Preparation of PC

Poly (bisphenol – A-carbonate) or PC, is a condensation

product of bisphenol A, a carbonate precursor such as phosgene or
diphenyl carbonate and a monophenol chain terminator such as
phenol [11] or 6-butyl phenol.

The structure of PC is given below :

 Manufacturing of PC

Poly carbonates are commercially produced by either

interfacial polymerization or melt polymerization. The solution
process, which was once a major commercial process is no longer
used in industry because of its inferior economics.

•Interfacial polymirization techniques.

•Melt polymerization techniques.
 Interfacial Polymerization

The interfacial polymerization of polycarbonates involves

a reaction of BPA (Bisphenol A) with phosgene at the interface
between an inert organic methylene chloride solution and an
aqueous caustic solution. The reaction takes place in two steps.
First, phosgene reacts with BPA to form monochloroformates.
Then the poly condensation takes place between BPA hydroxyl
groups and chloroformates in the presence of triethylamine as a
catalyst, yielding the polymer that remains dissolved in the
organic phase.
 Interfacial Polymerization

During the polymerization, the by-product

(hydrochloric acid) reacts with aqueous caustic phase to
form sodium chloride. After the polymerization, the organic
polymer solution is separated from the aqueous phase and
purified. The polymer is recovered from the purified polymer
solution by precipitation or evaporation. The solid polymer is
crushed and extruded into pellets.
 Interfacial Polymerization

The interfacial polymerization can be conducted by

batch or continuous reactors.

Fig. 21. Batch Poly Carbonate polymerization process

 Interfacial Polymerization

Gaseous or liquid phosgene is pumped into a well – stirred

reactor containing BPA in an organic aqueous dispersion. Aqueous
sodium hydroxide is added during reaction to maintain an alkaline PH.

A molecular weight regulator, most often para-tert –butyl

phenol or phenol is added to the reactor to inactivate some of the end
groups in the oligomer carbonates. At the end of polymerization, the
polymer containing organic phase is separated and washed to remove
the catalyst and impurities such as sodium chloride.
 Interfacial Polymerization
The washed solution is then concentrated by flashing and is passed through a
devolatilizing extruder to produce a molten ribbon, which is then cooled and chopped
into pellets. In the continuous process, multiple tubular reactors in series or a cascade of
stirred tank reactor is used.

In this process, oligomeric chloroformates are produced by the phosgenation of

BPA prior to polycondensation in the presence of a catalyst. Polymerization condition
for batch continuous processes are summarized as follows.

Process Phosgenation Poly Condensation

Temperature Time Temperature Time

(°C) (min) (°C) (min)

Batch Process 25-30 20-30 25-30 15-45

Continuous Process 34 12 34-36 24

Continuous Process (alternative) 71-75 1-3 74-85 4-21

 Melt Polymerization Processes

The melt polymerization process or the transesterification

process is another important commercial method for manufacturing
polycarbonate. There are several ways to carry out melt polymerization.

Conventionally, the polymer is produced by, transterifying

diphenyl carbonate with BPA in the presence of a catalyst such as a
sodium salt of BPA. Monophenyl carbonate of BPA is formed first. It
reacts further to produce oligomers having phenoxy and hydroxy end
groups. The oligomers are then poly condensed to give poly carbonate.
During the polymerization, the reaction temperature is kept above the
melting point of the reaction mass, initially about 150°C.
 Melt Polymerization Processes

It is increased in steps to a final temperature of 30°C.

Meanwhile, the pressure is reduced also in steps from an initial 760 torr
to less than 1 torr at the final stage of the polymerization. During the
high temperature low pressure polymerization, the viscosity of
polycarbonates increases dramaticallyand specially designed extruder
type reactors are required to finish the poly condensation. Fig 5 is a
schematic process flow diagram of a continuous melt polycarbonate
polymerization process.
 Melt Polymerization Processes

Fig. 22. Continuos melt polymerization process of poly carbonate

 Melt Polymerization Processes

An alternative process is to first prepare an oligomer,

with an average molecular weight less than 3000, from BPA and
phosgene by an interfacial process. The oligomer is then
transesterified with additional BPA to form the desired
polycarbonate. Another process is to prepare a prepolymer from
BPA and phosgene, also by an interfacial polymerization. The
prepolymer with a molecular weight greater than 10,000 is
polymerized by a melt polymerization to the finished polymer.
 Properties of PC

The poly carbonate has the following features

•Rigidity upto 140°C

•Toughness upto 140°C
•Transparency
•Very good electrical insulation characteristics
•Virtually self-extinguishing
•Physiological inertness.
 Properties of PC

The disadvantages of the material are

.Expensive than other thermoplastics

.Special care required in processing
.Pale yellow colour (now commonly masked with dyes)
.Limited resistance to chemicals and ultraviolet light.
 Properties of PC

The properties of PC is most interesting, particularly the value

given for impact strength. The resistance of PC resins to creep or
deformation under load is markedly superior to that of acetal and
polyamide thermoplastics. Although it has very good impact and
creep resistance the resin shows cracking or crazing under more
than 0.75% tensile strain.
 Properties of PC

Properties Units Values

Specific gravity ---- 1.2
Tensile strength MPa 62
Tensile modulus MPa 2379
Flexural modulus Mpa 2344
Elongation at break % 10
Impact strength izod, Notched, J/m 123
Hardness M70
Deflection temperature under load C
0
132
(1.82 Mpa)
Coefficient of linear expansion mm/mm/0C 122 x 10-5
Water absorption, 24hrs % 0.15
Refractive index 1.58 - 1.59
Dielectric strength KV/mm 15
Dielectric constant 10-6 Hz 2.97
Power factor 0.0021
Melting point 0
C 220 – 230
Glass transition temperature °C 145
Mould shrinkage % 0.4 – 0.7
 Properties of PC

The electrical insulation characteristics of bis-phenol A

polycarbonates are in line with those or a lightly polar polymer.

Because of a small dipole polarization effect the

dielectric constant is somewhat higher than that for PTFE and the
polyolefins but lower than those of polar polymer such as the
phenolic resins. The dielectric constant is almost unaffected by
temperature over the normal range of operation and little affected
by frequency change upto 106 Hz.
 Properties of PC

Above this frequency, however, the dielectric constant

starts to fall as is common with polar materials. The chemical
resistance of this material is well recognized to be limited because
of the comparative ease of hydrolysis of ester groups.

PC has a nominal refractive index of 1.538 compared to

glass with 1.52. the refractive index varies with the wave length
of the incoming light beam. At a wave length of greater than 600
nm, the refractive index is in the range of 1.58 and increases to
1.61 at wave length 400 nm.
 Properties of PC

The optical property coupled with its toughness

makes it a unique engineering thermoplastics for use in
precision optic applications PC has high heat
tolerance. Its Tg is in the range of 140-155°C. The
characteristics of PC is given below
 Characteristics of PC

•Good stain resistance

•Easy colourability
•Good bio-compatibility
•Chemically resistant to organic and inorganic liquids
•Non-toxic
•Good insulator
•Dielectric constant is independent of temperature
•High corrosion resistant
•High creep resistance over board temperature range
•Excellent toughness
•Dimensionally stable
•Very good impact resistance at small thickness
•Good property retention upto-20°C
•High clarity
•Low haze
•Transmission rate is between 86 to 89%
•High heat deflection temperature
•Flame resistance
•Self extinguishing in nature
•Limited scratch resistance
•Notch sensitive
•Hygroscopic in nature
•Turns yellow when exposed to UV light for a long period of time
•Crazing occurs when exposed to water at elevated temperature
 Processing of PC

Satisfactory production of poly carbonate parts may be

achieved only if consideration is given to certain characteristics of
the polymer. In the first place, although the moisture pick-up of the
resin is small it is sufficient to cause problems in processing. In the
extruder or injection moulding machine it will volatilise into steam
frothy products will emerge from die and nozzle. It is therefore
necessary to keep all materials scrupulously day. The use of heated
hopper is advocated. Drying in hopper dryer or in trays in an over
for four hours at 136°C will reduce the moisture level in the PC
below 0.02%
 Processing of PC

The melt viscosity of the resin is very high and the

processing equipment should be rugged. The use of in-line screw
plasticisers is to be particularly recommended. The effect of
increasing temperature on viscosity is less marked with PC than
with other polymers.

The apparent melt viscosity is also less dependent on the

rate of shear than usual with thermoplastics. Because of high melt
viscosities flow path ratio are in the range of 30:1 to 70:1 which is
substantially less than for many more general purpose
thermoplastics.
 Processing of PC

Processing temperature are high and fall between the

melting point (-230°C) and 300°C at which thermal degradation
occurs quite rapidly.

Polycarbonate adhere strongly to metal and if allowed to

cool in an injection cylinder or extrusion barrel may on shrinkage,
pull pieces of metal from the wall. It is therefore necessary to purge
all equipment free of the resin with a polymer such as PE, after
processing.

There is no crystallization on cooling and after

crystallization has not been observed. Mold shrinkage is
consequently of the order of 0.006-0.008 cm/cm and is the same
both along and across the flow. PC is available in the following
grades.
 Processing of PC

PC is available in the following grades.

•Unmodified grades
•Moulding grades
•Extrusion grades
•Transparent grades
•Tinted grades
•Flame retardant grades
•Blow moulding grade
 Processing of PC

PC can be processed by following techniques:

•Injection Moulding
•Extrusion
•Blow molding
•Rotational molding
•Foam molding
 Processing of PC

Casting process is also used for making films.

Like metals, polycarbonate can be cold formed by
punching and cold rolling.
 Serviceability

PC is normally fabricated at high melt

temperature (300° and above) where yellowing and
molecular weight degradation can occur in the presence
of impurities like water, oxygen iron and residual base.
Suitable thermal oxidative stabilizes are used for its
stability during processing and use.
 Serviceability

Heat aging effects are somewhat complex. Heating at 125°C

will cause reduction in elongation and impact strength and slight
increase in tensile strength in less than four days. Further aging does
not show any effect on properties but cause darkening effect. Under
prolonged exposure to UV-light, PC tends to yellow and degrade due
to photo oxidation reaction. For out door applications. PC is normally
protected by a adding UV stabilizers.

Unmodified PCs are usually rated as slow burning, with an

oxygen index of 26 and a UL-94V2 rating. Flame retarding grades
are available with an oxygen index as high as 35 and with a UL-94V-
0 rating. Some of those grades also have limited smoke and toxic gas
emission on burning.
 Applications of PC in appliances

Coffee filters, shaver housings, chocolate moulds, blenders,

tablewares, kitchen mixer bowls, grinder bowls, housing for ball point
and fountain pens, rim heater grills, motor bracket and housing,
camera, binocular casings, housings for hair dryers and coffee makers,
water tank for steam iron, films for labels and memory switches, fruits
juicer parts, high impact vacuum sweeper housing, mixers and power
tools, bobbins for textile industries, baby feeding bottles and cutlery

Fig. 23. Hair dryer housing

 Applications of PC in Automotive

Wind screen wiper brackets, car interior moulded trims, instruments

glazing, indicator lamps, wind shields for two wheelers, door handles, tail
and side marker lights, PC blends in instruments, panels as well as
bumpers, wheel cover and body panels protective hoods, fan wheels,
components for sewing machines, chaises, levers, valves, control cams,
directional signs, heating grill, ventilators and radiator grills, overrides,
fuse box & covers and housing for automobile & aerial motors.

Fig. 24. Cover for Tail lamps

 Applications of PC in Electrical &
Electronics
Wiring devices, insulators panels, plugs and socket terminal blocks,
coil formers, Slater enclosures, housing and cover for distributor
boxes. Panel light covers, battery boxes fuses, electric meter covers,
connectors, breaker boxes, gears, printers housings, slide window,,
telephone housing for mining operations, telephone dails, coil formers
and housings, winding supports, switch plates, fuse boxes, housing for
computers, calculation machine and magnetic disk packs.

Fig. 25. Power distributor box

 Applications of PC in Food Control articles

Mineral water bottles, microwave oven wares, beermugs

table wares and food storage containers.

Fig. 26. Water Bottle

 Applications of PC in Medical

Blood bottles, dispensers for inhalers, sterilisable lab-wares, tissue

culture dishes, posts for IV fluids, sterilizable container and
packaging materials, surgical lighting, disposable, diagnostic cardio-
vascular and intravenous devices, drug delivery systems and housings
for blood cleaning filters.

Fig. 27. Medical Equipment's

 Applications of PC in Optical
Diffusers, lenses for lighting, vacuum metallised reflectors, housing for
steel lamps and traffic signals, lamp holders, bulk heads, light fixture,
lenses and safety glasses, window panels ( for out door lighting)
sunglasses, ski goggles and face protective wires, audio compact discs,
film and slide cassettes

Fig. 28. Compact Disc

 Applications of PC in Miscellaneous

Sporting goods, stencils, ink ducts, slide rules

components and rulers