Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. By weight, it is considered a relatively cheap resin and a fairly poor barrier to oxygen and water vapor, with a relatively low melting point. Polystyrene is one of the most widely used plastics, with the scale of its production being several million tonnes per year. Polystyrene is naturally transparent to visible light, but can be colored with colorants. Uses include protective packaging (such as packing peanuts and optical disc jewel cases), containers, lids, bottles, trays, tumblers, disposable cutlery, models, and (as an alternative material to vinyl) phonograph records.
As a thermoplastic polymer, polystyrene is in a solid (glassy) state at room temperature but flows if heated above about 100 °C, its glass transition temperature. It becomes rigid again when cooled. This temperature behaviour, which can be controlled by photocrosslinking, is exploited for extrusion (as in Styrofoam) and also for molding and vacuum forming, since the material can cast in molds with fine detail.
Under ASTM standards, polystyrene is regarded as not biodegradable. It is accumulating as a form of litter in the outside environment, particularly along shores and waterways, especially in its foam form, and in the oceans.
History Polystyrene was discovered in 1839 by Eduard Simon, an apothecary from Berlin.Simon, E. (1839) "Ueber den flüssigen Storax (Styrax liquidus)" [On liquid storax (Styrax liquidus)], Annalen der Chemie, 31 : 265–277. From storax, the resin of the Oriental sweetgum tree Liquidambar orientalis, he distilled an oily substance that he named styrol, now called styrene. Several days later, Simon found that it had thickened into a jelly, now known to have been a polymer, that he dubbed styrol oxide ("Styroloxyd") because he presumed that it had resulted from oxidation (styrene oxide is a distinct compound). By 1845 the Jamaican-born chemist John Buddle Blyth and the German chemist August Wilhelm von Hofmann showed that the same transformation of styrol took place in the absence of oxygen.Blyth, John, and Hofmann, Aug. Wilh. (1845). "Ueber das Stryol und einige seiner Zersetzungsproducte" ("On styrol and some of its decomposition products"), Annalen der Chemie und Pharmacie, 53(3): 289–329. They called the product "meta styrol"; analysis showed that it was chemically identical to Simon's Styroloxyd.Blyth and Hofmann, 1845, p. 312. From p. 312: "Analysis, as well as synthesis, have equally demonstrated, that styrol and the solid, glassy material, for which we suggest the name 'meta styrol', possess the same percentage composition." In 1866 Marcellin Berthelot correctly identified the formation of meta styrol/Styroloxyd from styrol as a polymerisation process.Berthelot, M. (1866) "Sur Les caractères de la benzine et du styrolène, comparés avec ceux des Autres carburetors 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 stryolène 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 (polystyrene), and that this polymer, [when] distilled abruptly, reproduces styrene.") About 80 years later it was realized that heating of styrol starts a chain reaction that produces macromolecules, following the thesis of German organic chemist Hermann Staudinger (1881–1965). This eventually led to the substance's receiving its present name, polystyrene.
The company I. G. Farben began manufacturing polystyrene in Ludwigshafen about 1931, hoping it would be a suitable replacement for die-cast zinc in many applications. Success was achieved when they developed a reactor vessel that extruded polystyrene through a heated tube and cutter, producing polystyrene in pellet form.
Ray McIntire (1918–1996), a chemical engineer of Dow Chemical, rediscovered a process first patented in the early 1930s by the Swedish inventor Carl Munters. According to the Science History Institute, "Dow bought the rights to Munters's method and began producing a lightweight, water-resistant, and buoyant material that seemed perfectly suited for building docks and watercraft and for insulating homes, offices, and chicken sheds." In 1944, Styrofoam was patented.
Before 1949, the chemical engineer Fritz Stastny (1908–1985) developed pre-expanded PS beads by incorporating aliphatic hydrocarbons, such as pentane. These beads are the raw material for molding parts or extruding sheets. BASF and Stastny applied for a patent, which was issued in 1949. The molding process was demonstrated at the Kunststoff Messe 1952 in Düsseldorf. Products were named Styropor.
The crystal structure of isotactic polystyrene was reported by Giulio Natta.
In 1954, the Koppers Company in Pittsburgh, Pennsylvania, developed expanded polystyrene (EPS) foam under the trade name Dylite.Ferrigno, T.H. (1967). Rigid Plastics Foams, 2nd edition. p. 207. In 1960, Dart Container, the largest manufacturer of foam cups, shipped their first order.
Structure and production
In chemical terms, polystyrene is a long chain hydrocarbon wherein alternating carbon centers are attached to phenyl groups (a derivative of benzene). Polystyrene's chemical formula is ; it contains the chemical elements carbon and hydrogen.
The material's properties are determined by short-range van der Waals attractions between polymer chains. Since the molecules consist of thousands of atoms, the cumulative attractive force between the molecules is large. When heated (or deformed at a rapid rate, due to a combination of viscoelastic and thermal insulation properties), the chains can take on a higher degree of confirmation and slide past each other. This intermolecular weakness (versus the high intramolecular strength due to the hydrocarbon backbone) confers flexibility and elasticity. The ability of the system to be readily deformed above its glass transition temperature allows polystyrene (and thermoplastic polymers in general) to be readily softened and molded upon heating. Extruded polystyrene is about as strong as an unalloyed aluminium but much more flexible and much less dense (1.05 g/cm3 for polystyrene vs. 2.70 g/cm3 for aluminium).
Production Polystyrene is an addition polymer that results when styrene monomers polymerize (interconnect). This can be started by applying heat or benzoyl peroxide to styrene as initiators. As a liquid or a gas, pure styrene will polymerise spontaneously to polystyrene, without the need of external initiators. In the polymerization, the carbon–carbon π bond of the vinyl group is broken, and a new carbon–carbon σ bond is formed, attaching to the carbon of another styrene monomer to the chain. Since only one kind of monomer is used in its preparation, it is a homopolymer. The newly formed σ bond is stronger than the π bond that was broken, thus it is difficult to depolymerize polystyrene. About a few thousand monomers typically comprise a chain of polystyrene, giving a molar mass of 100,000–400,000 g/mol.
Each carbon of the backbone has tetrahedral geometry, and those carbons that have a phenyl group (benzene ring) attached are stereogenic. If the backbone were to be laid as a flat elongated zig-zag chain, each phenyl group would be tilted forward or backward compared to the plane of the chain.
The relative stereochemical relationship of consecutive phenyl groups determines the tacticity, which affects various physical properties of the material.
Tacticity
In polystyrene, tacticity describes the extent to which the phenyl group is uniformly aligned (arranged at one side) in the polymer chain. Tacticity has a strong effect on the properties of the plastic. Standard polystyrene is atactic. The diastereomer where all of the phenyl groups are on the same side is called isotactic polystyrene, which is not produced commercially.
Atactic polystyrene The only commercially important form of polystyrene is atactic, in which the phenyl groups are randomly distributed on both sides of the polymer chain. This random positioning prevents the chains from aligning with sufficient regularity to achieve any crystallinity. The plastic has a glass transition temperature Tg of ≈90 °C. Polymerization is initiated with free radicals.Maul, J.; Frushour, B. G.; Kontoff, J. R.; Eichenauer, H.; Ott, K.-H. and Schade, C. (2007) "Polystyrene and Styrene Copolymers" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, .
Syndiotactic polystyrene Ziegler–Natta polymerization can produce an ordered syndiotactic polystyrene with the phenyl groups positioned on alternating sides of the hydrocarbon backbone. This form is highly crystalline with a Tm (melting point) of . Syndiotactic polystyrene resin is currently produced under the trade name XAREC by Idemitsu corporation, who use a metallocene catalyst for the polymerisation reaction.
Degradation Polystyrene is relatively chemically inert. While it is waterproof and resistant to breakdown by many acids and bases, it is easily attacked by many organic solvents (e.g. it dissolves quickly when exposed to acetone), chlorinated solvents, and aromatic hydrocarbon solvents. Because of its resilience and inertness, it is used for fabricating many objects of commerce. Like other organic compounds, polystyrene burns to give carbon dioxide and water vapor, in addition to other thermal degradation by-products. Polystyrene, being an aromatic hydrocarbon, typically combusts incompletely as indicated by the sooty flame.
The process of depolymerizing polystyrene into its monomer, styrene, is called pyrolysis. This involves using high heat and pressure to break down the chemical bonds between each styrene compound. Pyrolysis usually goes up to . The high energy cost of doing this has made commercial recycling of polystyrene back into styrene monomer difficult.
Organisms Polystyrene is generally considered to be non-biodegradable. However, certain organisms are able to degrade it, albeit very slowly.
In 2015, researchers discovered that mealworms, the larvae form of the darkling beetle Tenebrio molitor, could digest and subsist healthily on a diet of EPS. About 100 mealworms could consume between and of this white foam in a day. The droppings of mealworm were found to be safe for use as soil for crops.
In 2016, it was also reported that superworms (Zophobas morio) may eat expanded polystyrene (EPS). A group of high school students in Ateneo de Manila University found that compared to Tenebrio molitor larvae, Zophobas morio larvae may consume greater amounts of EPS over longer periods of time.
In 2022 scientists identified several bacterial genera, including Pseudomonas, Rhodococcus and Corynebacterium, in the gut of superworms that contain encoded enzymes associated with the degradation of polystyrene and the breakdown product styrene.
The bacterium Pseudomonas putida is capable of converting styrene oil into the biodegradable plastic PHA. This may someday be of use in the effective disposing of polystyrene foam. It is worthy to note the polystyrene must undergo pyrolysis to turn into styrene oil.
Forms produced