Poly diacetylenes synthesis

Various polymerization route with unique starting monomer [64] have been developed, e.g., topochemical poly(diacetylene) synthesis with pyrrole-, thiophene-, -Si-groups dienophilic addition of maleic imides, Diels-Alder polymers via cyclopentadienone derivatives. 

Bloor, D., and R. R. Chance (eds.) Poly diacetylenes Synthesis, Structure, and Electronic Properties, Martinus Nijhoff, Leiden, The Netherlands, 1985. 

Paley, M.S., D.O. Frazier, H. Abeledeyem et al. 1992. Synthesis. Vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes). JAm Chem Soc 114 (9) 3247-3251. 

By using a cocatalyst of Pd-Cu, aryl-alkenyl halides couple efficiently widi alkynes to generate die disubstituted alkynes (Scheme 9.6).8 This coupling reaction has been applied to die synthesis of polyphenyleneethynylenes by Yamamoto et al. in 1984 (Scheme 9.7).9a Due to the ready availability of diacetylenes and the mild coupling condition, this strategy has been widely used for die preparation of many poly(aryleneethynylene)s.9... 

Many reactions familiar to acetylene and polyene chemistry have been used in the synthesis of natural polyacetylenes. The longer poly-yn-ene chains are usually unstable and the tendency is to form them as late as possible in the fabrication of the molecules. Generally, terminal fragments are prepared first by taking advantage of such simple acetylenes and diacetylenes as are commercially available or relatively easily synthesized . Two reactions are then predominantly used to join these fragments the Cadiot-Chodkiewicz coupling which permits the asymmetric... 

Figure 15.5 Synthesis of the poly (m-carborane-disiloxane-diacetylene) (1) reported by Henderson et al.

Synthesis. The synthesis of the tetraphenyl/tetramethyldisiloxyldiacetylene polymers and copolymers is shown in Scheme 1. The polymeric materials 5a-f were isolated as brown solids with yields in the 78-85 % range. These materials were prepared having molar ratios of 4 to 3 incorporated into the main chain as follows 100 0,5a 75 25, 5b 50 50, 5c and 25 75, 5d. Copolymers 5e and 5f were prepared having 2 and 6 incorporated into the main chain in molar ratios of 90 10 and 60 40, respectively. The synthetic strategy used is a one-pot, two step reaction sequence adapted from previously published procedures (7,8). The reaction of 4 with appropriate ratios of 2 and either 3 or 6 resulted in the formation of 5a-f with concomitant formation of LiCl. Poly( 1,3-dimethyl-1,3-diphenyldisiloxyl diacetylene), 7, was prepared similarly from the reaction of 4 with 1,3-dichloro-1,3-dimethyl-1,3-diphenyldisiloxane. 

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