rubberelastic substance obtained from the exudations of certain tropical plants (natural rubber) or derived from petroleum and natural gas (synthetic rubber). See also elastomer. Because of its elasticity, resilience, and toughness, rubber is the basic constituent of the tires used in automotive vehicles, aircraft, and bicycles. The same properties make it useful for machine belting and hoses of all kinds. Rubber is also used in electrical insulation, and because it is waterproof, it is a favoured material for shoe solesMore than half of all rubber produced goes into automobile tires; the rest goes into mechanical parts such as mountings, gaskets, belts, and hoses, as well as consumer products such as shoes, clothing, furniture, and toys.

The main chemical constituents of rubber are elastomers, or “elastic polymers,” large chainlike molecules that can be stretched to great lengths and yet recover their original shape. The first common elastomer was polyisoprene, from which natural rubber is made. Formed in a living organism, natural rubber consists of solids suspended in a milky fluid, called latex, that circulates in the inner portions of the bark of many tropical and subtropical trees and shrubs, but predominantly Hevea brasiliensis, a tall softwood tree originating in Brazil. Natural rubber was first scientifically described by C.Charles-M. Marie de la La Condamine and François Fresneau of France following an expedition to South America in 1735. The English chemist Joseph Priestley gave it the name rubber in 1770 when he found it could be used to rub out pencil marks. Its major commercial success came only after the vulcanization process was invented by Charles Goodyear in 1839.

Natural rubber continues to hold an important place in the market today; its resistance to heat buildup makes it valuable for tires used on racing cars, trucks, buses, and airplanes. Nevertheless, it constitutes less than half of the rubber produced commercially; the rest is produced from a wide variety of plants, but predominantly from Hevea brasiliensis (family Euphorbiaceae), a tall softwood tree originating in Brazil. Hevea trees descended from seedlings transplanted to South and Southeast Asia now produce most of the modern world’s natural rubber. The largest producing countries are Indonesia, Malaysia, Thailand, India, Sri Lanka, and China.

The latex found in the inner bark of H. brasiliensis is obtained by tapping—cutting or shaving the bark with a sharp knife—and collecting the latex in cups. Solid rubber is coagulated from the fluid by the addition of chemicals, such as formic acid, that cause the rubber to form curds on the surface of the liquid. The curds can then be pressed between rollers to remove excess moisture and to form sheets. The sheets are commonly packed in bales for shipping. Rubber is also commonly transported in the form of a concentrated latex.

Despite the competition of synthetic rubber, natural rubber continues to hold an important place; its resistance to heat buildup makes it valuable for tires used on racing cars, trucks, buses, and airplanes.

Research on the chemistry of natural rubber led in the 19th century to the isolation of isoprene, the chemical compound from which natural rubber is polymerized. Polymerization, the process by which long chainlike molecules are built up from smaller molecules, attracted continued research in the early 20th century. During World War I, German scientists produced a crude synthetic rubber, and during the 1920s and ’30s several polymerizing processes were developed in Germany, the Soviet Union, Britain, and the United States. During World War II huge quantities of synthetic rubber, mostly based on polymers of butadiene, were produced. By the early 1960s synthetic rubbers had overtaken natural rubber in quantity produced.

Among the most important synthetics are polybutadiene; styrene-butadiene copolymer; polychloroprene (neoprene); the polysulfides (Thiokol); the isobutylene-isoprene copolymers (butyl rubbers); and the polysiloxanes (silicone rubbers). Synthetic rubbers, like natural rubbers, can be toughened by vulcanization and improved and modified for special purposes by reinforcement with other materials.


Essential properties of the polymers used to produce the principal commercial rubbers are listed in the table.

Natural rubber production
The rubber tree

Commercially, natural rubber is obtained almost exclusively from Hevea brasiliensis, a tree indigenous to South America, where it grows wild to a height of 34 metres (120 feet). Cultivated in plantations, however, the tree grows only to about 24 metres (80 feet) because carbon, necessary for growth, is also an essential constituent of rubber. Since only atmospheric carbon dioxide can supply carbon to the plant, the element has to be rationed between the two needs when the tree is in active production. Also, with foliage limited to the top of the tree (to facilitate tapping), the intake of carbon dioxide is less than in a wild tree. Other trees, shrubs, and herbaceous plants produce rubber, but, because none of them compares for efficiency with Hevea brasiliensis, industry botanists have concentrated their efforts exclusively on this species.

In the cultivation of Hevea, the natural contours of the land are followed, and the trees are protected from wind. Cover crops planted adjacent to the rubber trees hold rainwater on sloping ground and help to fertilize the soil by fixing atmospheric nitrogen. Standard horticultural techniques, such as nursery growing of hardy rootstocks and grafting on top of them, hand pollination, and vegetative propagation (cloning) to produce a genetically uniform product, are also employed.

Hevea grows only within a well-defined area of the tropics and subtropics where frost is never encountered. Heavy annual rainfall of about 2,500 mm (100 inches) is essential, with emphasis on a wet spring. As a consequence of these requirements, growing areas are limited. Southeast Asia is particularly well situated for rubber culture; so too are parts of South Asia and West Africa. Cultivation of Hevea in Brazil, its native habitat, was virtually destroyed by blight early in the 20th century.

Tapping and coagulation






Development of the natural rubber industry

If latex is allowed to evaporate naturally, the film of rubber that forms can be dried and pressed into usable articles such as bottles, shoes, and balls. South American Indians made such objects in early times: rubber balls, for instance, were used in an Aztec ceremonial game (called ollama) long before Christopher Columbus explored South America and the Caribbean. On his second voyage to the New World in 1493–96, Columbus is said to have seen natives in present-day Haiti play a game with balls made from the gum of a tree. In 1615 a Spaniard related how the Indians, having gathered the milk from incisions made in various trees, brushed it onto their cloaks and also obtained crude footwear and bottles by coating earthen molds and allowing them to dry.

The first serious accounts of rubber production and the primitive Native American system of manufacture were given in the 18th century by Charles-Marie de La Condamine, a member of a French geographic expedition sent to South America in 1735. La Condamine described “caoutchouc” (the French spelling of a native term for “weeping wood”) as the condensed juice of the Hevea tree, and in 1736 he sent rubber samples to Europe. Initially the new material was merely a scientific curiosity. Some years later the British scientist Joseph Priestley remarked on its usefulness for rubbing pencil marks from paper, and so the popular term rubber was coined. Other applications gradually developed, notably for waterproofing shoes and clothing.

Important progress toward a true rubber industry came at the beginning of the 19th century from the separate experiments of a Scottish chemist, Charles Macintosh, and an English inventor, Thomas Hancock. Macintosh’s contribution was the rediscovery, in 1823, of coal-tar naphtha as a cheap and effective solvent. He placed a solution of rubber and naphtha between two fabrics and in so doing avoided the sticky surfaces that had been common in earlier single-texture garments treated with rubber. Manufacture of these double-textured waterproof cloaks, henceforth known as “mackintoshes,” began soon afterward.

The work of Hancock, who became Macintosh’s colleague and partner, is of even greater importance. He first attempted to dissolve the rubber in turpentine, but his hand-coated fabrics were unsatisfactory in surface texture and smell. He then turned to the production of elastic thread. Strips of rubber were cut from the imported lumps and applied in their crude state to clothing and footwear. In 1820, in an effort to find a use for his waste cuttings, Hancock invented a masticator. Constructed of a hollow wooden cylinder equipped with teeth in which a hand-driven spiked roller was turned, this tiny machine, originally taking a charge of two ounces of rubber, exceeded Hancock’s greatest hopes. Instead of tearing the rubber to shreds, it produced enough friction to weld the scraps of rubber into a coherent mass that could be applied in further manufacture.

Macintosh’s and Hancock’s efforts resolved the initial problem of handling the raw material, but there remained one principal obstacle to the full exploitation of natural rubber: it softened with heat and hardened with cold (particularly annoying in North America, where the climate was more extreme than in Britain). It also was tacky, odorous, and perishable. These fundamental weaknesses were removed by the invention of vulcanization in 1839 by Charles Goodyear. Developing a compound of rubber, white lead, and sulfur and a heat treatment (or curing) process, Goodyear created a product—at first called fireproof gum, afterward vulcanized rubber—that exhibited impressive durability.

Vulcanization made the modern rubber industry possible by permitting use of the substance in machinery and in tires for bicycles and, later, for automobiles. Though subsequent discoveries have refined Goodyear’s original techniques, the vulcanization process remains fundamentally the same as it was in his day. (For the chemical processes underlying vulcanization, see elastomer.)

With the advent of the bicycle and, somewhat later, the automobile and the invention of the solid and later the pneumatic rubber tire, demand for rubber grew rapidly. By 1900 more than 40,000 tons were used each year, about one-half from Brazil and one-half from Central Africa, where rubber was obtained principally from Landolphia vines. However, as an important industrial material, rubber was required in larger amounts than could easily be obtained from wild and widely dispersed trees in the Brazilian jungle or from African vines that produced only about one kilogram per hectare and were destroyed to obtain the rubber. With a view to cultivating rubber trees elsewhere, in 1876 seeds of the Hevea brasiliensis tree from the upper Orinoco basin were taken from Brazil to England at the instigation of the British India Office. Seedlings were raised at Kew Gardens and shipped to Ceylon (Sri Lanka) and Singapore. These trees were the origin of the rubber plantation industry in Asia, which now produces more than 90 percent of the world’s supply. The industry developed largely as a result of the work of Henry N. Ridley, director of the Singapore Botanic Gardens from 1888 until 1912. Ridley introduced horticultural and tapping methods that are still used today. Total natural rubber production is now approximately 6.5 million tons per year, of which some 70 percent is used in automobile and truck tires. The principal rubber-producing countries are Thailand, Indonesia, and Malaysia, each producing more than one million tons per year. Smaller amounts are produced in China, India, the Philippines, Vietnam, Sri Lanka, and the West African states of Nigeria, Côte d’Ivoire, Cameroon, and Liberia.

The first decade of the 20th century saw the establishment of the motorcar in Europe and North America, and the automotive industry remained entirely dependent on natural rubber for its tires and other components until World War II. After Japan entered the war in 1941, Asian sources, except for Sri Lanka, were cut off from the Allies. In response, the United States and the Soviet Union attempted to cultivate alternative sources of natural rubber, such as the guayule shrub and the Russian dandelion. These attempts met with little success, but far better results were obtained from synthetic rubber. The United States in particular developed a synthetic rubber industry almost overnight, achieving a production of 800,000 tons per year. At the war’s end, with natural rubber again available, the U.S. synthetic rubber industry went into a sharp decline, but by the early 1950s superior and more uniform synthetics had become available. The export of these materials stimulated development of a synthetic rubber industry in Europe. In the early 1960s production of natural rubber was surpassed by that of synthetic elastomers, which now represent some 60 percent of the total.

Synthetic rubber production
Polymerization methods

Synthetic elastomers are produced on an industrial scale in either solution or emulsion polymerization methods. (Solution polymerization and emulsion polymerization are described in the article chemistry of industrial polymers.) Polymers made in solution generally have more linear molecules (that is, less branching of side chains from the main polymer chain), and they also have a narrower distribution of molecular weight (that is, greater length) and flow more easily. In addition, the placement of the monomer units in the polymer molecule can be controlled more precisely when polymerization is conducted in solution. The monomer or monomers are dissolved in a hydrocarbon solvent, usually hexane or cyclohexane, and polymerized, using an organometallic catalyst such as butyllithium.

In emulsion polymerization, the monomer (or monomers) is emulsified in water with a suitable soap (e.g., sodium stearate) employed as a surfactant, and a water-soluble free-radical catalyst (e.g., potassium persulfate, peroxides, a redox system) is added to induce polymerization. After polymerization has reached the desired level, the reaction is stopped by adding a radical inhibitor. About 10 percent of synthetic elastomer produced through emulsion techniques is sold as latex. The rest is coagulated with acidified brine, washed, dried, and pressed into 35-kg (77-pound) bales.

When emulsion polymerization of SBR is carried out “hot” (i.e., at 50 °C, or 120 °F), the polymer molecules are more branched. When polymerization is carried out “cold” (i.e., at 5 °C, or 40 °F), they are more linear and generally higher in molecular weight—features that improve the rolling resistance and wear resistance of tires. In some cases polymerization is continued in order to give products of such high molecular weight that they would normally be intractable. In these cases about 30 percent of a heavy oil is added before coagulation to yield “oil-extended” elastomers with superior wear resistance.

The rise of synthetic rubber

The origins of the elastomers forming the base of synthetic rubber can be traced to the first half of the 19th century, when attempts were made to elucidate the composition and structure of natural rubber with the eventual goal of reproducing the material. In 1838 the German F.C. Himly obtained a volatile distillate from the substance, and in 1860 the Englishman C. Greville Williams broke down rubber by distillation into three parts—oil, tar, and “spirit”—this last part being the more volatile fraction and the main constituent, which Williams named isoprene. The Frenchman Georges Bouchardat, with the aid of hydrogen chloride gas and prolonged distillation, converted isoprene to a rubberlike substance in 1875, and in 1882 another Briton, W.A. Tilden, produced isoprene by the destructive distillation of turpentine. Tilden also assigned isoprene the structural formula CH2=C(CH3)−CH=CH2.

The efforts outlined above were attempts to replicate natural rubber. It was only when the search for chemical equivalents to natural rubber was abandoned and comparable physical properties were emphasized that synthetic rubber came into being. The choice fell upon butadiene (CH2=CH−CH=CH2), a compound similar to isoprene, as the basis for a synthetic product. Several significant contributions came from Russia. In 1901 Ivan Kondakov discovered that dimethyl butadiene, when heated with potash, produced a rubberlike substance, and in 1910 S.V. Lebedev polymerized butadiene, which he obtained from ethyl alcohol. During World War I, Germany, under the stimulus of the blockade imposed by the Allies, began production of “methyl rubber” by using Kondakov’s process. This was an inferior substitute by present-day standards, and after the war German manufacturers returned to the cheaper and more satisfactory natural product. Research and experiments continued, however, and in 1926 the German G. Ebert succeeded in producing a sodium-polymerized rubber from butadiene. During the following decade this material evolved into various types of “buna” rubber (so called from the initial syllables of the two materials used to make them: butadiene and natrium [sodium]).

In the Soviet Union, production of polybutadiene by using Lebedev’s process was begun in 1932–33, using potatoes and limestone as raw materials. By 1940 the Soviet Union had the largest synthetic rubber industry in the world, producing more than 50,000 tons per year. In Germany, meanwhile, the first synthetic elastomer that could be used to replace natural rubber and make satisfactory tires was developed at I.G. Farben by Walter Bock and Eduard Tschunkur, who synthesized a rubbery copolymer of styrene and butadiene in 1929, using an emulsion process. The Germans referred to this rubber as Buna S; the British called it SBR, or styrene-butadiene rubber. Because styrene and butadiene can be made from petroleum, grain alcohol, or coal, SBR was in great demand during World War II. Immense amounts were made—as much as 100,000 tons per year in Germany and the Soviet Union. About 800,000 tons of SBR were produced per year in the United States, where it received the wartime designation GR-S (government rubber-styrene). During the war German chemical engineers perfected low-temperature, or “cold,” polymerization of SBR, producing a more uniform product.

Other important synthetic elastomers were discovered in the decades before World War II, though none was suitable for making tires. Among these were polysulfides, synthesized in the United States by Joseph Patrick in 1926 and commercialized after 1930 as oil-resistant thiokol rubbers; polychloroprene, discovered by Arnold Collins in 1931 and commercialized by the DuPont Company in 1932 as Duprene (later neoprene), a high-strength oil-resistant rubber; nitrile rubber (NBR), an oil-resistant copolymer of acrylonitrile and butadiene synthesized by Erich Konrad and Tschunkur in 1930 and known as Buna N in Germany; and butyl rubber (IIR), a copolymer of isoprene and isobutylene discovered in 1937 by the Americans R.M. Thomas and W.J. Sparks at Standard Oil Company (New Jersey).

After World War II, increasing sophistication in synthetic chemistry led to many new polymers and elastomers. In 1953–54 two chemists, Karl Ziegler of Germany and Giulio Natta of Italy, developed a family of organometallic catalysts that were able to control precisely the placing and arrangement of units along the polymer chain and thus produce regular (stereospecific) structures. With the use of such catalysts, isoprene was polymerized in such a manner that each unit in the chain was linked to its predecessor in a cis configuration, virtually identical to the structure of natural rubber. In this way virtually 100 percent cis-polyisoprene, “synthetic natural rubber,” was made. In 1961 the same type of catalyst with butadiene as the monomer was used to produce cis-1,4-polybutadiene, a rubber that was found to have excellent abrasion resistance, especially in tires subjected to severe service conditions.

Several other advances characterized the postwar years. For example, block copolymers, in which a long sequence of one chemical unit is followed in the same molecule by a long sequence of another, were made, using many different units and sequence lengths. New oil-resistant and heat-resistant elastomers were introduced, including the styrene-acrylonitrile copolymers, the polysulfides, and chlorinated and chlorosulfonated polyethylene. Control has been achieved, to some degree, over the wide range of molecular length found in most polymers, so narrow or broad distributions can be produced in many cases, with quite different viscous properties. In addition, polymers have been synthesized with branched molecules, either with many small branches along the main chain or with several long “arms” radiating from a central point, giving different flow properties and more facile cross-linking.

World consumption of synthetic rubber reached nine million tons in 1993. About 55 percent of all synthetic rubber produced is used in automobile tires.


A number of ingredients are added to both natural and synthetic rubber in order to obtain certain desirable properties. By convention, mix formulations begin with the amount of the designated elastomer—for instance, natural rubber (NR), butadiene rubber (BR), or styrene-butadiene rubber (SBR)—given as 100 parts by weight. The amount of each other ingredient is then expressed in parts by weight added per 100 parts by weight of the elastomer. If two or more elastomers are used, then they are shown in the recipe as fractions of 100 parts—for example, “NR, 60 parts; BR, 40 parts.” When the elastomer contains oil already added by the producer, allowance is made for this dilution in the recipe. For example, if SBR 1702 is used, the mix formulation may begin “SBR 1702, 137.5 parts by weight,” because that amount of SBR 1702 contains 37.5 parts by weight of oil and 100 parts by weight of SBR elastomer.

The cure package

The most important ingredients are those, known as the cure package, that cause interlinking reactions to take place when the mix is “cured.” In order to minimize the risk of premature cure, they are usually added at the end of mixing. The cure package usually consists of sulfur and one or more “accelerators” (e.g., sulfenamides, thiurams, or thiazoles), which make the sulfur interlinking reaction occur faster and more efficiently. When the ratio of sulfur to accelerator is less than one, the recipe is known as an “efficient vulcanization” (EV) system and gives products with sulfur interlinks of shorter length. EV products have improved resilience but lower strength.

Two other ingredients that play an important role in vulcanization chemistry are known as “activators,” commonly zinc oxide and stearic acid. These compounds react together and with accelerators to form a zinc sulfurating compound, which in turn is the key intermediary in adding sulfur to a diene elastomer and creating sulfur interlinks.

Other less widely used interlinking reagents are sulfur compounds known as sulfur donors—e.g., tetramethylthiuram disulfide—which introduce monosulfide interlinks between polymer molecules, and peroxides, notably dicumyl peroxide. Peroxides decompose on heating to form radicals, which abstract hydrogen from groups on the polymer molecules. Carbon radicals formed in this way on different molecules then combine to create carbon-carbon interlinks. Although products with C−C interlinks are more resistant to heat and oxidative attack, their strength is lower than products with sulfur interlinks. In addition, monosulfide links give weaker products than polysulfide links. This paradoxical result—that inherently strong C−C interlinks give the weakest products, whereas inherently weak polysulfide links give the strongest products—is attributed to the fact that weak interlinks will break under stress before the main chain does, so failure of the elastomer molecule itself is delayed.


Almost every conceivable material has been added to rubber in attempts to cheapen and stiffen it. Two particulate fillers are outstanding because they also strengthen elastomers to a remarkable degree. The most important, used almost universally, is finely divided carbon black, prepared by incomplete combustion of oil or gas. Carbon black consists of small spherical particles having diameters of only 10–100 nanometres (10–100 billionths of a metre) and made up of concentric graphitic layers of carbon. The surface of the particles also contains some oxygen and hydrogen. During manufacture, chains of particles become fused together to create extended open “structures,” still very small in size.

Another reinforcing filler with particles of similar shape and size is finely divided silica (silicon dioxide, SiO2), prepared either by burning silicon tetrachloride or by acid precipitation from a sodium silicate solution.

Both carbon black and silica, when added to a mix compound at a concentration of about 30 percent by volume, raise the elastic modulus of the rubber by a factor of two to three. They also confer remarkable toughness, especially resistance to abrasion, on otherwise weak materials such as SBR. If greater amounts are added, the modulus will be increased still further, but the strength will then begin to fall. Disadvantages of reinforcement with carbon black or silica are lower springiness (resilience) and a decrease in the initial high stiffness after flexing.

For a filler to be reinforcing, it appears that the fundamental particles must be small—for instance, 10–50 nanometres in diameter—and that the elastomer must adhere well to them. If either of these conditions is absent, the reinforcing power will be lessened. Indeed, the smaller the particle size (and hence the greater the surface area), the greater the observed reinforcing effect. It is still not understood how fine particles are able to confer high strength and toughness on elastomer compounds. Strengthening and toughening are possibly associated with debonding of highly stressed elastomer molecules from the filler particles, reducing the stress on the polymer chains and delaying catastrophic fracture.

Protective chemicals

Certain additives confer resistance to heat, sunlight, oxygen, and ozone. Amines, particularly paraphenylene diamines, are powerful retarders of oxidation, or antioxidants. Added to rubber compounds in small amounts (1–2 percent), they appear to disrupt the free-radical oxidation reactions that lead either to molecular rupture and softening or to increased interlinking and hardening as rubber ages. Hindered phenols, another antioxidant class, are less powerful than amines but have less tendency to stain light-coloured rubber compounds. Small amounts of certain metals, notably copper, manganese, and iron, act as powerful catalysts of oxidation; sequestering agents are therefore used to block the action of these elements if their presence is unavoidable.

Atmospheric ozone reacts readily with elastomers containing C=C double bonds, leading to breakage of molecules lying in the surface. As a result, small, deep fissures, termed ozone cracks, are formed if the rubber is stretched slightly (by more than about 10 percent). Cracks one millimetre long appear in unprotected rubber after only a few weeks of exposure to a typical outdoor concentration of ozone, about 5 parts per 100 million. However, certain diamines (e.g., alkyl-aryl paraphenylene diamines) prevent cracking, probably by competing with the C=C bonds in rubber for reaction with ozone. These antiozonants “bloom” to the surface and react there, protecting the rubber. A few percent of an antiozonant is therefore commonly included in the mix formulation of rubber compounds based on unsaturated elastomers. An alternative method of protection, often employed simultaneously, is to include a few percent of a microcrystalline paraffin wax in the mix formulation. Because it is incompatible with the elastomer, the wax blooms to the surface and forms a protective skin.

Plasticizers and processing aids

Liquids are added to elastomer mixes in order to soften and plasticize the compound, either in processing or later in use. For example, elastomers with high glass transition temperatures (and correspondingly slow molecular motions) can be improved by adding low-temperature plasticizers—i.e., compatible liquids that act as internal lubricants. Plasticizers must have low vapour pressure and a high boiling point in order to be retained within the compound over long periods of service. Examples are aliphatic esters and phthalates. Phosphate plasticizers also confer a measure of flame resistance. Other liquids are added to rubber compounds as processing aids in order to make mixing and extrusion easier. Typically, 5 percent of a petroleum oil is used.









