POLYESTER FIBER
Module 9
Content
Introduction
Types of Polyester
Chemistry of PET
Fiber Production Methods
Physical & Chemical Properties
End Uses
KEY QUESTIONS
Key Questions
1. Define polyester fiber.
2. Write about different types of polyester fiber.
3. Show the chemical reactions occur during polyester fiber production.
4. What kind of impurities are produced during polyester fiber manufacture?
5. Discuss batch/continuous method of polyester fiber production.
6. State main physical and chemical properties of polyester fiber.
7. What do you know about modified polyesters?
8. Indicate application areas of polyester fiber.
9. Write about polyester fibers made from polymers other than PET.
INTRODUCTION
Introduction
• The most popular and versatile of all textile fibers.
• Discovered by JR Whinfield and JT Dickson in 1941 in UK while
commercial production started in 1953.
• Commonly used polyester fiber is made from poly(ethylene
terephthalate) or PET, a condensation polymer.
• Global production approx. 57m ton (2020, 52% share).
• China is the largest producer (70% share).
The Magnificent Discovery
JR Whinfield (left) and JT
Dickson (right) re-enact the
discovery of fiber-forming
PET (1942)
Definition by FTC
A manufactured fiber in which the fiber forming substance is any
long-chain synthetic polymer composed of at least 85% by weight
of an ester of a substituted aromatic carboxylic acid, including but
not restricted to substituted terephthalate units, and para
substituted hydroxy-benzoate units.
Definition by ISO
Fiber composed of
linear macromolecules
having in the chain at
least 85% by mass of
an ester of a diol and
terephthalic acid.
ISO 2076:2013
TYPES OF POLYESTER
Modified and Other Polyesters
Based on Monomer
➢The most common polyester
Poly(ethylene terephthalate) or PET.
➢Other polyesters
• Poly(trimethylene terephthalate) or PTT
• Poly(butylene terephthalate) or PBT
• Poly(cyclohexylenedimethylene terephthalate) or PCT/PCDT
• Poly(ethylene naphthalate) or PEN (not recognized by ISO)
Based on Chemical Modification of PET
➢Modified Polyesters
• Carrier-free dyeable polyester
• Cationic dyeable polyester
• Anionic dyeable polyester
• Flame retardant polyester
• Hydrophilic polyester
CHEMISTRY OF PET
The most common Polyester
Synthesis Route
• Formed by step-growth polymerization of dimethyl
terephthalate (DMT) or terephthalic acid (TPA) with ethylene
glycol (EG).
• Pure terephthalic acid (PTA) is the dominant feedstock today.
Advantages of PTA Over DMT
• 15% higher production ☞ difference in molar mass
• High productivity ☞ faster esterification & polycondensation
• 20% less construction cost ☞ less storage space, higher density
• Less hazardous ☞ flammable methanol is not evolved
• Better polymer quality ☞ little/no catalyst required
Synthesis Route
The polymerization takes place in two stages:
1. Transesterification (DMT) or Esterification (PTA).
2. Polycondensation.
Transesterification or Ester Interchange
In presence of catalyst and heat, DGT is formed and methanol evolved.
Direct Esterification
In presence of catalyst and heat, DGT is formed and water evolved.
Polycondensation
In presence of catalyst, heat and vacuum, PET is formed and EG evolved.
Typical Molar Mass
Mn = 17,000-20,000
Apparel & Home Textiles
Mn = 28,000-40,000
Technical Textiles
FIBER PRODUCTION
Batch and Continuous Method
Commercial Fiber Production
• Typically the fiber is produced either from chip (batch process) or
by continuous polymerization.
• In batch process, the polymer is produced as chip and then the
fiber is produced by melt spinning at 280-290o C temperature and
drawn at a temperature above Tg (69o C).
• In continuous polymerization process, the polymer and fiber
production is synchronized to produce a much better quality fiber
economically.
Batch Polymerization
Lower productivity ☞ 1-40 tons/day
Raw
Material Polycondensation
Preparation Transesterification
/Esterification 270-280o C, 2-6h Fiber/Chip
Melt DMT/ vacuum system Production
TPA 180-210o C/ 240-260o C,
1.5-2 bar, 3h EG recycling
Mixed with
hot EG
Transesterification or Direct Esterification
• DMT is dissolved in the hot EG.
• In case of transesterification, catalyst (acetates of Cd, Zn,Pb,Sb)
and delustrant are added and the reaction is carried out at 180 to
210o C for 3-6 hours at normal pressure with methanol distilled off.
• In case of direct esterification, the quantity of catalyst is less and
the reaction is carried out at 240-260o C at 1.5-2 bar pressure with
water distilled off. Phosphates are used as stabilizer.
Polycondensation
• In polycondensation, the reaction is carried out at 270 to 280o C for
2-6 hours under vacuum (0.13 kPa). If vacuum breaks, air will enter
and thermo-oxidative degradation will give inferior quality
polymer.
• EG liberated is recovered through a column and recycled.
• After polycondensation, the polymer is extruded as ribbon on to a
casting wheel where it solidifies and is then cut into chips and
dried.
Continuous Polymerization
Higher productivity ☞ 100-400 tons/day
Pre-
Esterification polycondensa Poly-
Paste (2) condensation Additive
tion (2) Master-
Preparation 200o C 280-290o C, 2- batch
250-285o C,
TPA mixed normal 6h vacuum, System
vacuum, 10mm
with EG & pressure 1.5mm Hg, Mn
Hg Fiber or
Catalyst = 17-40K
Water Mn = 4-7K Chip Prod
removed EG recovery
EG recovery
Continuous Polymerization
• PTA is mixed with EG and catalyst in a mixer to form paste which is
continuously fed to the esterification reactor(s).
• The esterification takes place at atmospheric pressure by splitting
off water which is then removed along with excess EG.
• The product is then fed to the prepolycondensation system under
vacuum consisting of at least 2 reactors where temperatures are
gradually increased to 285o C and pressure reduced to 10 mm Hg.
Low molar mass polymer (Mn =4000-7000) is formed.
Continuous Polymerization
▪ Final polycondensation is performed with a pressure less than
1.5mm Hg. Phosphorus additives are added as stabilizer.
▪ A catalyst is needed to make a polymer of high molecular weight,
and the most common catalyst is antimony trioxide (Sb2O3) or
triacetate [Sb(CH3COO)3].
Impurities/Side Reactions
• DEG formation: Etherification of MEG gives DEG and formed
during esterification and initial stage of polycondensation.
Increased DEG content leads to reduction in heat and light
resistance, decrease in glass transition and melting temperatures.
• Oligomer formation: Cyclic oligomers are usually formed during
ester interchange reaction or at the early stage of
polycondensation, the total content is 1 to 3%, mainly cyclo-tri-
ethylene glycol terephthalic acid ester c(G-T)3.
PHYSICAL PROPERTIES
Main Physical Properties
Main Physical Properties
• Strong (up to 85 cN/tex, regular 30-50, HT 60-85)
• Lightweight (1.38 g/cc)
• Moisture regain (0.4%)
• Melting temp (250-265 C)
• High resiliency (wrinkle-resistant), mildew resistant
• High resistance to abrasion and sunlight (turns yellow on long exposure)
• High dimensional stability (heat-set at 200 C, retain pleats)
• Machine washable, quick drying (PP, wash and wear)
• Extensibility 20-30%
Sustainability Issues
• Economical compared to all other natural and manmade fibers.
• Better properties (strong, high MP, color fastness, low shrinkage).
• Fully recyclable, postconsumer bottles are recycled into staples.
• Full environmental impact better than natural fibers.
• Recycled PET is much better than all other fibers.
• Half life of PET 500 to 2500 years!
CHEMICAL PROPERTIES
Main Chemical Properties
Main Chemical Properties
• Acid and alkali: Unaffected by dilute, damaged by conc. alkali.
• Bleaching agent: Not damaged
• Organic solvent: Unaffected, can be dry-cleaned
• Dyeing behavior: Dyed at high temperature (135-140 C) with
disperse dye due to high crystallinity and presence of rigid
benzene rings in the amorphous region.
POLYESTER AND NYLON
Comparison between Properties
Chemically Same or Different?
Polyester and polyamide fibers are made in the same way by melt spinning
from linear condensation polymers. The PET molecule contains two sorts of
group, the aliphatic sequence, -[Link]-, containing about the
same number of chain links as the –CH2- sequences in nylon are flexible at
room temperature and would give rise to weak van der Walls interactions
with neighboring chains. The differences are mostly due to the benzene ring.
This will give some stiffness to the chain and will impede deformation of
disordered regions. Furthermore, there is an electronic interactions between
neighboring benzene rings, which gives intermolecular bonding with a
function similar to the hydrogen bonding in polyamides.
Comparison
Polyesters carry ester functional group whereas, in PA, amide
functional group is [Link] monomer should have a carboxylic &
an amine group, whereas polyesters should have a carboxylic group
along with a hydroxyl [Link] is a thermoplastic kind of polymer
but, polyesters can be thermoplastic or thermoset depending on
their chemical structure. They provide more natural feeling than the
polyesters. The polyester fabrics are more wrinkle resistant than
these. PA (Nylons) is always synthetic in nature but polyesters can
be produced by natural ingredients also (like cutin obtained from
plant cuticles).
MODIFIED POLYESTERS
Chemical Modification of PET
Modified Polyesters
• The unique properties of polyester fiber are due to the presence
of aliphatic and aromatic parts in macromolecular chains and the
regular molecular structure. Poly(ethylene terephthalate) (PET) is
the predominant polyester used for fiber production, not only
because of its good end-use properties and economy of
production but in particular because of the ease of physical and
chemical modification, suppressing negative and enhancing
positive properties of PET.
Modified Polyesters
▪ As polyester fibres are easily flammable, flame retardancy is a significant issue.
▪ One of the classical solutions to flame retard polyester is to incorporate a comonomeric phosphinic acid
unit into the PET polymeric chain (trade name Trevira CS).20 Trevira CS polyester does not promote any
char formation and there is evidence that the phosphorus compound acts in the gas phase. Several
flame retardants have also been designed for polyester extrusion (bisphenol-S-oligomer derivatives
from Toyobo, cyclic phosphonates (Antiblaze CU and 1010) from Rhodia or phosphinate salts from
Clariant). Note that the cyclic phosphonate may also be applied as textile finish as well as a melt
additive. All those flame retardants were developed in the 1980s (except the phosphinate salt) and their
modes of action have been described in the literature20 but very little on this topic has been published
recently.
▪ In the recent published literature, Chen et al.65 proposed the use of a novel anti-dripping flame
retardant, poly(2-hydroxy propylene spirocyclic pentaerythritol bisphosphonate) (PPPBP) (Fig. 2.8) to
impart flame retardancy and dripping resistance to PET fabrics. Flammability of PET fabrics treated
with PPPBP was investigated by the vertical burning test which showed a significant enhancement of
the flame retardancy (producing a non-ignitable fabric) and either a significant reduction of melt
dripping at low levels or absence of dripping at higher levels of PPPBP.
Modified Polyesters
▪ Concurrently, a new halogen-free FR master batch for polyester has been developed in our laboratories which at only 5 wt-%
incorporation enables PET to obtain classification according to several standards such as the NF P 92 501 or NF P 92 503 (M
classification), FMVSS 302 or BS 5852 (Crib 5).6
▪ While polyester fibers are inherently hydrophobic, the absorptive capacity of
a poly(ethylene terephthalate) fiber can be increased by chemical
modifications and treatment. For example, treatment in aqueous
hydroxyamine solutions provides hydroxy sorption sites on the fiber [63].
After twelve clear water washings of materials treated with ethanolamine,
diethanolamine and 2-diethylaminoethanol, the time for absorption of a
water droplet was one to two orders of magnitude less than the absorption
time of an untreated sample. In another approach to increased hydrophilicity
in polyester, water soluble aliphatic polyamide polymers are coextruded with
the polyester [64]. After fiber formation the polyamide is extracted with
water to leave a more porous absorptive polyester substrate.
Modified Polyesters
• Polyester fibres are extremely crystalline, hydrophobic in nature and have a high glass
transition temperature (Tg). Hence the fibre requires a high temperature around 130°C for its
dyeing. To obtain such a high temperature high pressure (HTHP) is required. This method of
dyeing is therefore called the HTHP dyeing method. For dyeing using the HTHP method
special equipment is required which can withstand such conditions. Alternatively, the fibre
can be dyed in a boiling dyebath at atmospheric pressure in the presence of some plasticisers
which are capable of reducing the Tg of the fibre. These agents are known as carriers; the
method of dyeing is therefore called the carrier dyeing method. There are various
explanations available for the mechanism of carrier action. Amongst them the most modern
explanation is the reduction of the Tg. Many scientists claim that the carriers work by swelling
the fibre but there are many carriers available that cannot swell the fibre and still they are
efficient in their carrier action. As disperse dyes are insoluble or only slightly soluble in water,
they are applied from an aqueous dispersion in the presence of a dispersing agent. Disperse
dyes require slight acidity for their exhaustion into the fibre. The acidity is achieved by adding
acetic acid to achieve a pH of 4.0–4.5. The insolubility of the disperse dyes enables them to
leave the dye liquor as they are more substantive to the hydrophobic polyester fibre. Heating
the dye liquor will accelerate the strike rate and the diffusion of the dyes inside the fibre
structure. Once within the fibre polymer system, the dye molecules are held by hydrogen
bonds and van der Waals forces.
OTHER POLYESTERS
Polyesters made from Polymers Other than PET
Other Polyesters
• Poly(trimethylene terephthalate, 3GT) or PTT
• Poly(butylene terephthalate, 4GT) or PBT
• Poly(cyclohexylenedimethylene terephthalate) or PCDT
• Poly(ethylene naphthalate) or PEN
PBT Polyester
• PBT could be melt-spun at lower temperatures (Tm 225o C)
• Can be dyed at boil with disperse dyes.
• Resistant to photo-oxidative yellowing, whiter than PET.
• More expensive than PET & PA (BD costlier than EG)
• Lower pleat-retaining property than PET
• Popular as BCF carpet (higher resilience & resistance to staining)
PTT Polyester
• Much cheaper route to 1,3-propanediol available since 1990.
• Outstanding resilience.
PCDT Polyester
• Introduced in 1958 by Eastman Kodak as staple fiber Kodel.
• Higher glass transition and melting temperature (Tm 290-295o C).
• Higher resiliency and elasticity.
• Carpets, upholstery, curtain and engineering plastics.
END USES
Applications
Applications
• Polyester fibres are used in apparel for overcoats, jackets, leisure and
sportswear, protective clothing, and so forth. In home furnishings,
their uses range from drapery and curtain fabrics to furniture
coverings, pillows and pillow stuffing, and table and bed linen to wall
and floor coverings.
• Polyesters are also used to make bottles, films, tarpaulin,
canoes, liquid crystal displays, holograms, filters, dielectric film
for capacitors, film insulation for wire and insulating tapes. Polyesters
are widely used as a finish on high-quality wood products such
as guitars, pianos and vehicle/yacht interiors. Thixotropic properties of
spray-applicable polyesters make them ideal for use on open-grain
timbers, as they can quickly fill wood grain, with a high-build film
thickness per coat. Cured polyesters can be sanded and polished to a
high-gloss, durable finish.
Applications
▪ On the basis of application, carpets & rugs, non-woven fabrics,
fiberfill, apparels, home textiles, and others are the major
segments of polyester fiber market, where, the others segment
includes industrial fabric,
▪ Global production expected to reach 56m(17.9m PSF+38m FY)
tons by 2018.
Thank You