Polysulfide, oxidation

PolysuWde Process. One modification to the kraft process being appHed commercially is the polysulfide process (38). Under alkaline conditions and relatively low temperature (100—120°C), polysulfides oxidize the active end group of the polysaccharide polymer to an alkaH-stable aldonic acid. This reaction, known for many years (39), was not produced on a commercial scale until the development of an efficient method for in situ generation of the polysulfide in kraft white Hquor. 

Lead dioxide is electrically conductive and is formed ia place as the active material of the positive plates of lead-acid storage batteries. Because it is a vigorous oxidizing agent when heated, it is used ia the manufacture of dyes, chemicals, matches (qv), pyrotechnics (qv), and Hquid polysulfide polymers (42) (see Polypous containing sulfur). 

Both the m- and -phenylenediamines are used to manufacture sulfur dyes, either by refluxing in aqueous sodium polysulfide, or heating with elementary sulfur at 330°C to give the leuco form of the dye. These dyes are polymeric, high molecular weight compounds, and soluble in base. The color is developed by oxidation on the fabric. 2,4-Toluenediamine and sulfur give Sulfur Orange 1 (14). 

The additional sulfur for polysulfide pulping can upset the sodium—sulfur balance in the kraft recovery cycle and increase sulfur emission problems. In the MOXY (Mead Corp.) process, polysulfide is formed from kraft white Hquor by catalytic oxidation of sodium sulfide in the white Hquor using air. 

Thiuram Sulfides. These compounds, (8) and (9), are an important class of accelerator. Thiurams are produced by the oxidation of sodium dithiocarbamates. The di- and polysulfides can donate one or more atoms of sulfur from their molecular stmcture for vulcanization. The use of these compounds at relatively high levels with litde or no elemental sulfur provides articles with improved heat resistance. The short-chain (methyl and ethyl) thiurams and dithiocarbamates ate priced 2/kg. Producers have introduced ultra-accelerators based on longer-chain and branched-chain amines that are less volatile and less toxic. This development is also motivated by a desire to rninirnize airborne nitrosamines. 

In the absence of zinc oxide, cross-linking proceeds through an accelerator polysulfide. With TBSI (14) and other sulfenamides, the accelerator decomposes upon heating during the induction period (before cross-linking) as shown in Figure 2 (13). 

Sulfur. Low sulfur stocks and EV sulfur-accelerated systems have better aging resistance. Normally, the oxidation rate increases with the amount of sulfur used in the cure. The increased rate may be due to activation of adjacent C—H groups by high levels of combined sulfur. Saturated sulfides are more inert to oxidation than aHyUc sulfides. Polysulfidic cross-links impart excessive hardening of SBR as compared to more stable monosulfidic cross-links. 

Traditionally, these dyes are appHed from a dyebath containing sodium sulfide. However, development in dyeing techniques and manufacture has led to the use of sodium sulfhydrate, sodium polysulfide, sodium dithionite, thiourea dioxide, and glucose as reducing agents. In the reduced state, the dyes have affinity for cellulose (qv) and are subsequendy exhausted on the substrate with common salt or sodium sulfate and fixed by oxidation. 

Tendering Effects. CeUulosic materials dyed with sulfur black have been known to suffer degradation by acid tendering when stored under moist warm conditions. This effect may result from the Hberation of small quantities of sulfuric acid which occurs when some of the polysulfide links of the sulfur dye are mptured. A buffer, such as sodium acetate, or a dilute alkaH in the final rinse, especially after oxidation in acidic conditions, may prevent this occurrence. Copper salts should never be used with sulfur black dyes because they cataly2e sulfuric acid generation. Few instances of tendering with sulfur dyes other than black occur and the problem is largely confined to cotton. 

Manufacture. Sodium thiosulfate has been produced commercially by the air oxidation of sulfides, hydrosulfides, and polysulfides. 

Barium sulfide solutions undergo slow oxidation in air, forming elemental sulfur and a family of oxidized sulfur species including the sulfite, thiosulfate, polythionates, and sulfate. The elemental sulfur is retained in the dissolved bquor in the form of polysulfide ions, which are responsible for the yellow color of most BaS solutions. Some of the mote highly oxidized sulfur species also enter the solution. Sulfur compound formation should be minimized to prevent the compounds made from BaS, such as barium carbonate, from becoming contaminated with sulfur. 

The polysulfide base material contains 50—80% of the polyfunctional mercaptan, which is a clear, amber, sympy Hquid polymer with a viscosity at 25°C of 35, 000 Pa-s(= cP), an average mol wt of 4000, a pH range of 6—8, and a ntild, characteristic mercaptan odor. Fillers are added to extend, reinforce, harden, and color the base. They may iaclude siUca, calcium sulfate, ziac oxide, ziac sulfide [1314-98-3] alumina, titanium dioxide [13463-67-7] and calcium carbonate. The high shear strength of the Hquid polymer makes the compositions difficult to mix. The addition of limited amounts of diluents improves the mix without reduciag the set-mbber characteristics unduly, eg, dibutyl phthalate [84-74-2], tricresyl phosphate [1330-78-5], and tributyl citrate [77-94-1]. 

The second catalyst paste of the two-paste product is a curing agent. A wide variety of materials convert the Hquid polysulfide polymers to elastomeric products. Alkalies, sulfur, metallic oxides, metallic peroxides, organic peroxides, and many metal—organic salts, ie, paint driers, are all potential curing agents. 

Sulfur dyes are used for dyeing ceUulosic fibers. They are insoluble in water and are reduced to the water-soluble leuco form for appHcation to the substrate by using sodium sulfide solution. The sulfur dye proper is then formed within the fiber pores by atmospheric oxidation (5). Sulfur dyes constitute an important class of dye for producing cost-effective tertiary shades, especially black, on ceUulosic fibers. One of the most important dyes is Cl Sulfur Black 1 [1326-82-5] (Cl 53185), prepared by heating 2,4-dinitrophenol with sodium polysulfide. 

Polysulfide Good resistance to aromatic solvents unusually high impermeability to gases poor compression set and poor resistance to oxidizing acids... 

Reactions with sulfides, polysulfides, sulfur oxides and the oxoacids of sulfur are complex and the products depend markedly on reaction conditions (see also p. 745 for blue crystals in chamber acid). Some examples are ... 

Aerial oxidation of polysulfides offers an alternative industrial route ... 

Polychalcogenides are less stable than polysulfides (p. 681). Reaction of alkali metals with Se in liquid ammonia affords M2Se2, M2Se3 and M2Se4, and analogous polytellurides have also been reported (see preceding section). However many of these compounds are rather unstable thermally and tend to be oxidized in air. 

Figure 3 Thermal oxidative breakdown of polypropylene (temperature 200°C Poj = 350 Tor stabilizer concentration 0.5 mass percent). 1-without stabilizer 2-Santanox 3-polythiosemicarbazide disulfide 4-polyamineaniline disulfide 5-polydi-iminodiphenyloxide disulfide 6-polyaniline disulfide 7-polydiiminodiphenylmethane disulfide 8-hydrorubeanicpoly disulfide 9-thiocarbamide polysulfide 10-polyiminoazobenzene disulfide.

Howard B.J. Alley, Determination of Ferric Oxide, Aluminum, and Magnesium Oxide in Polysulfide Propellants , ARGMA TR-1D2R (1960) 6) Anon, Polysulfide, Polymer,... 

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