Poly_methyl methacrylate_ _PMMA_
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Poly(methyl methacrylate) (PMMA)
Poly(methyl methacrylate) (PMMA) was created in 1877 when the German chemists Fittig and
Paul discovered the polymerization process that turns methyl methacrylate into polymethyl
methacrylate. (Acrylic acid was first prepared in 1843. Methacrylic acid, which is a derivative of
acrylic acid, was formulated in 1865. When methacrylic acid is reacted with methyl alcohol, it
results in an ester known as methyl 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, and windshields, canopies, and gun turrets for airplanes
Structure
Methyl methacrylate is the basic molecule, or monomer, from which polymethyl methacrylate
and many other acrylic plastic polymers are formed. The chemical notation for this material is
CH2=C(CH3) COOCH3. It is written in this format, rather than the more common chemical
notation C5H8O2, to show the double bond (=) between the two carbon atoms in the middle.
During polymerization, one leg of this double bond breaks and links up with the middle carbon
atom of another methyl methacrylate molecule to start a chain. This process repeats itself until
the final polymer is formed.
Methyl methacrylate may be formed in several ways. One common way is to react acetone
[CH3COCH3] with sodium cyanide [NaCN] to produce acetone cyanhydrin [(CH3)2C(OH)CN]. This
in turn is reacted with methyl alcohol [CH3OH] to produce methyl methacrylate.
Other similar monomers such as methyl acrylate [CH2=CHCOOCH,] and acrylonitrile [CH2=CHCN]
can be joined with methyl methacrylate to form different acrylic plastics. When two or more
monomers are joined together, the result is known as a copolymer. Just as with methyl
methacrylate, both of these monomers have a double bond on the middle carbon atoms that
splits during polymerization to link with the carbon atoms of other molecules. Controlling the
proportion of these other monomers, produces changes in elasticity and other properties in the
resulting plastic.
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Typical properties of PMMA:
• Has a density of 1,150–1,190 kg/m3. This is less than half the density of glass, and similar
to that of other plastics.
• Has a good impact strength higher than that of glass or polystyrene, but significantly
lower than that of polycarbonate or engineering polymers. In the majority of
applications, it will not shatter but instead breaks into large dull pieces.
• Is softer and more easily scratched than glass. Scratch‐resistant coatings (which may
also have other functions) are often added to PMMA sheets.
• 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 of 1.4893 to 1.4899.
Skeletal structure of methyl methacrylate, the monomer that makes up PMMA
Structure of the PMMA polymer
• Filters ultraviolet (UV) light at wavelengths below about 300 nm. Some manufacturers
add coatings or additives to PMMA to improve absorption in the 300–400 nm range.
• Allows infrared light of up to 2800 nm wavelength to pass. IR of longer wavelengths, up
to 25,000 nm, are essentially blocked. Special formulations of colored PMMA exist to
allow specific IR wavelengths to pass while blocking visible light (for remote control or
heat sensor applications, for example).
• Has excellent environmental stability compared to other plastics such as polycarbonate,
and is therefore often the material of choice for outdoors applications.
• Has poor resistance to solvents, as it swells and dissolves easily. It also has poor
resistance to many other chemicals on account of its easily hydrolyzed ester groups.
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Processing
Thermoplastic PMMA is typically processed at 240–250 °C. 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.
PMMA can be joined using cyanoacrylate cement (so‐called "Superglue"), with heat (melting),
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 vaporises to
gaseous compounds (including its monomers) upon laser cutting, so a very clean cut is made,
and cutting is performed very easily. In this respect PMMA has an advantage over competing
polymers such as polystyrene and polycarbonate, which require higher laser powers and give
messier and charred laser cuts.
The storage, handling, and processing of the chemicals that make acrylic plastics are done
under controlled environmental conditions to prevent contamination of the material or unsafe
chemical reactions. The control of temperature is especially critical to the polymerization
process. Even the initial temperatures of the monomer and catalyst are controlled before they
are introduced into the mold. During the entire process, the temperature of the reacting
material is monitored and controlled to ensure the heating and cooling cycles are the proper
temperature and duration.
Samples of finished acrylic materials are also given periodic laboratory analysis to confirm
physical, optical, and chemical properties.
Applications
Impact resistant substitute for glass
• Shower doors, bath enclosures, windows and skylights.
• Residential and commercial aquariums.
• PMMA is used in the lenses of exterior lights of automobiles.
• Motorcycle helmet visors.
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• Police vehicles for riot control often have the regular glass replaced with acrylic to
protect the occupants from thrown objects.
• Acrylic is used for viewing ports and even complete hulls of submersibles, such as the
• Polycast acrylic sheet is the most widely used material in aircraft transparencies
(windows). In applications where the aircraft is pressurized, stretched acrylic is used.
• Acrylic is an important material in the making of certain lighthouse lenses.
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. 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 orthopaedics, PMMA bone cement is used to affix implants and to remodel lost bone.
Dentures are often made of PMMA, and can be colour‐matched to the patient's teeth &
gum tissue. In cosmetic surgery, tiny PMMA microspheres suspended in some biological
fluid are injected under the skin to reduce wrinkles or scars permanently.
Artistic and aesthetic uses
• 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 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 inexpensive cost, light weight, shatter‐resistant
nature, and aesthetic reasons and for the fact that it can be ordered in larger sizes than
standard picture‐framing glass.
Recycling
Acrylic plastic is not easily recycled. It is considered a group 7 plastic among recycled plastics
and is not collected for recycling in most communities. Large pieces can be reformed into other
useful objects if they have not suffered too much stress, crazing, or cracking, but this accounts
for only a very small portion of the acrylic plastic waste. In a landfill, acrylic plastics, like many
other plastics, are not readily biodegradable. Some acrylic plastics are highly flammable and
must be protected from sources of combustion.
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The Future
The average annual increase in the rate of consumption of acrylic plastics has been about 10%.
A future annual growth rate of about 5% is predicted. Despite the fact that acrylic plastics are
one of the oldest plastic materials in use today, they still hold the same advantages of optical
clarity and resistance to the outdoor environment that make them the material of choice for
many applications.
Advantages:
• Half as heavy as glass. This makes working with acrylic much easier. It can also be sawed,
whereas glass must be scored.
• The transparency rate of 93% makes acrylic the clearest material known. Very thick glass will
have a green tint, while acrylic remains clear.
• A unique property of plastic is its ability to be shaped. There are also no seams in acrylic
structures, as chemical welding at the molecular level actually "melts" seams into one piece of
solid material. Seams that are welded and polished are invisible.
• Scratches can be easily bugged out of the acrylic.
Disadvantages:
• It is more expensive than glass, and
• If exposed to a direct flame it will melt and eventually burn.
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