Polyacetylene Crystalline Form

Before 1985, six crystalline forms of carbon were known two forms of graphite, two forms of diamond, and chaoit and carbon (VI) discovered in 1968 and 1972, respectively. In addition a number of almost pure amorphous forms exist, such as polyacetylene (7.60) and cumulene (7.61) and recently a number of interesting nanostructured forms of carbon have been produced (Section 15.8). The year 1985 marked the discovery of the fullerenes, which represent the only truly pure molecular form of carbon, are produced under very extreme conditions as carbon vapour condenses in an atmosphere of an inert gas such as helium. Harold Kroto s interest in this chemistry originated with microwave spectroscopic studies of the atmosphere of stars and interstellar dust clouds. Kroto wanted to try to reproduce in the laboratory spectra of carbon... 

The discovery of conducting poljrmers (like polyacetylene) was honored with the Nobel Prize in 2000 for Hideki Shirakawa (who synthesized a crystalline form of polyacetylene), as well as Allan G.MacDiarmid and Allan J. Heeger, who increased its electric conductivity by 18 orders of magnitude by doping the crystal with some eleciron acceptors and donors. This incredible increase is probably the largest known to humanity in any domain of experimental sciences [H.Shirakawa, E.J. Louis, A.G. MacDiarmid, C.K. Chiang, and A.J. Heeger, Chem.Soc.Chem.Commun.. 578 (1977)]. 

The resulting porous, fibrillar polyacetylene film is highly crystalline, so is therefore insoluble, infusible, and otherwise nonprocessible. It is also unstable in air in both the conducting and insulating form. 

To a large extent, current interest in solid-state polymerization of monoacetylenes derives from the observation of interesting electrical, magnetic, and optical phenomena in polyacetylene, (CH)j (45), a pEutially crystalline material unstable to ambient conditions typically synthesized by Ziegler-Natta techniques. The fundamental study of (CH), and its electron-transferred ( doped ) forms has been retarded by the lack of fully ordered materials. Ftilly ordered polyacetylenes are also of interest because it is conceivable that their crystal structures could allow significant interchain interactions, a situation precluded in most PDA by side chains. 

When acetylene gas is polymerized in a solid solution of the Shirakawa catalyst and polybutadiene, a heterogenous blend consisting of a amorphous polybutadiene phase and a crystalline polyacetylene phase is formed. (5) The mechanical and electrical properties of this composite are critically dependent on the composition of the blend components and on their relative arrangement. In our initial Blend paper, (5) for example, we showed that the mechanical properties of PA/PB blends are a function of the blend composition, with low polyacetylene compositions ex-... 

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