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Poly(methyl methacrylate)

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This article is about the transparent plastic sometimes called acrylic glass. For the glass/plastic laminate often called "safety glass", see laminated glass.
Poly(methyl methacrylate)
Names
IUPAC name
Poly(methyl 2-methylpropenoate)
Other names
Poly(methyl methacrylate) (PMMA)
methyl methacrylate resin
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.112.313 Edit this at Wikidata
KEGG
  • C[C](C)C(=O)OC
Properties
(C5O2H8)n
Molar mass varies
Density 1.18 g/cm3[1]
Melting point 160 °C (320 °F)[2]
1.4914 at 587.6 nm.[3]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
B-17G Plexiglas bombardier nose compartment, an early large-scale use of Plexiglas in 1943. Note the pilot cockpit above and behind.
World War II era Lucite sweetheart pin.

Poly(methyl methacrylate) (PMMA) is a transparent thermoplastic, often used as a lightweight or shatter-resistant alternative to glass. It is sometimes called acrylic glass. Chemically, it is the synthetic polymer of methyl methacrylate. The material was developed in 1928 in various laboratories, and was first brought to market in 1933 by the Rohm and Haas Company, under the trademark Plexiglas.[4] It has since been sold under many different names, including Lucite and Perspex.

The often-seen spelling poly(methyl 2-methylpropanoate) with -an- is an error for poly(methyl 2-methylpropenoate), based on propenoic acid.

PMMA is an economical alternative to polycarbonate (PC) when extreme strength is not necessary. Additionally, PMMA does not contain the potentially harmful bisphenol-A subunits found in polycarbonate. It is often preferred because of its moderate properties, easy handling and processing, and low cost. The non-modified PMMA behaves in a brittle manner when loaded, especially under an impact force, and is more prone to scratching than conventional inorganic glass. However, the modified PMMA achieves very high scratch and impact resistance.

History

The first acrylic acid was created in 1843. Methacrylic acid, derived from acrylic acid, was formulated in 1865. The reaction between methacrylic acid and methanol results in the ester methyl methacrylate. The German chemists Fittig and Paul discovered in 1877 the polymerization process that turns methyl methacrylate into polymethyl methacrylate. In 1933 the German chemist Otto Röhm patented and registered the brand name PLEXIGLAS. In 1936 the first commercially viable production of acrylic safety glass began. During World War II acrylic glass was used for submarine periscopes, windshields, canopies, and gun turrets for airplanes.[5]

Names

PMMA has been sold under a variety of brand names and generic names. It is often generically called acrylic glass,[6] although it is chemically unrelated to glass. It is sometimes called simply acrylic, although acrylic can also refer to other polymers or copolymers containing polyacrylonitrile. Other notable trade names include:

Synthesis

PMMA is routinely produced by emulsion polymerization, solution polymerization, and bulk polymerization. Generally, radical initiation is used (including living polymerization methods), but anionic polymerization of PMMA can also be performed. To produce 1 kg (2.2 lb) of PMMA, about 2 kg (4.4 lb) of petroleum is needed. PMMA produced by radical polymerization (all commercial PMMA) is atactic and completely amorphous.

Processing

The glass transition temperature (Tg) of atactic PMMA is 105 °C. The Tg values of commercial grades of PMMA range from 85 to 165 °C (185 to 329 °F); the range is so wide because of the vast number of commercial compositions which are copolymers with co-monomers other than methyl methacrylate. PMMA is thus an organic glass at room temperature; i.e., it is below its Tg. The forming temperature starts at the glass transition temperature and goes up from there.[12] All common molding processes may be used, including injection molding, compression molding, and extrusion. The highest quality PMMA sheets are produced by cell casting, but in this case, the polymerization and molding steps occur concurrently. The strength of the material is higher than molding grades owing to its extremely high molecular mass. Rubber toughening has been used to increase the strength of PMMA owing to its brittle behavior in response to applied loads.

Handling, cutting, and joining

PMMA can be joined using cyanoacrylate cement (commonly known as superglue), with heat (welding), or by using solvents such as di- or trichloromethane to dissolve the plastic at the joint, which then fuses and sets, forming an almost invisible weld. Scratches may easily be removed by polishing or by heating the surface of the material.

Laser cutting may be used to form intricate designs from PMMA sheets. PMMA vaporizes to gaseous compounds (including its monomers) upon laser cutting, so a very clean cut is made, and cutting is performed very easily. However, the pulsed lasercutting introduces high internal stresses along the cut edge, which on exposure to solvents produce undesirable "stress-crazing" at the cut edge and several millimetres deep. Even ammonium-based glass-cleaner and almost everything short of soap-and-water produces similar undesirable crazing, sometimes over the entire surface of the cut parts, at great distances from the stressed edge. Annealing the PMMA sheet/parts is therefore an obligatory post-processing step when intending to chemically bond lasercut parts together. This involves heating the parts in an air circulating oven from room temperature up to 90 °C (at a rate of no more than 18 degrees per hour) down to room temperature (at a rate of no more than 12 degrees per hour). Temperature should be maintained as follows: one hour for 3 mm thickness, two hours for up to 6 mm thickness, four hours for up to 12 mm thickness, and six hours for up to 20 mm thickness. A rapid annealing cycle is reliable for thin sheets and involves placing them in a pre-heated oven to 80  °C for one hour, then removing parts from the oven and allowing to cool to room temperature. This added time component should be factored into the whole fabrication process, and the alternative Zero-rake sawcutting technique may provide better cost-effectiveness, unless complex non-straight line edges are required. In this respect PMMA has an advantage over competing polymers such as polystyrene and polycarbonate, which require higher laser powers and give more messy and charred laser cuts.

In the majority of applications, it will not shatter. Rather, it breaks into large dull pieces. Since PMMA is softer and more easily scratched than glass, scratch-resistant coatings are often added to PMMA sheets to protect it (as well as possible other functions).

Acrylate resin casting

Illustrative and secure bromine chemical sample used for teaching. The sample vial of corrosive and poisonous liquid has been cast into an acrylic plastic cube

Methyl methacrylate "synthetic resin" for casting (simply the bulk liquid chemical) may be used in conjunction with a polymerization catalyst such as MEKP, to produce hardened transparent PMMA in any shape, from a mold. Objects like insects or coins, or even dangerous chemicals in breakable quartz ampules, may be embedded in such "cast" blocks, for display and safe handling.

Properties

Skeletal structure of methyl methacrylate, the constituent monomer of PMMA

PMMA is a strong and lightweight material. It has a density of 1.17–1.20 g/cm3,[1][13] which is less than half that of glass.[1] It also has good impact strength, higher than both glass and polystyrene; however, PMMA's impact strength is still significantly lower than polycarbonate and some engineered polymers. PMMA ignites at 460 °C (860 °F) and burns, forming carbon dioxide, water, carbon monoxide and low-molecular-weight compounds, including formaldehyde.[14]

PMMA transmits up to 92% of visible light (3 mm thickness), and gives a reflection of about 4% from each of its surfaces on account of its refractive index (1.4914 at 587.6 nm).[3] It filters ultraviolet (UV) light at wavelengths below about 300 nm (similar to ordinary window glass). Some manufacturers[15] add coatings or additives to PMMA to improve absorption in the 300–400 nm range. PMMA passes infrared light of up to 2800 nm and blocks IR of longer wavelengths up to 25000 nm. Colored PMMA varieties allow specific IR wavelengths to pass while blocking visible light (for remote control or heat sensor applications, for example).

PMMA swells and dissolves in many organic solvents; it also has poor resistance to many other chemicals on account of its easily hydrolyzed ester groups. Nevertheless, its environmental stability is superior to most other plastics such as polystyrene and polyethylene, and PMMA is therefore often the material of choice for outdoor applications.[16]

PMMA has a maximum water absorption ratio of 0.3–0.4% by weight.[13] Tensile strength decreases with increased water absorption.[17] Its coefficient of thermal expansion is relatively high at (5–10)×10−5 /K.[18]

Modification of properties

Pure poly(methyl methacrylate) homopolymer is rarely sold as an end product, since it is not optimized for most applications. Rather, modified formulations with varying amounts of other comonomers, additives, and fillers are created for uses where specific properties are required. For example,

  • A small amount of acrylate comonomers are routinely used in PMMA grades destined for heat processing, since this stabilizes the polymer to depolymerization ("unzipping") during processing.
  • Comonomers such as butyl acrylate are often added to improve impact strength.
  • Comonomers such as methacrylic acid can be added to increase the glass transition temperature of the polymer for higher temperature use such as in lighting applications.
  • Plasticizers may be added to improve processing properties, lower the glass transition temperature, or improve impact properties.
  • Dyes may be added to give color for decorative applications, or to protect against (or filter) UV light.
  • Fillers may be added to improve cost-effectiveness.

Poly(methyl acrylate)

Main article: Poly(methyl acrylate)

The polymer of methyl acrylate, PMA or poly(methyl acrylate), is similar to poly(methyl methacrylate), except for the lack of methyl groups on the backbone carbon chain.[19] PMA is a soft white rubbery material that is softer than PMMA because its long polymer chains are thinner and smoother and can more easily slide past each other.

Uses

PMMA is a versatile material and has been used in a wide range of fields and applications.

Transparent glass substitute

Close-up of pressure sphere of Bathyscaphe Trieste, with single conical window of PMMA (Plexiglas) set into sphere hull. The very small black circle (smaller than the man's head) is the inner side of the plastic "window," and is only a few inches in diameter. The larger circular clear black area represents the larger outer-side of the thick one-piece plastic cone "window."
10 meter deep Monterey Bay Aquarium tank has acrylic windows up to 33 cm thick to withstand the water pressure
  • PMMA acrylic glass is commonly used for constructing residential and commercial aquariums. Designers started building big aquariums when poly(methyl methacrylate) could be used. It is less-used in other building types due to incidents such as the Summerland disaster.
  • Acrylic is used for viewing ports and even complete pressure hulls of submersibles, such as the Alicia submarine's viewing sphere and the window of the bathyscaphe Trieste.
  • PMMA is used in the lenses of exterior lights of automobiles.[20]
  • The spectator protection in ice hockey rinks is made from PMMA.
  • Historically, PMMA was an important improvement in the design of aircraft windows, making possible such iconic designs as the bombardier's transparent nose compartment in the Boeing B-17 Flying Fortress.
  • Police vehicles for riot control often have the regular glass replaced with acrylic to protect the occupants from thrown objects.
  • Acrylic is an important material in the making of certain lighthouse lenses.[21]
  • PMMA (under the brand name "Lucite") was used for the ceiling of the Houston Astrodome.

Daylight redirection

  • Laser cut acrylic panels have been used to redirect sunlight into a light pipe or tubular skylight and, from there, to spread it into a room.[22] Their developers Veronica Garcia Hansen, Ken Yeang, and Ian Edmonds were awarded the Far East Economic Review Innovation Award in bronze for this technology in 2003.[23][24]
  • Attenuation being quite strong for distances over one meter (more than 90% intensity loss for a 3000 K source[25]), acrylic broadband light guides are then dedicated mostly to decorative uses.
  • Pairs of acrylic sheets with a layer of microreplicated prisms between the sheets can have reflective and refractive properties that let them redirect part of incoming sunlight in dependence on its angle of incidence. Such panels act as miniature light shelves. Such panels have been commercialized for purposes of daylighting, to be used as a window or a canopy such that sunlight descending from the sky is directed to the ceiling or into the room rather than to the floor. This can lead to a higher illumination of the back part of a room, in particular when combined with a white ceiling, while having a slight impact on the view to the outside compared to normal glazing.[26][27]

Medical technologies and implants

  • PMMA has a good degree of compatibility with human tissue, and can be used for replacement intraocular lenses in the eye when the original lens has been removed in the treatment of cataracts. This compatibility was discovered in WWII RAF pilots, whose eyes had been riddled with PMMA splinters coming from the side windows of their Supermarine Spitfire fighters – the plastic scarcely caused any rejection, compared to glass splinters coming from aircraft such as the Hawker Hurricane.[28] Historically, hard contact lenses were frequently made of this material. Soft contact lenses are often made of a related polymer, where acrylate monomers containing one or more hydroxyl groups make them hydrophilic.
  • In orthopedic surgery, PMMA bone cement is used to affix implants and to remodel lost bone. It is supplied as a powder with liquid methyl methacrylate (MMA). When mixed these yield a dough-like cement that gradually hardens. Surgeons can judge the curing of the PMMA bone cement by pressing their thumb on it. Although PMMA is biologically compatible, MMA is considered to be an irritant and a possible carcinogen. PMMA has also been linked to cardiopulmonary events in the operating room due to hypotension.[29] Bone cement acts like a grout and not so much like a glue in arthroplasty. Although sticky, it does not bond to either the bone or the implant, it primarily fills the spaces between the prosthesis and the bone preventing motion. A disadvantage of this bone cement is that it heats up to 82.5 °C (160.5º F) while setting that may cause thermal necrosis of neighboring tissue. A careful balance of initiators and monomers is needed to reduce the rate of polymerization, and thus the heat generated. A major consideration when using PMMA cement is the effect of stress shielding. Since PMMA has a Young's modulus greater than that of natural bone, the stresses are loaded into the cement and so the bone no longer receives the mechanical signals to continue bone remodeling and so resorption will occur.[30]
  • Dentures are often made of PMMA, and can be color-matched to the patient's teeth & gum tissue. PMMA is also used in the production of ocular prostheses, such as the osteo-odonto-keratoprosthesis.
  • In cosmetic surgery, tiny PMMA microspheres suspended in some biological fluid are injected under the skin to reduce wrinkles or scars permanently.
  • A large majority of white Dental filling materials (i.e. composites) have PMMA as their main organic component.
  • Emerging biotechnology and Biomedical research uses PMMA to create microfluidic lab-on-a-chip devices, which require 100 micrometre-wide geometries for routing liquids. These small geometries are amenable to using PMMA in a biochip fabrication process and offers moderate biocompatibility.
  • Bioprocess chromatography columns use cast acrylic tubes as an alternative to glass and stainless steel. These are pressure rated and satisfy stringent requirements of materials for biocompatibility, toxicity and extractables.
Lexus Perspex car sculpture.

Artistic and aesthetic uses

Kawai acrylic grand piano.
Plexiglas art by Manfred Kielnhofer
  • Acrylic paint essentially consists of PMMA suspended in water; however since PMMA is hydrophobic, a substance with both hydrophobic and hydrophilic groups needs to be added to facilitate the suspension.
  • Modern furniture makers, especially in the 1960s and 1970s, seeking to give their products a space age aesthetic, incorporated Lucite and other PMMA products into their designs, especially office chairs. Many other products (for example, guitars) are sometimes made with acrylic glass to make the commonly opaque objects translucent.
  • Perspex has been used as a surface to paint on, for example by Salvador Dalí.
  • Diasec is a process which uses acrylic glass as a substitute for normal glass in picture framing. This is done for its relatively low cost, light weight, shatter-resistance, aesthetics and because it can be ordered in larger sizes than standard picture framing glass.
  • From approximately the 1960s onward, sculptors and glass artists such as Leroy Lamis began using acrylics, especially taking advantage of the material's flexibility, light weight, cost and its capacity to refract and filter light.
  • In the 1950s and 1960s, Lucite was an extremely popular material for jewelry, with several companies specialized in creating high-quality pieces from this material. Lucite beads and ornaments are still sold by jewelry suppliers.
  • Acrylic Sheets are produced in dozens of standard colors, most commonly sold using color numbers developed by Rohm & Haas in the 1950's.

Other uses

High heel shoes made of Lucite
An electric bass guitar with a perspex body
A fashion accessory using PMMA to conserve its content
  • Sheets of PMMA are commonly used in the sign industry to make flat cut out letters in thicknesses typically varying from 3 to 25 millimeters (0.1 to 1.0 in). These letters may be used alone to represent a company's name and/or logo, or they may be a component of channel letters which are neon or LED illuminated. Acrylic's attractiveness, durability and resistance to warping make it an ideal interior and exterior sign material. Acrylic is also used extensively throughout the sign industry as a component of wall signs where it may be a backplate, painted on the surface or the backside, a faceplate with additional raised lettering or even photographic images printed directly to it, or a spacer to separate sign components. One of the most popular sheets is a non-glare, translucent which is sold in 1.6 millimeters (0.06 in) or 3 millimeters (0.12 in) in thicknesses.
  • PMMA was used in LaserDisc optical media. (CDs and DVDs use both acrylic and polycarbonate for higher impact resistance.)
  • It is used as a light guide for the backlights in TFT-LCDs.
  • Plastic optical fiber used for short distance communication is made from PMMA, and perfluorinated PMMA, clad with fluorinated PMMA, in situations where its flexibility and cheaper installation costs outweigh its poor heat tolerance and higher attenuation over glass fiber.
  • PMMA, in a purified form, is used as the matrix in laser dye-doped solid-state gain media for solid state dye lasers.[31]
  • In semiconductor research and industry, PMMA aids as a resist in the electron beam lithography process. A solution consisting of the polymer in a solvent is used to spin coat silicon and other semiconducting and semi-insulating wafers with a thin film. Patterns on this can be made by an electron beam (using an electron microscope), deep UV light (shorter wavelength than the standard photolithography process), or X-rays. Exposure to these creates chain scission or (de-cross-linking) within the PMMA, allowing for the selective removal of exposed areas by a chemical developer, making it a positive photoresist. PMMA's advantage is that it allows for extremely high resolution (nanoscale) patterns to be made. It is an invaluable tool in nanotechnology. Smooth PMMA surface can be easily nanostructured by treatment in oxygen radio-frequency plasma[32] and nanostructured PMMA surface can be easily smoothed by vacuum ultraviolet (VUV) irradiation.[32]
  • PMMA is used as a shield to stop beta radiation emitted from radioisotopes.
  • Small strips of PMMA are used as dosimeter devices during the Gamma Irradiation process. The optical density of PMMA changes as the Gamma dose increases and can be measured with a spectrophotometer.
  • A blacklight-reactive tattoo ink using PMMA microcapsules has been developed. This ink is reportedly safe for use, and claims to be Food and Drug Administration (FDA) approved in 1995 for use on wildlife like fish, that may enter the food supply.[33]
  • PMMA can be used as a dispersant for ceramic powders to stabilize colloidal suspensions in non-aqueous mediums.
  • PMMA has also been used extensively as a hybrid rocket fuel.
  • In the 1960s, luthier Dan Armstrong developed a line of electric guitars and basses whose bodies were made completely of acrylic. These instruments were marketed under the Ampeg brand. Ibanez[34] and B.C. Rich have also made acrylic guitars.
  • Ludwig-Musser makes a line of acrylic drums called Vistalites, well known as being used by Led Zeppelin drummer John Bonham.
  • Artificial fingernails are sometimes made of acrylic.
  • Some modern briar, and occasionally meerschaum, tobacco pipes sport stems made of Lucite, although the vast majority of stems for such pipes are still made with the traditional vulcanized rubber.
  • PMMA technology is utilized in roofing and waterproofing applications. By incorporating a polyester fleece sandwiched between two layers of catalyst-activated PMMA resin, a fully reinforced liquid membrane is created in situ. Such a membrane construction is flexible while also being tear and puncture resistant.

See also

References

  1. ^ a b c Compare Materials: Acrylic and Soda-Lime Glass. Makeitfrom.com. Retrieved on 2012-05-09.
  2. ^ Smith & Hashemi 2006, p. 509.
  3. ^ a b Refractive index and related constants – Poly(methyl methacrylate) (PMMA, Acrylic glass). Refractiveindex.info. Retrieved on 2012-05-09.
  4. ^ Rohm and Haas Innovation – Plexiglas Triumphs. Rohmhaas.com. Retrieved on 2010-08-29.
  5. ^ "Acrylic Plastic: How Products are Made". 080515 enotes.com
  6. ^ PMMA (Altuglas International) and Methacrylics. Arkema.com (2010-05-20). Retrieved on 2010-08-29.
  7. ^ Lucite, Merriam Webster dictionary
  8. ^ "Plexiglas". Altuglas International.
  9. ^ "FAQ". Plaskolite. Retrieved 2011-01-23. Manufacturer of Optix
  10. ^ Perspex, Merriam Webster dictionary
  11. ^ "Altuglas International". Retrieved 2010-07-14. more than a quarter of the world's production of PMMA
  12. ^ Ashby 2005, p. 519.
  13. ^ a b DATA TABLE FOR: Polymers: Commodity Polymers: PMMA. Matbase.com. Retrieved on 2012-05-09.
  14. ^ "Preliminary studies on burning behavior of polymethylmethacrylate (PMMA)". 090521 CAT.INIST
  15. ^ Altuglas International Plexiglas UF-3 UF-4 and UF-5 sheets. Plexiglas.com. Retrieved on 2012-05-09.
  16. ^ Myer Ezrin Plastics failure guide: cause and prevention, Hanser Verlag, 1996 ISBN 1-56990-184-8, p. 168
  17. ^ Chiemi Ishiyama, Yoshito Yamamoto and Yakichi Higo (2005). "Effects of Humidity History on the Tensile Deformation Behaviour in Poly(methyl-methacrylate) (PMMA) Films". MRS Proceedings. 875: O12.7.
  18. ^ "Tangram Technology Ltd. – Polymer Data File – PMMA".
  19. ^ Polymethyl acrylate and polyethyl acrylate, Encyclopædia Britannica. Britannica.com. Retrieved on 2012-05-09.
  20. ^ Kutz, Myer (2002). Handbook of Materials Selection. John Wiley & Sons. p. 341. ISBN 0-471-35924-6.
  21. ^ Terry Pepper, Seeing the Light, Illumination. Terrypepper.com. Retrieved on 2012-05-09.
  22. ^ Ken Yeang:Light Pipes: An Innovative Design Device for Bringing Natural Daylight and Illumination into Buildings with Deep Floor Plan, Nomination for the Far East Economic Review Asian Innovation Awards 2003
  23. ^ Lighting up your workplace – Queensland student pipes light to your office cubicle, May 9, 2005
  24. ^ Kenneth Yeang, World Cities Summit 2008, June 23–25, 2008, Singapore
  25. ^ V Mossman M Whitehead L Gerchikov (2005). "Modeling attenuation versus length in practical light guide". LEUKOS. 1 (4): 47. doi:10.1582/LEUKOS.01.04.003.
  26. ^ How Serraglaze works. Bendinglight.co.uk. Retrieved on 2012-05-09.
  27. ^ Glaze of light, Building Design Online, June 8, 2007
  28. ^ Robert A. Meyers, "Molecular biology and biotechnology: a comprehensive desk reference", Wiley-VCH, 1995, p. 722 ISBN 1-56081-925-1
  29. ^ Kaufmann, TJ; Jensen, ME; Ford, G; Gill, LL; Marx, WF; Kallmes, DF (2002). "Cardiovascular Effects of Polymethylmethacrylate Use in Percutaneous Vertebroplasty". American Journal of Neuroradiology. 23 (4): 601–604. PMID 11950651.
  30. ^ Miller (1996). Review of Orthopedics (4 ed.). Philadelphia: W. B. Saunders. p. 129. ISBN 0-7216-5901-2.
  31. ^ F. J. Duarte (Ed.), Tunable Laser Applications (CRC, New York, 2009) Chapters 3 and 4.
  32. ^ a b R. V. Lapshin, A. P. Alekhin, A. G. Kirilenko, S. L. Odintsov, V. A. Krotkov (2010). "Vacuum ultraviolet smoothing of nanometer-scale asperities of poly(methyl methacrylate) surface" (PDF). Journal of Surface Investigation. X-ray, Synchrotron and Neutron Techniques. 4 (1). Russia: Pleiades Publishing: 1–11. doi:10.1134/S1027451010010015. ISSN 1027-4510.{{cite journal}}: CS1 maint: multiple names: authors list (link) (Russian translation).
  33. ^ – Blacklight Tattoo Ink – Blacklight Tattoo Ink FAQ. Crazychameleonbodyartsupply.com. Retrieved on 2012-05-09.
  34. ^ JS2K-PLT. Ibanezregister.com. Retrieved on 2012-05-09.

Bibliography

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