Polyethylene

Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bottles, cups, jars, etc.). As of 2017^[update], over 100 million tonnes of polyethylene resins are being produced annually, accounting for 34% of the total plastics market.

Many kinds of polyethylene are known, with most having the chemical formula (C₂H₄)_n. PE is usually a mixture of similar polymers of ethylene, with various values of n. It can be low-density or high-density and many variations thereof. Its properties can be modified further by crosslinking or copolymerization. All forms are nontoxic as well as chemically resilient, contributing to polyethylene's popularity as a multi-use plastic. However, polyethylene's chemical resilience also makes it a long-lived and decomposition-resistant pollutant when disposed of improperly. Being a hydrocarbon, polyethylene is colorless to opaque (without impurities or colorants) and combustible.

Polyethylene was first synthesized by the German chemist Hans von Pechmann, who prepared it by accident in 1898 while investigating diazomethane. When his colleagues Eugen Bamberger and Friedrich Tschirner characterized the white, waxy substance that he had created, they recognized that it contained long −CH₂− chains and termed it polymethylene.

The first industrially practical polyethylene synthesis (diazomethane is a notoriously unstable substance that is generally avoided in industrial syntheses) was again accidentally discovered in 1933 by Eric Fawcett and Reginald Gibson at the Imperial Chemical Industries (ICI) works in Northwich, England. Upon applying extremely high pressure (several hundred atmospheres) to a mixture of ethylene and benzaldehyde they again produced a white, waxy material. Because the reaction had been initiated by trace oxygen contamination in their apparatus, the experiment was difficult to reproduce at first. It was not until 1935 that another ICI chemist, Michael Perrin, developed this accident into a reproducible high-pressure synthesis for polyethylene that became the basis for industrial low-density polyethylene (LDPE) production beginning in 1939. Because polyethylene was found to have very low-loss properties at very high frequency radio waves, commercial distribution in Britain was suspended on the outbreak of World War II, secrecy imposed, and the new process was used to produce insulation for UHF and SHF coaxial cables of radar sets. During World War II, further research was done on the ICI process and in 1944, DuPont at Sabine River, Texas, and Union Carbide Corporation at South Charleston, West Virginia, began large-scale commercial production under license from ICI.

The landmark breakthrough in the commercial production of polyethylene began with the development of catalysts that promoted the polymerization at mild temperatures and pressures. The first of these was a catalyst based on chromium trioxide discovered in 1951 by Robert Banks and J. Paul Hogan at Phillips Petroleum. In 1953 the German chemist Karl Ziegler developed a catalytic system based on titanium halides and organoaluminium compounds that worked at even milder conditions than the Phillips catalyst. The Phillips catalyst is less expensive and easier to work with, however, and both methods are heavily used industrially. By the end of the 1950s both the Phillips- and Ziegler-type catalysts were being used for high-density polyethylene (HDPE) production. In the 1970s, the Ziegler system was improved by the incorporation of magnesium chloride. Catalytic systems based on soluble catalysts, the metallocenes, were reported in 1976 by Walter Kaminsky and Hansjörg Sinn. The Ziegler- and metallocene-based catalysts families have proven to be very flexible at copolymerizing ethylene with other olefins and have become the basis for the wide range of polyethylene resins available today, including very-low-density polyethylene and linear low-density polyethylene. Such resins, in the form of UHMWPE fibers, have (as of 2005) begun to replace aramids in many high-strength applications.

The properties of polyethylene depend strongly on type. The molecular weight, crosslinking, and presence of comonomers all strongly affect its properties. It is for this structure-property relation that intense effort has been invested into diverse kinds of PE. LDPE is softer and more transparent than HDPE. For medium- and high-density polyethylene the melting point is typically in the range 120 to 130 °C (248 to 266 °F). The melting point for average commercial low-density polyethylene is typically 105 to 115 °C (221 to 239 °F). These temperatures vary strongly with the type of polyethylene, but the theoretical upper limit of melting of polyethylene is reported to be 144 to 146 °C (291 to 295 °F). Combustion typically occurs above 349 °C (660 °F).

Most LDPE, MDPE, and HDPE grades have excellent chemical resistance, meaning that they are not attacked by strong acids or strong bases and are resistant to gentle oxidants and reducing agents. Crystalline samples do not dissolve at room temperature. Polyethylene (other than cross-linked polyethylene) usually can be dissolved at elevated temperatures in aromatic hydrocarbons such as toluene or xylene, or in chlorinated solvents such as trichloroethane or trichlorobenzene.

Polyethylene absorbs almost no water. The permeability for water vapor and polar gases of is lower than for most plastics. On the other hand, non-polar gases such as Oxygen, carbon dioxide, and flavorings can pass it easily.