Sulfide polymers

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... 

H. A. Smith and C. E. Handlovits, Report on Conference on High Temperature Polymer and Fluid Research, Partll, Phenylene Sulfide Polymers, ASD-TDR-62-322, Dayton, Ohio, 1962, pp. 18,19. 

The finely divided yellow sulfide polymer formed is then allowed to settle and the reaction liquor is separated by decantation. The product is washed by decantation five times with water and finally filtered by suction. The moist cake of polymer is then air dried. The yield is 988 parts including approximately 75 parts of magnesium hydroxide. 

Poly sulfide Polymers. These polymers are made up of aliphatic hydrocarbon units connected by di-, tri- or tetrasulfide links. The synthetic rubber found useful in ordn has hydrocarbon units linked by either O or formal segments. The polymers are usually prepd by the condensation of a suitable organic dihalide, usually the chloride, with aq Na polysulfide. According to Ref 8, the most practical organic dichloride is dichlorodiethylformal viz, Bis[ 2[Pg.827]

A.V. Tobolsky, Polymer Sulfur and Other Poly sulfide Polymers , ONR Tech Rept RLT-BO, Contract Nonr-1853(07), Princeton Univ, Princeton (1964) 8) Urbaiiski 3 (1967), 368-80... 

This method offered a route to metal-sulfide-polymer 680 composites... 

Swern oxidations have been performed using the PEG2000 bound sulfoxide 34 as a dimethylsulfoxide (DMSO) substitute (reaction 13).49-50 Several alcohols were efficiently oxidized to their aldehydes or ketones using this reagent, oxalyl chloride, and triethylamine. Precipitation of the polymer with cold diethyl ether and filtration through a pad of silica afforded the desired oxidized products in very good yields and purities. The reduced sulfide polymer could be reoxidized to sulfoxide 34 with sodium metaperiodate and used again in reactions with no appreciable loss in oxidation capacity. 

N,N-Bis(2-mercaptoethyl)2-methylthioethylamine. In a flame-dried and argon-flushed tube (15 x 3.75 cm) fitted with a teflon needle valve, a solution of ethylene sulfide (4.40 g, 73 mmole) in toluene (13 mL) is added to a solution of 2-methylmercaptoethylamine (2.65 g, 29 mmole) in toluene (10 mL). The valve is then closed to seal the tube and the mixture is allowed to stand for 8 h at room temperature. The sealed tube containing the reaction mixture is then heated to 110-130°C for 30-40 h. After cooling to room temperature, the tube is attached to a Schlenk line and opened under N2. The product mixture is filtered to remove a white precipitate (ethylene sulfide polymer), and the solvent is removed under vacuum. The residual liquid is fractionally distilled at reduced pressure (1I4-II6°C 0.03 mm) to yield N,N-bis(2-mercaptoethyl)2-methylthioethylamine as a colorless liquid. Yield = 3.56 g (58%). 

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... 

Epoxy-polysulfide systems can be formulated either as a liquid DGEBA epoxy mixed with liquid poly sulfide polymer or as an epoxy-terminated polysulfide polymer either may be cured with a tertiary amine such as DMP-30. Table 11.19 describes the formulation and shows the physical properties of these epoxy-polysulfide adhesives compared to an unmodified epoxy adhesive. 

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... 

A polypropylene sulfide polymer with just a single ferrocene unit [88] is formed in the ring-opening polymerisation of propylene sulfide (i.e., methyl thiirane) initiated by fc(SNa)2 (Scheme 5-19). 

In early work on organosulfur compounds, Duess (I) and Hil-ditch (2) reported the preparation of various aromatic disulfides by condensation reactions of thiophenol on treatment with aluminum chloride and sulfuric acid, respectively. Macallum (3) was the first to report the preparation of a phenylene sulfide polymer. His procedure involved the reaction of sulfur, sodium carbonate, and dichlorobenzene in a sealed vessel. Polymers made by this scheme generally have more than one sulfur atom between benzene rings, as indicated by the structure —( C6H4S )w-. 

Thiokol A, Eihanite, Perdu ren. The first commercial poly-sulfide polymer, prepd from ethylene dichloride and sodium polysulfide. Sulfur content 84% d about 1.6. Mixes with natural rubber. Cured polymer retains unpleasant odor irritating fumes evolve during manuf. Stable to the usual organic solvents and dil mineral acids. Unstable to alkalies and oxidizing substances. Of low tensile strength and abrasion resistance. Not recommended where tropic or arctic climates prevail,... 

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