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Synthetic rubber. History of invention and production

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Rubbers are natural or synthetic elastomers characterized by elasticity, water resistance and electrical insulating properties, from which rubbers and ebonites are obtained by vulcanization.

Synthetic rubber

Europe first learned about rubber in the XNUMXth century. Christopher Columbus brought it from America along with many other curiosities. During the anchorage of the ships off the island of Haiti, Columbus and his companions observed the natives playing with a ball made of some kind of elastic material, completely unknown in Europe. The balls easily bounced when they hit the ground, compressed and again restored their original shape.

Returning to Spain, Columbus took with him samples of this wonderful material, which was later known in the Old World under the name "rubber". Translated from the Indian "rubber" means "tears of a tree." As it became known later, it was a juice collected from incisions in the bark of a tropical tree - Brazilian hevea. It was taken from a tree when the hevea was seven years old: at a height of half a meter, an incision was made on the bark, and when white juice, like milk, began to flow from under it, they collected it in hanging cups, and then poured it into a large vessel. In the air, the juice coagulated relatively quickly and turned into a dark resinous product - rubber.

Hevea latex collection (Sri Lanka)

Europeans did not immediately appreciate the merits of this material. For two centuries they treated rubber as a savage curiosity. Meanwhile, travelers who came to South America continued to deliver more and more new items made from rubber to Europe. Among them were bottles, waterproof boots and rain clothes. All this was very curious, but had no practical significance. Only after a long time did the Europeans find the first use for rubber - they began to use it in the form of rubber bands, reminiscent of modern school erasers.

At the end of the 1839th century, the English chemist Mackintosh took out a patent for the manufacture of waterproof raincoats from rubber. They are called Macintosh. Raincoats, however, were not good enough for the European climate; at low temperatures they became hard as tin, and in the heat - sticky. After many experiments, they found a way to avoid these unpleasant features of rubber by vulcanizing it. (This important discovery was made in XNUMX by the American chemist Goodyear.) It was found that when rubber is heated with sulfur, it changes its properties quite strongly - it becomes more flexible, elastic and not so sensitive to temperature changes.

This new vulcanized rubber became known as rubber. It quickly gained popularity as it proved to be extremely convenient in many ways. The demand for it has grown every year. There is no other product similar to rubber in nature - it is waterproof, has electrical insulating properties, is flexible and is capable of very large changes in shape. Under the action of an external force, it can stretch several times and shrink again. No other substance has such elasticity. However, it is strong, durable, resistant to abrasion and easy to process. Therefore, rubber has been and remains an ideal material for the manufacture of car tires, all kinds of drive belts, transport tapes, sleeves, shock absorbers, gaskets, flexible insulation and much more. Without rubber, the life of a modern industrial society is simply impossible.

From the middle of the XNUMXth century, mass production of rubber products began. This created a real rubber fever. The areas where rubber trees grew became the object of wars and speculation. Wild hevea soon ceased to meet the needs of the industry. In addition, mining rubber in the jungle was difficult and costly. Successful experiments were made to create rubber plantations. Hevea moved to the tropics of Java, Sumatra, the Malay Archipelago. Rubber production increased several times, but the demand for it continued to grow.

For a hundred years, the scientific world has been looking for the answer to the mystery of rubber in order to learn how to make it artificially by chemical means. Gradually it became clear that natural rubber from hevea juice is a mixture of several substances, but 9/10 of its mass falls on the polyisoprene hydrocarbon with the formula (C5H8) n, where n is very large - more than a thousand. Substances with a similar structure belong to the group of high-molecular products - polymers, which are formed by the combination of several, sometimes very many, identical molecules of simpler monomer substances (in this case, C5H8 isoprene molecules). Under favorable conditions, individual monomer molecules are connected to each other in long and flexible linear or branched chain threads.

This polymer formation reaction is called polymerization. It occurs only with organic substances that have multiple bonds (double or triple). As a result of the separation of these bonds, the connection of individual molecules to each other occurs (due to the released valences). In addition to polyisoprene, natural rubber contains resin-like proteins and minerals. Pure polyisoprene, purified from resins and proteins, is very unstable and quickly loses its valuable technical properties in air: elasticity and strength.

Thus, in order to produce artificial rubber, it was necessary to learn at least three things: 1) to obtain isoprene from other substances; 2) carry out the polymerization reaction of isoprene; 3) treat the resulting rubber with suitable substances to protect it from decomposition. All these tasks proved to be extremely difficult. In 1860, the English scientist Williams, by dry distillation of rubber, isolated isoprene from it, which turned out to be a light, mobile, colorless liquid with a peculiar odor.

In 1879, the French chemist Gustav Bouchard, heating isoprene and acting on it with hydrochloric acid, carried out the reverse reaction - he obtained a rubber-like product. In 1884, the English chemist Tilden obtained isoprene by high-temperature decomposition of turpentine. Although each of these scientists contributed to the study of the properties of rubber, the secret of its synthesis remained unsolved in the XNUMXth century - all open methods turned out to be unsuitable for industrial use either due to the high cost of raw materials, or because of the low yields of isoprene, or because of the complexity technical processes that ensure the reaction.

But is isoprene really necessary for rubber production? Perhaps a macromolecule with similar properties can be formed from other hydrocarbons? In 1901, the Russian chemist Kondakov found that dimethylbutadiene also turns into a rubbery substance if left to stand in the dark or in diffused light for about a year. (During the First World War in Germany, cut off from sources of natural rubber, the production of synthetic rubber from dimethyl butadiene was launched. However, products from it came out of very poor quality, but their price turned out to be prohibitive due to technical difficulties. After the war, this methyl rubber never produced again.)

Later it was discovered that all hydrocarbons with a molecular skeleton can be synthesized into rubber-like substances

The first member of this series is butadiene (or divinyl)

Back in 1914, the British Matthews and Strange obtained a very good rubber from divinyl in the presence of metallic sodium. But their work did not go beyond laboratory experiments due to the fact that, firstly, a method for the production of divinyl was not found, and secondly, it was not possible to create an installation that could synthesize rubber in the factory. Both of these problems were solved fifteen years later by the Russian chemist Sergei Lebedev.

Before the First World War, Russian factories produced up to 12 thousand tons of rubber from imported rubber. After the revolution, when the industrialization of industry began, the needs of the Soviet Union for rubber increased many times over. One ship required 68 tons of rubber, each tank - 800 kg, aircraft - 600 kg, car - 160 kg. Every year more and more rubber had to be bought from abroad. Meanwhile, in 1923-1924, the price of natural rubber reached 2400 gold rubles per ton. The need to pay such big money, and to an even greater extent, the dependence into which the young Soviet state fell in this way from suppliers, posed serious problems for the country's leadership. There was only one way to solve them - by developing an industrial method for the production of synthetic rubber.

At the end of 1925, the Supreme Economic Council announced an international competition for the best way to produce synthetic rubber. The terms of the competition were quite strict: rubber had to be made in the USSR from products mined in the USSR, the price of artificial rubber could not exceed the average world price over the past five years. By January 1, 1928, it was required to deliver 2 kg of the finished sample to Moscow.

Lebedev at that time headed the Department of General Chemistry at Leningrad University. Even before the revolution, he had been working on the problem of synthetic rubber for several years and was well aware of the difficulties that faced all the participants in the competition. Nevertheless, he decided to take part in it. Several pupils and students agreed to help him in his work. The times were very difficult. All assistants and Lebedev himself worked completely free of charge during off-duty hours, in the evenings and on weekends. In order to meet the deadline, they worked with the greatest effort. Complex technological experiments had to be carried out in the most unfavorable conditions. Literally everything was missing. As the participants of this amazing enterprise later recalled, they did everything they needed with their own hands. Lebedev had to work not only as a chemist, but also as a glass blower, mechanic and electrician. For cooling during chemical processes, ice was needed - it was all harvested together on the Neva. And yet, things were progressing well.

During the previous many years of research, Lebedev became convinced that obtaining synthetic rubber that completely reproduces the properties of natural rubber is a very difficult task and, under those circumstances, hardly achievable. He immediately abandoned experiments with isoprene and decided to take divinyl as a starting material. After the research of Matthews and Strange in the production process of divinyl (butadiene) rubber, there was one more missing link - it was necessary to develop a method for the production of divinyl from cheap and readily available raw materials. At first, Lebedev wanted to take oil as such, but then he focused all his attention on alcohol. Alcohol was then the most real raw material. If the problem of divinyl synthesis had been successfully solved, it would have been possible to immediately produce rubber in any required quantity, and this was just what the country needed.

The essence of the reaction, in which ethyl alcohol decomposes into divinyl, water and hydrogen (it is generally described by the equation: 2CH3CH2OH = C4H6 + 2H2O + H2), was clear to Lebedev. But the big difficulty was in the selection of a suitable catalyst. Having deeply understood the essence of the ongoing processes, Lebedev suggested that one of the active natural clays could serve as such a catalyst. During his vacation in the Crimea and the Caucasus in the summer of 1927, he constantly collected and studied clay samples. In the end, he found the right clay in Koktebel. The reaction in her presence gave an excellent result. So, in the middle of 1927, the first success was achieved - the reaction went in the right direction, and divinyl was obtained from alcohol.

The next process - the polymerization of divinyl - Lebedev decided to carry out according to the method of Matthews and Strange. To do this, sodium in a special installation was evenly distributed over divinyl, after which the reaction continued for 3-5 days. However, its final product was not yet commercial rubber. It was saturated with gases, sodium was unevenly distributed in it, the mixture was unstable and rapidly oxidized in air, losing elasticity. Therefore, the resulting rubber was processed in a mixer, where it was kneaded together with the sodium included in it. Then it was mixed with enhancers, carbon black, kaolin, magnesia and other components that were supposed to protect the rubber from decay.

Ready rubber was received in insignificant portions - only a few grams per day. Therefore, the work continued literally until the last minute. At the end of December, when only a few days remained before the deadline, the synthesis of 2 kg of rubber was completed, and it was urgently sent to Moscow. In February 1928, the jury, having considered all the samples sent (by the way, there were very few of them), recognized the rubber grown in Lebedev's laboratory as the best.

However, this was only the beginning. Laboratory methods are often unacceptable in a factory environment. Lebedev was instructed to continue research and develop industrial technology for his method of producing rubber. The hard work began again. True, now Lebedev had much more funds and opportunities. Knowing well the importance of his work, the government provided him with everything he needed. Soon a special laboratory for synthetic rubber was established at Leningrad University. Within a year, a pilot plant was designed and built in this laboratory, which produced 2-3 kg of rubber per day. By the end of 1929, the entire technology of the factory process was developed.

In February 1930, the construction of a pilot plant began in Leningrad on Gutuevsky Island. In the summer, the factory laboratory was opened. Equipped according to the personal instructions of Lebedev, it was one of the best chemical laboratories of that time and turned into a real scientific center for synthetic rubber. In addition to the laboratory, Lebedev had at his disposal the best specialists they could find. For all questions, he could personally contact the secretary of the Leningrad regional party committee, Kirov.

The great difficulty was in creating the necessary equipment. Chemical engineering was just in its infancy. Orders were distributed to all Leningrad factories, but their implementation progressed slowly, as they lacked the necessary experience. Even Lebedev himself sometimes found it difficult to give precise technical advice. Nevertheless, the construction of the pilot plant was completed in January 1931. In February, the first 250 kg of rubber were obtained on it. It was the world's first cheap factory-made synthetic rubber. In the same year, three giant rubber plants were laid - in Yaroslavl, Voronezh and Efremov. All of them were declared shock Komsomol construction projects and were built with amazing speed.

In 1932, the Yaroslavl plant already produced the first rubber. At first, the synthesis of divinyl in the factory was carried out with great difficulty. Instead of a simple mixture of alcohol decomposition products consisting of divinyl, water and hydrogen, a complex "vinaigrette" of 30 components was obtained, and the yield of divinyl in this mass did not exceed 20-25%. Lebedev had to urgently go to Yaroslavl with a group of his employees to help set up production. Then the same difficulties arose in Voronezh and Efremov. In the spring of 1934, during a trip to a factory in Efremov, Lebedev contracted typhus and died shortly after returning to Leningrad. But the cause, to which he laid such an important foundation, grew stronger and developed. Following the first three synthetic rubber plants, several new ones were built.

In 1934, 11 thousand tons of synthetic rubber were produced, in 1935 - 25 thousand, in 1936 - 40 thousand. In 1937, the share of synthetic rubber in the total rubber production was already 73%. The most complex scientific and technical problem was successfully solved.

However, the method for the production of synthetic rubber, developed by Lebedev, was not the only possible one. He himself understood this very well and in recent years he thought a lot about how to replace food raw materials (alcohol was produced from food products, and 1 tons of potatoes were spent to produce 12 ton of alcohol) with other, cheaper ones, for example, oil. Another disadvantage of divinyl rubber was its low adhesiveness. In the manufacture of rubber products from it, it was necessary to go to additional costs. Subsequently, several more methods for the production of synthetic rubber were developed, and in 1965 in the USSR synthetic rubber was first obtained under industrial conditions from isoprene.

Author: Ryzhov K.V.

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