How to pull the rubber, or the history of the creation of synthetic rubber
Rubber got its name from the Indian word "rubber", meaning literally "tree tears". Maya and Aztec mined it from the juice of Brazilian Hevea (Hevea brasiliensis or rubber tree), similar to white dandelion juice, which darkened and hardened in the air. From the juice, they evaporated a sticky dark resinous substance “rubber”, making from it primitive waterproof shoes, fabrics, vessels, children's toys. The Indians also had a team-like basketball game in which special rubber balls were used, characterized by amazing jumping ability. At the time of the great geographical discoveries, Columbus brought several such balls to Spain, among other wonders of South America. They fell in love with the Spaniards, who, changing the rules of Indian competitions, invented something that has become the prototype of today's football.The next mention of rubber appeared only in 1735, when the French traveler and naturalist Charles Condamine, exploring the Amazon basin, discovered the Hevea tree and its milky sap for Europeans. The tree discovered by the members of the expedition gave off a strange, rapidly hardening resin, which was later named "rubber" by thinkers from the Paris Academy of Sciences. After in 1738, Condamine brought to the continent samples of rubber and various products from it, along with a detailed description of the methods of extraction, in Europe began the search for ways to use this substance. The French weaved rubber threads with cotton and used them as garters and suspenders. Hereditary English shoemaker Samuel Peel in 1791 received a patent for the manufacture of fabrics impregnated with a solution of rubber in turpentine, creating the Peal & Co. At the same time, the first experiments on protecting shoes with covers from such a fabric arose. In 1823, a certain Charles Mackintosh from Scotland invented the first waterproof raincoat, adding a thin piece of rubber between two layers of fabric. The raincoats quickly became popular, were named after their creator and marked the beginning of a real "rubber boom". And soon in America, in damp weather, they began to put on clumsy Indian rubber shoes - galoshes - over their shoes. Until his death, Macintosh continued to mix rubber with various substances such as soot, oils, sulfur in an attempt to change its properties. But his experiments did not lead to success.
Clothes, hats, roofs of vans and houses were made of rubberized fabric. However, these products had one drawback - the narrow temperature range of elasticity of rubber. In cold weather, such a fabric hardened and could crack, and in warm weather, on the contrary, softening, turned into a fetid, sticky mass. And if the clothes could be removed in a cool place, then the owners of the roofs of rubberized fabric had to put up with unpleasant odors. Thus, the fascination with new material quickly passed. And the hot summer days brought ruin to the companies that established the production of rubber, since all their products turned into foul-smelling jelly. And the world again for a few years forgot about rubber and everything related to it.
Survive the rebirth of rubber products helped case. Charles Nelson Goodyear, who lived in America, always believed that rubber can turn into good material. He hatched this idea for many years, stubbornly mixing it with everything that came to hand: with sand, with salt, even with pepper. In the 1939 year, having spent all his savings and owing more than 35 thousands of dollars, he achieved success.
Contemporaries scoffed at the eccentric explorer: “If you meet a person in rubber boots, a rubber coat, a rubber top hat and a purse made of rubber, in which there will not be a single cent, then rest assured you have Goodyear in front of you”.
There is a legend that the chemical process discovered by him, called vulcanization, appeared due to a piece of the macintosh cloak forgotten on the stove. One way or another, it is the sulfur atoms that combined the molecular chains of natural rubber, turning it into a heat and frost-resistant, elastic material. It is his custom today called rubber. History This stubborn man has a happy ending, he sold a patent for an invention and paid all his debts.
During the life of Goodyear, the rapid production of rubber began. The United States immediately took the lead in the production of galoshes, which were sold throughout the world, including Russia. They were expensive, and only rich people could afford to buy them. The most curious thing is that galoshes were used not to save the main footwear from getting wet, but as house slippers for guests, so that they would not stain carpets and parquet. In Russia, the first rubber product manufacturing company opened in St. Petersburg in 1860. The German businessman Ferdinand Krauzkopf, who already had a factory for the production of galoshes in Hamburg, appreciated the prospects of the new market, found investors and created the “Partnership of Russian-American Manufactory”.
Few people know that the Finnish company Nokia, among other things, from 1923 to 1988, specialized in the production of rubber boots and overshoes. In fact, during the crisis years, this helped keep the company afloat. The world famous "Nokia" has become thanks to its cell phones.
In the second half of 19, Brazil was at the peak of its heyday, being a monopolist for the growing of the hevea. Manaus, the former center of rubbery areas, has become the richest city in the western hemisphere. What only cost a terrific opera house, built in a hidden jungle city. He was created by the best architects of France, and building materials for him were brought from Europe itself. Brazil has carefully guarded the source of its luxury. For an attempt to export seeds Hevea relied on the death penalty. However, in 1876, Englishman Henry Wickham secretly brought seventy thousand Hevea seeds in the holds of the Amazonas ship. They served as the basis for the first rubber plantations planted in the colonies of England in Southeast Asia. This is how cheap, natural British rubber originated on the world market.
Soon, a variety of rubber products conquered the whole world. Conveyor belts of conveyors, various drive belts, shoes, flexible electrical insulation, underwear gum, children's balloons, shock absorbers, sealing gaskets, hoses, and much more, were made of rubber. There is simply no other rubber product. It has insulating properties, waterproof, flexible, can stretch and shrink. It is durable, strong, easy to handle and resistant to abrasion. The heritage of the Indians was much more valuable than all the gold of the famous Eldorado. Without rubber it is impossible to imagine our entire technical civilization.
The main use of the new material was with the discovery and distribution of rubber carriage first, and then car tires. Despite the fact that the crews with metal tires were very uncomfortable and made terrible noise and shaking, the new invention was greeted reluctantly. In America, even the crews on massive solid tires were banned, because they were considered very dangerous because of the impossibility of notifying passers-by about the proximity of the vehicle.
In Russia, such horse-drawn carriages also caused discontent. The main problem lay in the fact that they often showered dirt on pedestrians who did not bounce. The Moscow authorities had to issue a special law on equipping crews with rubber tires with special license plates. This was done so that citizens could notice and bring their offenders to justice.
Rubber production has increased many times, but the need for it continued to grow. For about a hundred years, scientists around the world have been looking for a way to learn how to make it chemically. Gradually, it was found that natural rubber is a mixture of several substances, but 90 percent of its mass is polyisoprene hydrocarbon. Such substances belong to the group of polymers - high-molecular products, formed by the combination of very many identical molecules of much simpler substances called monomers. In the case of rubber, these were isoprene molecules. Under favorable conditions, the monomer molecules were connected to each other in long, flexible thread-chains. A similar reaction to the formation of a polymer is called polymerization. The remaining ten percent in rubber was resin-like mineral and proteinaceous substances. Without them, polyisoprene became very unstable, losing its valuable properties of elasticity and strength in the air. Thus, in order to learn how to obtain artificial rubber, scientists needed to solve three things: synthesize isoprene, polymerize it, and protect the resulting rubber from decomposition. Each of these tasks turned out to be extremely difficult. In the 1860 year, the English chemist Williams obtained isoprene from rubber, which was a colorless liquid with a specific odor. In the 1879 year, the Frenchman Gustav Bouchard, heated the isoprene and with the help of hydrochloric acid was able to carry out the reverse reaction - to obtain rubber. In 1884, British scientist Tilden identified isoprene, decomposing turpentine during heating. Despite the fact that each of these people contributed to the study of rubber, the secret of its manufacture remained unsolved in the 19th century, because all the methods found were unsuitable for industrial production due to the low yield of isoprene, the high cost of raw materials, the complexity of technical processes and a number of other factors.
At the beginning of the twentieth century, researchers began to think, but is isoprene really necessary for the manufacture of rubber? Is there a way to get the necessary macromolecule from other hydrocarbons? In the 1901 year, the Russian scientist Kondakov discovered that dimethylbutadiene, which had been left in the dark for a year, turned into a rubbery substance. This method was later used during World War Germany by Germany, cut off from all sources. Synthetic rubber was of very poor quality, the manufacturing process was very complicated, and the price was prohibitively high. After the war, such methyl rubber was never produced anywhere else. In 1914, research scientists Matthews and Strange from England got very good divinyl rubber using metallic sodium. But further discoveries in the laboratory did not go to their discoveries, because it was not clear how, in turn, to produce divinyl. They also failed to create a plant for synthesis in the factory.
Fifteen years later, our compatriot Sergey Lebedev found the answer to both of these questions. Before World War II, Russian factories produced about twelve thousand tons of rubber a year from imported rubber. After the revolution ended, the needs of the new government, which is industrializing industry, have grown many times in rubber. One tank required a kilogram of rubber 800, a car 160 a kilogram, a plane 600 a kilogram, a ship 68 tons. Every year, purchases of rubber abroad increased and increased, despite the fact that in 1924, its price reached two and a half thousand gold rubles per ton. The leadership of the country was not so much concerned with the need to pay such huge money as with the addiction into which the Soviet state put suppliers. At the highest level, it was decided to develop an industrial method for manufacturing synthetic rubber. To this end, at the end of 1925, the Supreme Council of National Economy proposed a competition for the best way to obtain it. The competition was international, however, according to the conditions, rubber should have been made from products mined in the Soviet Union, and the price for it should not exceed the average for the last five years. The results of the competition were summed up on 1 on January 1928 of the year in Moscow according to the results of the analysis of the samples provided, weighing at least two kilograms.
Sergey Vasilyevich Lebedev was born on July 25 of the 1874 year in the family of a priest in Lublin. When the boy was seven years old, his father died, and his mother was forced to move with the children to his parents in Warsaw. While studying at the Warsaw Gymnasium, Sergei became friends with the son of the famous Russian scientist and chemist Wagner. Often in their home, Sergei listened to the professor's fascinating stories about his fellow friends Mendeleev, Butlerov, Menshutkin, and also about the mysterious science involved in the transformation of substances. In the 1895 year, having successfully completed a gymnasium, Sergey entered the Physics and Mathematics Faculty of St. Petersburg University. The young youth spent all his free time in the house of Maria Ostroumova, who was his mother's sister. She had six children, but Sergey was especially interested in her cousin Anna. She was a promising artist, studied with Ilya Repin. When young people realized that their feelings were far from their relatives, they decided to get engaged. In 1899, Lebedev was arrested for participating in student riots and expelled from the capital for a year. However, this did not prevent him from graduating from university brilliantly at 1900. During the Russian-Japanese war, Sergei Vasilyevich was drafted into the army, and after returning to 1906, he devoted himself entirely to research. He lived in the laboratory for whole days, making himself a bed of blankets in case of fire. Anna Petrovna Ostroumova several times found Sergei in the hospital, treated for burns resulting from dangerous experiments, which the chemist always conducted himself. Already at the end of 1909, working almost alone, he managed to achieve impressive results by demonstrating to the colleagues the rubbery polymer of divinyl.
Sergey Vasilyevich Lebedev was perfectly aware of all the difficulties in the production of synthetic rubber, but decided to take part in the competition. It was a difficult time, Lebedev headed the department of general chemistry at Leningrad University, so he had to work in the evenings, on weekends, and completely free of charge. Fortunately, several students decided to help him. To meet the deadline, everyone worked with great effort. Complex experiments were carried out in the worst conditions. The participants of this company later recalled that there was absolutely nothing and had to do or find on their own. For example, ice for cooling chemical processes all pricked on the Neva. In addition to his specialty, Lebedev mastered the profession of glassblower, mechanic and electrician. And yet it moved. Thanks to previous years of research, Sergey Vasilyevich immediately abandoned experiments with isoprene and settled on divinyl as the starting product. As a readily available raw material for the production of divinyl, Lebedev tried oil, but then still stopped on alcohol. Alcohol was the most real primary raw material. The main problem of the reaction of the decomposition of ethyl alcohol to divinyl, hydrogen and water was the absence of a suitable catalyst. Sergey Vasilyevich suggested that one of the natural clays could be one. In the 1927 year, spending holidays in the Caucasus, he constantly searched for and studied clay samples. He found the necessary one on Koktebel. The reaction in the presence of the clay it found gave an excellent result, and at the end of 1927, divinyl was obtained from alcohol.
The wife of the great chemist, Anna Lebedeva, recalled: “Sometimes, while resting, he lay on his back with his eyes closed. It seemed that Sergey Vasilyevich was asleep, and then he took out a notebook and began to write chemical formulas. Many times, sitting in a concert, and being agitated by music, he hastily took out his notebook or even a poster and began to write something down, and then put everything in his pocket. The same thing could happen at exhibitions. ”
Lebedev carried out the polymerization of divinyl according to the method of British researchers with the presence of metallic sodium. At the final stage, the resulting rubber was mixed with magnesia, kaolin, soot, and some other components to prevent decay. Since the finished product was produced in meager quantities - a couple grams per day - the work went almost until the last days of the competition. At the end of December, the synthesis of two kilograms of rubber was over, and he was sent to the capital.
Anna Petrovna wrote in her memoirs: “On the last day, a revival reigned in the laboratory. Those present were joyful and contented. As usual, Sergei Vasilyevich was silent and restrained. Smiling slightly, he looked at us, and everything indicated that he was pleased. The rubber looked like a large gingerbread, similar in color to honey. The smell was sharp and rather unpleasant. After the description of the method of manufacturing rubber was completed, it was packed in a box and taken to Moscow. ”
The jury finished examining the sent samples in February of the 1928 year. It turned out quite a bit. The results of the work of scientists from France and Italy, but the main struggle unfolded between Sergey Lebedev and Boris Byzov, who received divinyl from oil. In total, Lebedeva rubber was recognized as the best. The production of divinyl from crude oil was more difficult to implement on an industrial scale at that time.
Newspapers around the world have written about the invention of synthetic rubber in Russia. Many did not like it. The famous American scientist Thomas Edison publicly stated: “It’s basically impossible to manufacture synthetic rubber. I tried to do the experience myself and made sure of it. therefore news from Country of the Soviets is another lie. ”
The event was of great importance for the Soviet industry, allowing to reduce the consumption of natural rubbers. Also, the synthetic product had new properties, for example, resistance to gasoline and oils. Sergey Vasilyevich was instructed to continue research and manufacture an industrial method for the production of rubber. The hard work began again. However, now there were plenty of opportunities for Lebedev. Understanding the importance of the work, the government gave all the necessary. The Leningrad University created a laboratory of synthetic rubber. For the year, an experimental facility was built in it, producing two to three kilograms of rubber per day. At the end of 1929, the technology of the plant process was completed, and in February of 1930, the construction of the first plant began in Leningrad. The factory laboratory, equipped by Lebedev's orders, was a real scientific center of synthetic rubber and at the same time one of the best chemical laboratories of that time. Here the famous chemist later formulated the rules that allowed his followers to correctly identify substances for synthesis. In addition, Lebedev had the right to choose any specialists for himself. If you have any questions, he should apply personally to Kirov. The construction of the pilot plant was completed in January of 1931, and in February the first cheap 250 kilograms of synthetic rubber were already received. In the same year, Lebedev was awarded the Order of Lenin and elected to the Academy of Sciences. Soon, the construction of three more giant plants was started according to a single project - in Efremov, Yaroslavl and Voronezh. And before the war, the plant appeared in Kazan. The capacity of each of them was ten thousand tons of rubber per year. They were built near the places where alcohol was produced. Raw materials for alcohol initially served as food products, mainly potatoes. One ton of alcohol required twelve tons of potatoes, and for the manufacture of tires for the car at the time it took about five hundred kilograms of potatoes. The factories were declared Komsomol construction sites and erected with astonishing speed. In 1932, the first rubber was given by the Yaroslavl plant. Initially, under production conditions, the synthesis of divinyl passed with difficulty. The equipment needed to be adjusted, so Lebedev, together with his staff, went first to Yaroslavl, and then to Voronezh and Efremov. In the spring of 1934 in Efremov, Lebedev caught typhus. He died shortly after returning home in the sixtieth year of life. His body was buried in the Alexander Nevsky Monastery.
However, the case to which he gave such a meaningful basis, has developed. In 1934, the Soviet Union produced eleven thousand tons of artificial rubber, in 1935, twenty-five thousand, and in 1936, forty thousand. The most difficult scientific and technical problem was successfully solved. The ability to equip vehicles with tires of domestic production has played an important role in the victory over fascism.
The second place in the production of synthetic rubbers at that time was the Germans, who were actively preparing for war. Their production was established at a factory in the town of Shkopau, which the USSR, after its victory under the terms of reparations, took to Voronezh. The third steelmaker was the United States of America after losing the natural rubber market at the beginning of 1942. The Japanese captured Indochina, the Netherlands India and Malaya, where more than 90 percent of the natural product was mined. After America’s entry into World War II, it suspended its sale; in response, the US government built the 51 plant in less than three years.
Science also did not stand still. Improved manufacturing methods and raw materials base. Synthetic application rubbers are divided into general and special with specific properties. There were special groups of artificial rubbers like latex, cured oligomers, plasticizer mixtures. By the end of the last century, global production of these products reached twelve million tons per year, produced in twenty-nine countries. Up to 1990, our country held the first place in terms of synthetic rubber production. Half of the artificial rubbers produced in the USSR were exported. However, after the collapse of the Soviet Union, the situation changed radically. From a leading position, our country hit first among the laggards, and then dropped to the category of catch-up. In recent years, there has been an improvement in the industry. Russia's share in the global market for the production of synthetic rubber today is nine percent.
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