1,3-Butadiene

1,3-Butadiene is a simple conjugated diene with the formula C4H6. It is an

1,3-Butadiene
important industrial chemical used as a monomer in the production of
synthetic rubber. The molecule can be viewed as two vinyl groups (CH
2=CH2)
joined together. The word butadiene usually refers to 1,3-butadiene, which
has the structure H2C=CHCH=CH2.

Although butadiene breaks down quickly in the atmosphere, it is nevertheless

found in ambient air in urban and suburban areas as a consequence of its
constant emission from motor vehicles.[4] The EPA lists it as the "mobile-
source air toxic" with the highest normalized risk factor, exceeding that of
formaldehyde, the second riskiest air toxic emitted by motor vehicles, by a
factor of more than 20.[5]
Names
The name butadiene can also refer to the isomer, 1,2-butadiene, which is a Preferred IUPAC name
cumulated diene with structure H2C=C=CHCH3. However, this allene is Buta-1,3-diene[1]
difficult to prepare and has no industrial significance. This diene is also not Other names
expected to act as a diene in a DielsAlder reaction due to its structure. To Biethylene
effect a DielsAlder reaction, only a conjugated diene will suffice. The rest of Erythrene
this article concerns only 1,3-butadiene. Divinyl
Vinylethylene
Bivinyl
Butadiene
Contents Identifiers
1 History CAS Number 106-99-0
2 Production
2.1 Extraction from C4 hydrocarbons 3D model (JSmol) Interactive image
2.2 From dehydrogenation ofn-butane ChEBI CHEBI:39478
2.3 From ethanol
2.4 From butenes ChemSpider 7557
2.5 For laboratory use
ECHA InfoCard 100.003.138
3 Uses
EC Number 271-039-0
4 Environmental health and safety
KEGG C16450
5 See also
6 References PubChem CID 7845
7 External links RTECS number EI9275000
UNII JSD5FGP5VD

UN number 1010
History
InChI
In 1863, the French chemist E. Caventou isolated a previously unknown
InChI=1S/C4H6/c1-3-4-2/h3-4H,1-2H2
hydrocarbon from the pyrolysis of amyl alcohol.[6] This hydrocarbon was Key: KAKZBPTYRLMSJV-UHFFFAOYSA-N
identified as butadiene in 1886, after Henry Edward Armstrong isolated it InChI=1/C4H6/c1-3-4-2/h3-4H,1-2H2
from among the pyrolysis products of petroleum.[7] In 1910, the Russian Key: KAKZBPTYRLMSJV-UHFFFAOYAZ

SMILES
C=CC=C
chemist Sergei Lebedev polymerized butadiene and obtained a material with Properties
rubber-like properties. This polymer was, however, found to be too soft to Chemical formula C4H6
replace natural rubber in many applications, notably automobile tires.
Molar mass 54.0916 g/mol
The butadiene industry originated in the years leading up to World War II. Appearance Colourless gas
Many of the belligerent nations realized that in the event of war, they could be or refrigerated liquid
cut off from rubber plantations controlled by the British Empire, and sought to
Odor mildly aromatic or
reduce their dependence on natural rubber.[8] In 1929, Eduard Tschunker and
gasoline-like
Walter Bock, working for IG Farben in Germany, made a copolymer ofstyrene
Density 0.6149 g/cm3 at
and butadiene that could be used in automobile tires. Worldwide production
25 C, solid
quickly ensued, with butadiene being produced from grain alcohol in the
0.64 g/cm3 at 6 C,
Soviet Union and the United States and from coal-derived acetylene in
liquid
Germany.
Melting point 108.9 C
(164.0 F; 164.2 K)
Production
Boiling point 4.4 C (24.1 F;
268.8 K)
Extraction from C4 hydrocarbons Solubility in water 1.3g/L at 5, 735
In the United States, western Europe, and Japan, butadiene is produced as a mg/L at 20
byproduct of the steam cracking process used to produce ethylene and other Solubility very soluble in
olefins. When mixed with steam and briefly heated to very high temperatures acetone
(often over 900 C), aliphatic hydrocarbons give up hydrogen to produce a soluble in ether,
complex mixture of unsaturated hydrocarbons, including butadiene. The ethanol
quantity of butadiene produced depends on the hydrocarbons used as feed. Vapor pressure 2.4 atm (20C)[2]
Light feeds, such as ethane, give primarily ethylene when cracked, but heavier
Refractive index 1.4292
feeds favor the formation of heavier olefins, butadiene, and aromatic (nD)
hydrocarbons.
Viscosity 0.25 cP at 0 C
Butadiene is typically isolated from the other four-carbon hydrocarbons Hazards
produced in steam cracking by extractive distillation using a polar aprotic
Main hazards Flammable, irritative,
solvent such as acetonitrile, N-methylpyrrolidone, furfural, or
carcinogen
dimethylformamide, from which it is then stripped bydistillation.[9]
Safety data sheet See: data page
ECSC 0017
From dehydrogenation of n-butane R-phrases R45 R46 R12
Butadiene can also be produced by the catalytic dehydrogenation of normal (outdated)
butane (n-butane). The first such post-war commercial plant, producing 65,000 S-phrases S45 S53
tons per year of butadiene, began operations in 1957 in Houston, Texas.[10] (outdated)
Prior to that, in the 1940s the Rubber Reserve Company, a part of the United
NFPA 704
States government, constructed several plants in Borger, TX, Toledo, OH, and 4
El Segundo, CA to produce synthetic rubber for the war effort as part of the 3 2
United States Synthetic Rubber Program.[11] Total capacity was 68 KMTA
(Kilo Metric Tons per Annum).
Flash point 85 C (121 F;
Today, butadiene from n-butane is commercially practiced using the Houdry 188 K) liquid flash
catadiene process, which was developed during W
orld War II. point[2]
Autoignition 420 C (788 F;
temperature 693 K)
From ethanol
Explosive limits 212%
In other parts of the world, including South America, Eastern Europe, China, Lethal dose or concentration (LD, LC):
and India, butadiene was also produced from ethanol. While not competitive LD50 (median 548 mg/kg (rat, oral)
with steam cracking for producing large volumes of butadiene, lower capital dose)
costs make production from ethanol a viable option for smaller-capacity LC50 (median 115,111 ppm
plants. Two processes were in use. concentration) (mouse)
122,000 ppm
In the single-step process developed by Sergei Lebedev, ethanol is converted
(mouse, 2 h)
to butadiene, hydrogen, and water at 400450 C over any of a variety of
126,667 ppm (rat, 4
metal oxide catalysts:[12]
h)
130,000 ppm (rat, 4
h)[3]
LCLo (lowest 250,000 ppm (rabbit,
published) 30 min)[3]
US health exposure limits (NIOSH):
PEL TWA 1 ppm ST 5
(Permissible) ppm[2]
REL potential
(Recommended) occupational
carcinogen[2]
IDLH 2000 ppm[2]
(Immediate
danger)
Related compounds
Related alkenes Isoprene
and dienes Chloroprene
Related Butane
compounds
Supplementary data page
Structure and Refractive index (n),
properties Dielectric constant
(r), etc.
Thermodynamic Phase behaviour
data solidliquidgas
Spectral data UV, IR, NMR, MS
Except where otherwise noted, data are
given for materials in their standard state
(at 25 C [77 F], 100 kPa).
verify (what is ?)
Infobox references
 2 CH3CH2OH CH2=CHCH=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 remained in limited
use in Russia and other parts of eastern Europe until the end of the 1970s. At the same time this type of manufacture was canceled in
Brazil. Nowadays there is no industrial production of butadiene from ethanol.

In the other, two-step process, developed by the Russian emigree chemist Ivan Ostromislensky, ethanol is oxidized to acetaldehyde,
which reacts with additional ethanol over atantalum-promoted porous silica catalyst at 325350 C to yield butadiene:[12]

CH3CH2OH + CH3CHO CH2=CHCH=CH2 + 2 H2O

This process was one of the three used in the United States to produce "government rubber" during World War II, though it was not
preferred because it is less economical than the butane or butene routes for the large volumes needed. Still, three plants with a total
capacity of 200 KMTA were constructed in the US (Institute, WV; Louisville, KY; and Kobuta, PA ) with start-ups completed in
1943, the Louisville plant initially created butadiene from acetylene generated by an associated Calcium Carbide plant. The process
remains in use today in China and India.

From butenes
1,3-Butadiene can also be produced by catalytic dehydrogenation of normal butenes. This method was also used by the United States
Synthetic Rubber Program(USSRP) during World War II. The process was much more economical than the alcohol or n-butane route
but competed with aviation gasoline for available butene molecules (fortunately, butenes were plentiful thanks to catalytic cracking).
The USSRP constructed several plants in Baton Rouge and Lake Charles, LA; Houston, Baytown, and Port Neches, TX; and
Torrance, CA.[11] Total annual production was 275 KMTA.

In the 1960s, a Houston company known as "Petro-Tex" patented a process to produce butadiene from normal butenes by oxidative
dehydrogenation using a proprietary catalyst. It is thought to be no longer practiced commercially
.

After World War II, the production from butenes became the major type of production in USSR.

For laboratory use

1,3-Butadiene is inconvenient for laboratory use because it is a flammable gas and is subject to polymerization on storage. Sulfolene
(3-butadiene cyclic sulfone) is a convenient solid storable source for 1,3-butadiene for many laboratory purposes when the generation
of sulfur dioxide byproduct in the reaction mixture is not objectionable.
Uses
Most butadiene is polymerized to produce synthetic rubber. While polybutadiene itself is a very soft, almost liquid material,
copolymers prepared from mixtures of butadiene with styrene and/or acrylonitrile, such as acrylonitrile butadiene styrene (ABS),
acrylonitrile butadiene(NBR) and styrene-butadiene (SBR) are tough and/or elastic. SBR is the material most commonly used for the
production of automobile tires.

Smaller amounts of butadiene are used to make the nylon intermediate, adiponitrile, by the addition of a molecule of hydrogen
cyanide to each of the double bonds in a process called hydrocyanation developed by DuPont. Other synthetic rubber materials such
as chloroprene, and the solvent sulfolane are also manufactured from butadiene. Butadiene is used in the industrial production of 4-
vinylcyclohexene via a Diels Alder dimerization reaction.[13] Vinylcyclohexene is a common impurity found in butadiene upon
storage due to dimerization. Cyclooctadiene and cyclododecatriene are produced via nickel- or titanium-catalyzed dimerization and
trimerization reactions, respectively. Butadiene is also useful in the synthesis of cycloalkanes and cycloalkenes, as it reacts with
double and triple carbon-carbon bonds through theDiels-Alder reaction.

Environmental health and safety

Acute exposure results in irritation of the mucous membranes, Higher levels can result in neurological effects such as blurred vision,
[14]
fatigue, headache and vertigo. Exposure to the skin can lead to frostbite.

Long-term exposure has been associated with cardiovascular disease, there is a consistent association with leukemia, and weaker
association with other cancers.[14]

1,3-Butadiene is listed as a known carcinogen by the Agency for Toxic Substances Disease Registry and the US EPA.[15][16] The
American Conference of Governmental Industrial Hygienists (ACGIH) lists the chemical as a suspected carcinogen.[16] The Natural
Resource Defense Council (NRDC) lists some disease clusters that are suspected to be associated with this chemical.[17] Some
researchers have concluded it is the most potent carcinogen incigarette smoke, twice as potent as the runner upacrylonitrile[18]

1,3-Butadiene is also a suspected human teratogen.[19][20][21] Prolonged and excessive exposure can affect many areas in the human
body; blood, brain, eye, heart, kidney, lung, nose and throat have all been shown to react to the presence of excessive 1,3-
butadiene.[22] Animal data suggest that women have a higher sensitivity to possible carcinogenic effects of butadiene over men when
exposed to the chemical. This may be due to estrogen receptor impacts. While these data reveal important implications to the risks of
human exposure to butadiene, more data are necessary to draw conclusive risk assessments. There is also a lack of human data for the
effects of butadiene on reproductive and development shown to occur in mice, but animal studies have shown breathing butadiene
[23]
during pregnancy can increase the number of birth defects, and humans have the same hormone systems as animals.

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 (popcorn polymer, named for its appearance) inside the vapor space of 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. The hazard presented by popcorn polymer is also present in bulk commercial storage tanks.
It is important to keep the oxygen concentration in the tanks and any process wash water low in order to reduce the rate of
polymerization.

As with other light hydrocarbons, butadiene leaks can be detected by the formation of ice balls (from the evaporative freezing of
water out of the atmosphere) even when the temperature is well above 0 C.

1,3-Butadiene is recognized as a Highly Reactive Volatile Organic Compound (HRVOC) for its potential to readily form ozone, and
as such, emissions of the chemical are highly regulated by TCEQ in parts of the Houston-Brazoria-GalvestonOzone Non-Attainment
Area.[1]

See also
 Cyclobutadiene
Polybutadiene
Hydroxyl-terminated polybutadiene

References
1. Nomenclature of Organic Chemistry : IUP
AC Recommendations and Preferred Names 2013 (Blue Book) .
Cambridge: The Royal Society of Chemistry. 2014. p. 374. doi:10.1039/9781849733069-FP001(https://doi.org/10.10
39%2F9781849733069-FP001). ISBN 978-0-85404-182-4.
2. "NIOSH Pocket Guide to Chemical Hazards #0067"(https://www.cdc.gov/niosh/npg/npgd0067.html). National
Institute for Occupational Safety and Health(NIOSH).
3. "1,3-Butadiene" (http://www.cdc.gov/niosh/idlh/106990.html). Immediately Dangerous to Life and Health. National
Institute for Occupational Safety and Health(NIOSH).
4. Technology Transfer Network Air Toxics Web Site. "1,3-Butadiene" (http://www.epa.gov/ttn/atw/hlthef/butadien.htm
l). US Environmental Protection AgencyUS EPA. Retrieved 2014-09-02.
5. Alternative Fuels and Advanced Vehicles Data Center. "Alternative & Advanced Vehicles: Pollutants and Health" (htt
p://www.afdc.energy.gov/afdc/vehicles/emissions_pollutants.html). Energy Efficiency and Renewable Energy, US
DOE. Retrieved 2014-09-02.
6. Caventou, E. (1863). "Ueber eine mit dem zweifach-gebromten Brombutylen isomereerbindung
V und ber die
bromhaltigen Derivate des Brombutylens".Justus Liebigs Annalen der Chemie. 127: 9397.
doi:10.1002/jlac.18631270112(https://doi.org/10.1002%2Fjlac.18631270112)
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7. 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".J. Chem. Soc. 49: 7493. doi:10.1039/CT8864900074(https://d
oi.org/10.1039%2FCT8864900074).
8. Simple Things Won't Save the Earth (https://books.google.com/books?id=7yHlAgAAQBAJ&pg=P
A23&dq=butadiene
+dependence+on+natural+rubber&hl=pt-BR&sa=X&redir_esc=y#v=onepage&q=butadiene%20dependence%20on%
20natural%20rubber&f=false), J. Robert Hunter
9. Sun, H.P. Wristers, J.P. (1992). Butadiene. In J.I. Kroschwitz (Ed.), Encyclopedia of Chemical Technology, 4th ed.,
vol. 4, pp. 663690. New York: John Wiley & Sons.
10. Beychok, M.R. and Brack, W.J., "First Postwar Butadiene Plant", Petroleum Refiner, June 1957.
11. Herbert, Vernon, "Synthetic Rubber: A Project That Had to Succeed", Greenwood Press, 1985,ISBN 0-313-24634-3
12. Kirshenbaum, I. (1978). Butadiene. In M. Grayson (Ed.),Encyclopedia of Chemical Technology, 3rd ed., vol. 4, pp.
313337. New York: John Wiley & Sons.
13. "4-Vinylcyclohexene" (http://monographs.iarc.fr/ENG/Monographs/vol60/mono60-13.pdf)(PDF). IARC. Retrieved
2009-04-19.
14. NPI sheet (http://www.npi.gov.au/database/substance-info/profiles/16.html#health)
15. http://www.atsdr.cdc.gov/substances/toxsubstance.asp?toxid=81
16. Health Effects https://www.osha.gov/SLTC/butadiene/index.html
17. http://www.nrdc.org/health/diseaseclusters/
18. Fowles, J; Dybing, E (4 September 2003)."Application of toxicological risk assessment principles to the chemical
constituents of cigarette smoke"(http://tobaccocontrol.bmj.com/content/12/4/424). Institute of Environmental Science
and Research. New Zealand: Centers for Disease Control and Prevention.12 (4): 424430. doi:10.1136/tc.12.4.424
(https://doi.org/10.1136%2Ftc.12.4.424). PMC 1747794 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1747794) .
PMID 14660781 (https://www.ncbi.nlm.nih.gov/pubmed/14660781). Retrieved 12 October 2014.
19. Landrigan, PJ (1990). "Critical assessment of epidemiologic studies on the human carcinogenicity of 1,3-butadiene"
(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1567758). Environmental Health Perspectives. 86: 143147.
doi:10.1289/ehp.9086143 (https://doi.org/10.1289%2Fehp.9086143). PMC 1567758 (https://www.ncbi.nlm.nih.gov/p
mc/articles/PMC1567758) . PMID 2205484 (https://www.ncbi.nlm.nih.gov/pubmed/2205484).
20. "1,3-Butadiene CAS No. 106-99-0"(https://web.archive.org/web/20090508210250/http://ntp.niehs.nih.gov/ntp/roc/ele
venth/profiles/s025buta.pdf)(PDF). Report on Carcinogens(11th ed.). Archived fromthe original (http://ntp.niehs.nih.
gov/ntp/roc/eleventh/profiles/s025buta.pdf)(PDF) on 2009-05-08.
21. Melnick, Ronald L.; Kohn, Michael C. (1995). "Mechanistic data indicate that 1,3-butadiene is a human carcinogen".
Carcinogenesis. 16 (2): 15763. doi:10.1093/carcin/16.2.157(https://doi.org/10.1093%2Fcarcin%2F16.2.157) .
PMID 7859343 (https://www.ncbi.nlm.nih.gov/pubmed/7859343).
22. http://www.environment-agency.gov.uk/business/topics/pollution/27.aspx
23. EPA website (http://www.epa.gov/ttn/atw/hlthef/butadien.html)

External links
1,3-Butadiene Agency for Toxic Substances and DiseaseRegistry
1,3-Butadiene CDC - NIOSH Pocket Guide to Chemical Hazards
National Pollutant Inventory 1,3-Butadiene

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