Synthetic mbbers

The principal direct appHcation of furfural is as a selective solvent. It is used for separating saturated from unsaturated compounds in petroleum refining, for the extractive distillation of butadiene and other hydrocarbons in the manufacture of synthetic mbber and for the production of... 

Other furan compounds, best derived from furfural, are of interest although commercial volumes are considerably less than those of furfural, furfuryl alcohol, furan, or tetrahydrofurfuryl alcohol. Some of these compounds are stiU in developmental stages. Apphcations include solvents, resin intermediates, synthetic mbber modifiers, therapeutic uses, as well as general chemical intermediates. 

Rubber Modifiers. Derivatives of furan and tetrahydrofurfuryl alcohol are used in the polymerization of synthetic mbber to control stereoregularity and otherproperti.es (149,150). 

Historically, the use of acetylene as raw material for chemical synthesis has depended strongly upon the avadabihty of alternative raw materials. The United States, which until recendy appeared to have limitless stocks of hydrocarbon feeds, has never depended upon acetylene to the same extent as Germany, which had more limited access to hydrocarbons (1). During Wodd War 1 the first manufacture of a synthetic mbber was undertaken ia Germany to replace imported natural mbber, which was no longer accessible. Acetylene derived from calcium carbide was used for preparation of... 

Methyl mbber, obtained by polymerization of this monomer, was expensive and had inferior properties, and its manufacture was discontinued at the end of Wodd War 1. By the time Wodd War 11 again shut off access to natural mbber, Germany had developed better synthetic mbbers based upon butadiene... 

Butadiene Separation. Solvent extraction is used in the separation of butadiene (qv) [106-99-0] from other C-4 hydrocarbons in the manufacture of synthetic mbber. The butadiene is produced by catalytic dehydrogenation of butylene and the Hquid product is then extracted using an aqueous cuprammonium acetate solution with which the butadiene reacts to form a complex. Butadiene is then recovered by stripping from the extract. Distillation is a competing process. 

The first reported synthesis of acrylonitrile [107-13-1] (qv) and polyacrylonitrile [25014-41-9] (PAN) was in 1894. The polymer received Htde attention for a number of years, until shortly before World War II, because there were no known solvents and the polymer decomposes before reaching its melting point. The first breakthrough in developing solvents for PAN occurred at I. G. Farbenindustrie where fibers made from the polymer were dissolved in aqueous solutions of quaternary ammonium compounds, such as ben2ylpyridinium chloride, or of metal salts, such as lithium bromide, sodium thiocyanate, and aluminum perchlorate. Early interest in acrylonitrile polymers (qv), however, was based primarily on its use in synthetic mbber (see Elastomers, synthetic). 

NR, natural mbber CR, chloroprene SRs, synthetic mbbers IR, natural isoprene SBR, styrene—butadiene mbber BR, butadiene EPDM, ethylene—propjiene-diene EPM, ethylene—propylene polymer HR, isobutylene—isoprene NBR, nitrile—butadiene. 

In another extractor (Automatic Machinery and Electronics Inc. (AMC)) the individual fmits are cut in half as they pass a stationary knife. The halves are oriented in a vertical plane, picked up by synthetic mbber cups, and positioned across plastic serrated reamers revolving in a synchronized carrier in a vertical plane. As the fmit halves progress around the extractor turntable, the rotating reamers exert increasing pressure and express the juice. The oil and pulp contents in the juice increase with greater reaming pressure. The recoverable oil is removed in a separate step prior to juice extraction. Needle-sharp spikes prick the peel of the whole fmit, releasing oil that is washed away with water and recovered from the oil—water emulsion. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

Electric Discharge Processes. The synthetic mbber plant built by the 1. G. Farbenindustrie during World War 11 at Hbls, contained the first successful commercial instaUation for the electric arc cracking of lower hydrocarbons to acetylene. The plant, with a capacity of 200 t/d, was put into operation in August 1940. 

Of the estimated 710,000 t consumed in 1990, 25% was used to produce vinyl chloride [75-01-4] monomer (VCM), 14% for vinyl acetate [108-05-4] monomer (VAM), 23% for butanediol, 14% for industrial use, and the balance to produce other products such as acryUc acid, synthetic mbber, chlorinated solvents, and acetylene black. The demand for PVC is expected to decrease as legislation limiting its use in packaging is pending. Consequentiy, VCM consumption will also suffer. 

Dehydrogenation. Dehydrogenation of / -butane was once used to make 1,3-butadiene, a precursor for synthetic mbber. There are currently no on-purpose butadiene plants operating in the United States butadiene is usually obtained as a by-product from catalytic cracking units. 

Other than fuel, the largest volume appHcation for hexane is in extraction of oil from seeds, eg, soybeans, cottonseed, safflower seed, peanuts, rapeseed, etc. Hexane has been found ideal for these appHcations because of its high solvency for oil, low boiling point, and low cost. Its narrow boiling range minimises losses, and its low benzene content minimises toxicity. These same properties also make hexane a desirable solvent and reaction medium in the manufacture of polyolefins, synthetic mbbers, and some pharmaceuticals. The solvent serves as catalyst carrier and, in some systems, assists in molecular weight regulation by precipitation of the polymer as it reaches a certain molecular size. However, most solution polymerization processes are fairly old it is likely that those processes will be replaced by more efficient nonsolvent processes in time. 

Hydrogen chloride and the aqueous solution, muriatic acid, find appHcation in many industries. In general, anhydrous HCl is consumed for its chlorine value, whereas aqueous hydrochloric acid is often utilized as a nonoxidizing acid. The latter is used in metal cleaning operations, chemical manufacturing, petroleum well activation, and in the production of food and synthetic mbber. 

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

Early efforts to produce synthetic mbber coupled bulk polymerization with subsequent emulsification (9). Problems controlling the heat generated during bulk polymerization led to the first attempts at emulsion polymerization. In emulsion polymerization hydrophobic monomers are added to water, emulsified by a surfactant into small particles, and polymerized using a water-soluble initiator. The result is a coUoidal suspension of fine particles,... 

Liquids. Approximately 170,000 railroad tank cars are used in the United States. The interior surfaces of these cars are tailored to carry a wide variety of products and are constmcted of steel which is either unlined or lined with materials to enhance the chemical compatibiUty with a specific product these lining materials include synthetic mbber, phenoHc or modified epoxy resins, or corrosion-resistant materials such as aluminum, nickel-bearing steel, or stainless steel. 

The shipment of many commodities may require special barriers on the sacks to impart resistance against hquids or vapors. Other treatments are used to provide grease resistance, acid resistance, and scuff resistance. Special coatings are used in sacks for packing commodities, eg, synthetic mbbers, asphalts, waxes (qv), and resins, to prevent the contents from sticking to the paper. 

Carbon black, also classed as an inorganic petrochemical, is made predominandy by the partial combustion of carbonaceous (organic) material in a limited supply of air. Carbonaceous sources vary from methane to aromatic petroleum oils to coal tar by-products. Carbon black is used primarily for the production of synthetic mbber (see Carbon, carbon black). 

Emulsion Polymerization. When the U.S. supply of natural mbber from the Far East was cut off in World War II, the emulsion polymerization process was developed to produce synthetic mbber. In this complex process, the organic monomer is emulsified with soap in an aqueous continuous phase. Because of the much smaller (<0.1 jira) dispersed particles than in suspension polymerization and the stabilizing action of the soap, a proper emulsion is stable, so agitation is not as critical. In classical emulsion polymerization, a water-soluble initiator is used. This, together with the small particle size, gives rise to very different kinetics (6,21—23). 

These new synthetic mbbers were accessible from potentially low cost raw materials and generated considerable woddwide interest. For a time, it was hoped that the polysulftde mbbers could substitute for natural mbber in automobile tires. Unfortunately, these original polymers were difficult to process, evolved irritating fumes during compounding, and properties such as compression set, extension, and abrasion characteristics were not suitable for this apphcation. 

The bulk of 4-methylphenol is used in the production of phenoHc antioxidants. The alkylation of 4-methylphenol with isobutylene under acid catalysis yields 2-/ f2 -butyl-4-methylphenol [2409-55-4] and 2,6-di-/ f2 -butyl-4-methylphenol [128-37-0]. The former condenses with formaldehyde under acid catalysis to yield 2,2 -methylene bis(6-/ f2 -butyl-4-methylphenol) [119-47-1], which is widely used in the stabilization of natural and synthetic mbber (43). The reaction of 2-/ l -butyl-4-methylphenol with sulfur dichloride yields 2,2 -thiobis(6-/ l -butyl-4-methylphenol) [90-66-4]. 

Liquid polyalurninum chloride is acidic and corrosive to common metals. Suitable materials for constmction of storage and handling facilities include synthetic mbber-lined steel, corrosion resistant fiber glass reinforced plastics (FRP), ceramics, tetrafluoroethylene polymer (PTFE), poly(vinyhdene fluoride) (PVDF), polyethylene, polypropylene, and poly(vinyl chloride) (PVG). Suitable shipping containers include mbber-lined tank tmcks and rail cars for bulk shipment and plastic-lined or aH-plastic dmms and tote bins for smaller quantities. Except for aluminum chlorohydrates, PAG products are shipped as hazardous substances because of their acidity. 

Diarylamiaes fuactioa as mbber antioxidants by breaking the peroxidative chain reactions leading to mbber deterioration. Nearly all commercial synthetic mbbers (see Elastomers, synthetic), including neoprene, butyl, styrene—butadiene, and the acrylonitrile—butadiene mbbers, can be protected with about 1—2% of an alkylated diphenylamine. DPA itself is not used as a mbber antioxidant. An objectionable feature of these antioxidants is that they cause discoloration and staining which limits their use to applications where this is not important. 

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