1,3-Butadiene is a simple
conjugatedA conjugated system occurs in an organic compound where atoms covalently bond with alternating single and multiple bonds and influence each other to produce a region called electron delocalization. In this region electrons do not belong to a single bond or atom, but rather a group...
dieneDienes or diolefins are hydrocarbons which contain two double bonds. Dienes are intermediate between alkenes and polyenes.-Classes:Dienes can be divided into three classes:...
. It is an important industrial chemical used as a
monomerA monomer is a small molecule that may become chemically bonded to other monomers to form a polymer...
in the production of
synthetic rubberSynthetic rubber is any type of artificially made polymer material, which acts as an elastomer. An elastomer is a material with the mechanical property that it can undergo much more elastic deformation under stress, than most materials and still return to its previous size without permanent...
. 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 dieneDienes or diolefins are hydrocarbons which contain two double bonds. Dienes are intermediate between alkenes and polyenes.-Classes:Dienes can be divided into three classes:...
. However, this
alleneAn allene is a hydrocarbon in which one atom of carbon is connected by double bonds with two other atoms of carbon. Allene also is the common name for the parent compound of this series, propadiene....
is difficult to prepare and has no industrial significance.
In 1863, a French chemist isolated a previously unknown hydrocarbon from the
pyrolysisPyrolysis is the chemical decomposition of condensed organic substances by heating. The word is coined from the Greek-derived elements pyro "fire" and lysys "decomposition"....
of
amyl alcoholAmyl alcohol is an organic compound with the formula C
5H
12O. All eight isomers of amyl alcohol are known:Three of these alcohols, active amyl alcohol, methyl propyl carbinol, and methyl isopropyl carbinol, are optically active, as they contain an asymmetric carbon atom.The...
.
1,3-Butadiene is a simple
conjugatedA conjugated system occurs in an organic compound where atoms covalently bond with alternating single and multiple bonds and influence each other to produce a region called electron delocalization. In this region electrons do not belong to a single bond or atom, but rather a group...
dieneDienes or diolefins are hydrocarbons which contain two double bonds. Dienes are intermediate between alkenes and polyenes.-Classes:Dienes can be divided into three classes:...
. It is an important industrial chemical used as a
monomerA monomer is a small molecule that may become chemically bonded to other monomers to form a polymer...
in the production of
synthetic rubberSynthetic rubber is any type of artificially made polymer material, which acts as an elastomer. An elastomer is a material with the mechanical property that it can undergo much more elastic deformation under stress, than most materials and still return to its previous size without permanent...
. 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 dieneDienes or diolefins are hydrocarbons which contain two double bonds. Dienes are intermediate between alkenes and polyenes.-Classes:Dienes can be divided into three classes:...
. However, this
alleneAn allene is a hydrocarbon in which one atom of carbon is connected by double bonds with two other atoms of carbon. Allene also is the common name for the parent compound of this series, propadiene....
is difficult to prepare and has no industrial significance.
History
In 1863, a French chemist isolated a previously unknown hydrocarbon from the
pyrolysisPyrolysis is the chemical decomposition of condensed organic substances by heating. The word is coined from the Greek-derived elements pyro "fire" and lysys "decomposition"....
of
amyl alcoholAmyl alcohol is an organic compound with the formula C
5H
12O. All eight isomers of amyl alcohol are known:Three of these alcohols, active amyl alcohol, methyl propyl carbinol, and methyl isopropyl carbinol, are optically active, as they contain an asymmetric carbon atom.The...
. This hydrocarbon was identified as butadiene in 1886, after
Henry Edward ArmstrongHenry Edward Armstrong FRS was an English chemist. Although Armstrong was active in many areas of scientific research, such as the chemistry of naphthalene derivatives, he is remembered today largely for his ideas and work on the teaching of science.- Life and work :Armstrong was born and lived...
isolated it from among the pyrolysis products of
petroleumPetroleum or crude oil is a naturally occurring, flammable liquid found in rock formations in the Earth consisting of a complex mixture of hydrocarbons of various molecular weights, plus other organic compounds.The term "petroleum" was first used in the treatise De Natura Fossilium, published in...
. In 1910, the
RussiaRussia , officially known as both Russia and the Russian Federation , is a country in northern Eurasia . It is a semi-presidential republic, comprising 83 federal subjects...
n 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 IIWorld War II, or the Second World War , was a global military conflict which involved a majority of the world's nations, including all great powers, organized into two opposing military alliances: the Allies and the Axis...
. Many of the belligerent nations realized that in the event of war, they could be cut off from rubber plantations controlled by the
British EmpireThe British Empire comprised the dominions, colonies, protectorates, mandates, and other territories ruled or administered by the United Kingdom, that had originated with the overseas colonies and trading posts established by England in the late 16th and early 17th centuries. At its height it was...
, and sought to remove their dependence on natural rubber. In 1929, Eduard Tschunker and Walter Bock, working for
IG FarbenI.G. Farbenindustrie AG was a German chemical industry conglomerate. Its name is taken from Interessen-Gemeinschaft Farbenindustrie AG . The company was formed in 1925 from a number of major companies that had been working together closely since World War I...
in
GermanyGermany , officially the Federal Republic of Germany , is a country in Central Europe. It is bordered to the north by the North Sea, Denmark, and the Baltic Sea; to the east by Poland and the Czech Republic; to the south by Austria and Switzerland; and to the west by France, Luxembourg, Belgium,...
, made a copolymer of
styreneStyrene, also known as vinyl benzene as well as many other names , is an organic compound with the chemical formula C
6H
5CH=CH
2. This aromatic hydrocarbon is a colorless oily liquid that evaporates easily and has a sweet smell, although high concentrations confer a...
and butadiene that could be used in
automobileAn automobile, motor car or car is a wheeled motor vehicle used for transporting passengers, which also carries its own engine or motor...
tireA tire is a ring-shaped covering that fits around a wheel to protect it and enable better vehicle performance by providing a flexible cushion that absorbs shock while keeping the wheel in close contact with the ground...
s. Worldwide production quickly ensued, with butadiene being produced from
grain alcoholEthanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug, best known as the type of alcohol found in alcoholic beverages and in modern thermometers. Ethanol is one of the oldest recreational drugs...
in the
Soviet UnionThe Union of Soviet Socialist Republics was a constitutionally socialist state that existed in Eurasia from 1922 to 1991. The name is a translation of the , tr. Soyuz Sovetskikh Sotsialisticheskikh Respublik, abbreviated СССР, SSSR. The common short name is Soviet Union, from , Sovetskiy Soyuz...
and the
United StatesThe United States of America is a federal constitutional republic comprising fifty states and a federal district...
and from
coalCoal is a readily combustible black or brownish-black sedimentary rock normally occurring in rock strata in layers or veins called coal beds. The harder forms, such as anthracite coal, can be regarded as metamorphic rock because of later exposure to elevated temperature and pressure...
-derived
acetyleneAcetylene is the chemical compound with the formula HC
2H. It is a hydrocarbon and the simplest alkyne. This colourless gas is widely used as a fuel and a chemical building block...
in
GermanyGermany , officially the Federal Republic of Germany , is a country in Central Europe. It is bordered to the north by the North Sea, Denmark, and the Baltic Sea; to the east by Poland and the Czech Republic; to the south by Austria and Switzerland; and to the west by France, Luxembourg, Belgium,...
.
Production
In the
United StatesThe United States of America is a federal constitutional republic comprising fifty states and a federal district...
, western
EuropeEurope is, by convention, one of the world's seven continents. Comprising the westernmost peninsula of Eurasia, Europe is generally divided from Asia to its east by the water divide of the Ural Mountains, the Ural River, the Caspian Sea, the Caucasus Mountains , and the Black Sea to the southeast...
, and
Japanis an island country in East Asia. Located in the Pacific Ocean, it lies to the east of the Sea of Japan, People's Republic of China, North Korea, South Korea and Russia, stretching from the Sea of Okhotsk in the north to the East China Sea and Taiwan in the south...
, butadiene is produced as a byproduct of the steam cracking process used to produce
ethyleneEthylene is the chemical compound with the formula C
2H
4. It is the simplest alkene. Because it contains a carbon-carbon double bond, ethylene is called an unsaturated hydrocarbon or an olefin. It is extremely important in industry and also has a role in biology as a hormone...
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
ethaneEthane is a chemical compound with chemical formula C
2H
6. It is the only two-carbon alkane that is an aliphatic hydrocarbon. At standard temperature and pressure, ethane is a colorless, odorless gas....
, give primarily
ethyleneEthylene is the chemical compound with the formula C
2H
4. It is the simplest alkene. Because it contains a carbon-carbon double bond, ethylene is called an unsaturated hydrocarbon or an olefin. It is extremely important in industry and also has a role in biology as a hormone...
when cracked, but heavier favor the formation of heavier olefins, butadiene, and aromatic hydrocarbons.
Butadiene is typically isolated from the other four-carbon
hydrocarbonIn organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. With relation to chemical terminology, aromatic hydrocarbons or arenes, alkanes, alkenes and alkyne-based compounds composed entirely of carbon and hydrogen are referred to as "pure"...
s produced in steam cracking by
extractionLiquid-liquid extraction, also known as solvent extraction and partitioning, is a method to separate compounds based on their relative solubilities in two different immiscible liquids, usually water and an organic solvent. It is an extraction of a substance from one liquid phase into another liquid...
into a polar aprotic solvent such as
acetonitrileAcetonitrile is the chemical compound with formula CH3CN. This colourless liquid is the simplest organic nitrile. It is produced mainly as a byproduct of acrylonitrile manufacture. It is widely used as a polar aprotic solvent in synthetic chemistry, and as a medium-polarity solvent in...
or
dimethylformamideDimethylformamide is the organic compound with the formula
2NCH. Commonly abbreviated DMF , this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions...
, from which it is then stripped by
distillationDistillation is a method of separating mixtures based on differences in their volatilities in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction....
.
Butadiene can also be produced by the catalytic
dehydrogenationDehydrogenation is a chemical reaction that involves the elimination of hydrogen . It is the reverse process of hydrogenation. Dehydrogenation reactions may be either large scale industrial processes or smaller scale laboratory procedures....
of normal butane. The first such commercial plant, producing 65,000
tonThe term ton or tonne generally refers to a unit of mass. However, there exists more than one measure of mass that are named "ton", so one has to be specific when using the term. While they do vary considerably, a ton is generally one of the heaviest units of mass referred to in colloquial speech...
s per year of butadiene, began operations in 1957 in
Houston, TexasHouston is the fourth-largest city in the United States and the largest city within the state of Texas. As of the 2008 U.S. Census estimate, the city has a population of 2.2 million within an area of 600 square miles . Houston is the seat of Harris County and the economic center of...
.
From ethanol
In other parts of the world, including eastern Europe,
ChinaChina is a cultural region, an ancient civilization, and, depending on perspective, a national or multinational entity extending over a large area in East Asia....
, and
IndiaIndia, officially the Republic of India , is a country in South Asia. It is the seventh-largest country by geographical area, the second-most populous country, and the most populous democracy in the world. Bounded by the Indian Ocean on the south, the Arabian Sea on the west, and the Bay of Bengal...
, butadiene is also produced from
ethanolEthanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug, best known as the type of alcohol found in alcoholic beverages and in modern thermometers. Ethanol is one of the oldest recreational drugs...
. 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
Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug, best known as the type of alcohol found in alcoholic beverages and in modern thermometers. Ethanol is one of the oldest recreational drugs...
→ CH2=CH-CH=CH2 + 2 H2OWater is an ubiquitous chemical substance that is composed of hydrogen and oxygen and is essential for all known forms of life.In typical usage, water refers only to its liquid form or state, but the substance also has a solid state, ice, and a gaseous state, water vapor or steam. Water covers 71%...
+ H2Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. At standard temperature and pressure, hydrogen is a colorless, odorless, nonmetallic, tasteless, highly flammable diatomic gas with the molecular formula H
2...
This process was the basis for the
Soviet UnionThe Union of Soviet Socialist Republics was a constitutionally socialist state that existed in Eurasia from 1922 to 1991. The name is a translation of the , tr. Soyuz Sovetskikh Sotsialisticheskikh Respublik, abbreviated СССР, SSSR. The common short name is Soviet Union, from , Sovetskiy Soyuz...
'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
acetaldehydeAcetaldehyde is an organic chemical compound with the formula CH3CHO or MeCHO. It is a flammable liquid. Acetaldehyde occurs naturally in ripe fruit, coffee, and bread, and is produced by plants as part of their normal metabolism...
, which reacts with additional ethanol over a
tantalumTantalum is a chemical element with the symbol Ta and atomic number 73. A rare, hard, blue-gray, lustrous transition metal, tantalum is highly corrosion resistant and occurs naturally in the mineral tantalite, always together with the chemically similar niobium...
-promoted porous silica catalyst at 325–350 °C to yield butadiene:
- CH3CH2OH
Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug, best known as the type of alcohol found in alcoholic beverages and in modern thermometers. Ethanol is one of the oldest recreational drugs...
+ CH3CHOAcetaldehyde is an organic chemical compound with the formula CH3CHO or MeCHO. It is a flammable liquid. Acetaldehyde occurs naturally in ripe fruit, coffee, and bread, and is produced by plants as part of their normal metabolism...
→ CH2=CH-CH=CH2 + 2 H2OWater is an ubiquitous chemical substance that is composed of hydrogen and oxygen and is essential for all known forms of life.In typical usage, water refers only to its liquid form or state, but the substance also has a solid state, ice, and a gaseous state, water vapor or steam. Water covers 71%...
This process was used in the United States to produce government rubber during World War II, and remains in use today in China and India.
Uses
Most butadiene is
polymerA polymer is a large molecule composed of repeating structural units typically connected by covalent chemical bonds. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials with a variety of properties.Due to the extraordinary...
ized to produce synthetic rubber. While
polybutadienePolybutadiene is a synthetic rubber that is a polymer formed from the polymerization of the monomer 1,3-butadiene. It has a high resistance to wear and is used especially in the manufacture of tires. It has also been used to coat or encapsulate electronic assemblies, offering extremely high...
itself is a very soft, almost liquid material, polymers prepared from mixtures of butadiene with styrene or
acrylonitrileAcrylonitrile is the chemical compound with the formula CH2CHCN. This pungent-smelling colorless liquid often appears yellow due to impurities. It is an important monomer for the manufacture of useful plastics...
, such as
ABSAcrylonitrile butadiene styrene is a common thermoplastic used to make light, rigid, molded products such as piping , musical instruments , golf...
, are both tough and elastic. Styrene-butadiene rubber is the material most commonly used for the production of automobile tires.
Smaller amounts of butadiene are used to make
nylonNylon is a generic designation for a family of synthetic polymers known generically as polyamides and first produced on February 28, 1935 by Wallace Carothers at DuPont...
via the intermediate
adiponitrileAdiponitrile is the organic compound with the formula 42. This dinitrile, a viscous, colourless liquid, is an important precursor to the polymer nylon 66. About one billion kilograms are produced annually....
, other synthetic rubber materials such as
chloropreneChloroprene is the common name for the organic compound 2-chloro-1,3-butadiene, which has the formula CH2=CCl-CH=CH2. This colorless liquid is the monomer for the production of the polymer polychloroprene, a type of synthetic rubber...
, and the solvent
sulfolaneSulfolane is a clear, colorless liquid commonly used in the chemical industry as an extractive distillation solvent or reaction solvent. Sulfolane was originally developed by the Shell Oil Company in the 1960s as a solvent to purify butadiene...
. Butadiene is used in the industrial production of
4-vinylcyclohexene4-Vinylcyclohexene is an organic compound formed when 1,3-butadiene dimerizes in a Diels-Alder reaction. It is found in industrial processes involving 1,3-butadiene, including the manufacture of dodecanoic acid...
via a dimerization reaction and
cyclododecatrieneCyclododecatriene C
12H
18 is a cycloalkene with three alkene groups. The 1,3,5-trans-trans-cis isomer has some industrial importance and is obtained by cyclotrimerization of butadiene with titanium tetrachloride and an organo-aluminium co-catalyst :This compound is the raw...
via a trimerization reaction.
Safety
At acute high exposure, damage to the central nervous system will start to occur. Symptoms such as distorted blurred vision, vertigo, general tiredness, decreased blood pressure, headache, nausea, decreased pulse rate, and fainting may be witnessed. As the exposure to butadiene occurs at a higher level and for a longer duration, the effects witnessed will become more serious. 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 suggest the carcinogenic effects of butadiene may have a higher sensitivity to women over men when exposed to the chemical. While these data reveal important implications to the risks of human exposure to butadiene, more data are 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.
External links