PMMA

• In the early 1930s a more rigid plastic,

polymethylacrylate , was discovered in England by
Rowland Hill and John Crawford at Imperial Chemical
Industries, which gave the material the trademarked
name Perspex.
• Rohm attempted to produce safety glass by polymerizing
methyl methacrylate between glass layers.
• The polymer separated from the glass as a clear plastic
sheet, which Rohm gave the name Plexiglas. Both
Perspex and Plexiglas were commercialized in the 1930s.
 PMMA
• Polymethyl methacrylate (PMMA)
• Methyl methacrylate is polymerized in bulk or
suspension methods using free-radical
initiators. As a polymer repeating unit, its
structure is:
 PMMA
• 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 transparent and rigid plastic.
• Because it retains these properties over years of
exposure to ultraviolet radiation and weather, PMMA
is an ideal substitute for glass.
•
POLY(METHYL METHACRYLATE)
Preparation of Monomer
The esterified stream, which may contain inhibitors to
prevent premature polymerisation, is then passed to a
stripping column which separates the methyl
methacrylate, methanol and some water from the
residue made up of sulphuric acid, ammonium bisulphate
and the remainder of the water.
The methyl methacrylate is subsequently separated and
purified by further distillation.
 PMMA
• 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 sold in the form
of sheets that are machined or thermoformed, but
it is also injection-molded into headlights and
taillights and lighting-fixture covers.
PMMA
 PMMA
• Poly (methyl acrylate) is an addition polymer.
The reaction can be represented as:
 PMMA
• Because the high rate and heat of polymerization of
acrylates make control of bulk polymerization impractical,
the most important method of preparation is by emulsion
polymerization.
• Water serves as a moderator and a solvent for the catalyst
system.
• The catalyst is produced by the reaction of bromate ions
and hydrogen sulfite ions and is known to produce hydroxyl
radicals (OH.) and hydrogen bisulfite radicals (HSO3.).
•
 PMMA
• Other water soluble catalysts such as ammonium
peroxydisulfate or potassium peroxydisulfate (often called
persulfate), may be used, but the mixture must be heated to
generate free radicals.
• In this demonstration, methyl acrylate in an aqueous
emulsion polymerizes in the presence of a free-radical
catalyst.
• The polymer is coagulated in a concentrated solution of
sodium chloride to yield a white product.
• An acetone solution can be used to produce a film.
• Time: 20 -25 minutes are required
 Bulk polymerisation
• Bulk polymerisation is extensively used in the manufacture of the
sheet ,rod and tube. In order to produce a marketable material it is
important to take the following factors into account:
(1) The exotherm developed during cure.
(2) The acceleration in conversion rate due to increasing viscosity.
( 3 ) The effect of oxygen.
(4) The extensive shrinkage in conversion from monomer to polymer (-
20%).
(5) The need to produce sheet of even thickness.
(6) The need to produce sheet of constant quality.
(7) The need to produce sheet free from impurities and imperfections.
 Bulk polymerisation
• In order to reduce the shrinkage in the casting cell,
and also to reduce problems of leakage from the cell,
it is normal practice to prepare a ‘prepolymer’.
• In a typical process monomer freed from inhibitor is
heated with agitation for about 8 minutes at 90°C
with 0.5% benzoyl peroxide and then cooled to room
temperature.
• Plasticiser, colouring agents and ultraviolet light
absorbers may be incorporated at this stage if
required.
 Bulk polymerisation
• The resulting syrup, consisting of a solution of
polymer in monomer, is then filtered and
stored in a refrigerator if it is not required for
immediate use.
• The heating involved in making the
prepolymer may also be of assistance in
removing oxygen dissolved in the monomer.
 Bulk polymerisation
• The preparation of a prepolymer requires careful
control and can be somewhat
• difficult in large-scale operations.
• An alternative approach is to prepare a syrup by
dissolving some polymer in the monomer and
adding some peroxide to the mixture.
• As in the case of a prepolymer syrup, such a
syrup will cause less shrinkage on
polymerisation and fewer leakage problems.
 Bulk polymerisation
• Acrylic sheet is prepared by pouring the syrup into a casting
cell.
• This consists of two plates of heat-resistant polished glass
provided with a separating gasket round the edges.
• The gasket commonly consists of a hollow flexible tube
made from a rubber, or from plasticised poly(viny1 alcohol).
• The cell is filled by opening up the gasket at a corner or edge
and metering in the syrup, care being taken to completely fill
the cell before closing up the gasket.
.
 Bulk polymerisation
• The cell is held together by spring-loaded
clamps or spring clips so the plates will come
closer together as the reacting mixture shrinks
during polymerisation.
• This technique will enable the sheet to be
free of sink marks and voids.
 Bulk polymerisation
• The filled cells are then led through a heating
tunnel.
• In a typical system the time to pass through
the tunnel is about 16 hours.
• For the first 14 hours the cell passes through
heating zones at about 40°C. Under these
conditions polymerisationoccurs slowly.
 Bulk polymerisation
• Any acceleration of the rate due to either the rise in
temperature through the exothermic reaction or due
to the viscosity-chain termination effect will be small.
• It is particularly important that the temperature of
any part of the syrup is not more than 100°C since
this would cause the monomer to boil.
• By the end of this period the bulk of the monomer
has reacted and the cell passes through the hotter
zones.
 Bulk polymerisation
• After 15 hours (total time) the cell is at about 97”C,
at which temperature it is held for a further half-
hour.
• The sheet is then cooled and removed from the cell.
• In order to reduce any internal stresses the sheet
may be annealed by heating to about 140°C and,
before being dispatched to the customer, the sheet
is masked with some protective paper using gelatine
or, preferably, with a pressure-sensitive adhesive.