Temperature polyacetylene

By using a modified technique of synthesis, applying an aged catalyst system at room temperature, polyacetylene samples with room temperature conductivities between 20 000 S/cm and 80 000 S/cm are obtained after mechanical stretching by a factor of 6.5 and subsequent doping with iodine, though some samples exhibit even higher or lower values. 

Although polyacetylene has served as an excellent prototype for understanding the chemistry and physics of electrical conductivity in organic polymers, its instabiUty in both the neutral and doped forms precludes any useful appHcation. In contrast to poly acetylene, both polyaniline and polypyrrole are significantly more stable as electrical conductors. When addressing polymer stabiUty it is necessary to know the environmental conditions to which it will be exposed these conditions can vary quite widely. For example, many of the electrode appHcations require long-term chemical and electrochemical stabihty at room temperature while the polymer is immersed in electrolyte. Aerospace appHcations, on the other hand, can have quite severe stabiHty restrictions with testing carried out at elevated temperatures and humidities. 

Whilst the conductivity of these polymers is generally somewhat inferior to that of metals (for example, the electrical conductivity of polyacetylenes has reached more than 400 000 S/cm compared to values for copper of about 600 000 S/cm), when comparisons are made on the basis of equal mass the situation may be reversed. Unfortunately, most of the polymers also display other disadvantages such as improcessability, poor mechanical strength, poor stability under exposure to common environmental conditions, particularly at elevated temperatures, poor storage stability leading to a loss in conductivity and poor stability in the presence of electrolytes. In spite of the involvement of a number of important companies (e.g. Allied, BASF, IBM and Rohm and Haas) commercial development has been slow however, some uses have begun to emerge. It is therefore instructive to review briefly the potential for these materials. 

Fig. 1. (a) Comparison of normalised electrical conductivity of individual MWCNTs (Langer 96 [17], Ebbesen [18]) and bundles of MWCNTs (Langer 94 [19], Song [20]). (b) Temperature dependence of resistivity of different forms (ropes and mats) of SWCNTs [21], and chemically doped conducting polymers, PAc (FeClj-doped polyacetylene [22]) and PAni (camphor sulfonic acid-doped polyaniline [2. ]) [24]. 

An alternative interpretation for the activated behavior of the photocurrent and the PIA-decrease with temperature was proposed by Townsend et al. [35], They assigned their experimental results to a thermally activated interchuin-hoppmg mechanism for bipolaron-like charged soliton pairs, the experiments of which were carried out on Durham /ran.v-polyacetylene. 

The excellent agreement between the TSC and P1A results has two implications. First, since the TSC method probes the product of mobility and carrier density, while the P1A probes only the carrier density, there seems to be no dominant influence of temperature on the carrier mobility. This was also found in other conjugated polymers like /ra/ry-polyacetylene [19, 36]. Second, photoconductivity (observed via the thermal release of photoexcited and trapped earners) and photo-induced absorption probe the same charged entity [36, 37J. 

Shirakawa polyacetylene, 444 Siloxanes, polymerization, 239 Size exclusion chromatography, 262-263 Solubility, specialty polymers, 256 Spacers, flexible polymer backbones, 97 Specialty polymers, polar/ionic groups, 256 Stability, polymers, 256 Storage moduli, vs. temperature behavior, 270... 

Poly(4-phenoxybenzoyl-1,4-phenylene) (PPBP), sulfonated, 23 718 Polyacetal, antioxidant applications, 3 121 Polyacetaldehyde, 1 103 Polyacetal fiber, 13 392 Polyacetylene, 7 514-515 26 953 conduction in, 7 527 22 208 molecular structure of, 22 211 optical band gap, 7 529t Peierls distortion in, 22 203, 208 room temperature conductivity, 7 532 synthesis of, 22 213... 

The tendency towards explosive decomposition noted for dihalo-2,4-hexadiyne derivatives appears to be associated more with the co-existence of halo- and acetylene functions in the same molecule, than with its being a polyacetylene. Haloacetylenes should be used with exceptional precautions [1], Explosions may occur during distillation of bromoacetylenes when bath temperatures are too high, or if air is admitted to a hot vacuum-distillation residue [2], Precautions necessary in isolating and handling such compounds on the small (1 g) scale are detailed [3], Individually indexed compounds are ... 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

The acetylene reaction has been studied also at 77 K [409]. It has been reported that at this temperature the reaction occurs at 12.5 GPa and that the reaction proceeds to saturation and then accelerates on pressure release. In this low-temperature experiment, it has been found that the product contains also c -polyacetylene and that a transformation to the trans isomer occurs on heating. 

An observant smdent has also heard of many new and old technologies that seemed powerful and promising, but have not found much application. The buckminster-fullerene and the related carbon tubules seem like marvelous materials with unmatched and fascinating properties, but they are not used in the marketplace. Neither are the electrically conducting polyacetylenes, which hold the promise of a moldable conductor that can be made at low temperature. Almost every professor of chemical engineering and chemistry has numerous research results that are not used in the marketplace today. A visit to their offices and discussions wifh fheir research sfaff may resulf in several suggestions that are worth further investigations. 

Metallic conduction has recently been observed in specially-prepared organic compounds, such as polyacetylene, polypyrrole, and polyaniline, having conductivities of the order 10 9 (ohm-cm)1 but by proper doping these conductivities can be increased to 102 (ohm-cm)-1. Some of the organic metallic systems have also been converted into the superconducting state by proper doping, but in all cases the Tc remains at very low temperature. 

The soliton conductivity model for rrans-(CH) was put forward by Kivelson [115]. It was shown that at low temperature phonon assisted electron hopping between soliton-bound states may be the dominant conduction process in a lightly doped one - dimensional Peierls system such as polyacetylene. The presence of disorder, as represented by a spatially random distribution of charged dopant molecules causes the hopping conduction pathway to be essentially three dimensional. At the photoexitation stage, mainly neutral solitons have to be formed. These solitons maintain the soliton bands. The transport processes have to be hopping ones with a highly expressed dispersive... 

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