CASTING ACRYLIC

PROCESS
Cast Acrylic Manufacturer
Firman M Mar 2016

Raw Material

Figure 1 shows the polymerization of methyl methocrylate into polymethyl

methacrylate (PMMA). Figure 2 shows other acrylic plastic monomers that may
be copolymerized with methyl methacrylate.

Casting Acrylic
Monomer: Methyl Methacrylate
Bulk polymerization
High transparency/optical
clarity
A wide range of color

Light transmission >

92%

Rigidity
Cast Acrylic

Moderate impact strength

Thermal and chemical
resistance
Excellent weatherability
Low Specific Gravity

(1.14) Lighter than glass

(2.5)

Shatter resistance

Casting process: the mold is removed from hardened cast resin

material

The ManufacturingProcess
Acrylic plastic polymers are formed by reacting a monomer, such as methyl
methacrylate, with a catalyst. A typical catalyst would be an organic peroxide.
The catalyst starts the reaction and enters into it to keep it going, but does
not
become
part
of the
resulting
Acrylic
plastic
sheets
are
formed polymer.
by a
Manufacturing
process known as bulk polymerization. In
Process of Cast
this process, the monomer and catalyst
Acrylic Sheet
are poured into a mold where the reaction
takes place.
Two methods of bulk polymerization may
Batch
Continue
be used: batch cell or continuous.
Cell
s
Batch cell is the most common because it
is simple and is easily adapted for making
acrylic sheets in thicknesses from 0.06 to
6.0 inches (0.16-15 cm) and widths from 3
feet (0.9 m) up to several hundred feet.
The batch cell method may also be used to
form rods and tubes.
The continuous method is quicker and
involves less labor. It is used to make
sheets of thinner thicknesses and smaller
widths than those produced by the batch
cell method.

Batch Cell Bulk

Polymerization

Batch cell bulk polymerization is the most common way to make acrylic plastic sheets because
it is simple and easily adapted for making sheets in thicknesses from 0.06 to 6 inches.

1. The mold for producing sheets is assembled from two

plates of polished glass separated by a flexible "windowframe" spacer. The spacer sits along the outer perimeter
of the surface of the glass plates and forms a sealed
cavity between the plates. The fact that the spacer is
flexible allows the mold cavity to shrink during the
polymerization process to compensate for the volume
contraction of the material as the reaction goes from
individual molecules to linked polymers. Several plates
may be stacked on top of each other with the upper
surface of one plate becoming the bottom surface of the
next higher mold cavity. The plates and spacers are
clamped together with spring clamps

2. An open comer of each mold cavity is filled with a pre-measured liquid syrup of methyl methacrylate monomer and catalyst. In some cases, a methyl
methacrylate prepolymer is also added. A prepolymer is a material with partially formed polymer chains used to further help the polymerization
process. The liquid syrup flows throughout the mold cavity to fill it.
3. The mold is then sealed and heat may be applied to help the catalyst start the reaction.
4. As the reaction proceeds, it may generate significant heat by itself. This heat is fanned off in air ovens or by placing the molds in a water bath. A
programmed temperature cycle is followed to ensure proper cure time without additional vaporization of the monomer solution. This also prevents
bubbles from forming. Thinner sheets may cure in 10 to 12 hours, but thicker sheets may require several days.
5. When the plastic is cured, the molds are cooled and opened. The glass or metal plates are cleaned and reassembled for the next batch.
6. The plastic sheets are either used as is or are annealed by heating them to 284-302F (140-150C) for several hours to reduce any residual
stresses in the material that might cause warping or other dimensional instabilities.

Cell Casting Process

The monomer based
polymerization was poured into a
mold or cell
Residual air removal within the
filled cell
Sealed cell
Polymerization of monomer mix in
the presence of heat
Casting acrylic

Cell: consisting of two flat sheets or glass

separated by an elastomeric material or
gasket around the periphery
Reduce surface tension by adding
surfactant or increase temp. apply vacuum,
careful filling
The presence of air and oxygen inhibit
polymerization reaction

The reaction generate heat, the

programmed temp cycle is required to
prevent excessive heat that will form
bubbles

Excellent optical and surface

quality

Cell Casting Process

Sheet or Cell
casting

Bulk
polymerization
processContinuou
s
Batch

Prepolymerizati
on

Syrup (monomer + polymer + initiator)

Polymerizati
on

The filled glass mould is heated to polymerize

Annealing

To achieve higher monomer conversion.

The moulding is heated at temperature greater than the
Tg of PMMA

Cell Casting Process

Prepolymerizati
on

MMA

AIBN (18
ppm)
Syrup (7
10%
monomer
conversion)
R
T

AIBN: 2,2-azobisisobutylonitrile
ADVN: 2,2-azobis-(2,4-dimethyl valeronitrile)

ADVN
(0.030
0.038%)

One-step
process

Filtered
Degassed

Two-step
process

Poured

Polymerizati
on
Careful monitoring of the sample temperature
is necessary to prevent the unreacted MMA to
boil (which is the main cause for the bubbling
defects observed in the finished product).

Annealing

Mould
Water bath
60 70 oC (x
hrs)
Hot air oven
105 125 oC (x
hrs)

X hours:
4 6 hrs

Calculate Monomer
Conversion

Gravimetric method was used to determine both dynamic

and ultimate percentage of monomer conversion for each
sample.
Specifically, 5 g of liquid sample or a 3 x 10 x 15 mm 3 solid
sample was first dissolved in 30 mL of acetone (99.5%
purity) at room temperature for at least 24 h.
A volume of 70 mL of methanol (99.8% purity) was then
added to precipitate out PMMA while leaving unreacted
MMA (including, perhaps, oligo-MMA) in the clear solution.
The precipitated PMMA was then put in a vacuum oven for 6
h to remove both acetone and methanol.
The percentage of monomer conversion of each sample can
then be calculated according to eqn (1) where W1 and W2
are, respectively, the dry weights of sample before and
after the precipitation procedure.

Mechanical Properties
Factor that affected the mechanical properties of polymer:
Molecular weight (higher MW, better mechanical properties)
Higher and longer annealing time and temperature, higher impact
strength. This is due to higher monomer conversion.
The annealing step in the two-step process was responsible for the
much higher ultimate percentage of monomer conversion achieved in
the finished products, which, in turn, was responsible for the much
better mechanical integrity that these products exhibited.

Reference

Parinya Wanwanichai, et. al. Sheet-cast Poly(methyl

methacrylate): One-step (Water) versus Two-step (WaterAir) Isothermal Processes, Iranian Polymer Journal, 2005

Continuous bulk polymerization

1. The continuous process is similar to the batch cell process, but
because the sheets are thinner and smaller, the process times
are much shorter. The syrup of monomer and catalyst is
introduced at one end of a set of horizontal stainless steel belts
running parallel, one above the other. The distance between
the belts determines the thickness of the sheet to be formed.
2. The belts hold the reacting monomer and catalyst syrup
between them and move it through a series of heating and
cooling zones according to a programmed temperature cycle to
cure the material.
3. Electric heaters or hot air may then anneal the material as it
comes out of the end of the belts.
4. The sheets are cut to size and masking paper or plastic film is
applied

Continues Casting process

Continues casting acrylic lightly cross linked to
improve post thermoforming characteristic
Limited color
Inferior to cell-cast sheet in optical and surface
quality because of inherent or induced defects
in the metal casting belts , and, to a lesser
degree, the use of partially polymerized, viscous
acrylic syrup formulation
Continues casting offers better thickness control
and post thermoformability than cell casting

Casting vs extruded
Casting offers high MW (> 1,000,000
vs < 200,000)
Superior internal optical and surface
quality
Improved physical properties
Superior outdoor serviceablity

Key Factor requiring close control in

Casting process
Casting formulation
Prevention of entrapped or internally
generated of air bubbles or voids
Supply and removal of heat (or light
energy)
Rate of polymerization/resin cure
Shrinkage
Adhesion of the resin to the mold
surface

Bulk polymerization of MMA

The bulk, solvent free, polymerization of MMA monomer is conducted
during casting by means of a peroxide-initiated free-radical process

Initiation

Thermal decomposition of peroxide catalyst

free
radical
The free
radical (peroxide) attack the double
bond of the vinyl monomer radical

Propagation

Termination

Radical attack another monomer, thus extending

the chain by one unit and regenerating a new
active end site
No monomer remain at casting cell, final
termination of polymer radical occurs
predominantly due to disproportionation

Initiation and propagation may be inhibited by dissolved oxygen, Thermal

polymerization at high temp can boiling away dissolved oxygen in the
monomer

Polymerization Reaction
At initial, polymerization rate increase linearly (polymer
concentration vs time), promoted by local exothermic heating,
increase viscous mass (gel) and reduce polymer chain termination
Autoacceleration or gel effect: decrease rate of polymer molecul
diffusion thru the viscous polymer-monomer medium. The ability of
two long chain polymer radicals to come together/termination
become difficult
Small monomer molecule still can diffuse to the medium
continue chain growth increase polymerization rate increase
average MW
Polymerization rate falls off rapidly as the monomer concentration
diminishes
At initial process monomer act as the medium
At the end of the polymerization polymer as the medium in which
the reaction is completed

Increase polymerization rate

Incorporating fillers that act as a
heat sink or prepolymers (powder or
syrups) into the monomer
Applying pressure effectively
increase Bp of the monomer
Without a catalyst, thermal initiation
is slow

Control MW of polymer
Adjust
the concentration and activity of the
catalyst/initiator
the concentration of monomer and
prepolymer
The concentration and activity of
chain transfer agent (what is CTA???)
The temperature and pressure of
reaction

PMMA stereoregularity
PMMA produced by free-radical
initiated casting process, is 70 75%
syndiotactic in nature1, some
literature said completely atactic
The lack of complete
stereoregularity

Bulky side group

Amorphous
Polymer

Photoinitiated
polymerization
Radical generation can be controlled by the light intensity, applied
for thin casting
Light of short wavelength (320 700 nm) intiates polymerization
directly
Photochemical initiator: AIBN (azobis isobutyronitrile), benzoin, or
vicinal polyketaldonyl compounds decompose into free radical
upon exposure to UV
This initiator must be used at low temp (25 45 oC) to avoid
thermal decomposition
Radiation and concentration in the monomer control the MW of
polymer
Oxygen impedes polymerization, supply nitrogen to support
reactivity (noninhibitory)
Source of radiation: sunlight, mercury vapor lamp, fluorescent lamp
with special phosphors.

Casting equipment and

procedure
Transparent acrylic sheet is normally cast
between individual plates of glass or hghly
polished metal
Filled or opaque acrylic may be manufactured
in plaster, reinforced plastic, metal, wood, or
concrete molds that provide adequate heat
transfer and surface release characteristics.
Cell casting: Utilize two flat glass plates
(tempered glass) separated by an
elastomeric gasket.

Manufacture of Acrylic
Syrup
Polymerization rates are increased and shrinkage is
reduced by addition of fine PMMA powder or a
prepolymerized acrylic syrup
The syrup affords a cleaner operation and better optical
quality
The syrup prepared by prepolymerization of monomer in a
jacketted SS vessel equipped with heavy duty agitation.
Both heating and cooling are circulated through the jacket
Low conc of of peroxide catalyst are added and conversion
is limited to 15 40 %. Batch or continuos process
Syrup is not suitable for thin cells (time consuming,
entrapped bubbles, fill patterns)

Casting Formulation
Additives
Must be dry
Free of retained air
Stable to the
casting temp and
pressure
Not inhibit
polymerization
Permit resin
shrinkage

Catalyst
Catalyst mixture are preferred
Amine promoters, such as morpholine are
recommended
Combination of methyl chlorosulfite, magnesium
oxide, and hydroperoxides can be utilized
The half-life temp decompostion characteristics
of catalyst must be compatible with the
temperature-time cycle of conditions employed
The catalyst concentration is chosen to impart
rapid but controllable polymerization rates,
generally maintaining exotherms within 5 oC of
the casting environment
Excessive amount of catalyst can result in
bubbles, voids, or prerelease from the mold
Catalyst concentation is usually 0.005 1% (50
10,000 ppm) based on Monomer weight , but
lower with increasing sheet thickness

Casting Formulation
MW is controlled by chain transfer agents, such as sulfur compounds,
chlorinated aliphatic compounds, certain solvents, and water, at
concentration of 0.001 0.2 % (10 2000 ppm)
Cross linking is achieved by multifunctional monomers such as di- and
tri-acrylates and methacrylates, hydroxyglycol methacrylates, and
methacrylamide. Addition of cross-linking agents increase Tg and improve
craze resistance. Methacrylic acid and a diepoxide raise heat-distortion
temperature
Thermal stabilizers include alkyl sulfides, alkyl and dialkyl
thiopropionates, thiocarboxylic acids, and metallic (cobalt, lead, nickel,
zinc) napthenates
Plasticizers, such as diethyl and dibutyl phthalate, tricresyl phosphate,
diethyl succinate, dibutyl tartrate, and castor oil, have limited
compatibility with MMA monomer
The ductility and impact resistance of acrylic sheet is improved by
natural rubber, butadiene and butadiene-styrene rubber, polyurethane,
ethylene-vinyl acetate, and other ethylene copolymers

Casting formulation
Mold release agents include silanes, siloxane, stearic acid,
fatty alcohol, phosphates, gelatin, and water. Quaternary
ammonium phosphates and sulfates are efficient release
agents and impart antistatic properties
Fillers, such as antimony oxide, contribute to flame inhibition.
Phosphites, phosphoric acid, phosphates, and other
phosphorus compounds are effective flame retardants.
Methacrylic acid and water reduce the burning rate.
Flame retardant affect weathering qualities adversely
Translucent color using polystyrene beads and colloidal silica.
Abrasion resistant coating are applied to the sheet after
polymerization and removal from the mold. Some applied to
the mold first and transferred to the castind during
polymerization

Prevention of air bubbles

and voids
Air bubbles entrapment during casting process depend on the viscosity and
surface tension of the monomer formulation, solubility of air in the monomer
mix, design of the mold, and the filling operation. Air and oxygen inhibit
polymerization and must be avoided
High speed mixing and vortexing should be avoided during preparation of the
casting formulation. Vacuum before filling may be applied to remove
entrained air
Careful pouring or pumping of the liquid mixture into the mold minimizes the
formation of air bubbles.
Heating the monomer mix to reduce viscosity
Adding surfactant to reduce surface tension
Applying mechanical vibration
Subjecting the casting to high pressure
Autoclaves: Bp of monomer is raised thus permitting the use of higher temp
with minimum bubbling and shorter cure time. By employing pressure of 345
1200 Kpa (50 175 psi), methyl methacrylate castings can be polymerized
at 150 oC without bubbles

Polymerization control
In the casting of thin sheet with a high ratio of surface area
to total volume, the temperature can be easily controlled.
Heat generated during polymerization of MMA monomer
systems can be dissipated rapidly by external cooling
For every temp rise 10 oC, the polymerization rate of resin
nearly doubles.
Control by: selection of catalyst, prepolymer dissolved in the
monomer, fillers to serve as heat sink, optimum timetemperature process cycle, and selection of mold materials.
Casting resin shrink upon solidification. Shrinkage 21%
(density change 0.94 1.19).
To reduce shrinkage (internal stresses) : incorporate
prepolymer, nonvolatile diluents, fillers, slow cooling

Polymerization rate and sheet

thickness
Acrylic sheet thickness, cm

Polymerization time at 60 oC
(h)

0.31 0.63

8 12

0.94 1.25

14 20

1.56 2.5

24 60

2.81 5.0

66 144

5.3 7.5

168 500

Formulation contain mixed peroxide initiators at decreasing

concentration with increasing sheet thickness.

Literature
1. Processing and finishing of
polymeric materials, book
2. http://www.madehow.com/Volume2/Acrylic-Plastic.html