butadiene n : a gaseous hydrocarbon C4H6; used in making synthetic rubbers

English

Noun

1. An unsaturated hydrocarbon, CH2=CH-CH=CH2; it is obtained from petroleum and is used in the preparation of the synthetic rubber polybutadiene.

Translations

1,3-Butadiene is a simple conjugated diene. It is an important industrial chemical used as a monomer in the production of synthetic rubber. When the word butadiene is used, most of the time it refers to 1,3-butadiene.

The name butadiene can also refer to the isomer, 1,2-butadiene, which is a cumulated diene. However, this allene is difficult to prepare and has no industrial significance.

History

In 1863, a French chemist isolated a previously unknown hydrocarbon from the pyrolysis of amyl alcohol. This hydrocarbon was identified as butadiene in 1886, after Henry Edward Armstrong isolated it from among the pyrolysis products of petroleum. In 1910, the Russian chemist Sergei Lebedev polymerized butadiene, and obtained a material with rubber-like properties. This polymer was, however, too soft to replace natural rubber in many roles, especially automobile tires.

The butadiene industry originated in the years leading up to World War II. Many of the belligerent nations realized that in the event of war, they could be cut off from rubber plantations controlled by the British Empire, and sought to remove their dependence on natural rubber. In 1929, Eduard Tschunker and Walter Bock, working for IG Farben in Germany, made a copolymer of styrene and butadiene that could be used in automobile tires. Worldwide production quickly ensued, with butadiene being produced from grain alcohol in the Soviet Union and the United States and from coal-derived acetylene in Germany.

Production

In the United States, western Europe, and Japan, butadiene is produced as a byproduct of the steam cracking process used to produce ethylene and other olefins. When mixed with steam and briefly heated to very high temperatures (often over 900 °C), aliphatic hydrocarbons give up hydrogen to produce a complex mixture of unsaturated hydrocarbons, including butadiene. The quantity of butadiene produced depends on the hydrocarbons used as feed. Light feeds, such as ethane, give primarily ethylene when cracked, but heavier favor the formation of heavier olefins, butadiene, and aromatic hydrocarbons.

Butadiene is typically isolated from the other four-carbon hydrocarbons produced in steam cracking by extraction into a polar aprotic solvent such as acetonitrile or dimethylformamide, from which it is then stripped by distillation.

Butadiene can also be produced by the catalytic dehydrogenation of normal butane. The first such commercial plant, producing 65,000 tons per year of butadiene, began operations in 1957 in Houston, Texas.

From ethanol

In other parts of the world, including eastern Europe, China, and India, butadiene is also produced from ethanol. While not competitive with steam cracking for producing large volumes of butadiene, lower capital costs make production from ethanol a viable option for smaller-capacity plants. Two processes are in use.

In the single-step process developed by Sergei Lebedev, ethanol is converted to butadiene, hydrogen, and water at 400–450 °C over any of a variety of metal oxide catalysts:

2 CH3CH2OH → CH2=CH-CH=CH2 + 2 H2O + H2

This process was the basis for the Soviet Union's synthetic rubber industry during and after World War II, and it remains in limited use in Russia and other parts of eastern Europe.

In the other, two-step process, developed by the Russian chemist Ivan Ostromislensky, ethanol is oxidized to acetaldehyde, which reacts with additional ethanol over a tantalum-promoted porous silica catalyst at 325–350 °C to yield butadiene: The actual link between chronic effects of butadiene has been argued over the years, though human epidemiological studies have been performed over the years showing increased risks in serious adverse health effects.

Several studies show butadiene exposure increases risk in cardiovascular diseases and cancer. Animal data suggests the carcinogenic effects of butadiene may have a higher sensitivity to females over men when exposed to the chemical. While this data reveals important implications to the risks of human exposure to butadiene, more data is necessary to draw more conclusive risk assessments. There is also a lack of human data on the effects butadiene has on reproductive and developmental effects shown to occur in mice, but animal studies have shown breathing butadiene during pregnancy can increase the number of birth defects.

Storage of butadiene as a compressed, liquified gas carries a specific and unusual hazard. Over time, polymerization can begin, creating a crust of solidified material (which looks like popcorn) inside the cylinder. If the cylinder is then disturbed, the crust can contact the liquid and initiate an auto-catalytic polymerization. The heat released accelerates the reaction, possibly leading to cylinder rupture. Inhibitors are typically added to reduce this hazard, but butadiene cylinders should still be considered short-shelf life items.

See also

• Cyclobutadiene
• Polybutadiene
• Hydroxyl-terminated polybutadiene

External links

• National Pollutant Inventory - 1,3-Butadiene

References