Arylene sulfides

The synthesis of poly(arylene sulfide)s via the thermolysis of bis(4-iodophenyl) disulfide has been reported (78). The process leads to the formation of PPS and elemental iodine. This process presumably occurs analogously to that reported by Eastman Chemical Company. 

Alternative synthetic routes to poly(arylene sulfide)s have been pubHshed (79—82). The general theme explored is the oxidative polymerization of diphenyl disulfide and its substituted analogues by using molecular oxygen as the oxidant, often catalyzed by a variety of reagents ... 

In another process for the synthesis of PPS, as well as other poly(arylene sulfide)s and poly(arylene oxide)s, a pentamethylcyclopentadienylmthenium(I) TT-complex is used to activate -dichlorobenzene toward displacement by a variety of nucleophilic comonomers (92). Important facets of this approach, which allow the polymerization to proceed under mild conditions, are the tremendous activation afforded by the TT-coordinated transition-metal group and the improved solubiUty of the resultant organometaUic derivative of PPS. Decomplexation of the organometaUic derivative polymers may, however, be compHcated by precipitation of the polymer after partial decomplexation. 

The PEEK resia is marketed as aeat or filled pellets for iajectioa mol ding, as powder for coatiags, or as preimpregaated fiber sheet and tapes. Apphcations iaclude parts that are exposed to high temperature, radiation, or aggressive chemical environments. Aerospace and military uses are prominent. At present, polyamideimide (PAl) resia and poly(arylene sulfides) are the main competitors for apphcations requiring service temperatures of 280°C. At lower temperatures, polyethersulfones, amorphous nylons, and polyetherimides (PEI) can be considered. 

Polysulfonation of self-polycondensation of 4-(phenylthio)benzenesulfonyl chloride was also used to prepare poly(arylene sulfide sulfone)s.245,246 Condensation of diphenyl sulfide with d -oxydibenzenesulfonic acid or d.d -thiodibcn/cnc-sulfonic acid247 or by poly etherification of poly condensation of DC DPS with d.d -dihydroxydiphenol sulfide occurred.5... 

Poly(monosulfide)s, 23 702-711 aliphatic, 23 702-704 aromatic, 23 706 conjugated polymers, 23 709 macrocyclic polythioethers, 23 707 poly(arylene sulfide)s, 23 704-706 poly(monosulfide ketone)s, 23 709-711 polythiophenes, 23 708 tetrathiafulvalene polymers,... 

In a study of the carbonization (- 525°C) and graphitization (- 2500°C) of thianthrene in comparison with anthracene, it was shown that the carbons of the heterocycle are nongraphitable between 1200°C and 2500°C, sulfur was evolved continuously (85MI3). Aluminum chloride catalytic carbonization of thianthrene has also been studied. At lower temperatures than without a catalyst, thianthrene produced an isotropic coke catalytic co-carbonization with anthracene and 9,10-dihydroanth-racene gave mosaic and needle cokes, respectively (80MI6, 80MI7). Po-ly(arylene sulfides) were shown to be produced by aluminum chloride treatment of thianthrene at 180-350°C (79URP659582). 

Oxidative polymerization of aryl disulfides has been carried out under high dilution conditions for the preparation of cyclic arylene sulfides for synthesizing cyclic arylene sulfide polymers. The readily available diphenyl disulfide and dichloro disulfide with diphenyl sulfide, diphenyl ether, or p-xylene are useful monomers for the synthesis of the corresponding cyclic oligo(thio arylene)s. The reaction scheme is shown in Fig. 30 [101]. 

Liang YF (1987) Arylene sulfide polymers of improved impact strength. US Patent 4708983... 

Liang YF, Beever WH (1985) Rubbery compounds as modifiers for poly(arylene sulfide). US Patent 4 888 390... 

The process discovered by workers in the laboratories of Phillips Petroleum Co. marked a significant departure from prior processes, and made it possible to prepare a variety of arylene sulfide polymers from the readily available starting materials.33... 

PPE with co-poly(arylene sulfide), [(-< -S-)jJ-fS-S-)J processabUity, good mechanical properties Bagrodia et al., 1994... 

Earlier suggested syntheses for poly(arylene sulfides) are shown in Scheme 4. Most of these syntheses involve either electrophilic or thermal reactions. 

Scheme 4 Earlier preparations of Poly(arylene sulfides) [92,102-109],...

Preparation of poly(arylene sulfide) with low metal contamination by the process involving contacting a dihaloaromatic compound, a sulfur source, and organic amide, alkali metal carboxylate, and water in a reaction vessel made of titanium [172]. 

Poly(arylene sulfide) polymer containing sulfone, ether, and biphenyl groups [175]. 

S. B. Brown, C.-F. R. Hwang, H. Ishida, J. J. Scobbo, Jr., and J. B. Yates, III. Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof. US Patent 6303708, assigned to General Electric Company (Pittsfield, MA), October 16, 2001. 

C. E. Ash, J. F. Geibel, and H. D. Yelton. Process for preparing high molecular weight poly(arylene sulfide) polymers using lithium salts. US Patent 5 929 203, assigned to Phillips Petroleum Company (Bartlesville, OK), July 27, 1999. 

F. C. Vidaurri, A. South, Jr., D. A. Soules, and J. S. Fodor. Method of measuring extent of curing of compacted poly(arylene sulfide). US Patent 6 946 540, assigned to Chevron Phillips Chemical Company, LP (The Woodlands, TX), September 20,2005. 

V. J. Sullivan and A. B. Auerbach. Ductile poly(arylene sulfide) resin compositions. US Patent 5652287, assigned to Hoechst Celanese Corporation (Somerville, NJ), July 29, 1997. 

Y. Satake and T. Ono. Poly (arylene sulfide) resin composition. US Patent 5650459, assigned to Kureha Kagaku Kogyo K.K. (Tokyo, JP), July 22, 1997. 

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