Polymethyl Methacrylate

polymethyl methacrylate (PMMA), a synthetic resin produced from the polymerization of methyl methacrylate. A transparent and rigid plastic, PMMA is often used as a substitute for glass in products such as shatterproof windows, skylights, illuminated signs, and aircraft canopies. It is sold under the trademarks Plexiglas, Lucite, and Perspex.

PMMA, an ester of methacrylic acid (CH₂=C[CH₃]CO₂H), belongs to the important acrylic family of resins. In modern production it is obtained principally from propylene, a compound refined from the lighter fractions of crude oil. Propylene and benzene are reacted together to form cumene, or isopropylbenzene; the cumene is oxidized to cumene hydroperoxide, which is treated with acid to form acetone; the acetone is in turn converted in a three-step process to methyl methacrylate (CH₂=C[CH₃]CO₂CH₃), a flammable liquid. Methyl methacrylate, in bulk liquid form or suspended as fine droplets in water, is polymerized (its molecules linked together in large numbers) under the influence of free-radical initiators to form solid PMMA. The structure of the polymer repeating unit is: .

The presence of the pendant methyl (CH₃) groups prevents the polymer chains from packing closely in a crystalline fashion and from rotating freely around the carbon-carbon bonds. As a result, PMMA is a tough and rigid plastic. In addition, it has almost perfect transmission of visible light, and, because it retains these properties over years of exposure to ultraviolet radiation and weather, it is an ideal substitute for glass. A most successful application is in internally lighted signs for advertising and directions. PMMA is also employed in domed skylights, swimming pool enclosures, aircraft canopies, instrument panels, and luminous ceilings. For these applications the plastic is drawn into sheets that are machined or thermoformed, but it is also injection-molded into automobile lenses and lighting-fixture covers. Because PMMA displays the unusual property of keeping a beam of light reflected within its surfaces, it is frequently made into optical fibres for telecommunication or endoscopy.

Polymethyl methacrylate was discovered in the early 1930s by British chemists Rowland Hill and John Crawford at Imperial Chemical Industries (ICI) in England. ICI registered the product under the trademark Perspex. About the same time, chemist and industrialist Otto Röhm of Rohm and Haas AG in Germany attempted to produce safety glass by polymerizing methyl methacrylate between two layers of glass. The polymer separated from the glass as a clear plastic sheet, which Röhm gave the trademarked name Plexiglas. Both Perspex and Plexiglas were commercialized in the late 1930s. In the United States, E.I. du Pont de Nemours & Company (now DuPont Company) subsequently introduced its own product under the trademark Lucite. The first major application of the new plastic took place during World War II, when PMMA was made into aircraft windows and bubble canopies for gun turrets. Civilian applications followed after the war.