Disulfide-containing polymers Poly

Despite their inherent electronic advantages, CT complexes and radical cation salts tend to be brittle and unprocessable. This problem might be overcome by the incorporation of oligomeric tetrathiafulvalenes in polymers, whereby the TTFs can be part of a main-chain or side-chain polymer. The key concern thereby is to achieve the suitable packing of the donor moieties, which is, of course, less perfect than in the crystalline state. Remarkably, the rigid-rod poly-TTF 164 could be made recently by a precursor route in which 164 is made by dimethyl disulfide extrusion of the precursor polymer (scheme 39). The electrical conductivity after iodine doping amounts to 0.6 S/cm [221]. Other examples of TTF-containing polymers, either in the backbone [222] or in the side-chain [223], are summarized in chart 25. 

Addition of solvents as solubilizers is important in the dissolution of polymers. Poly(vinyl acetate) is insoluble in pure ethanol, but dissolves fairly readily in ethanol containing 3% water. Cellulose triacetate is sparingly soluble in pure trichloromethane, but is readily soluble in trichloromethane containing 3% methanol. Many paint resins dissolve more readily in aromatic-containing naphtha fractions than in pure naphtha. Poly(vinyl chloride) is sparingly soluble in acetone and carbon disulfide, but is more readily soluble in a mixture of the two solvents. 

A novel one-pot synthesis of sulfur-containing polymers including poly(monosulfide)s (polythioethers), poly(disulfide)s, polythioesters, and poly-thiourethanes from a five-membered cyclic dithiocarbonate (5-phenoxjunethyl-l,3-oxathiolane-2-thione) and diamines has been examined. Polythioethers with Mn = 2600-17,700 were obtained by condensation of in situ forming dithiol with o ,a -dibromo-p-xylene [623-24-5] (25). A synthesis by using a bifimctional five-membered cyclic dicarbonate and benzylamine [100-46-9] has also been reported (26). 

The Eastman Chemical Company has pubHshed extensively in the patent Hterature (65—74) and the scientific Hterature (75—77) on processes for making poly(phenylene sulfide)- (9-(phenylene disulfide), and related copolymers. The Eastman process involves the reaction of elemental sulfur with Ndiiodobenzene to yield a phenylene sulfide polymer that also contains phenylene disulfide repeating units in the polymer. The fraction of repeating groups containing... 

From the analyses of NMR and electron-spray ionization mass (ESI-MS) spectroscopy, the polymers obtained from the polymerization of cyclic disulfides were found to be a cyclic structure [202], The cyclic structure consisting of poly(DT) is assumed to be formed by a backbiting reaction of propagating species [203]. Thermal and mechanical properties of the polymers, and decomposition behaviors of the polymers demonstrate that the polymers obtained from thermal polymerization of cyclic disulfides include a polycatenane structure. From polymerization of cyclic disulfides in the presence of cyclic polyethylene oxide), a polycatenane consisting of two different cyclic polymers was obtained [199]. Thus, poly(DT) contains spatial entanglements of cyclic polymers with each other (a polycatenane structure was presumed) (Fig. 61). 

Oligomer 163 represents a stabilizer having PA chain with pendant phenolic moiety [31], Pendant hindered piperidine or piperazine moieties were attached to oligomeric stabilizers having polysulfonamide, polyurea (e.g. 164), or PA (e.g. 165) unis [213]. Polyhydrazide 166 was tested as HD AO and copper deactivator in PP [214]. Poly (nitrophenylene-carbazide disulfide) 167 was prepared for thermal stabilization of PVC. Phosphorus containing crosslinkable polymers having polyamide, polyimide and polyurea chains were prepared for flame and heat resistant applications [215]. 

Poly(arylene SUlfidG)S. The best-known polymer in this class is PPS (6). The commercial product produced from dichlorobenzene and sodium sulfide (Na2S) by pol5mierization in a polar solvent, eg, AT-methyl-2-pyrrolidinone (NMP) [872-50-4], contains up to a few percent of disulfide linkages. 

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