1,3-Butadiene 464821 222618879 2008-06-30T08:22:50Z Epbr123 1395162 Reverted edits by [[Special:Contributions/145.19.1.220|145.19.1.220]] to last version by Rickjpelleg (using [[WP:HG|Huggle]]) {{Chembox new | Name = 1,3-Butadiene | ImageFile = Butadiene structures.svg | ImageSize = 250px | ImageName = 1,3-Butadiene | ImageFile1 = 1,3-Butadiene-3d.png | ImageSize1 = 150px | IUPACName = 1,3-Butadiene | OtherNames = Buta-1,3-diene<br />Biethylene<br />Erythrene<br />Divinyl<br />Vinylethylene | Section1 = {{Chembox Identifiers | SMILES = C=CC=C | CASNo = 106-99-0 | UNNumber = [[List of UN Numbers 1001 to 1100|1010]] | RTECS = EI9275000 }} | Section2 = {{Chembox Properties | Formula = C<sub>4</sub>H<sub>6</sub> | MolarMass = 54.09 g/mol | Appearance = Colourless gas<br /> or refrigerated liquid | Density = 0.64 g/cm³ at -6 °C, liquid | Solubility = 735 ppm (25 °C) | MeltingPt = -108.9 °C (164.3 K) | BoilingPt = -4.4 °C (268.8 K) | Viscosity = 0.25 c[[Poise|P]] at 0 °C }} | Section3 = {{Chembox Structure | Dipole = }} | Section7 = {{Chembox Hazards | MainHazards = Flammable, irritative | FlashPt = -85 °C | RPhrases = {{R45}} {{R46}} {{R12}} | SPhrases = {{S45}} {{S53}} }} | Section8 = {{Chembox Related | Function = [[alkenes]]<br /> and [[dienes]] | OtherFunctn = [[1,2-Butadiene]]<br />[[Isoprene]]<br />[[Chloroprene]] | OtherCpds = [[Butane]] }} }} '''1,3-Butadiene''' is a simple [[Conjugated system|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 [[diene|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]].<ref name=Caventou>Caventou, E. (1863), '' Annalen der Chemie und Pharmacie'' '''127''', 93.</ref> This hydrocarbon was identified as butadiene in [[1886]], after [[Henry Edward Armstrong]] isolated it from among the pyrolysis products of [[petroleum]].<ref name=Armstrong>Armstrong, H.E. Miller, A.K. (1886). "The decomposition and genesis of hydrocarbons at high temperatures. I. The products of the manufacture of gas from petroleum." ''Journal of the Chemical Society'' '''49''', 80.</ref> In [[1910]], the [[Russia]]n chemist [[Sergei Vasilyevich Lebedev|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]] [[tire]]s. Worldwide production quickly ensued, with butadiene being produced from [[ethanol|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 [[olefin]]s. 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 [[hydrocarbon]]s produced in steam cracking by [[Liquid-liquid extraction|extraction]] into a [[polar aprotic solvent]] such as [[acetonitrile]] or [[dimethylformamide]], from which it is then stripped by [[distillation]].<ref name=ECT4thEd>Sun, H.P. Wristers, J.P. (1992). Butadiene. In J.I. Kroschwitz (Ed.), ''Encyclopedia of Chemical Technology, 4th ed.'', vol. 4, pp. 663&ndash;690. New York: John Wiley & Sons.</ref> Butadiene can also be produced by the catalytic [[dehydrogenation]] of normal butane. The first such commercial plant, producing 65,000 [[ton]]s per year of butadiene, began operations in 1957 in [[Houston, Texas]].<ref name=Beychok>Beychok, M.R. and Brack, W.J., "First Postwar Butadiene Plant", ''Petroleum Refiner'', June 1957.</ref> ===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 Vasilyevich Lebedev|Sergei Lebedev]], ethanol is converted to butadiene, hydrogen, and water at 400&ndash;450 °C over any of a variety of metal oxide catalysts:<ref name=ECT3rdEd>Kirshenbaum, I. (1978). Butadiene. In M. Grayson (Ed.), ''Encyclopedia of Chemical Technology, 3rd ed.'', vol. 4, pp. 313&ndash;337. New York: John Wiley & Sons.</ref> :2 [[ethanol|CH<sub>3</sub>CH<sub>2</sub>OH]] → CH<sub>2</sub>=CH-CH=CH<sub>2</sub> + 2 [[water|H<sub>2</sub>O]] + [[hydrogen|H<sub>2</sub>]] :[[Image:Lebedev reaction.png|500px]] 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 [[oxidation|oxidized]] to [[acetaldehyde]], which reacts with additional ethanol over a [[tantalum]]-promoted porous [[silica]] catalyst at 325&ndash;350 °C to yield butadiene:<ref name=ECT3rdEd/> :[[ethanol|CH<sub>3</sub>CH<sub>2</sub>OH]] + [[acetaldehyde|CH<sub>3</sub>CHO]] → CH<sub>2</sub>=CH-CH=CH<sub>2</sub> + 2 [[water|H<sub>2</sub>O]] :[[Image:Ostromislensky reaction.png|500px]] 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 [[polymer]]ized to produce synthetic rubber. While [[polybutadiene]] itself is a very soft, almost liquid material, polymers prepared from mixtures of butadiene with styrene or [[acrylonitrile]], such as [[Acrylonitrile butadiene styrene|ABS]], 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 [[nylon]] via the intermediate [[adiponitrile]], other synthetic rubber materials such as [[chloroprene]], and the solvent [[sulfolane]]. Butadiene is used in the industrial production of [[cyclododecatriene]] via a trimerization reaction. ==Safety== {{Original research|date=February 2008}} 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.<ref>[http://www.npi.gov.au/database/substance-info/profiles/16.html#health NPI sheet]</ref> 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.<ref>[http://www.epa.gov/ttn/atw/hlthef/butadien.html EPA website]</ref> 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== * [http://www.npi.gov.au/database/substance-info/profiles/16.html National Pollutant Inventory - 1,3-Butadiene] ==References== <references/> {{DEFAULTSORT:Butadiene, 1,3-}} [[Category:Dienes]] [[Category:Hazardous air pollutants]] [[Category:Monomers]] [[de:1,3-Butadien]] [[es:1,3-butadieno]] [[fr:Butadiène]] [[it:Butadiene]] [[lv:Butadiēns]] [[nl:Butadieen]] [[ja:ブタジエン]] [[pl:Butadien]] [[pt:1,3-Butadieno]] [[ru:Бутадиен]] [[fi:Butadieeni]] [[sv:Butadien]] [[uk:Бутадієн]] [[zh:丁二烯]]