Polyacetylene conjugated polymer

Polyacetylenes. The first report of the synthesis of a strong, flexible, free-standing film of the simplest conjugated polymer, polyacetylene [26571-64-2] (CH), was made in 1974 (16). The process, known as the Shirakawa technique, involves polymerization of acetylene on a thin-film coating of a heterogeneous Ziegler-Natta initiator system in a glass reactor, as shown in equation 1. 

The excellent agreement between the TSC and P1A results has two implications. First, since the TSC method probes the product of mobility and carrier density, while the P1A probes only the carrier density, there seems to be no dominant influence of temperature on the carrier mobility. This was also found in other conjugated polymers like /ra/ry-polyacetylene [19, 36]. Second, photoconductivity (observed via the thermal release of photoexcited and trapped earners) and photo-induced absorption probe the same charged entity [36, 37J. 

Oxidative polymerization of trans-bis-deprotected 79 under Hay coupling conditions [54] yielded, after end-capping with phenylacetylene, the high-melting and readily soluble oligomers 80a-e with the poly (triacetylene) backbone [87,106] (Scheme 8). Poly(triacetylene)s [PTAs,-(C=C-CR=CR-C=C) -] are the third class of linearly conjugated polymers with a non-aromatic allcarbon backbone in the progression which starts with polyacetylene [PA,... 

Both theoretical and experimental evidence suggest that the precise nature of the charge carriers in conjugated polymer systems varies from material to material, and it is still a subject of debate in many cases. A discussion of the various theoretical models for the electronic structure of conjugated polymers is given below, using polyacetylene and poly(paraphenylene) as examples. More detailed information on these materials and the applicability of these theoretical models is given in subsequent sections. 

Fig. 6. Synthetic routes to conjugated polymers via precursor polymers for (a) polyacetylene, and (b) arylene vinylenes.

A route to processible polyacetylene, devised initially using classical initiators (Scheme 1i) 576-578 has been developed using well-defined molybdenum initiators to prepare conjugated polymers.579-585 They have also been employed to prepare polyacetylene via the polymerization of cyclooctate-traene, COT,586 and by the isomerization of poly(benzvalene).587 588 Substituted, and hence soluble, polyacetylene derivatives may be synthesized by polymerizing monosubstituted COT substrates.589-591... 

Polyacetylene, (CH),(, is a simple, conjugated polymer which may have either a trans or a cis configuration (Fig. 9.1). Free-standing films of polyacetylene can be easily obtained by catalytic polymerisation of gaseous acetylene, the most common procedure being the Shirikawa... 

The polaronic strategy has also been applied to polymers, incorporating m-phenylene units as coupling links in n-conjugated polymer chains of polyfthienylene ketone) (Dal Colle et al. 1999) as well as of polyarylamine, polyacetylene, and polythiophene (Kaisaki et al. 1991, Murray et al. 1994, Bushby et al. 1997a). Scheme 1.44 represents these polaronic polymers. 

Note 2 The electric conductivity of a conjugated polymer is markedly increased by doping it with an electron donor or acceptor, as in the case of polyacetylene doped with iodine. 

In real tran -polyacetylene, the structure is dimerized with two carbon atoms in the repeat unit. Thus the tt band is divided into occupied tt and unoccupied n bands. The bond-alternated structure of polyacetylene is characterishc of conjugated polymers. Consequently, since there are no partially filled bands, conjugated polymers are expected to be semiconductors, as pointed out earlier. However, for conducting polymers the interconnection of chemical and electronic structure is much more complex because of the relevance of non-linear excitations such as solitons (Heeger, 2001). 

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. 

Polyacetylene is very susceptible to attack by oxygen. The polymer loses its metallic lustre and becomes brittle when exposed to air. However, other conjugated polymers were found. Polypyrrole, polythiophene, polyaniline, polyphenylenevinylene (Figure 6.4), and others are conjugated polymers whose bonding and con-... 

Polyphenylenevinylene has a % system delocalised over the benzene ring. It is likely that this is also delocalised over the conjugated double bond and hence to the benzene ring of the next unit. Thus, like polyacetylene, this polymer will have a delocalised % system, but it will include the % ring orbitals. 

Solitons are considered to be important defect states in these conjugated polymers (see Fig. 6.48). It has however been shown that correlation energy is the more important factor in giving rise to the energy gap in (CH) (Soos Ramasesha, 1983). Other polymers related to polyacetylene are polythiophene, polypyrrole, poly-phenylenesulphide, and polyparaphenylene (Section 3.3). Extensive measurements on doped polyacetylenes have been reported in the last five years and these materials, unlike other conducting polymers such as (SN), seem to have good technological potential. 

Most photoeonductive polymers can be used in solar batteries. The high resistivity of the polymers decreases the actual power of the devices. Possibilities may be connected with electron-donor doping of the polymers. As stated earlier some success has been achieved in this field for polyacetylenes and other conjugated polymers. 

An exciting development in polymer chemistry has been the synthesis of highly conjugated polymers, including polyacetylene. This is due to their... 

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