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 although aged samples can appear yellowish. The compound 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 of styrene were produced in 2010, increasing to around 35 million tonnes by 2018.
Styrene is named after storax balsam, the resin of Liquidambar trees of the Altingiaceae 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 1839, the German apothecary Eduard Simon isolated a volatile liquid from the resin (called storax or styrax (Latin)) of the American sweetgum tree (Liquidambar styraciflua). He called the liquid "styrol" (now styrene). He also noticed that when styrol was exposed to air, light, or heat, it gradually transformed into a hard, rubber-like substance, which he called "styrol oxide". By 1845, the German chemist August Hofmann and his student John Blyth (1814-1871) had determined styrene's empirical formula: C8H8. They had also determined that Simon's "styrol oxide" -- which they renamed "metastyrol" -- had the same empirical formula as styrene. Furthermore, they could obtain styrene by dry-distilling "metastyrol". In 1865, the German chemist Emil Erlenmeyer found that styrene could form a dimer, and in 1866 the French chemist Marcelin Berthelot stated that "metastyrol" was a polymer of styrene (i.e. polystyrene). Meanwhile, other chemists had been investigating another component of storax, namely, cinnamic acid. They had found that cinnamic acid could be decarboxylated to form "cinnamene" (or "cinnamol"), which appeared to be styrene. In 1845, French chemist Emil Kopp suggested that the two compounds were identical, and in 1866, Erlenmeyer suggested that both "cinnamol" and styrene might be vinylbenzene. However, the styrene that was obtained from cinnamic acid seemed different from the styrene that was obtained by distilling storax resin: the latter was optically active. Eventually, in 1876, the Dutch chemist van 't Hoff resolved the ambiguity: the optical activity of the styrene that was obtained by distilling storax resin was due to a contaminant.
The crude ethylbenzene/styrene product is then purified by distillation. As the difference in boiling points between the two compounds is only 9°C at ambient pressure this necessitates the use of a series of distillation columns. This is energy intensive and is further complicated tendency of styrene to undergo thermally induced polymerisation into polystyrene, requiring the continuous addition of polymerization inhibitor to the system.
Via 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, which is also recovered as a co-product. The remaining 1-phenylethanol is dehydrated to give styrene:
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. 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 that an approximately 9:1 mixture of styrene and ethylbenzene is obtained, with a total styrene yield of over 60%.
From benzene and ethane
Another route to styrene involves the reaction of benzene and ethane. This process is being developed by Snamprogetti 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.
Styrene is regarded as a "known carcinogen", especially in case of eye contact, but also in case of skin contact, of ingestion and of inhalation, according to several sources. 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. 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". On 10 June 2011, the U.S. National Toxicology Program has described styrene as "reasonably anticipated to be a human carcinogen". However, a STATS author describes 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". 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". In 2012 the Danish EPA concluded that the styrene data do not support a cancer concern for styrene. The U.S. EPA does not have a cancer classification for styrene, but it has been the subject of their Integrated Risk Information System (IRIS) program. 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". 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 "probably carcinogenic to humans".
The neurotoxic properties of styrene have also been studied and reported effects include effects on vision and on hearing functions. Studies with experimental animals, as well as epidemiologic studies have observed a synergistic interaction with noise in causing hearing difficulties.
^Simon, E. (1839) "Ueber den flüssigen Storax (Styrax liquidus)" (On liquid storax (Styrax liquidus), Annalen der Chemie, 31 : 265-277. From p. 268: "Das flüchtige Oel, für welches ich den Namen Styrol vorschlage, ... " (The volatile oil, for which I suggest the name "styrol", ... )
^For further details of the history of styrene, see: F. W. Semmler, Die ätherischen Öle nach ihren chemischen Bestandteilen unter Berücksichtigung der geschichtlichen Entwicklung [The volatile liquids according to their chemical components with regard to historical development], vol. 4 (Leipzig, Germany, Veit & Co., 1907), § 327. Styrol, pp. 24-28.Archived 1 May 2018 at the Wayback Machine
^(Simon, 1839), p. 268. From p. 268: "Für den festen Rückstand würde der Name Styroloxyd passen." (For the solid residue, the name "styrol oxide" would fit.)
Note that Blyth and Hofmann state the empirical formula of styrene as C16H8 because at that time, some chemists used the wrong atomic mass for carbon (6 instead of 12).
^(Blyth and Hofmann, 1845a), p. 348. From p. 348: "Analysis as well as synthesis has equally proved that styrol and the vitreous mass (for which we propose the name of metastyrol) possess the same constitution per cent."
^Berthelot, M. (1866) "Sur les caractères de la benzine et du styrolène, comparés avec ceux des autres carbures d'hydrogène" (On the characters of benzene and styrene, compared with those of other hydrocarbons), Bulletin de la Société Chimique de Paris, 2nd series, 6 : 289-298. From p. 294: "On sait que le styrolène chauffé en vase scellé à 200°, pendant quelques heures, se change en un polymère résineux (métastyrol), et que ce polymère, distillé brusquement, reproduit le styrolène." (One knows that styrene [when] heated in a sealed vessel at 200°C, for several hours, is changed into a resinous polymer (metastyrol), and that this polymer, [when] distilled abruptly, reproduces styrene.)
^Kopp, E. (1845), "Recherches sur l'acide cinnamique et sur le cinnamène"Archived 8 November 2016 at the Wayback Machine (Investigations of cinnamic acid and cinnamen), Comptes rendus, 21 : 1376-1380. From p. 1380: "Je pense qu'il faudra désormais remplacer le mot de styrol par celui de cinnamène, et le métastyrol par le métacinnamène." (I think that henceforth one will have to replace the word "styrol" with that of "cinnamène", and "metastyrol" with "metacinnamène".)
^Berthelot, Marcellin (1867). "Sur les états isomériques du styrolène" [On the isomeric states of styrene]. Annales de Chimie et de Physique. 4th series (in French). 12: 159-161. From p. 160: "1° Le carbure des cinnamates est privé de pouvoir rotatoire, tandis que le carbure du styrax dévie de 3 degrés la teinte de passage (l = 100 mm)." (1. The carbon [atom] of cinnamates is bereft of rotary power [i.e., the ability to rotate polarized light], whereas the carbon of styrax deflects by 3 degrees the neutral tint [i.e., the relative orientation of the polarized quartz plates at which the light through the polarimeter appears colorless] (length = 100 mm). [For further details about 19th century polarimeters, see: Spottiswode, William (1883). Polarisation of Light (4th ed.). London, England: Macmillan and Co. pp. 51-52. Archived from the original on 10 September 2010. Retrieved 2016.])
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