Rubber sulfur

When heated in the presence of sulfur, rubber forms cross-links between polymer chains. 

Uses. Manufacture of rayon viscose fibers and cellophane film solvent for lipids, sulfur, rubber, phosphorus, oils, resins, and waxes insecticide... 

Rubber can be prepared with a wide range of physical properties by controlling the amount of sulfur used in vulcanization. Low-sulfur rubber, made with about 1 to 3% sulfur, is soft and stretchy. It is good for rubber bands and inner tubes. Medium-sulfur rubber (about 3 to 10% sulfur) is somewhat harder, but still flexible, making good tires. High-sulfur rubber (20 to 30% sulfur) is called hard rubber and was once used as a hard synthetic plastic. 

The method of vulcanization of cured rubbers using thiuram disulfides, in the absence of elementary sulfur, is widely used in the rubber industry. The basic advantage of thiuram rubbers is their high resistance to thermal aging. Thus, for example, cured rubbers based on butadiene nitrile rubbers, vulcanized with thiuram, manifest ability to work at 150-180°C, while the temperature limit of the operation of sulfur rubbers does not exceed 100-110°C. 

The concentration of zinc accelerator-thiolate complexes in the rubber is not the only factor determining the balance of the two reactions in NR. Both the rate of desulfuration of polysulfide crosslinks and the rate of their thermal decomposition depend upon the positions of attachment of the sulfur chains to the backbone rubber chains and the detailed structure of the hydrocarbon at the ends of the crosslinks. In the course of normal accelerated vulcanization there are three different positions of attack on the polyisoprene backbone two of these are methylene groups in the main chain (labelled d and a in 3), and the third is the side chain methyl group (labelled b in 3). Direct analysis of the distribution of the sites of attack cannot yet be made on actual rubber vulcanizates, and information has had to be obtained solely by sulfuration of the model alkene 2-methyl-2-pentene and, more recently, 2,6-dimethyl-2,6-octadiene. The former (4) models the a-methylic site but only one of the two a-methylenic sites of polyisoprene the latter (5) models all three sites, but at the present time these are not all supported by the synthesis of relevant sulfides. Because allylic rearrangements are common in subsequent reactions of the sulfurated rubber, sulfur substituents appear not only on allylic carbon atoms but on isoallylic carbon atoms. Thus, from 2-methyl-2-pentene, the groups shown in Scheme 2 are formed. 

Early rubber products were of limited use because they were sticky in hot weather and stiff in cold weather. In 1839, Charles Goodyear accidentally discovered that by heating a sulfur-rubber mixture, a product could be made that was stronger, more elastic, and more resistant to heat and cold than natural rubber. This process is now called vulcanization (after Vulcan, the Roman god of fire). The purpose of vulcanization is to form cross-links between long polymer chains. An example of a cross-link through two sulfur atoms is shown here ... 

Sulfur is a component of black gunpowder, and is used in the vulcanization of natural rubber and a fungicide. It is also used extensively in making phosphatic fertilizers. A tremendous tonnage is used to produce sulfuric acid, the most important manufactured chemical. 

A typical example is total monomers. 100 sodium stearate, 5 potassium persulfate, 0.3 lauryl mercaptan, 0.4 to 0.7 and water, 200 parts. In this formula, 75 parts of 1,3-butadiene and 25 parts of 4-methyl-2-vinylthiazole give 86% conversion to a tacky rubber-like copolymer in 15 hr at 45°C. The polymer contains 62% benzene-insoluble gel. Sulfur analysis indicates that the polymer contains 21 parts of combined 4-methyl-2-vinylthiazole (312). Butadiene alone in the above reaction normally requires 25 hr to achieve the same conversion, thus illustrating the acceleration due to the presence of 4-methyl-2-vinylthiazole. 

Originally, vulcanization implied heating natural rubber with sulfur, but the term is now also employed for curing polymers. When sulfur is employed, sulfide and disulfide cross-links form between polymer chains. This provides sufficient rigidity to prevent plastic flow. Plastic flow is a process in which coiled polymers slip past each other under an external deforming force when the force is released, the polymer chains do not completely return to their original positions. 

Ethylene-propylene-diene rubber is polymerized from 60 parts ethylene, 40 parts propylene, and a small amount of nonconjugated diene. The nonconjugated diene permits sulfur vulcanization of the polymer instead of using peroxide. 

Natural rubber, cis-1,4-polyisoprene, cross-linked with sulfur. This reaction was discovered by Goodyear in 1839, making it both historically and commercially the most important process of this type. This reaction in particular and crosslinking in general are also called vulcanization. 

Natural-mbber-based pressure-sensitive adhesives can be cured by standard mbber curatives, eg, sulfur plus an accelerator (see Rubber, natural) ... 

Rubber. A thin coating of mica acts as a mold-release compound in the priming of mbber goods such as tires. It prevents the migration of sulfur from the tire to the air bag when the tire is being vulcani2ed (see Tire cords). Mica is also dusted on mbber inner tubes to prevent sticking. 

Insoluble Sulfur. In natural mbber compounds, insoluble sulfur is used for adhesion to brass-coated wire, a necessary component in steel-belted radial tires. The adhesion of mbber to the brass-plated steel cord during vulcanization improves with high sulfur levels ( 3.5%). Ordinary rhombic sulfur blooms at this dose level. Crystals of sulfur on the surface to be bonded destroy building tack and lead to premature failure of the tire. Rubber mixtures containing insoluble sulfur must be kept cool (<100°C) or the amorphous polymeric form converts to rhombic crystals. 

Ethylene—Propylene Rubber. Ethylene and propjiene copolymerize to produce a wide range of elastomeric and thermoplastic products. Often a third monomer such dicyclopentadiene, hexadiene, or ethylene norbomene is incorporated at 2—12% into the polymer backbone and leads to the designation ethylene—propylene—diene monomer (EPDM) mbber (see Elastomers, synthetic-ethylene-propylene-diene rubber). The third monomer introduces sites of unsaturation that allow vulcanization by conventional sulfur cures. At high levels of third monomer it is possible to achieve cure rates that are equivalent to conventional mbbers such as SBR and PBD. Ethylene—propylene mbber (EPR) requires peroxide vulcanization. 

Accelerators. During sulfur vulcanization of rubber, accelerators serve to control time to onset of vulcanization, rate of vulcanization, and number and type of sulfur cross-links that form. These factors in turn play a significant role in determining the performance properties of the vulcanizate. 

W. H. Helt and D. Accelerated Sulfur Uulcanicyation, at the CL Meeting of the 147th Rubber Division, Philadelphia, Pa., Mery 2—5, 1995, American Chemical... 

Cure Characteristics. Methods of natural rubber production and raw material properties vary from factory to factory and area to area. Consequentiy, the cure characteristics of natural mbber can vary, even within a particular grade. Factors such as maturation, method and pH of coagulation, preservatives, dry mbber content and viscosity-stabilizing agents, eg, hydroxylamine-neutral sulfate, influence the cure characteristics of natural mbber. Therefore the consistency of cure for different grades of mbber is determined from compounds mixed to the ACSl formulation (27). The ACSl formulation is as follows natural mbber, 100 stearic acid, 0.5 zinc oxide, 6.0 sulfur, 3.5 and 2-mercaptobenzothiazole (MBT), 0.5. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

The principal commercial uses of sulfur monochloride are in the manufacture of lubricant additives and vulcanising agents for mbber (147,154,155) (see Lubrication AND lubricants Rubber chemicals). The preparation of additives for wear and load-bearing improvement of lubricating oils is generally carried out in two steps and the technology is described in numerous patents (155) (see Sulfurization and sulfchlorination). 

Ethylene—Propylene (Diene) Rubber. The age-resistant elastomers are based on polymer chains having a very low unsaturation, sufficient for sulfur vulcanization but low enough to reduce oxidative degradation. EPDM can be depicted by the following chain stmcture ... 

Butyl Rubber. Butyl mbber was the first low unsaturation elastomer, and was developed ia the United States before World War II by the Standard Oil Co. (now Exxon Chemical). It is a copolymer of isobutylene and isoprene, with just enough of the latter to provide cross-linking sites for sulfur vulcanization. Its molecular stmcture is depicted ia Table 1. 

Sulfuric Acid, Below 55% Hard Rubber Lined C.l. Special Rubber Carbon Steel Hastelloy C Ring Packing Special Rubber Special Rubber... 

Caution Rubber gloves and a protective pace shield should be worn while handling liquid sulfur trioxide, and the reaction should be carried out in a hood. 

Tsai et al. have also used RAIR to investigate reactions occurring between rubber compounds and plasma polymerized acetylene primers deposited onto steel substrates [12J. Because of the complexities involved in using actual rubber formulations, RAIR was used to examine primed steel substrates after reaction with a model rubber compound consisting of squalene (100 parts per hundred or phr), zinc oxide (10 phr), carbon black (10 phr), sulfur (5 phr), stearic acid (2 phr). 

The Auger depth profile obtained from a plasma polymerized acetylene film that was reacted with the same model rubber compound referred to earlier for 65 min is shown in Fig. 39 [45]. The sulfur profile is especially interesting, demonstrating a peak very near the surface, another peak just below the surface, and a third peak near the interface between the primer film and the substrate. Interestingly, the peak at the surface seems to be related to a peak in the zinc concentration while the peak just below the surface seems to be related to a peak in the cobalt concentration. These observations probably indicate the formation of zinc and cobalt complexes that are responsible for the insertion of polysulfidic pendant groups into the model rubber compound and the plasma polymer. Since zinc is located on the surface while cobalt is somewhat below the surface, it is likely that the cobalt complexes were formed first and zinc complexes were mostly formed in the later stages of the reaction, after the cobalt had been consumed. 

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