Polyacetylenes mechanism

The polymers which have stimulated the greatest interest are the polyacetylenes, poly-p-phenylene, poly(p-phenylene sulphide), polypyrrole and poly-1,6-heptadiyne. The mechanisms by which they function are not fully understood, and the materials available to date are still inferior, in terms of conductivity, to most metal conductors. If, however, the differences in density are taken into account, the polymers become comparable with some of the moderately conductive metals. Unfortunately, most of these polymers also have other disadvantages such as improcessability, poor mechanical strength, instability of the doped materials, sensitivity to oxygen, poor storage stability leading to a loss in conductivity, and poor stability in the presence of electrolytes. Whilst many industrial companies have been active in their development (including Allied, BSASF, IBM and Rohm and Haas,) they have to date remained as developmental products. For a further discussion see Chapter 31. 

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. 

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). 

Using a mechanical model and a set of force constants, Popov and Lubuzh (66ZPS498) have calculated vibration frequencies for polyacetylenic groups. But these calculations are rather complex and the data on the IR spectra of acetylenic... 

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. 

Polyacetylene in the doped state is sensitive to air and moisture. Other polymers (e.g., those of pyrrole, thiophene, and benzene) are stable in air and/or toward humidity in their doped and undoped states. Generally, when stored in the doped state, the polymers lose doping level by mechanisms not fully understood in most cases the loss is reversible. 

Matsunaga FI, Saita T, Nagumo F, Mori M, Katano M. (1995). A possible mechanism for the cytotoxicity of a polyacetylenic alcohol, panaxytriol inhibition of mitochondrial respiration. Cancer Chemother Pharmacol. 35(4) 291-96. 

In 1958, Natta and co-workers polymerized acetylene for the first time by using a Ti-based catalyst. This polymerization proceeds by the insertion mechanism like the polymerization of olefins. Because of the lack of processability and stability, early studies on polyacetylenes were motivated by only theoretical and spectroscopic interests. Thereafter, the discovery of the metallic conductivity of doped polyacetylene in 1977 stimulated research into the chemistry of polyacetylene, and now poly acetylene is recognized as one of the most important conjugated polymers. Many publications are now available about the chemistry and physics of polyacetylene itself. 

A striking feature of the stereoregular polyacetylenes is their simple NMR spectral patterns, which facilitates elucidation of the polymerization mechanism as well as the polymer structure. A co-polymer of phenylacetylene with partly G-labeled phenylacetylene (Ph G= GH) shows two doublet carbon signals with /i3c-i3C of 72 Hz, indicating the presence of G= G bond in the polymer backbone.This is a clear indication of the insertion mechanism instead of the metathesis pathway. 

Coated materials are evaluated in S-SBR and in 50 50 blends of S-SBR and EPDM rubbers. In blends, the partitioning of fillers and curatives over the phases depends on differences in surface polarity. In S-SBR, polythiophene-modified silica has a strong positive effect on the mechanical properties because of a synergistic reaction of the sulfur-moieties in the polythiophene coating with the sulfur cure system. In S-SBR/EPDM blends, a coating of polyacetylene is most effective because of the chemical similarity of polyacetylene with EPDM. The effect of... 

Polyacetylene-modified sulfur is evaluated as a curative in a 50 50 blend of S-SBR/EPDM. In pure S-SBR, the mechanical properties decrease with the polyacetylene coating due to a reduced release rate of the sulfur out of its shell. The cure and mechanical properties of the S-SBR/EPDM blend are nearly doubled because of improved compatibility. 

Several attempts to induce orientation by mechanical treatment have been reviewed 6). Trans-polyacetylene is not easily drawn but the m-rich material can be drawn to a draw ratio of above 3, with an increase in density to about 70% of the close-packed value. More recently Lugli et al. 377) reported a version of Shirakawa polyacetylene which can be drawn to a draw ratio of up to 8. The initial polymer is a m-rich material produced on a Ti-based catalyst of undisclosed composition and having an initial density of 0.9 g cm-3. On stretching, the density rises to 1.1 g cm-3 and optical and ir measurements show very high levels of dichroism. The (110) X-ray diffraction peak showed an azimuthal width of 11°. The unoriented material yields at 50 MPa while the oriented film breaks at a stress of 150 MPa. The oriented material, when iodine-doped, was 10 times as conductive (2000 S cm-1) as the unstretched film. By drawing polyacetylene as polymerized from solution in silicone oil, Basescu et al.15,16) were able to induce very high levels of orientation and a room temperature conductivity, after doping with iodine, of up to 1.5 x 10s S cm-1. 

The random orientation of the crystalline order in typical Shirakawa polyacetylene means that diffraction studies are limited to powder methods. For such studies, and many others, it would be very useful to have much more oriented polymers and many attempts have been made to orient polyacetylene, either by mechanical treatment of the polymer or by appropriate modifications to the polymerization reaction. These have been reviewed earlier. 

Pron et al.569) looked at polyacetylene treated from the gas phase with H2S04 which leads to HS04 counter-ions. They found that the conductivity drops in air with the appearance of C=O bands in the ir, although the rate of decay is much lower than would be expected for undoped samples. The polymer was more rapidly degraded by exposure to water but could be redoped with further acid treatment. Pron et al.570) have also reported hydrolytic instability in polyacetylene with A1C14 as the counterion. In both cases the proposed mechanism involves addition of OH" to the chain and keto-enol tautomerism to form carbonyl groups. 

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