. After transformation and isomerization at 80 °C, the polyacetylene produced is a continuous dense film. The physical chemistry of the transformation and isomerization reactions has been studied in detail229,230) and the properties of the polyacetylene are reviewed 231). The great advantage of this route is that the precursor is a soluble polymer so that it can be characterized and the physical form of the polyacetylene can be controlled. 

During the past three years we have been studying the chemical (SbCl5) oxidation of well-characterized oligomers of polyacetylene, poly[p-phenylene vinylene] (PPV) and poly[2,5-thienylene vinylene] (PTV) in order to determine how polaron and bipolaron states can be preferentially formed and stabilized. 

Polarization, and NLO properties, 12, 102 Polarized optical microscopy, metallomesogen mesophase characterization, 12, 208 Polar monomers, polymerization, 1, 147 Polar polyolefins, co-polymerizations, 11, 723 Polyacetylenes... 

The synthesis and characterization of polyacetylene (PA) provided new incentive for understanding 7r-electronic spectra, electron-phonon interactions and electronic correlations[l, 2, 14]. The electrical conductivity of chemically doped PA rivals that of metals. Families in Fig. 2 such as polydiacetylenes (PDAs), poly thiophenes (PTs), cr-conjugated polysilane (PSs) and polyparaphenylene vinylene (PPVs), among... 

The properties of such apparently soluble materials differed greatly from those containing stabilized polyacetylene crystallites. Attempts to dope the soluble copolymers yielded materials with low conductivities, and chemistry typical of solution chemistry (bromination) was observed rather than the formation of a stable bromine-doped polyacetylene phase. A poly(isoprene-fo-acetylene) copolymer oxidized with iodine gave conductivities as high as 1-10 S/cm, but the characterization of the copolymer was insufiScient to unambiguously identify it as a soluble copolymer. On the basis of previously reported work, this material is likely to correspond to a stabilized suspension rather than a solution. 

Despite a report that complex 4(Sc Me) catalyzes the formation of oligo- and polyacetylene [95], alkyne chemistry is characterized by ligand exchange and dimerization reactions. 

Zeolites. The weak Raman signals arising from the aluminosilicate zeolite framework allow for the detection of vibrational bands of adsorbates, especially below 1200 cm which are not readily accessible to infrared absorption techniques. Raman spectroscopy is an extremely effective characterization method when two or more colored species coexist on the surface, since the spectrum of one of the species may be enhanced selectively by a careful choice of the exciting line. A wide range of adsorbate/zeolite systems have been examined by Raman spectroscopy and include SO2, NO2, acety-lene/polyacetylene, dimethylacetylene, benzene, pyridine, pyrazine, cyclopropane, and halogens. Extensive discussions of these absorbate/zeolite studies are found in a review article by Bartlett and Cooney. ... 

From a consideration of the defects in Figure 2 as they relate to the product structure in Scheme 2, it is possible to describe the mixed polyacetylene case as an alternating copolymer of AC CA and BCaCB, or a homopolymer of AC CB. The latter situation invites a synthetic experiment, that is, the attempted solid-state polymerization of N-(3-bromo-2-propynyl)carbazole (j0. We have isolated this compound in two polymorphic forms. Both forms are melt-stable, but undergo reaction upon exposure to soco gaituna radiation. Characterization of the reaction products has been initiated. 

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