Polyacetylenes carbonization

Sun, Q., Yang, Y., Wei, Y., Zhao, X., and Wang, F., Study on the synthesis of polyacetylene/carbon fibre composite film and the properties of the composites of the composite cell. Chin. J. Appl Chem., 6, 79-82 (1989). 

A common example of the Peieds distortion is the linear polyene, polyacetylene. A simple molecular orbital approach would predict S hybddization at each carbon and metallic behavior as a result of a half-filled delocalized TT-orbital along the chain. Uniform bond lengths would be expected (as in benzene) as a result of the delocalization. However, a Peieds distortion leads to alternating single and double bonds (Fig. 3) and the opening up of a band gap. As a result, undoped polyacetylene is a semiconductor. 

Growth mechanism of a (9n,0) tubule, over 24n coordination sites of the catalyst. The growth of a general (9 ,0) tubule on the catalyst surface is illustrated by that of the (9,0) tubule in Fig. 16 which shows the unsaturated end of a (9,0) tubule in a planar representation. At that end, the carbons bearing a vacant bond are coordinatively bonded to the catalyst (grey circles) or to a growing cis-polyacetylene chain (oblique bold lines in Fig. 16). Tlie vacant bonds of the six c/s-polyacetylene chains involved are taken to be coordinatively bonded to the catalyst [Fig. 16(b)]. These polyacetylene chains are continuously extruded from the catalyst particle where they are formed by polymerization of C2 units assisted by the catalyst coordination sites. Note that in order to reduce the number of representations of important steps, Fig. 16(b) includes nine new Cj units with respect to Fig. 16(a). 

The 12 catalyst coordination sites — drawn further away from the surface of the particle (closer to the tubule) — are acting in pairs, each pair being always coordinatively bonded to one carbon of an inserted (F) or of a to-be-inserted (2 ) Cj unit and to two other carbons which are members of two neighbouring cis-polyacetylene chains (3°). It should be emphasized that, as against the (5n,5n) tubule growth, the C2 units extruded from the catalyst particle are positioned in this case parallel to the tubule axis before their insertion. 

In the context of fra/u-polyacetylene cjia and c are, respectively, the creation and annihilation operators of an electron with spin projection a in the n-orbital of the nth carbon atom (n= l,...,N) that is perpendicular to the chain plane (see Fig. 3-3). Furthermore, u is the displacement along the chain of the nth CH unit from its position in the undimerized chain, P denotes the momentum of this unit, and M is its mass. 

All conducting polymers have a common feature a long chain of sp2 hybridized carbon atoms, often with nitrogen or sulfur atoms included in the chains. Polyacetylene, the first conducting polymer, is also the simplest, consisting of thousands of —CH=CH -units ... 

Propiolaldehyde diethyl acetal has found numerous synthetic applications in the literature which may be briefly summarized. The compound has been utilized in the synthesis of unsaturated and polyunsaturated acetals and aldehydes by alkylation of metal-lated derivatives, " by Cadiot-Chodkiewicz coupling with halo acetylenes, " and by reaction with organocuprates. Syntheses of heterocyclic compounds including pyrazoles, isoxazoles, triazoles, and pyrimidines have employed this three-carbon building block. Propiolaldehyde diethyl acetal has also been put to use in the synthesis of such natural products as polyacetylenes " and steroids. ... 

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. 

Polyacetylene proved qnite incapable of working in a realistic battery context, and MacDiarmid did not mention this application in his Nobel lectnre of October, 8 2000. However, other materials have proven their worth, and prototype batteries made with polypyrrole and polyaniline as cathodes (positives), and metal or lithiated carbon materials as anodes (negatives), have been demonstrated in dne conrse by the Japanese and German indnstry, for instance. Novdk et al. (1997) have reviewed the field in detail. 

Figure 13 shows the irreversible conversion of a nonconjugated poly (p-phenylene pentadienylene) to a lithiun-doped conjugated derivative which has a semiconducting level of conductivity (0.1 to 1.0 S/cm) (29). Obviously, the neutral conjugated derivative of poly (p-phenylene pentadienylene) can then be reversibly generated from the n-type doped material by electrochemical undoping or by p-type compensation. A very similar synthetic method for the conversion of poly(acetylene-co-1,3-butadiene) to polyacetylene has been reported (30), Figure 14. This synthesis of polyacetylene from a nonconjugated precursor polymer containing isolated CH2 units in an otherwise conjugated chain is to be contrasted with the early approach of Marvel et al (6) in which an all-sp3 carbon chain was employed.

Although it was initially believed that polyacetylene was unstable in contact with water under all conditions, it has been successfully chemically doped in aqueous solutions with no apparent degradation of the material [82] and its electrochemistry has also been investigated [135-137] from which it is clear that no degradation occurs in concentrated aqueous electrolytes. Reaction with water can occur under some circumstances however giving rise to sp3 carbons and carbonyl-type structures [129, 138-141],... 

Polyacetylenes are the most important class of synthetic polymers containing conjugated carbon-carbon double bonds. Some optically active monomers have been used with the following conclusions. Polymers of 1-alkynes having a branched side-chain assume in solution a helical conformation. A chiral side-chain induces a predominant screw sense in these helices. In particular, for alkyl branching, it has been shown that (S) monomers lead to a left-handed screw sense. 

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],... 

Most carbon fibers use PAN as their precursor however, other polymer precursors, such as rayon [8], pitch (a by-product of petroleum or coal-coking industries), phenolic resins, and polyacetylenes [6,7], are available. Each company usually uses different precursor compositions for its products and thus it is difficult to know the exact composition used in most commercially available carbon fiber products. 

A second major event in the saga of polymer conductors was the discovery that the doping processes of polyacetylene could be promoted and driven electrochemically in a reversible fashion by polarising the polymer film electrode in a suitable electrochemical cell (MacDiarmid and Maxfield, 1987). Typically, a three-electrode cell, containing the (CH) film as the working electrode, a suitable electrolyte (e.g. a non-aqueous solution of lithium perchlorate in propylene carbonate, here abbreviated to LiC104-PC) and suitable counter (e.g. lithium metal) and reference (e.g. again Li) electrodes, can be used. 

Polyacetylene is a polymer which has a degenerate ground state it possesses two geometric structures having exactly the same energy and differing only in the sequence of the carbon-carbon single and double bonds (Fig. 9.6). 

Fig. 9.10 shows a typical CV of a (CH), film in a LiClO -propylene carbonate electrolyte. The voltammogram presents well-defined peaks both in the anodic (doping) and in the following cathodic (undoping) scans this confirms that the doping process of polyacetylene, as suggested by (9.10), can indeed be driven electrochemically and in a reversible way. 

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