Phillips Sulfides

Ryton fibers are high performance products developed by Phillips Petroleum Co. by reaction of -dichloroben2ene with sodium sulfide in the presence of a polar solvent according to the following ... 

Researchers at Phillips Petroleum Company developed a commercially viable process for the synthesis of PPS involving the polymerization of /)-dich1orohenzene and a sodium sulfide source in a polar organic compound at elevated temperature and pressure. This Phillips process was patented in 1967 (18). Between 1967 and 1973, Phillips built and operated a pilot plant, estabhshed market demand, and constmcted a hiU-scale commercial plant. In 1973, the world s first PPS plant came on-stream in Phillips faciUty in Borger, Texas. 

Bayer marketed PPS compounds in the United States under the trade name Tedur, but the company has exited the PPS business. PPS is also marketed in the United States by GE Plastics, whose source of neat resin is Tosoh Corporation of Japan. GE Plastics markets PPS under the trade name Supec PPS. Patent activity by Tennessee Eastman describes an alternative process for the production of poly(phenylene sulfide/disulfide), although samples of such product have not appeared as of early 1996. Both Phillips and Hoechst Celanese have aimounced plans to debotdeneck their existing U.S. faciUties in order to meet anticipated market growth. 

The process implications of equation 3 go beyond the weU-known properties (27—29) of NMP to faciUtate S Ar processes. The function of the aminocarboxylate is also to help solubilize the sulfur source anhydrous sodium sulfide and anhydrous sodium hydrogen sulfide are virtually insoluble in NMP (26). It also provides a necessary proton acceptor to convert thiophenol intermediates into more nucleophilic thiophenoxides. A block diagram for the Phillips low molecular weight linear PPS process is shown in Eigure 1. 

Eig. 1. The key steps for the Phillips PPS process are (/) production of aqueous sodium sulfide from aqueous sodium hydrogen sulfide (or hydrogen sulfide) and aqueous sodium hydroxide 2) dehydration of the aqueous sodium sulfide and NMP feedstocks 5) polymerization of the dehydrated sulfur source with -dichlorobenzene to yield a slurry of PPS and by-product sodium chloride in the solvent (4) polymer recovery (5) polymer washing for the removal of by-product salt and residual solvent (6) polymer drying (7) optional curing, depending on the appHcation and (< ) packaging. 

Poly(phenylene sulfide) (PPS) is another semicrystalline polymer used in the composites industry. PPS-based composites are generally processed at 330°C and subsequently cooled rapidly in order to avoid excessive crystallisation and reduced toughness. The superior fire-retardant characteristics of PPS-based composites result in appHcations where fire resistance is an important design consideration. Laminated composites based on this material have shown poor resistance to transverse impact as a result of the poor adhesion of the fibers to the semicrystalline matrix. A PPS material more recently developed by Phillips Petroleum, AVTEL, has improved fiber—matrix interfacial properties, and promises, therefore, an enhanced resistance to transverse impact (see PoLYAffiRS containing sulfur). 

PPS resins must compete with PEI and phenoHcs. There are two domestic manufacturers of poly(phenylene sulfide) Phillips and Fortron Industries. Worldwide there is currently large overcapacity (Table 15). Four Japanese companies, ie, Toso Susteel, a joint venture of Toso/Hodogaya Chemical Toray Toprene, a joint venture of Toto Kasei/Toren Petrochemical and Kureha Chemical have a combined capacity of 82,500 t. U.S. agents sell their materials in the U.S. markets General Electric sells for Toso Susteel Soltex Polymer, part of Solvay, Belgium, sells for Toprene Hoechst-Celanese sells for Kureha. Prices for PPS resins and compounds range from 8.80/kg for unreinforced resin to 3.30/kg for 65% filled resins. 

Graphite/ Thermo- plastic AS4/PPS Phillips Petroleum Phillips Petroleum Polyphenylene sulfide, semicrystalline thermoplastic... 

Gilman A, Phillips FS The biological actions and therapeutic applications of the (3-chloroethyl amines and sulfides. Science 103 409M15, 1946... 

Ryton Poly(phenylene sulfide) Phillips Petroleum... 

The terf-butyl polysulfide used was kindly supplied by Phillips Petroleum Co. The polysulfide (MW 190.00) was greater than 90% pure. The polysulfide contained an average of four and five sulfur atoms per molecule. No pretreatment of the sulfides was performed. 

RYTON Polyphenylene sulfide Physical, Chemical, Thermal, and Electrical Properties, TSM-266, Phillips Chemical Co., Bartlesville, Okla., Apr. 1981, p. 2. 

SMITH PHILLIPS Isotopic Study of Coal-Associated Hydrogen Sulfide 571... 

Over the past 20 years a considerable chemical research effort was devoted to developing new high temperature polymers. It is interesting to note that some of these materials are now finding new applications and solutions to old problems of processing through blending. A commercial series of products trade-named Tribolon XT has been announced which are based on an aromatic polymide (Upjohn s 2080) with Phillips poly(phenylene sulfide), trade-named Ryton. A recent publication (88) describes some of the unique characteristics of this new family of materials. 

In 1973, Phillips Petroleum Company introduced linear and branched products under the trade name Ryton by reacting 1,4-dichlorobezene with sodium sulfide in a dipolar aprotic solvent. In 1983, the same company succeeded in stable melt-spinning of PPS. In 1986, the Federal Trade Commission gave the fiber the generic name Sulfar, defined as a manufactured fiber in... 

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... 

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