Styrene

Styrene
Names
Preferred IUPAC name
Phenylethene
Other names
Vinyl benzene; cinnamene; styrol; phenylethene; diarex HF 77; styrolene; styropol; vinylbenzene; phenylethylene
Identifiers
100-42-5 YesY
ChEBI CHEBI:27452 YesY
ChEMBL ChEMBL285235 YesY
ChemSpider 7220 YesY
Jmol interactive 3D Image
KEGG C07083 N
PubChem 7501
RTECS number WL3675000
UNII 44LJ2U959V YesY
Properties
C8H8
Molar mass 104.15 g/mol
Appearance colorless oily liquid
Odor sweet, floral[1]
Density 0.909 g/cm3
Melting point −30 °C (−22 °F; 243 K)
Boiling point 145 °C (293 °F; 418 K)
0.03% (20°C)[1]
Vapor pressure 5 mmHg (20°C)[1]
1.5469
Viscosity 0.762 cP at 20 °C
Structure
0.13 D
Hazards
Main hazards flammable, toxic
Safety data sheet MSDS
R-phrases R10 R36
S-phrases S38 S20 S23
NFPA 704
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g., gasoline) Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazards (white): no codeNFPA 704 four-colored diamond
3
2
2
Flash point 31 °C (88 °F; 304 K)
Explosive limits 0.9%-6.8%[1]
Lethal dose or concentration (LD, LC):
2194 ppm (mouse, 4 hr)
5543 ppm (rat, 4 hr)[2]
10,000 ppm (human, 30 min)
2771 ppm (rat, 4 hr)[2]
US health exposure limits (NIOSH):
TWA 100 ppm C 200 ppm 600 ppm (5-minute maximum peak in any 3 hours)[1]
TWA 50 ppm (215 mg/m3) ST 100 ppm (425 mg/m3)[1]
700 ppm[1]
Related compounds
Related styrenes;
related aromatic compounds
 Polystyrene, Stilbene;
Ethylbenzene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Styrene, also known as ethenylbenzene, vinylbenzene, and phenylethene, is an organic compound with the chemical formula C6H5CH=CH2. This derivative of benzene is a colorless oily liquid that evaporates easily and has a sweet smell, although high concentrations have a less pleasant odor. Styrene is the precursor to polystyrene and several copolymers. Approximately 25 million tonnes (55 billion pounds) of styrene were produced in 2010.[3]

Occurrence, history, and use

Natural occurrence

Styrene is named for styrax balsam, the resin of Liquidambar trees of the Hamamelidaceae plant family. Styrene occurs naturally in small quantities in some plants and foods (cinnamon, coffee beans, and peanuts), and is also found in coal tar. In the nineteenth century, styrene was isolated by distillation of the natural storax balsam. The yeast-like fungus Exophiala jeanselmei can be used to treat air polluted with styrene.[4]

Industrial production from ethylbenzene

The modern method for production of styrene by dehydrogenation of ethylbenzene was first achieved in the 1930s.[5] The production of styrene increased dramatically during the 1940s, when it was popularized as a feedstock for synthetic rubber. Because it is produced on such a large scale, ethylbenzene in turn prepared on a prodigious scale (by alkylation of benzene with ethylene).[5] Ethylbenzene is mixed in the gas phase with 10–15 times its volume in high-temperature steam, and passed over a solid catalyst bed. Most ethylbenzene dehydrogenation catalysts are based on iron(III) oxide, promoted by several percent potassium oxide or potassium carbonate.

Steam serves several roles in this reaction. It is the source of heat for powering the endothermic reaction, and it removes coke that tends to form on the iron oxide catalyst through the water gas shift reaction. The potassium promoter enhances this decoking reaction. The steam also dilutes the reactant and products, shifting the position of chemical equilibrium towards products. A typical styrene plant consists of two or three reactors in series, which operate under vacuum to enhance the conversion and selectivity. Typical per-pass conversions are ca. 65% for two reactors and 70-75% for three reactors. Selectivity to styrene is 93-97%. The main byproducts are benzene and toluene. Because styrene and ethylbenzene have similar boiling points (145 and 136 °C, respectively), their separation requires tall distillation towers and high return/reflux ratios. At its distillation temperatures, styrene tends to polymerize. To minimize this problem, early styrene plants added elemental sulfur to inhibit the polymerization. During the 1970s, new free radical inhibitors consisting of nitrated phenol-based retarders were developed. More recently, a number of additives have been developed that exhibit superior inhibition against polymerization. However, the nitrated phenols are still widely used because of their relatively low cost. These reagents are added prior to the distillation.

Improving conversion and so reducing the amount of ethylbenzene that must be separated is the chief impetus for researching alternative routes to styrene. Other than the POSM process, none of these routes like obtaining styrene from butadiene have been commercially demonstrated.

Other industrial routes

From ethylbenzene hydroperoxide

Styrene is also co-produced commercially in a process known as POSM (Lyondell Chemical Company) or SM/PO (Shell) for styrene monomer / propylene oxide. In this process ethylbenzene is treated with oxygen to form the ethylbenzene hydroperoxide. This hydroperoxide is then used to oxidize propylene to propylene oxide. The resulting 1-phenylethanol is dehydrated to give styrene:

From toluene and methanol

Styrene can be produced from toluene and methanol, which are cheaper raw materials than those in the conventional process. This process has suffered from low selectivity associated with the competing decomposition of methanol.[6] Exelus Inc. claims to have developed this process with commercially viable selectivities, at 400-425 °C and atmospheric pressure, by forcing these components through a proprietary zeolitic catalyst. It is reported[7] that an approximately 9:1 mixture of styrene and ethylbenzene is obtained, with a total styrene yield of over 60%.[8]

From benzene and ethane

Another route to styrene involves the reaction of benzene and ethane. This process is being developed by Snamprogetti S.p.A. and Dow. Ethane, along with ethylbenzene, is fed to a dehydrogenation reactor with a catalyst capable of simultaneously producing styrene and ethylene. The dehydrogenation effluent is cooled and separated and the ethylene stream is recycled to the alkylation unit. The process attempts to overcome previous shortcomings in earlier attempts to develop production of styrene from ethane and benzene, such as inefficient recovery of aromatics, production of high levels of heavies and tars, and inefficient separation of hydrogen and ethane. Development of the process is ongoing.[9]

Laboratory synthesis

A laboratory synthesis of styrene entails the decarboxylation of cinnamic acid:[10]

C6H5CH=CHCO2H →  :C6H5CH=CH2 + CO2

Styrene was first prepared by this method.[11]

Polymerization

The presence of the vinyl group allows styrene to polymerize. Commercially significant products include polystyrene, ABS, styrene-butadiene (SBR) rubber, styrene-butadiene latex, SIS (styrene-isoprene-styrene), S-EB-S (styrene-ethylene/butylene-styrene), styrene-divinylbenzene (S-DVB), styrene-acrylonitrile resin (SAN), and unsaturated polyesters used in resins and thermosetting compounds. These materials are used in rubber, plastic, insulation, fiberglass, pipes, automobile and boat parts, food containers, and carpet backing.

Health effects

Styrene is regarded as a "hazardous chemical", especially in case of eye contact, but also in case of skin contact, of ingestion and of inhalation, according to several sources.[5][12][13][14] Styrene is largely metabolized into styrene oxide in humans, resulting from oxidation by cytochrome P450. Styrene oxide is considered toxic, mutagenic, and possibly carcinogenic. Styrene oxide is subsequently hydrolyzed in vivo to styrene glycol by the enzyme epoxide hydrolase.[15] The U.S. Environmental Protection Agency (EPA) has described styrene to be "a suspected toxin to the gastrointestinal tract, kidney, and respiratory system, among others."[16][17] On 10 June 2011, the U.S. National Toxicology Program has described styrene as "reasonably anticipated to be a human carcinogen".[18][19] However, a STATS author describes[20] a review that was done on scientific literature and concluded that "The available epidemiologic evidence does not support a causal relationship between styrene exposure and any type of human cancer".[21] Despite this claim, work has been done by Danish researchers to investigate the relationship between occupational exposure to styrene and cancer. They concluded, "The findings have to be interpreted with caution, due to the company based exposure assessment, but the possible association between exposures in the reinforced plastics industry, mainly styrene, and degenerative disorders of the nervous system and pancreatic cancer, deserves attention".[22] The Danish EPA recently concluded that the styrene data do not support a cancer concern for styrene.[23]

Various regulatory bodies refer to styrene, in various contexts, as a possible or potential human carcinogen. The International Agency for Research on Cancer considers styrene to be "possibly carcinogenic to humans".[24] Chronic exposure to styrene leads to tiredness/lethargy, memory deficits, headaches and vertigo.[25]

The U.S. EPA does not have a cancer classification for styrene,[26] but is has been the subject of their Integrated Risk Information System (IRIS) program.[27] The U.S. National Toxicology Program of the U.S. Department of Health and Human Services has determined that styrene is "reasonably anticipated to be a human carcinogen." [28]

References

  1. 1 2 3 4 5 6 7 "NIOSH Pocket Guide to Chemical Hazards #0571". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 "Styrene". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
  3. ↑ New Process for Producing Styrene Cuts Costs, Saves Energy, and Reduces Greenhouse Gas Emissions, U.S. Department of Energy.
  4. ↑ title=Isolation and characterisation of fungi growing on volatile aromatic hydrocarbons as their sole carbon and energy source|author1=Francesc X. Prenafeta|author2=Andrea KUHN|author3=Dion M. A. M. Lyykx|author4=Heidrun Anke|author5=Johan W. van Groenestijn|author6=Jan A. M. de Bont|volume=105|issue=4|pages=477-484|date=April 2001|
  5. 1 2 3 Denis H. James; William M. Castor (2007), "Styrene", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 1
  6. ↑ Yashima, Tatsuaki; Sato, Keiichi; Hayasaka, Tomoki; Hara, Nobuyoshi (1972). "Alkylation on synthetic zeolites: III. Alkylation of toluene with methanol and formaldehyde on alkali cation exchanged zeolites". Journal of Catalysis 26: 303–312. doi:10.1016/0021-9517(72)90088-7.
  7. ↑ Peter Taffe, ICIS.com, 21 Jan 2008 (based on an paper given at The 6th European.Aromatics & Derivatives Conference – Antwerp, Belgium - 14-15 November, 2007.)
  8. ↑ Stephen K. Ritter, Chemical & Engineering News, 19 March 2007, p.46.
  9. ↑ Styrene/Ethylbenzene 07/08-4 Report, ChemSystems, March 2009, p.64-73.
  10. ↑ Abbott, T. W.; Johnson, J. R. (1941). "Phenylethylene (Styrene)". Org. Synth.; Coll. Vol. 1, p. 440
  11. ↑ R. Fittig und F. Binder "Ueber die Additionsproducte der Zimmtssaure" in "Untersuchungen über die ungesättigten Säuren. I. Weitere Beiträge zur Kenntnifs der Fumarsäure und Maleïnsäure" Rudolph Fittig, Camille Petri, Justus Liebigs Annalen der Chemie 1879, volume 195, p 56-179. doi:10.1002/jlac.18791950103
  12. ↑ MSDS (1 November 2010). "Material Safety Data Sheet Styrene (monomer) MSDS". MSDS. Retrieved 2011-06-11.
  13. ↑ US EPA (December 1994). "OPPT Chemical Fact Sheets (Styrene) Fact Sheet: Support Document (CAS No. 100-42-5)" (PDF). US EPA. Retrieved 2011-06-11.
  14. ↑ http://www.atsdr.cdc.gov/tfacts53.pdf
  15. ↑ Kenneth C. Liebman (1975). "Metabolism and toxicity of styrene" (PDF). Environmental Health Perspectives 11: 115–119. doi:10.2307/3428333. JSTOR 3428333.
  16. ↑ "EPA settles case against Phoenix company for toxic chemical reporting violations". U.S. Environmental Protection Agency. Retrieved 2008-02-11.
  17. ↑ "EPA Fines California Hot Tub Manufacturer for Toxic Chemical Release Reporting Violations". U.S. Environmental Protection Agency. Retrieved 2008-02-11.
  18. ↑ Harris, Gardiner (10 June 2011). "Government Says 2 Common Materials Pose Risk of Cancer". New York Times. Retrieved 2011-06-11.
  19. ↑ National Toxicology Program (10 June 2011). "12th Report on Carcinogens". National Toxicology Program. Retrieved 2011-06-11.
  20. ↑ http://stats.org/stories/2011/styrene_crosshairs_sept14_11.html
  21. ↑ Boffetta, P., et al., Epidemiologic Studies of Styrene and Cancer: A Review of the Literature, J. Occupational and Environmental Medicine, Nov.2009, V.51, N.11.
  22. ↑ Kolstad, HA; Juel K; Olsen J; Lynge E. (May 1995). "Exposure to styrene and chronic health effects: mortality and incidence of solid cancers in the Danish reinforced plastics industry.". Occupational and Environmental Medicine 52 (5): 5. doi:10.1136/oem.52.5.320. PMC 1128224. PMID 7795754.
  23. ↑ Danish EPA 2011 review http://www.compositesworld.com/cdn/cms/uploadedFiles/danish_epa_styrene_review(2).pdf
  24. ↑ Monographs on the Evaluation of Carcinogenic Risks to Humans, Volume 82 (2002), Some Traditional Herbal Medicines, Some Mycotoxins, Naphthalene and Styrene, pp. 436 - 550.
  25. ↑ http://www.epa.gov/ttnatw01/hlthef/styrene.html
  26. ↑ US environmental protection agency. Section I.B.4 relates to neurotoxicology.
  27. ↑ EPA IRIS track styrene page
  28. ↑ Styrene entry in National Toxicology Program's Thirteenth Report on Carcinogens

External links

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