Durham route, polyacetylenes

ANISOTROPIC PROPERTIES OF ORIENTED DURHAM ROUTE POLYACETYLENE... 

Figure 4 Optical transmission T for unoriented Durham-route polyacetylene measured at 20 and 300 K (Tq is the transmission without the sample present) [46].

Durham route, the metathesis polymerization of 7,8-bis(trifluoromethyl)tricyclo[4.2.2.0]deca-3,7,9-triene gives a high-molecular weight soluble precursor polymer that is thermally converted to polyacetylene (equation 19.6). The precursor polymer is soluble in common organic liquids and easily purified by reprecipitation. The end product can be aligned giving a more compact material with bulk densities on the order of 1.05 —1.1 g/cm. ... 

Polyacetylene may also be produced from a soluble precursor polymer by the Durham route, described earlier. In- this case the soluble precursor can be studied by conventional solution methods, provided that it is kept cold enough to prevent transformation. The molecular weight of the precursor has been determined by light scattering and low-temperature GPC 326) and corresponds to a polyacetylene chain with a molecular weight of about 200,000, with Mw/Mn of about 2. 

In our own studies of the isomerisation of the 75% e/s-polyacetylene produced by the Durham route 347> we have been unable to detect any effect on the isomerisation process of illumination with modest levels of light. We do find that the isomerisation is markedly affected by even trace amounts of oxygen, which lead to a change in the apparent order of reaction and a marked lowering of activation energy, somewhat similar to the observations of Chien and Yang 447) for conventional polymer. However, polymers prepared by the Durham route are very different from Shirakawa polymer and it would be unwise to extrapolate our results to Shirakawa materials. 

The Durham route to polyacetylene 103, 104) involves the metathesis polymerization of 1 to give a soluble but thermally unstable high polymer (Scheme 5.2). Slowly at room temperature, or more rapidly at 80 °C, the polymer undergoes a retro-Diels-Alder reaction. This reaction results in elimination of a substituted benzene and formation of amorphous polyacetylene. An enormous weight loss accompanies the conversion, but high-density films were produced with no apparent voids. The kinetics of the transformation reaction were extensively studied (JOS). 

A triumph of the Durham route was the preparation of oriented crystalline polyacetylene (107-109) by stretch orientation of the polymer during the transformation reaction. This material has highly anisotropic optical properties, but the anisotropy of the conductivity of the doped polymer was low. Oriented fibers as well as films were prepared. 

Scheme 5.2. Synthesis of polyacetylene by the Durham route. The precursor polymer is soluble and can be processed prior to conversion to poly acetylene.

Scheme 5.3. A revised synthesis of polyacetylene by the Durham route. When 2 is included in the polymer, the conversion to polyacetylene first requires that the diene be generated at 80 °C) before the retro-Diels-Alder reaction...

In principle, conjugated materials may either be directly synthesized via metathesis polymerization of acetylene or 1-alkynes, via ROMP of various cyclooctatetraenes (COTs) or via ROMP of polyene precursors as realized in the Durham route [107-111]. The first direct polymerization of acetylene to yield black untreatable unsubstituted polyacetylene was achieved with W(N-2,6-i-Pr2-C6H3)(CH-t-Bu)(OC-t-Bu)2 [112]. In order to obtain soluble polymers, polyenes were prepared via the ROMP of a polyene-precursor, 7,8-bis(trifluoromethyl)tricyclo[4.2.2.02 5]deca-3,7,9-triene (TCDTF6), using initiators such as W(N-2,6-i-Pr2-C6H3)(CH-t-Bu)(OC-t-Bu)2) (Scheme 5.10) [113, 114]. 

This chapter has provided some examples of the ways in which conjugated polymers can be prepared. While the account is not of course exhaustive, and indeed many extremely important synthetic routes have not been included, such as the formation of polyacetylene by the Durham route,it does serve to illustrate that the range of synthetic techniques vary from the simple to the extremely sophisticated. Electrochemical synthesis is largely in the former classihcation, however, it does have considerable potential in the design of materials for molecular electronics since it will allow patterns to be formed on the electrode surface. With the continuing demand for new materials both for electronic and power distribution needs, it is to be expected that this area will continue to develop in the foreseeable future. 

More recently, a Pd(II) salt was shown to catalyze the 1,2-insertion polymerization of a 7-oxanorbornadiene derivative (Fig. 10-16) [50]. The resulting saturated polymer, when heated, gives polyacetylene via a retro-Diels-Alder reaction. (This reaction is reminiscent of the Durham route to polyacetylene discussed below). One advantage of this technique over other routes is that it employs a late transition metal polymerization catalyst. Catalysts using later transition metals tend to be less oxophilic than the d° early transition metal complexes typically used for alkene and alkyne polymerizations [109,110]. Whereas tungsten alkylidene catalysts must be handled under dry anaerobic conditions, the Pd(II)-catalyzed reaction of water-insoluble monomers may be run as an aqueous emulson polymerization. 

The Durham route allows the preparation of polyacetylene in the form of continuous uniform and featureless films, as opposed to the entangled fibrillar morphology obtained by the direct polymerization of acetylene. 

As schematically shown in Figure 6.18, an unpaired 7i-electron is associated with the soliton in trans-polyacetylene. In this case, ENDOR spectroscopy can directly measure the spin density distribution of the soliton by the study of hyperfine coupling [98], according to the discussion in the preceding section. In fact ENDOR observations of the spin density distribution close to those predicted theoretically in the case of finite electron correlation have been reported independently for stretch-oriented cA-rich samples prepared by the conventional Shirakawa method [102-105] and for stretch-oriented trans samples prepared by the Durham route [99,106,107]. 

ENDOR frequency determination with the aid of ENDOR-induced ESR in cis-rich samples gives the half-width of the spin distribution of 18 carbon sites and the ratio of the peak value of the negative density to that of the positive density of p(l)/p(0)%0.44 [104,105], Similar results to those in cis-rich samples, that is similar spectra with resolved structures for the stretch direction and similar spectral frequencies, have been reported for stretch-oriented trans-polyacetylene prepared by the Durham route using pulsed ENDOR techniques [99,106,107], The unpaired electrons observed in Durham samples were conjectured to be trapped solitons from nearly temperature-independent ENDOR spectra. In the studies of this system the first successful application of TRIPLE resonance in polyacetylene has been reported [99,107], Readers can find reviews on the results of Durham samples [2,99] as... 

NBE and 7.8-bis(trifluoromethyl)tricyclo[4.2.2.0 ]-deca-3.7.9-triene may be used to generate ABA-triblock copolymers of NBE (A-block) and polyacetylene (B-block) via the Durham route ° ° (Scheme 39).354,355 -ppig poly-NBE blocks sufficiently solu-... 

The advantages of the Durham route are (1) contaminating catalyst residues can be removed because the precursor polymers are soluble and can be purified by dissolution and reprecipitation and (2) the precursors can be cast as films or drawn and oriented prior to conversion to the all-trans form of polyacetylene. This allows a degree of control over the morphology of the final product which in the pristine state appears to be fibrous and disordered. Because conductivity increases by alignment of the polymer chains, stretching the film or fiber assists this process and this can be performed using the prepolymer. 

Many of these problems have been solved by Feast (1985), who developed a very elegant synthetic method, now commonly known as the Durham route. This is a two-stage process in which soluble precursor polymers are prepared by a metathesis ringopening polymerization reaction, and these are subsequently heated to produce polyacetylene by a thermal elimination reaction. An example of the method is given below ... 

The Durham-route to polyacetylene An intelligent combination of organic and polymer chemistry leading to an interesting material. In the Editors view a most creative piece of modem... 

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