Polyesters

Polyesters are among the more versatile synthetic polymers.

The common methods of synthesing simple esters are used
to make polyesters.
These include direct esterification (1), transesterification (2)
and the reaction of alcohols (3) with acyl chlorides or
anhydrides (4).
Commercially important Polyesters

Poly(ethylene terephthalate)
(PET)

Poly(trimethylene terephthalate)

Poly (ethylene napthalate-2,6-

dicarboxylate) (PEN)
Commercially important Polyesters

Poly (butylene terephthalate)

(PBT)

Poly (4-hydroxybenzonate)

Polycarbonate
 Historical Development

 Linear polyesters were studied by Carothers during his classical

researches for development of Polyamides.
 But it was Whinfield and Dicson who developed PET at Calico Printers
Association, England in 1941 (As Fibres, Terylene and Dacron and as
Film, Melinex and Mylar, with the expiry of the basic ICI patents on PET
there was considerable development in terephthalate polymers in the
early 1970’s.
 More than a dozen companies introduced PBT as an Engineering
Plastics during this time.
 The fiber in the name of Kodel and Film in the name of Kodar was
developed by Kodak.
.
 Polyethylene Terephthalate (PET)

 PET was also the basis of glass filled engineering polymer

(Rynite) introduced by DuPont in 1970’s. Towards the end of
1970’s PET was used for the manufacture of biaxial oriented
bottles.
 Monomer Ingredients for PET

 The ingredients which are used for PET are ethylene glycol
and dimethyl teraphthalate.

HO – CH2 – CH2 – OH Ethylene glycol

Dimetyl terephthalate
 Chemistry of Preparation of PET

The PET polymers is produced by the reaction of ethylene glycol and

Terephthalic acid or Dimethyl terephthalate in the presence of metal acetate
catalyst. This process is called ester exchange process.

In this process, a low molecular weight diester, known as the monomer is

first produced by reacting 1 mol. or dimethyle terephthalate with about 2.1 –
2.2 mol ethylene glycol at 150°C in the presence of catalysts, such as
antimony trioxide and cobaltous acetate.
 Manufacturing of PET
PET Polymers are manufactured by a stage-wise melt polymerization
process consists of transesterification, pre-polymerization and finishing
polymerization steps.

(Bis hydroxyethylene terephthalate, BHET), purified isophthalic

acid (PIA) , purified terephthalic acid (PTA)
 Manufacturing of PET
In the transesterification stage dimethyl temphthalate (DMT) or
terephthalic acid (TPA) is converted into bishydroxy ethyl terephthalate
in the presence of metal acetate catalyst.
Ethylene glycol (EG) DMT, and catalyst are fed at a molar ratio of 1.7 to
2.0:1 (with TPA this ratio is 1-3 to 1.5:1) and a temperature of 100-
180°C. This stage takes 3-4 hr.
The reaction byproduct methanol (Water When TPA) is used is
separated from EG vapors in a reflux column.

After adding stabilizer and additives, the prepolymer is forced through

a superfine fitter to the second (pre-poly condensation) stage.

The poly condensation reaction is performed under vacuum (15-25 torr)

and elevated temperature (280 – 300°C).
 Manufacturing of PET

The finishing polymerization stage, which is operated at 0.5 – 1 torr,

requires special wiped film or extruder type reactor in order to handle the
high viscosity of the polymer ((DP = 100), few thousand poise).

Many manufacturer have devised their own proprietary agitation systems to

minimize the build-up of the solidifying polymer layers.

The EG vapours contaminated with oligomers are drawn off through a

special condensing system and sent to a recovery unit.

The polymers melt can be sent to a direct spinning plant or transformed into
pellets.
 Relations of Structure and Properties of
Polyesters

 There are various classes of linear polyesters.

 The concentration of ester groups has predominant effect on the
properties of linear polyesters.
 For the aromatic classes of linear polyester, decreasing the
concentration of ester groups apparently leads to a reduction in melting
point.
It is found from aliphatic polyester that the ester group concentration has
little effect on the melting point.
 In fact a decrease in ester group concentration leads to a slight
increase in the melting point.
 Relations of Structure and Properties of
Polyesters

 It is found that in an ester group the in chain ether link –C-O-C-

increase the chain flexibility compared with a polyethylene chain to
decrease the heat of fusion.
 At the same time there will be some increase in inter chain attraction
via the carbonyl group which will decrease the entropy of fusion.
 Since these two effects almost cancel each other out there is almost
no change in ester group concentration.
 With all linear series of polyester as the no. of methylene groups in the
repeating unit increases so the polymer becomes more like a linear
polyethylene.
 Relations of Structure and Properties of
Polyesters

 It is also observed that Tm (melting point) of a polymer with an odd no.

of methylene groups in the aliphatic portion of the repeat unit is lower than
for the polymer with one more but an even no. of methylene groups.
The materials have a disadvantage of sensitivity to water and alkaline
solution.
 These materials are crystalline.
 Characteristics of PET (For
Identification)

The PET is a semicrystalline material, normally amorphous with low

crystallinity and high transparency.

 It is identified by sweet smell, when burns, orange flame, soot

 forming and melt drips.

 It is scratch resistant

 Melting point is 220°C

 It is having short and long term thermal limit temperature respectively

135°C and 100°C

 Characteristics of PET

 Outstanding chemical resistance to organic and inorganic liquids

 Water repellent
 Sterilizable by ethylene oxide and X-rays
 Inherent good electrical property
 Ability to orient
 Good tensile strength
 Superior strength and stiffness
 Excellent dimensional stability
 Excellent melt strength with slower crystallization rate
 Good impact strength even at low temperature
 High tear strength
 Heat resistant
 Flame retardant
 Outstanding clarity
 High gloss
 Properties of PET
Properties Units Values
Specific gravity ---- 1.30-1.40
Tensile strength MPa 51
Tensile modulus MPa 175
Flexural modulus Mpa 204
Elongation at break % 7

Impact strength izod, Notched, kg.cm/cm 9.25

Hardness R 105
Deflection temperature under load 0C 205-210
(1.82 Mpa)
Vicat softening point °C 75
Coefficient of linear expansion mm/mm/ 0C 6.0 x
10-5
Water absorption, 24hrs % < 0.1
Refractive index 1.62
Dielectric strength KV/mm 26
Dielectric constant 10-6 Hz 3.3
Melting point 0C 265
Glass transition temperature °C 67-80
 Grades of PET

The PET is available in the following grades.

Injection moulding grade

Extrusion grade

Stretch blow moulding grade

 Processing considerations of PET

PET can be processed by the following techniques :

 Injection moulding

 Stretch blow moulding

 Thermoforming

 Extrusion
 Processing considerations of PET

PET resins are primarily for injection moulding.

PET is hygroscopic and in its melt state the resin hydrolyzes.

PET resin supplied in moisture porof containers can have a moisture content
upto 0.04%, but hydrolysis can occur at a moisture level above 0.02%.

Therefore, even virgin PET directly from suppliers containers, as well as

regrind, should be dried to level of less than 0.02% and maintained at that
level.

Dehumidifier hopper is recommended with injection moulded PET.

Drying time values from 4 hrs. for wet resin to 2 hrs. for virgin resin at 135°C.
 Processing considerations of PET

 The moulding must be carried out with dried material and

because of the free flowing nature of the melt, restricted nozzles
should be used and a back flow valve fitted to screw injection
moulding machine.

 Cylinder temperature are about 260 – 290°C.and mould

temperature as high as 140°C to promote a controlled crystallization.

 A significant degree of crystallinity occurs in the mould.

Therefore, mould temperature should be selected carefully in order to
enhance crystalline formation.

 Mould temperature also influence cycle time and products

quality, particularly warpage shrinkage, surface gloss depth or colour
and chemical resistance.
 Processing considerations of PET

 Although resin grades from the same supplier show the same
melt temperature, PET from different suppliers shows different melt
temperature ranging from 260 – 290°C .The recommended typical
injection moulding cylinder temperature also differ between suppliers.

 An interesting feature of PET is that according to the

moulding conditions two quite dissimilar products one amorphous,
the other transparent, may be obtained, this beings a consequence of
having a Tg of about 80°C.

 Because of the low melt viscosity injection moulding screw

for PET should be fitted with back flow valves and the barrel nozzles
should have shut-off-valves.
 Surface Finishing of PET

 The high chemical resistance of the polyalkylene terephthalates

necessitates the use of special purpose lacquers to ensure good
adhesion.
 The same applies to hot embossing (temperature range of the die
140 - 200°C).
 PET can be polished easily. Metallization can be only be carried
out by high vacuum deposition.
 Where high gloss surfaces are required on filled and reinforced
product, an intermediate lacquer must be used.
 Applications of PET
 Appliances

 Automotive

 Electrical/Electronics

 Films

 Furniture

 Packaging

 Miscellaneous
 Applications of PET

Appliances :
Oven and appliance handles, coil forms for
microwave oven transformers, small appliance
structural framers, panels, chassis and housing and
instrument covers.
 Applications of PET

Automotive:
Structural parts such as luggage racks and grills,
fuctional housing such as windshield, wiper motor
housing , fuel filters, blade supports and bells, sensor,
lamp sockets, relays, switches.

Grill opening retainer Door module

 Applications of PET

Electrical/Electronics:
Lamps sockets , coil forms for audio/video
transformers, terminal blocks, electrical. Electronic
connectors.

Electricals Connectors
 Applications of PET

Films:
X-ray films, photographic films, magnetic
tapes and printing sheets.

Food packaging
 Applications of PET

Furniture:

Pedestal bases, chair arms and castes.

 Applications of PET

Packaging :
Carbonated soft drink containers, distilled
spirits, toiletries, food products, mustard, pickle foods,
peanut butter, spices, edible oil cocktail mixer and
syrups.

Containers
 Applications of PET

Miscellaneous:
General purpose pumps housing , mirror
housings three dimensional circuit boards and
structural components in office automation equipment,
computer housing and structural components,
containers, trays, blisters and drinking cups.
 Applications of PET

Automobile engine cover Heat shield

Gear box Door washers

 Blends of PET

PET/PC

 Partially miscible blends (miscibility is controlled by the

level of transesterification) with co-continuous morphology
show improved processability, chemical resistance,
crystallinity, elongation, low temperature impact and tensile
strength.

 Blends also show decreased shrinkage and high heat

deflection temperature.

 These blends are especially interesting for reinforced

products because the warpage is significantly decreased.
 Blends of PET

PET/Elastomers

 These blends are formulated for extrusion, injection,

compression, blow and transfer molding.
 The blends contain up to 35 wt. of glass fiber.
 They show good processability rigidity impact and tensile
strength as well as excellent weatherability.
List of Manufacturers/Suppliers of PET
Polybutylene Terephthalate (PBT)

CORPORATE TRAINING AND PLANNING

 Monomer Ingredients for PBT

The ingredients which are used for preparing PBT are 1,4
butanediol and dimethyl terephthelate.

HO – CH2 – CH2- CH2- CH2 – OH

1,4 - butanediol

Dimethyl terephthelate
 Chemistry of Preparation of PBT

Polybutylene Terephthelate (PBT) also called

polytetramethylene terephthalate (PTMT) resin is a semicrystalline
polyester resin. It is produced by the catalytic polycondensation of 1,4
butanediol and dimethyl terephthelate.

n HO-CH2 -CH2 -CH2 CH2 -OH +n CH3 OOC - O COOCH3

o o
-[O-C- 0 -C-O CH2 -CH2 -CH2 -CH2- 0]+ 2n CH3 OH
 Manufacturing of PBT

PBT is manufactured using similar principles of PET

manufacturing.

At first step PBT is produced by the catalytic polycondensation

of 1,4 butanediol and dimethyl terephthalate, Subsequent post
condensation raises transerterified product to the desired
molecular weight.
 Characteristics of PBT ( For Identification)
 The PBT is semi crystalline material.

 It is having good wear characteristics and good

insulating properties.
 It is also having good dimensional stability.
 It is identified by orange colored sooty flame.
 When burns melt drips and gives sweet smell.
 The melting point is 220-230°C
 Short term and long term service temperature are
respectively 160 and 100°C
 Characteristics of PBT

 High strength & rigidity

 Excellent dimensional stability
 Low co-efficient of friction
 Good abrasion resistance
 Good resistance to creep at ambient & elevated
temperature
 Low moisture absorption
 Resistance to weak acid, bases, alcohols, ketones, oils, fats
and aliphatic hydrocarbons
 Good resistance to motor oil, gasoline and brake fluids
 High temperature resistance
 Excellent flame resistance
 Good electrical resistance
 High arc resistance & dielectric strength
 Properties of PBT

Properties Units Values

Specific gravity ---- 1.31
Tensile strength MPa 55
Tensile modulus MPa 2551
Flexural modulus Mpa 2275
Elongation at break % 200
Impact strength izod, Notched, J/m 53
Hardness R -72
Deflection temperature under load 0C 205-210
(1.82 Mpa)
Coefficient of linear expansion mm/mm/0C 7.4 x 10-5
Water absorption, 24hrs % 0.1
Dielectric strength KV/mm 15.8
Dielectric constant 10-6 Hz 3.24
Ohm.m 4 x 1017
Melting point 0C 225
Glass transition temperature °C 40
 Grades of PBT

The PBT is available in the following grades.

 Injection moulding grade

 Extrusion grade

CORPORATE TRAINING AND PLANNING

 Processing of PBT

PBT can be processed by the following techniques

 Injection Moulding

 Extrusion

 Blow Moulding

CORPORATE TRAINING AND PLANNING

 Processing considerations of PBT

This resin must be dried to a moisture of 0.02% or less before

processing to ensure desired quality performance. The drying
condition should be 120°C for 2-4 hours.

The injection moulding machine should be cleaned thoroughly with

polyolefin or polystyrene to remove any residual material in the
cylinder.

The cylinder temperature should be maintained at 230-260°C. The

recommended mould temperature should be 60-120°C.

 The maximum recommended regrind / reclaimed material which
can be mixed without adverse affect on resin properties is 25%.
 Applications of PBT

 Electrical and electronic applications

 Automobile applications

 Others
 Applications of PBT

Electrical and electronic applications:

Connector, IC Sockets, Terminal blocks,,

push-buttons of telephone set, micro switch, TV
parts, hair dryer parts, micro motor housing, etc.

Automotive plug connector

 Applications of PBT

Automobile applications:
Wiper gear case, outer handle, distributor, coupler, Ignition system
parts, bumper, valve of exhaust, gas treating system etc.

Application of PBT in
various areas
 Applications of PBT

Air bag cover Optical connector

Fuse holder

Car seat frame

 Applications of PBT

Iron box
Inhaler

Overhandle Blood filter

 Blends of PBT

PBT/PET
 The injection molding of glass fiber reinforced PBT leads
to long directional orientation and anisotropy in the molded
part.
 And additional deficiencies is the poor surface quality of
the molded parts.
 But when blended with PET warpage of the part is clearly
diminished and surface quality improved.
 The blends also show improvements in heat deflection
temperature and impact strength.
 Blends of PBT

PBT/Elastomers
 The blends developed for molding show good heat
deflection temperature processability, electrical
properties stiffness, strength, dimensional stability
impact strength, solvent and chemical resistance

PBT/ABS (contain upto 30% glass fiber)

 The blend shows excellent processability, high gloss,
stiffness at high temperature and mechanical strength, heat
deflection temperature, low shrinkage, good dimensional
stability, impact strength as well as solvent and chemical
resistance.
 List of Manufacturers/Suppliers of PBT

BASF (Ultradur),
Ticona (Celanex),
GE Plastics (Lomod, Valox),
Bayer (Pocan),
Huls (Vestoduv),
Mitsubishi Engineering Plastics (Novadur),
Teijin Chemicals.