Natural mbber

Figure C2.1.16. Tensile stress as a Hmction of the extension ratio registered for a sample of natural mbber (circles). The broken curve is calculated from equation (C2.1.20). (Data from [79].)...

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... 

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

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. 

Most elastomers can be made iato either opea-ceUed or closed-ceUed materials. Natural mbber, SBR, nitrile mbber, polychloroprene, chlorosulfonated polyethylene, ethylene—propylene terpolymers, butyl mbbers, and polyacrylates have been successfuUy used (4,111,112). 

Latex mbber foams are generally prepared in slab or molded forms in the density range 64—128 kg/m (4—8 lbs/fT). Synthetic SBR latexes have replaced natural mbber latexes as the largest volume raw material for latex foam mbber. Other elastomers used in significant quantities are polychloroprene, nitrile mbbers, and synthetic i j -polyisoprene (115). 

In the mbber industry, formic acid is used for coagulating latex in the production of natural mbber and in the production of certain mbber chemicals (qv) (see Rubber, natural). 

In unalloyed steel containers formamide discolors slowly during shipment and storage. Both copper and brass are also subject to corrosion, particularly in the presence of water. Lead is less readily attacked. Aluminum and stainless steel are resistant to attack by formamide and should be used for shipping and storage containers where the color of the product is important or when metallic impurities must be minimized. Formamide attacks natural mbber but not neoprene. As a result of the solvent action of formamide, most protective paints and finishes are unsatisfactory when in contact with formamide. Therefore, formamide is best shipped in containers made of stainless steel or in dmms made of, or coated with, polyethylene. Formamide supphed by BASF is packed in Lupolen dmms (230 kg) or Lupolen canisters (60 kg) both in continental Europe and overseas. 

Several biomass species have been found to contain oils and/or hydrocarbons (Table 13). It is apparent that oil or hydrocarbon formation is not limited to any one family or type of biomass. Interestingly, some species in the Euphorbiaceae family, which includes Hevea bra liensis form hydrocarbons having molecular weights considerably less than that of natural mbber at yields as high as 10 wt% of the plant. This corresponds to hydrocarbon yields of about 3.97 mVhm2-yr(25bbl/hm2-yr). 

Dimethipin. 2,3-Dihydro-5,6-dimethyl-l,4-dithiin-l,l,4,4-tetraoxide [55290-64-7] (dimethipin, oxidimetbiin, UBI-N252, Harvard) (25) is used as a cotton defoHant and has been used as an experimental desiccant in potato vines. In addition, it defoHates nursery stock, grapes, dry beans, and natural mbber and is used as a desiccant for seed of canola, flax (l lnum usitatlssimum), rice, and sunflower (He/lanthus annuus) (10). The product has been available since the mid-1970s and the experimental work was first reported in 1974 (44). 

Terpene-based hydrocarbon resins are typically based on natural products such as a-pinene, P-pinene, and ti-limonene [5989-27-5] which are obtained from the wood and citms industries, respectively. These resins, which were originally the preferred tackifiers for natural mbber appHcations, possess similar properties to aHphatic petroleum resins, which were developed later. Terpene-based resins have been available since the mid-1930s and are primarily used in the adhesives industry. 

Pressure sensitive adhesives typically employ a polymer, a tackifier, and an oil or solvent. Environmental concerns are moving the PSA industry toward aqueous systems. Polymers employed in PSA systems are butyl mbber, natural mbber (NR), random styrene—butadiene mbber (SBR), and block copolymers. Terpene and aUphatic resins are widely used in butyl mbber and NR-based systems, whereas PSAs based on SBR may require aromatic or aromatic modified aUphatic resins. 

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. 

Plastics and Elastomers. Common plastics and elastomers (qv) show exceUent resistance to hydrochloric acid within the temperature limits of the materials. Soft natural mbber compounds have been used for many years as liners for concentrated hydrochloric acid storage tanks up to a temperature of 60°C (see Rubber, natural). SemUiard mbber is used as linings in pipe and equipment at temperatures up to 70°C and hard mbber is used for pipes up to 50°C and pressures up to 345 kPa (50 psig). When contaminants are present, synthetic elastomers such as neoprene, nitrile, butyl. 

The use of alkaU metals for anionic polymerization of diene monomers is primarily of historical interest. A patent disclosure issued in 1911 (16) detailed the use of metallic sodium to polymerize isoprene and other dienes. Independentiy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-l,3-butadiene was described (17). Interest in alkaU metal-initiated polymerization of 1,3-dienes culminated in the discovery (18) at Firestone Tire and Rubber Co. that polymerization of neat isoprene with lithium dispersion produced high i7j -l,4-polyisoprene, similar in stmcture and properties to Hevea natural mbber (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE Rubber, natural). 

Typical dielectric constant values for taw materials are 2.6—3.0 for natural mbber iasulation, approximately 2.2 for polyethylene, and approximately... 

The first synthetic route for isocyanates was reported in 1848 (10,11)- Subsequent efforts by Hofmann, Curtius, and Hentschel pioneered alternative synthetic approaches (12). These efforts highlighted the phosgene—amine approach. Staudinger presented the stmctural similarities between isocyanates and ketenes and stimulated interest in this class of compounds (13). However, it was not until 1945, when the world was pressed for an alternative to natural mbber, that synthetic routes to isocyanates became an area of great importance. Several excellent review articles covering the synthesis and chemistry of isocyanates have been presented (1 9). 

From the time that isoprene was isolated from the pyrolysis products of natural mbber (1), scientific researchers have been attempting to reverse the process. In 1879, Bouchardat prepared a synthetic mbbery product by treating isoprene with hydrochloric acid (2). It was not until 1954—1955 that methods were found to prepare a high i i -polyisoprene which dupHcates the stmcture of natural mbber. In one method (3,4) a Ziegler-type catalyst of tri alkyl aluminum and titanium tetrachloride was used to polymerize isoprene in an air-free, moisture-free hydrocarbon solvent to an all i7j -l,4-polyisoprene. A polyisoprene with 90% 1,4-units was synthesized with lithium catalysts as early as 1949 (5). 

With the avadabihty of polymerization catalysts, extensive efforts were devoted to developing economical processes for manufacture of isoprene. Several synthetic routes have been commercialized. With natural mbber as an alternative, the ultimate value of the polymer was more or less dictated by that market. The first commercial use of isoprene in the United States started in 1940. It was used as a minor comonomer with isobutylene for the preparation of butyl mbber. Polyisoprene was commercialized extensively in the 1960s (6). In the 1990s isoprene is used almost exclusively as a monomer for polymerization (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE). 

Fig. 37. Diffusion coefficient as a function of molar volume for a variety of permeants in natural mbber and in poly(vinyl chloride) (PVC) (81—83).

Extreme caution must be taken to prevent the possibility of fire when using flammable removers. Extra care must be taken when stripping on location to secure the area of ignition sources. When used on lacquer finishes, the dissolved finish and remover combined are extremely flammable. Natural mbber, neoprene, or other gloves suitable for use with the remover formula must be worn. The effect of skin contact with the remover is limited because there is immediate irritation and discomfort. Canister respirators are available for most petroleum and oxygenate remover solvents. Symptoms of long-term overexposure should be compared to symptoms of the major ingredients in the formula. 

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. 

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