POLYESTER

Polyester is a category of polymers that contain the ester functional group in every
repeat unit of their main chain.[1] As a specific material, it most commonly refers to a type
called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such
as in the cutin of plant cuticles, as well as synthetics such as polybutyrate. Natural polyesters
and a few synthetic ones are biodegradable, but most synthetic polyesters are not. The material
is used extensively in clothing.
Polyester fibers are sometimes spun together with natural fibers to produce a cloth with blended
properties. Cotton-polyester blends can be strong, wrinkle- and tear-resistant, and reduce
shrinking. Synthetic fibers using polyester have high water, wind and environmental resistance
compared to plant-derived fibers. They are less fire-resistant and can melt when ignited.[2]
Liquid crystalline polyesters are among the first industrially used liquid crystal polymers. They are
used for their mechanical properties and heat-resistance. These traits are also important in their
application as an abradable seal in jet engines.[3]
Natural polyesters could have played a significant role in the origins of life.[4] Long heterogeneous
polyester chains and membraneless structures are known to easily form in a one-pot reaction
without catalyst under simple prebiotic conditions.[5][6]

Contents

 1Types
o 1.1Aliphatic vs. aromatic polymers
 2Uses and applications
 3Industry
o 3.1Basics
o 3.2Polyester processing
 4Synthesis
o 4.1Azeotrope esterification
o 4.2Melt esterification
o 4.3Alcoholic transesterification
o 4.4Acylation
o 4.5Acetate method (esterification)
o 4.6Ring-opening polymerization
o 4.7Other methods
o 4.8Thermodynamics of polycondensation reactions
 5History
 6Biodegradation and environmental concerns
o 6.1Cross-linking
o 6.2Pollution of freshwater and seawater habitats
o 6.3Non-renewable
 7See also
 8References
 9Further reading
  10External links

Types[edit]
Polyesters are one of the economically most important classes of polymers, driven especially by
PET, which is counted among the commodity plastics; in 2000 around 30 million tons were
produced worldwide.[7] The variety of structures and properties in the polyester family is very
large, depending on the nature of the R group (see first figure with blue ester group).[1]
The family of polyesters comprises:[1]

 Linear aliphatic high molecular weight polyesters (Mn >10,000) are low-melting (m.
p. 40 – 80 °C) semicrystalline polymers and exhibit relatively poor mechanical
properties. Their inherent degradability, resulting from their hydrolytic instability,
makes them suitable for applications where a possible environmental impact is a
concern, e.g. packaging, disposable items or agricultural mulch films[8] or in
biomedical and pharmaceutical applications.[9]
 Aliphatic linear low-molar-mass (Mn < 10,000) hydroxy-terminated polyesters are
used as macromonomers for the production of polyurethanes.
 hyperbranched polyesters are used as rheology modifiers in thermoplastics or as
crosslinkers in coatings[10] due to their particularly low viscosity, good solubility and
high functionality[11]
 Aliphatic–aromatic polyesters, including poly(ethylene terephthalate) and
poly(butylene terephthalate), are high-melting semicrystalline materials (m. p. 160–
280 °C) that and have found use as engineering thermoplastics, fibers and films.
 Wholly aromatic linear copolyesters present superior mechanical properties and heat
resistance and are used in a number of high-performance applications.
 Unsaturated polyesters are produced from multifunctional alcohols and unsaturated
dibasic acids and are cross-linked thereafter; they are used as matrices in composite
materials. Alkyd resins are made from polyfunctional alcohols and fatty acids and are
used widely in the coating and composite industries as they can be cross-linked in
the presence of oxygen. Also rubber-like polyesters exist, called thermoplastic
polyester elastomers (ester TPEs). Unsaturated polyesters (UPR) are
thermosetting resins. They are used in the liquid state as casting materials, in sheet
molding compounds, as fiberglass laminating resins and in non-metallic auto-body
fillers. They are also used as the thermoset polymer matrix in pre-pregs. Fiberglass-
reinforced unsaturated polyesters find wide application in bodies of yachts and as
body parts of cars.
Depending on the chemical structure, polyester can be a thermoplastic or thermoset. There are
also polyester resins cured by hardeners; however, the most common polyesters are
thermoplastics.[12] The OH group is reacted with an Isocyanate functional compound in a 2
component system producing coatings which may optionally be pigmented. Polyesters as
thermoplastics may change shape after the application of heat. While combustible at high
temperatures, polyesters tend to shrink away from flames and self-extinguish upon ignition.
Polyester fibers have high tenacity and E-modulus as well as low water absorption and
minimal shrinkage in comparison with other industrial fibers.
Increasing the aromatic parts of polyesters increases their glass transition temperature, melting
temperature, thermal stability, chemical stability...
Polyesters can also be telechelic oligomers like the polycaprolactone diol (PCL) and the
polyethylene adipate diol (PEA). They are then used as prepolymers.

Aliphatic vs. aromatic polymers[edit]

Thermally stable polymers, which have a high proportion of aromatic structures, are also
called high-performance plastics; this application-oriented classification compares such polymers
with engineering plastics and commodity plastics. The continuous service temperature of high-
performance plastics is generally stated as being higher than 150 °C,[13] whereas engineering
plastics (such as polyamide or polycarbonate) are often defined as thermoplastics that retain
their properties above 100 °C.[14] Commodity plastics (such as polyethylene or polypropylene)
have in this respect even greater limitations, but they are manufactured in great amounts at low
cost.
Poly(ester imides) contain an aromatic imide group in the repeat unit, the imide-based polymers
have a high proportion of aromatic structures in the main chain and belong to the class of
thermally stable polymers. Such polymers contain structures that impart high melting
temperatures, resistance to oxidative degradation and stability to radiation and chemical
reagents. Among the thermally stable polymers with commercial relevance
are polyimides, polysulfones, polyetherketones, and polybenzimidazoles. Of these, polyimides
are most widely applied.[15] The polymers’ structures result also in poor processing characteristics,
in particular a high melting point and low solubility. The named properties are in particular based
on a high percentage of aromatic carbons in the polymer backbone which produces a certain
stiffness.[16] Approaches for an improvement of processability include the incorporation of flexible
spacers into the backbone, the attachment of stable pendent groups or the incorporation of non-
symmetrical structures.[15] Flexible spacers include, for example, ether or
hexafluoroisopropylidene, carbonyl or aliphatic groups like isopropylidene; these groups allow
bond rotation between aromatic rings. Less symmetrical structures, for example based on meta-
or ortho-linked monomers introduce structural disorder and thereby decrease the crystallinity.[7]
The generally poor processability of aromatic polymers (for example, a high melting point and a
low solubility) also limits the available options for synthesis and may require strong electron-
donating co-solvents like HFIP or TFA for analysis (e. g. 1H NMR spectroscopy) which
themselves can introduce further practical limitations.

Basics[edit]
Polyethylene terephthalate, the polyester with the greatest market share, is a synthetic polymer
made of purified terephthalic acid (PTA) or its dimethyl ester dimethyl terephthalate (DMT)
and monoethylene glycol (MEG). With 18% market share of all plastic materials produced, it
ranges third after polyethylene (33.5%) and polypropylene (19.5%) and is counted as commodity
plastic.
There are several reasons for the importance of polyethylene terephthalate:

 The relatively easy accessible raw materials PTA or DMT and MEG
 The very well understood and described simple chemical process of its synthesis
 The low toxicity level of all raw materials and side products during production and
processing
 The possibility to produce PET in a closed loop at low emissions to the environment
 The outstanding mechanical and chemical properties
 The recyclability
 The wide variety of intermediate and final products.
In the following table, the estimated world polyester production is shown. Main applications
are textile polyester, bottle polyester resin, film polyester mainly for packaging and specialty
polyesters for engineering plastics. According to this table, the world's total polyester production
might exceed 50 million tons per annum before the year 2010.

World polyester production by year

Product type 2002 (million tonnes/year) 2008 (million tonnes/year)

 Textile-PET 20 39

Resin, bottle/A-PET 9 16

Film-PET 1.2 1.5

Special polyester 1 2.5

Total 31.2 59

Polyester processing[edit]
After the first stage of polymer production in the melt phase, the product stream divides into two
different application areas which are mainly textile applications and packaging applications. In
the following table, the main applications of textile and packaging of polyester are listed.

Textile and packaging polyester application list (melt or pellet)

Textile Packaging

Staple fiber (PSF) Bottles for CSD, water, beer, juice, detergents, etc.

Filaments POY, DTY, FDY A-PET film

Technical yarn and tire cord Thermoforming

Non-woven and spunbond biaxial-oriented film (BO-PET)

Mono-filament Strapping

Abbreviations:
PSF
Polyester-staple fiber;
POY
Partially oriented yarn;
DTY
Drawn textured yarn;
FDY
Fully drawn yarn;
CSD
Carbonated soft drink;
A-PET
Amorphous polyethylene terephthalate film;
BO-PET
Biaxial-oriented polyethylene terephthalate film;
A comparable small market segment (much less than 1 million
tonnes/year) of polyester is used to produce engineering plastics
and masterbatch.
In order to produce the polyester melt with a high efficiency, high-
output processing steps like staple fiber (50–300 tonnes/day per
spinning line) or POY /FDY (up to 600 tonnes/day split into about 10
spinning machines) are meanwhile more and more vertically
integrated direct processes. This means the polymer melt is directly
converted into the textile fibers or filaments without the common
step of pelletizing. We are talking about full vertical integration when
polyester is produced at one site starting from crude oil
or distillation products in the chain oil → benzene → PX → PTA →
PET melt → fiber/filament or bottle-grade resin. Such integrated
processes are meanwhile established in more or less interrupted
processes at one production site. Eastman Chemicals were the first
to introduce the idea of closing the chain from PX to PET resin with
their so-called INTEGREX process. The capacity of such vertically
integrated production sites is >1000 tonnes/day and can easily
reach 2500 tonnes/day.
Besides the above-mentioned large processing units to produce
staple fiber or yarns, there are ten thousands of small and very
small processing plants, so that one can estimate that polyester is
processed and recycled in more than 10 000 plants around the
globe. This is without counting all the companies involved in the
supply industry, beginning with engineering and processing
machines and ending with special additives, stabilizers and colors.
This is a gigantic industry complex and it is still growing by 4–8%
per year, depending on the world region.

Synthesis[edit]
Synthesis of polyesters is generally achieved by a polycondensation
reaction. See "condensation reactions in polymer chemistry". The
general equation for the reaction of a diol with a diacid is :
(n+1) R(OH)2 + n R´(COOH)2 → HO[ROOCR´COO]nROH + 2n H2O.
Polyesters can be obtained by a wide range of reactions of
which the most important are the reaction of acids and alcohols,
alcoholysis and or acidolysis of low-molecular weight esters or
the alcoholysis of acyl chlorides. The following figure gives an
overview over such typical polycondensation reactions for
polyester production. Furthermore, polyesters are accessible
via ring-opening polymerization.
Azeotrope esterification[edit]
In this classical method, an alcohol and a carboxylic acid react
to form a carboxylic ester. To assemble a polymer, the water
formed by the reaction must be continually removed
by azeotrope distillation.

Melt esterification[edit]
When melting points of the monomers are sufficiently low, a
polyester can be formed via direct esterification while removing
the reaction water via vacuum.

Direct bulk polyesterification at high temperatures (150 –

290 °C) is well-suited and used on the industrial scale for the
production of aliphatic polyesters, unsaturated polyesters and
aromatic–aliphatic polyesters. Monomers
containing phenolic or tertiary hydroxyl groups exhibit a low
reactivity with carboxylic acids and cannot be polymerized via
direct acid alcohol-based polyesterification.[7] In the case of PET
production, however, the direct process has several
advantages, in particular a higher reaction rate, a higher
attainable molecular weight, the release of water instead
of methanol and lower storage costs of the acid when compared
to the ester due to the lower weight.[1]

Alcoholic transesterification[edit]
Main article: Transesterification
Transesterification: An alcohol-terminated oligomer and an
ester-terminated oligomer condense to form an ester linkage,
with loss of an alcohol. R and R' are the two oligomer chains,
R'' is a sacrificial unit such as a methyl group (methanol is the
byproduct of the esterification reaction).
The term transesterification is typically used to describe
hydroxy–ester, carboxy–ester, and ester–ester exchange
reactions. The hydroxy–ester exchange reaction possesses the
highest rate of reaction and is used for the production of
numerous aromatic–aliphatic and wholly aromatic polyesters.
[7]
The transesterification based synthesis is particularly useful
for when high melting and poorly soluble dicarboxylic acids are
used. In addition, alcohols as condensation product are more
volatile and thereby easier to remove than water.[18]
The high-temperature melt synthesis between bisphenol
diacetates and aromatic dicarboxylic acids or in reverse
between bisphenols and aromatic dicarboxylic acid diphenyl
esters (carried out at 220 to 320 °C upon the release of acetic
acid) is, besides the acyl chloride based synthesis, the
preferred route to wholly aromatic polyesters.[7]

Acylation[edit]
In acylation, the acid begins as an acid chloride, and thus the
polycondensation proceeds with emission of hydrochloric
acid (HCl) instead of water.
The reaction between diacyl chlorides and alcohols or phenolic
compounds has been widely applied to polyester synthesis and
has been subject of numerous reviews and book chapters.[7][19][20]
[21]
The reaction is carried out at lower temperatures than the
equilibrium methods; possible types are the high-temperature
solution condensation, amine catalysed and interfacial
reactions. In addition, the use of activating agents is counted as
non-equilibrium method. The equilibrium constants for the acyl
chloride-based condensation yielding yielding arylates and
polyarylates are very high indeed and are reported to be 4.3 ×
103 and 4.7 × 103, respectively. This reaction is thus often
referred to as a ‘non-equilibrium’ polyesterification. Even though
the acyl chloride based synthesis is also subject of reports in
the patent literature, it is unlikely that the reaction is utilized on
the production scale.[22] The method is limited by the acid
dichlorides’ high cost, its sensitivity to hydrolysis and the
occurrence of side reactions.[23]
The high temperature reaction (100 to > 300 °C) of an diacyl
chloride with an dialcohol yields the polyester and hydrogen
chloride. Under these relatively high temperatures the reaction
proceeds rapidly without a catalyst:[21]

The conversion of the reaction can be followed by titration of

the evolved hydrogen chloride. A wide variety of solvents has
been described including chlorinated benzenes (e.g.
dichlorobenzene), chlorinated naphthalenes or diphenyls, as
well as non-chlorinated aromatics like terphenyls,
 benzophenones or dibenzylbenzenes. The reaction was also
applied successfully to the preparation of highly crystalline and
poorly soluble polymers which require high temperatures to be
kept in solution (at least until a sufficiently high molecular
weight was achieved).[24]
In an interfacial acyl chloride-based reaction, the alcohol
(generally in fact a phenol) is dissolved in the form of an
alkoxide in an aqueous sodium hydroxide solution, the acyl
chloride in an organic solvent immiscible with water such
as dichloromethane, chlorobenzene or hexane, the reaction
occurs at the interface under high-speed agitation near room
temperature.[21]

The procedure is used for the production

of polyarylates (polyesters based on
bisphenols), polyamides, polycarbonates, poly(thiocarbonate)s,
and others. Since the molecular weight of the product obtained
by a high-temperature synthesis can be seriously limited by
side reactions, this problem is circumvented by the mild
temperatures of interfacial polycondensation. The procedure is
applied to the commercial production of bisphenol-A-based
polyarylates like Unitika's U-Polymer.[7] Water could be in some
cases replaced by an immiscible organic solvent (e. g. in
the adiponitrile/carbon tetrachloride system).[21] The procedure is
of little use in the production of polyesters based on aliphatic
diols which have higher pKa values than phenols and therefore
do not form alcoholate ions in aqueous solutions.[7] The base
catalysed reaction of an acyl chloride with an alcohol may also
be carried out in one phase using tertiary amines (e.
g. triethylamine, Et3N) or pyridine as acid acceptors:

While acyl chloride-based polyesterifications proceed only very

slowly at room temperature without a catalyst, the amine
accelerates the reaction in several possible ways, although the
mechanism is not fully understood.[21] However, it is known
that tertiary amines can cause side-reactions such as the
formation of ketenes and ketene dimers.[25]
Silyl method
In this variant of the HCl method, the carboxylic acid chloride is converted with
the trimethyl silyl ether of the alcohol component and production of trimethyl silyl chloride
is obtained
Acetate method (esterification)[edit]

Silyl acetate method

Ring-opening polymerization[edit]
Aliphatic polyesters can be assembled
from lactones under very mild conditions,
catalyzed anionically, cationically, metallorganically
or enzyme-based[26][27] A number of catalytic
methods for the copolymerization of epoxides with
cyclic anhydrides have also recently been shown to
provide a wide array of functionalized polyesters,
both saturated and unsaturated. Ring-opening
polymerization of lactones and lactides is also
applied on the industrial scale.[28][29]

Other methods[edit]
Numerous other reactions have been reported for
the synthesis of selected polyesters, but are limited
to laboratory-scale syntheses using specific
conditions, for example using dicarboxylic acid
salts and dialkyl halides or reactions between
bisketenes and diols.[7]
Instead of acyl chlorides, so-called activating
agents can be used, such as 1,1'-
carbonyldiimidazole, dicyclohexylcarbodiimide,
or trifluoroacetic anhydride. The polycondensation
proceeds via the in situ conversion of the carboxylic
acid into a more reactive intermediate while the
activating agents are consumed. The reaction
proceeds, for example, via an intermediate N-
acylimidazole which reacts with catalytically acting
sodium alkoxide:[7]

The use of activating agents for the production of

high-melting aromatic polyesters and polyamides
under mild conditions has been subject of intensive
academic research since the 1980s, but the
reactions have not gained commercial acceptance
as similar results can be achieved with cheaper
reactants.[7]
 Thermodynamics of
polycondensation reactions[edit]
Polyesterifications are grouped by some authors[7]
[19]
into two main categories: a) equilibrium
polyesterifications (mainly alcohol-acid reaction,
alcohol–ester and acid–ester interchange
reactions, carried out in bulk at high temperatures),
and b) non-equilibrium polyesterifications, using
highly reactive monomers (for example acid
chlorides or activated carboxylic acids, mostly
carried out at lower temperatures in solution).
The acid-alcohol based polyesterification is one
example of an equilibrium reaction. The ratio
between the polymer-forming ester group (-C(O)O-)
and the condensation product water (H2O) against
the acid-based (-C(O)OH) and alcohol-based (-OH)
monomers is described by the equilibrium
constant KC.
The equilibrium constant of the acid-alcohol based
polyesterification is typically KC ≤ 10, what is not
high enough to obtain high-molecular weight
polymers (DPn ≥ 100), as the number average
degree of polymerization (DPn) can be calculated
from the equilibrium constant KC.[20]
In equilibrium reactions, it is therefore necessary to
remove the condensation product continuously and
efficiently from the reaction medium in order to
drive the equilibrium towards polymer.[20] The
condensation product is therefore removed at
reduced pressure and high temperatures (150–
320 °C, depending on the monomers) to prevent
the back reaction.[9] With the progress of the
reaction, the concentration of active chain ends is
decreasing and the viscosity of the melt or solution
increasing. For an increase of the reaction rate, the
reaction is carried out at high end group
concentration (preferably in the bulk), promoted by
the elevated temperatures.
Equilibrium constants of magnitude KC ≥ 104 are
achieved when using reactive reactants (acid
chlorides or acid anhydrides) or activating agents
like 1,1′-carbonyldiimidazole. Using these
reactants, molecular weights required for technical
applications can be achieved even without active
removal of the condensation product.

I BBBBBn 1926, United States-based E.I. du Pont de Nemours and Co. began research on large
molecules and synthetic fibers. This early research, headed by W.H. Carothers, centered on
what became nylon, which was one of the first synthetic fibers.[30] Carothers was working for
duPont at the time. Carother's research was incomplete and had not advanced to investigating
the polyester formed from mixing ethylene glycol and terephthalic acid. In 1928 polyester was
patented in Britain by the International General Electric company.[31] Carothers' project was
revived by British scientists Whinfield and Dickson, who patented polyethylene
terephthalate (PET) or PETE in 1941. Polyethylene terephthalate forms the basis for synthetic
fibers like Dacron, Terylene and polyester. In 1946, duPont bought all legal rights from Imperial
Chemical Industries (ICI).[32]