Iodine doping, highly orientated polyacetylene

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. 

As described in Section II.B.l above, doping causes a drastic change in the electrical properties of polyacetylene. The initial values of electrical conductivity were of the order of 10 S cm" for unoriented materials d24-i30 when doped by iodine and AsFs, were enhanced to the order of 10 S cm, which was obtained in the parallel direction of the doped films oriented by mechanical stretching 31 Improvements in polymerization methods and in the catalyst systems also enhanced the electrical conductivity. Highly oriented films prepared in liquid crystal solvents (Section II.A.l.d.iii) exhibited a conductivity higher than 10 S cm, as did also a well stretch-oriented film prepared by Ti(OBu)4-EtsAl dissolved in silicon oil and aged at 120°C. In further studies Naarmann and Theophilou and Tsukamoto and coworkers attained a conductivity of ca 10 S cm k... 

Recent diffraction data for highly oriented Tsuka-inoto polyacetylene [22,136] suggest stronger correlations between neighbouring polyiodide columns in this new, highly conductive (cr > 10 S cm ) material. Tsukamoto and Takahashi [136] report a monoclinic structure with a = 7.81 A, 6 = 15.62 A, c = 51.2 A and ) = 120 for their fully-iodine-doped polyacetylene. 

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