polyethylene terephthalate
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Polyethylene terephthalate (or poly(ethylene terephthalate), PET, PETE, or the obsolete PETP or PET-P), is the most common
thermoplastic A thermoplastic, or thermosoft plastic, is a plastic polymer A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules, or macromolecules, ...
polymer A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules, or macromolecules, composed of many Repeat unit, repeating subunits. Due to thei ...

polymer
resin of the
polyester Polyester is a category of polymer A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules, or macromolecules, composed of many Repe ...
family and is used in
fibre Fiber or fibre (from la, fibra, links=no) is a natural Nature, in the broadest sense, is the natural, physical, material world or universe The universe ( la, universus) is all of space and time and their contents, including ...
s for clothing,
containers box. File:Railroad car with container loads.jpg, A Flatcar#Spine car, spine car with a tank container and an open-top intermodal container, intermodal shipping container with canvas cover. A container is any receptacle or enclosure for holdin ...

containers
for liquids and foods, and
thermoforming Thermoforming is a manufacturing process where a plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingredient. Their Plasticity (physics), plasticity makes it possible for ...
for manufacturing, and in combination with glass fibre for engineering
resins In polymer chemistry and materials science The Interdisciplinarity, interdisciplinary field of materials science, also commonly termed materials science and engineering, covers the design and discovery of new materials, particularly solids. ...
. It may also be referred to by the brand names Terylene in the UK, Lavsan in Russia and the former Soviet Union, and Dacron in the US. Bio-PET is the bio-based counterpart of PET. The majority of the world's PET production is for synthetic fibres (in excess of 60%), with bottle production accounting for about 30% of global demand. In the context of textile applications, PET is referred to by its common name,
polyester Polyester is a category of polymer A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules, or macromolecules, composed of many Repe ...
, whereas the acronym ''PET'' is generally used in relation to packaging. Polyester makes up about 18% of world polymer production and is the fourth-most-produced polymer after
polyethylene Polyethylene or (incorrectly) polythene (abbreviated PE; IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations that represents chemists in individual countr ...

polyethylene
(PE),
polypropylene Polypropylene (PP), also known as polypropene, is a thermoplastic A thermoplastic, or thermosoftening plastic, is a plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling. Most the ...

polypropylene
(PP) and
polyvinyl chloride Polyvinyl chloride (colloquial: polyvinyl, Vinyl polymer, vinyl; abbreviated: PVC) is the world's third-most widely produced synthetic plastic polymer (after polyethylene and polypropylene). About 40 million tons of PVC are produced each year. ...
(PVC). PET consists of polymerized units of the monomer ethylene terephthalate, with repeating (C10H8O4) units. PET is commonly
recycled Recycling is the process of converting waste materials into new materials and objects. The recovery of energy from waste materials is often included in this concept. The recyclability of a material depends on its ability to reacquire the p ...
, and has the digit 1 (♳) as its
resin identification code The ASTM International Resin Identification Coding System, often abbreviated RIC, is a set of symbols appearing on plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingre ...

resin identification code
(RIC). Depending on its processing and thermal history, polyethylene terephthalate may exist both as an amorphous (transparent) and as a
semi-crystalline polymer Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymer ...
. The semicrystalline material might appear transparent (particle size less than 500  nm) or opaque and white (particle size up to a few
micrometerMicrometer can mean: * Micrometer (device) A micrometer, sometimes known as a micrometer screw gauge, is a device incorporating a calibrated screw widely used for Accuracy and precision, accurate measurement of components in mechanical engineeri ...
s) depending on its crystal structure and particle size. The monomer
bis(2-hydroxyethyl) terephthalate
bis(2-hydroxyethyl) terephthalate
can be synthesized by the
esterification An ester is a chemical compound derived from an acid (organic or inorganic) in which at least one –OH hydroxyl group is replaced by an –O– alkyl ( alkoxy) group, as in the substitution reaction of a carboxylic acid and an alcohol. Glycer ...

esterification
reaction between
terephthalic acid Terephthalic acid is an organic compound , CH4; is among the simplest organic compounds. In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen chemical bond, bonds. Due to carbon's ability to Catenatio ...

terephthalic acid
and
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
with water as a byproduct (this is also known as a condensation reaction), or by
transesterification In organic chemistry, transesterification is the process of exchanging the organic group R″ of an ester with the organic group R′ of an alcohol File:Alcohol general.svg, upright=0.8, The bond angle between a hydroxyl group (-OH) and a chai ...

transesterification
reaction between
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
and
dimethyl terephthalate Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.Richard J. Sheehan "Terephth ...
(DMT) with
methanol Methanol, also known as methyl alcohol, amongst other names, is a Chemical compound, chemical and the simplest alcohol, with the Chemical formula, formula Carbon, CHydrogen, H3Oxygen, OHydrogen, H (a methyl group linked to a Hydroxy group, hydro ...

methanol
as a byproduct. Polymerization is through a
polycondensation Condensation polymers are any kind of polymers formed through a condensation reaction—where molecules join together—''losing'' small molecules as byproducts such as water or methanol. Condensation polymers are formed by polycondensation, when ...

polycondensation
reaction of the monomers (done immediately after esterification/transesterification) with water as the byproduct. However, polyethylene terephthalate contributes to plastic waste leading to environmental pollution. :


Uses

Plastic-recyc-01.svg, PET has SPI 1 File:PETling.jpg, PET preform for injection stretch blow moulding of a bottle File:Clean the Bay 2012 (7324648864).jpg, A finished PET bottle File:Pet plastic crystallisation.jpg, A PET bottle which has been heated by a candle and has recrystallized, making it opaque. File:PET-Verpackung-offen.jpg, PET clamshell packaging, used to sell fruit, hardware, etc. File:Buso de Algodon y Poliester.JPG, Polyester yarn Mikrofaser-Handtuch für Unterwegs.JPG, Microfiber towels and cleaning cloths File:Mylar balloons.jpg, Aluminized Mylar ballons filled with
helium Helium (from el, ἥλιος, helios Helios; Homeric Greek: ), Latinized as Helius; Hyperion and Phaethon are also the names of his father and son respectively. often given the epithets Hyperion ("the one above") and Phaethon ("the shining") ...

helium
Plastic bottles made from PET are widely used for
soft drink A soft drink (see § Terminology for other names) is a drink A drink (or beverage) is a liquid A liquid is a nearly incompressible fluid In physics, a fluid is a substance that continually Deformation (mechanics), deforms (flows ...

soft drink
s (see
carbonation Carbonation is the chemical reaction of carbon dioxide Carbon dioxide (chemical formula ) is an acidic colorless gas with a density about 53% higher than that of dry air. Carbon dioxide molecules consist of a carbon atom covalent bond, covalen ...
). For certain specialty bottles, such as those designated for beer containment, PET sandwiches an additional
polyvinyl alcohol Poly(vinyl alcohol) (PVOH, PVA, or PVAl) is a water-soluble synthetic polymer. It has the idealized formula H2CH(OH). It is used in papermaking, sizing, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate, PVAc adhe ...

polyvinyl alcohol
(PVOH) layer to further reduce its oxygen permeability. Biaxially oriented PET film (often known by one of its trade names, "Mylar") can be aluminized by a
thin film A thin film is a layer of material ranging from fractions of a nanometer Image:Chiraltube.png, one nanometric carbon nano tube, photographed with Scanning Tunneling Microscope file:EM Spectrum Properties edit.svg, 330px, Different lengths as in ...
of metal onto it to reduce its permeability, and to make it reflective and opaque ( MPET). These properties are useful in many applications, including flexible food
packaging Packaging is the science Science (from the Latin word ''scientia'', meaning "knowledge") is a systematic enterprise that Scientific method, builds and Taxonomy (general), organizes knowledge in the form of Testability, testable explanations ...
and
thermal insulation insulation, 1600 dpi scan Thermal insulation is the reduction of heat transfer Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion, and exchange of thermal energy Thermal radiation in visible li ...

thermal insulation
(such as
space blanket Image:RescueFoil.jpg, A space blanket A space blanket (also known as a BoPET, Mylar blanket, emergency blanket, first aid blanket, safety blanket, thermal blanket, weather blanket, heat sheet, or shock blanket) is an especially low-weight, low-bulk ...
s). Because of its high mechanical strength, PET film is often used in tape applications, such as the carrier for
magnetic tape Magnetic tape is a medium for , made of a thin, magnetizable coating on a long, narrow strip of . It was developed in Germany in 1928, based on . Devices that record and playback audio and video using magnetic tape are s and s respectively. A ...

magnetic tape
or backing for pressure-sensitive adhesive tapes. Non-oriented PET sheet can be
thermoformed Thermoforming is a manufacturing process where a plastic sheet is heated to a pliable forming temperature, formed to a specific shape in a mold, and trimmed to create a usable product. The sheet, or "film" when referring to thinner gauges and cert ...
to make packaging trays and blister packs. If crystallizable PET is used, the trays can be used for frozen dinners, since they withstand both freezing and oven baking temperatures. Both amorphous PET and BoPET are transparent to the naked eye. Color-conferring dyes can easily be formulated into PET sheet. When filled with glass
particles In the Outline of physical science, physical sciences, a particle (or corpuscule in older texts) is a small wikt:local, localized physical body, object to which can be ascribed several physical property, physical or chemical , chemical properties ...
or
fibres Fiber or fibre (from la, fibra, links=no) is a natural or man-made substance that is significantly longer than it is wide. Fibers are often used in the manufacture of other materials. The strongest engineering materials often incorporate fi ...
, it becomes significantly stiffer and more durable. PET is also used as a substrate in thin film solar cells. PET is also used as a waterproofing barrier in
undersea cables File:France Telecom Marine Rene Descartes p1150247.jpg, Submarine cables are laid using special cable layer ships, such as the modern ', operated by Orange Marine. A submarine communications cable is a cable laid on the seabed, sea bed between lan ...
. Terylene (a trademark formed by inversion of (polyeth)ylene ter(ephthalate)) is also spliced into bell rope tops to help prevent wear on the ropes as they pass through the ceiling. PET is used since late 2014 as liner material in type IV composite high pressure
gas cylinder A gas cylinder is a pressure vessel for storage and containment of gases at above atmospheric pressure. High-pressure gas cylinders are also called ''bottles''. Inside the cylinder the stored contents may be in a state of compressed gas, vapor ...

gas cylinder
s. PET works as a much better barrier to oxygen than earlier used (LD)PE. PET is used as a
3D printing 3D printing, or additive manufacturing, is the construction of a three-dimensional object from a CAD Computer-aided design (CAD) is the use of computers (or ) to aid in the creation, modification, analysis, or optimization of a design. Th ...
filament, as well as in the 3D printing plastic PETG.


History

PET was patented in 1941 by John Rex Whinfield, James Tennant Dickson and their employer the
Calico Printers' Association The Calico Printers' Association Ltd was a British textile company founded in 1899, from the amalgamation of 46 textile printing companies and 13 textile merchants. The industry had prospered in the latter half of the 19th century but the fierce co ...
of
Manchester Manchester () is the most-populous city and metropolitan borough in North West England and Greater Manchester, England. The city has the country's List of English districts by population, fifth-largest population at 547,627 (as of 2018) and li ...

Manchester
, England. in Delaware, United States, first used the trademark Mylar in June 1951 and received registration of it in 1952. It is still the best-known name used for polyester film. The current owner of the trademark is DuPont Teijin Films US, a partnership with a Japanese company. In the Soviet Union, PET was first manufactured in the laboratories of the Institute of High-Molecular Compounds of the
USSR Academy of Sciences The Academy of Sciences of the Soviet Union was the highest scientific institution of the Soviet Union The Soviet Union,. officially the Union of Soviet Socialist Republics. (USSR),. was a that spanned during its existence from 1922 to ...
in 1949, and its name "Lavsan" is an acronym thereof (лаборатории Института высокомолекулярных соединений Академии наук СССР). The PET bottle was patented in 1973 by Nathaniel Wyeth.


Physical properties

PET in its natural state is a colorless, semi-crystalline resin. Based on how it is processed, PET can be semi-rigid to rigid, and it is very lightweight. It makes a good gas and fair moisture barrier, as well as a good barrier to alcohol (requires additional "barrier" treatment) and solvents. It is strong and impact-resistant. PET becomes white when exposed to chloroform and also certain other chemicals such as toluene. About 60% crystallization is the upper limit for commercial products, with the exception of polyester fibers. Clear products can be produced by rapidly cooling molten polymer below Tg
glass transition temperature The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous In condensed matter physics Condensed matter physics is the field of physics Physics (from grc, φυσική (ἐπιστήμ ...
to form an
amorphous solid In condensed matter physics Condensed matter physics is the field of physics Physics (from grc, φυσική (ἐπιστήμη), physikḗ (epistḗmē), knowledge of nature, from ''phýsis'' 'nature'), , is the natural science t ...
. Like glass, amorphous PET forms when its molecules are not given enough time to arrange themselves in an orderly, crystalline fashion as the melt is cooled. At room temperature the molecules are frozen in place, but, if enough heat energy is put back into them by heating above Tg, they begin to move again, allowing crystals to and grow. This procedure is known as solid-state crystallization. When allowed to cool slowly, the molten polymer forms a more crystalline material. This material has
spherulites , Arizona. Image:Rhyolite pmg ss 2006.jpg, Thin section, Photomicrograph of rhyolite showing spherulitic texture (brown, between grey to white crystals). In petrology, spherulites () are small, rounded bodies that commonly occur in Glass, vitreou ...
containing many small
crystallite A crystallite is a small or even microscopic crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice ...

crystallite
s when crystallized from an amorphous solid, rather than forming one large single crystal. Light tends to scatter as it crosses the boundaries between crystallites and the amorphous regions between them. This scattering means that crystalline PET is opaque and white in most cases. Fiber drawing is among the few industrial processes that produce a nearly single-crystal product.


Intrinsic viscosity

One of the most important characteristics of PET is referred to as intrinsic viscosity (IV). The intrinsic viscosity of the material, found by extrapolating to zero concentration of relative viscosity to concentration which is measured in deciliters per gram (dℓ/g). Intrinsic viscosity is dependent upon the length of its polymer chains but has no units due to being extrapolated to zero concentration. The longer the polymer chains the more entanglements between chains and therefore the higher the viscosity. The average chain length of a particular batch of resin can be controlled during
polycondensation Condensation polymers are any kind of polymers formed through a condensation reaction—where molecules join together—''losing'' small molecules as byproducts such as water or methanol. Condensation polymers are formed by polycondensation, when ...

polycondensation
. The intrinsic viscosity range of PET: ; Fiber grade: :* 0.40–0.70, textile :* 0.72–0.98, technical, tire cord ; Film grade: :* 0.60–0.70, BoPET, biaxially oriented PET film :* 0.70–1.00, wikt:sheet, sheet grade for
thermoforming Thermoforming is a manufacturing process where a plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingredient. Their Plasticity (physics), plasticity makes it possible for ...
; Bottle grade: :* 0.70–0.78, water bottles (flat) :* 0.78–0.85, carbonated soft drink grade ; Monofilament, engineering plastic: :* 1.00–2.00


Drying

PET is hygroscopic, meaning that it absorbs water from its surroundings. However, when this "damp" PET is then heated, the water hydrolysis, hydrolyzes the PET, decreasing its resilience. Thus, before the resin can be processed in a molding machine, it must be dried. Drying is achieved through the use of a desiccant or dryers before the PET is fed into the processing equipment. Inside the dryer, hot dry air is pumped into the bottom of the hopper containing the resin so that it flows up through the pellets, removing moisture on its way. The hot wet air leaves the top of the hopper and is first run through an after-cooler, because it is easier to remove moisture from cold air than hot air. The resulting cool wet air is then passed through a desiccant bed. Finally, the cool dry air leaving the desiccant bed is re-heated in a process heater and sent back through the same processes in a closed loop. Typically, residual moisture levels in the resin must be less than 50 parts per million (parts of water per million parts of resin, by weight) before processing. Dryer residence time should not be shorter than about four hours. This is because drying the material in less than 4 hours would require a temperature above 160 °C, at which level hydrolysis would begin inside the pellets before they could be dried out. PET can also be dried in compressed air resin dryers. Compressed air dryers do not reuse drying air. Dry, heated compressed air is circulated through the PET pellets as in the desiccant dryer, then released to the atmosphere.


Copolymers

In addition to pure (homopolymer) PET, PET modified by copolymerization is also available. In some cases, the modified properties of a copolymer are more desirable for a particular application. For example, cyclohexanedimethanol (CHDM) can be added to the polymer backbone in place of
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
. Since this building block is much larger (six additional carbon atoms) than the ethylene glycol unit it replaces, it does not fit in with the neighboring chains the way an ethylene glycol unit would. This interferes with crystallization and lowers the polymer's melting temperature. In general, such PET is known as PETG or PET-G (polyethylene terephthalate glycol-modified). It is a clear amorphous thermoplastic that can be injection-molded, sheet-extruded or extruded as filament for
3D printing 3D printing, or additive manufacturing, is the construction of a three-dimensional object from a CAD Computer-aided design (CAD) is the use of computers (or ) to aid in the creation, modification, analysis, or optimization of a design. Th ...
. PETG can be colored during processing. Another common modifier is isophthalic acid, replacing some of the 1,4-(''para-'') linked Terephthalic acid, terephthalate units. The 1,2-(''ortho-'') or 1,3-(''Arene substitution patterns, meta''-) linkage produces an angle in the chain, which also disturbs crystallinity. Such copolymers are advantageous for certain molding applications, such as
thermoforming Thermoforming is a manufacturing process where a plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingredient. Their Plasticity (physics), plasticity makes it possible for ...
, which is used for example to make tray or blister packaging from co-PET film, or amorphous PET sheet (A-PET/PETA) or PETG sheet. On the other hand, crystallization is important in other applications where mechanical and dimensional stability are important, such as seat belts. For PET bottles, the use of small amounts of isophthalic acid, CHDM, diethylene glycol (DEG) or other comonomers can be useful: if only small amounts of comonomers are used, crystallization is slowed but not prevented entirely. As a result, bottles are obtainable via stretch blow molding ("SBM"), which are both clear and crystalline enough to be an adequate barrier to aromas and even gases, such as carbon dioxide in carbonated beverages.


Production

Polyethylene terephthalate is produced from
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
and
dimethyl terephthalate Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.Richard J. Sheehan "Terephth ...
(DMT) (C6H4(CO2CH3)2) or
terephthalic acid Terephthalic acid is an organic compound , CH4; is among the simplest organic compounds. In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen chemical bond, bonds. Due to carbon's ability to Catenatio ...

terephthalic acid
. The former is a
transesterification In organic chemistry, transesterification is the process of exchanging the organic group R″ of an ester with the organic group R′ of an alcohol File:Alcohol general.svg, upright=0.8, The bond angle between a hydroxyl group (-OH) and a chai ...

transesterification
reaction, whereas the latter is an
esterification An ester is a chemical compound derived from an acid (organic or inorganic) in which at least one –OH hydroxyl group is replaced by an –O– alkyl ( alkoxy) group, as in the substitution reaction of a carboxylic acid and an alcohol. Glycer ...

esterification
reaction.


Dimethyl terephthalate process (DMT)

In
dimethyl terephthalate Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.Richard J. Sheehan "Terephth ...
(DMT) process, this compound and excess ethylene glycol are reacted in the melt at 150–200 °C with a base (chemistry), basic catalyst. Methanol (CH3OH) is removed by distillation to drive the reaction forward. Excess ethylene glycol is distilled off at higher temperature with the aid of vacuum. The second transesterification step proceeds at 270–280 °C, with continuous distillation of ethylene glycol as well. The reactions are idealized as follows: ;First step : C6H4(CO2CH3)2 + 2 HOCH2CH2OH → C6H4(CO2CH2CH2OH)2 + 2 CH3OH ;Second step : ''n'' C6H4(CO2CH2CH2OH)2 → [(CO)C6H4(CO2CH2CH2O)]n + ''n'' HOCH2CH2OH


Terephthalic acid process

In the
terephthalic acid Terephthalic acid is an organic compound , CH4; is among the simplest organic compounds. In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen chemical bond, bonds. Due to carbon's ability to Catenatio ...

terephthalic acid
process, esterification of ethylene glycol and terephthalic acid is conducted directly at moderate pressure (2.7–5.5 bar) and high temperature (220–260 °C). Water is eliminated in the reaction, and it is also continuously removed by distillation: : ''n'' C6H4(CO2H)2 + ''n'' HOCH2CH2OH → [(CO)C6H4(CO2CH2CH2O)]n + 2''n'' H2O


Degradation

PET is subject to various types of degradations during processing. The main degradations that can occur are hydrolytic, and probably most important, thermal oxidation. When PET degrades, several things happen: discoloration, chain Bond cleavage, scissions resulting in reduced molecular weight, formation of acetaldehyde, and cross-links ("gel" or "fish-eye" formation). Discoloration is due to the formation of various chromophoric systems following prolonged thermal treatment at elevated temperatures. This becomes a problem when the visual expectations for the polymer are very high, such as in packaging applications. The thermal and thermooxidative degradation results in poor processibility characteristics and performance of the material. One way to alleviate this is to use a copolymer. Comonomers such as CHDM or isophthalic acid lower the melting temperature and reduce the degree of crystallinity of PET (especially important when the material is used for bottle manufacturing). Thus, the resin can be plastically formed at lower temperatures and/or with lower force. This helps to prevent degradation, reducing the acetaldehyde content of the finished product to an acceptable (that is, unnoticeable) level. See #Copolymers, copolymers, above. Another way to improve the stability of the polymer is to use stabilizers, mainly antioxidants such as phosphites. Recently, molecular level stabilization of the material using nanostructured chemicals has also been considered.


Acetaldehyde

Acetaldehyde is a colorless, volatile substance with a fruity smell. Although it forms naturally in some fruit, it can cause an off-taste in bottled water. Acetaldehyde forms by degradation of PET through the mishandling of the material. High temperatures (PET decomposes above 300 °C or 570 °F), high pressures, extruder speeds (excessive shear flow raises temperature), and long barrel residence times all contribute to the production of acetaldehyde. When acetaldehyde is produced, some of it remains dissolved in the walls of a container and then diffusion, diffuses into the product stored inside, altering the taste and aroma. This is not such a problem for non-consumables (such as shampoo), for fruit juices (which already contain acetaldehyde), or for strong-tasting drinks like soft drinks. For bottled water, however, low acetaldehyde content is quite important, because, if nothing masks the aroma, even extremely low concentrations (10–20 parts per billion in the water) of acetaldehyde can produce an off-taste.


Antimony

Antimony (Sb) is a metalloid element that is used as a catalyst in the form of compounds such as antimony trioxide (Sb2O3) or antimony triacetate in the production of PET. After manufacturing, a detectable amount of antimony can be found on the surface of the product. This residue can be removed with washing. Antimony also remains in the material itself and can, thus, migrate out into food and drinks. Exposing PET to boiling or microwaving can increase the levels of antimony significantly, possibly above US EPA maximum contamination levels. The drinking water limit assessed by WHO is 20 parts per billion (WHO, 2003), and the drinking water limit in the United States is 6 parts per billion. Although antimony trioxide is of low toxicity when taken orally,Guidelines for drinking – water quality
who.int
its presence is still of concern. The Swiss Federal Office of Public Health investigated the amount of antimony migration, comparing waters bottled in PET and glass: The antimony concentrations of the water in PET bottles were higher, but still well below the allowed maximum concentration. The Swiss Federal Office of Public Health concluded that small amounts of antimony migrate from the PET into bottled water, but that the health risk of the resulting low concentrations is negligible (1% of the "tolerable daily intake" determined by the World Health Organization, WHO). A later (2006) but more widely publicized study found similar amounts of antimony in water in PET bottles. The WHO has published a risk assessment for antimony in drinking water. Fruit juice concentrates (for which no guidelines are established), however, that were produced and bottled in PET in the UK were found to contain up to 44.7 μg/L of antimony, well above the EU limits for tap water of 5 μg/L.


Biodegradation

At least one species of bacterium in the genus ''Nocardia'' can degrade PET with an esterase enzyme. In the PET monomers, Esterase is an enzyme family that able to cleave the ester bond. Also, the initial degradation of PET can be esterases by ''Bacillus'' and ''Nocardia''. Japanese scientists have isolated a bacterium ''Ideonella sakaiensis'' that possesses two enzymes which can break down the PET into smaller pieces that the bacterium can digest. A colony of ''I. sakaiensis'' can disintegrate a plastic film in about six weeks. In April 2020, a French university announced the discovery of a highly efficient, optimized enzyme that outperforms all PET hydrolases reported so far. This discovery may prove to be an important step towards the concept of a circular PET economy.


Environmental concerns

PET is fairly easily recycled from used beverage containers, although this material is still manufactured from crude oil. Compared to the use of petroleum as fuel, however, the amount of crude oil processed into PET is very small. The total production capacity of PET is around 30.5 million metric tons, compared to 4.2 billion metric tons of crude oil production, thus around 0.7% of crude oil is processed into PET. As municipal waste water systems often discharge into rivers and oceans, BOttles and other debris are observed. PET has a density of around 1.3, so will sink in both fresh and sea water. PET is known to degrade when exposed to sunlight and oxygen. Microplastics which are present on the bottom of the river or seabed can ingested by small marine life, thus entering the food chain. As PET has a higher density than water, a significant fraction of microplastics may be precipitated in sewage treatment plants. Very light PET fibers can become airborne, directly from clothes dryer vents or wind. Fibers can travel long distances and migrate to fields, where they are ingested by livestock or delivered to the human food supply on produce products. To this date, scarce information exists regarding the life-time of the synthetic polymers in the environment.


Safety

Commentary published in ''Environmental Health Perspectives'' in April 2010 suggested that PET might yield endocrine disruptors under conditions of common use and recommended research on this topic. Proposed mechanisms include leaching of phthalates as well as leaching of antimony. An article published in ''Journal of Environmental Monitoring'' in April 2012 concludes that antimony concentration in deionized water stored in PET bottles stays within EU's acceptable limit even if stored briefly at temperatures up to 60 °C (140 °F), while bottled contents (water or soft drinks) may occasionally exceed the EU limit after less than a year of storage at room temperature.


Bottle processing equipment

There are two basic molding methods for PET bottles, one-step and two-step. In two-step molding, two separate machines are used. The first machine injection molds the preform, which resembles a test tube, with the bottle-cap threads already molded into place. The body of the tube is significantly thicker, as it will be inflated into its final shape in the second step using stretch blow molding. In the second step, the preforms are heated rapidly and then inflated against a two-part mold to form them into the final shape of the bottle. Preforms (uninflated bottles) are now also used as robust and unique containers themselves; besides novelty candy, some Red Cross chapters distribute them as part of the Vial of Life program to homeowners to store medical history for emergency responders. In one-step machines, the entire process from raw material to finished container is conducted within one machine, making it especially suitable for molding non-standard shapes (custom molding), including jars, flat oval, flask shapes, etc. Its greatest merit is the reduction in space, product handling and energy, and far higher visual quality than can be achieved by the two-step system.


Polyester recycling industry

In 2016, it was estimated that 56 million tons of PET are produced each year. While most thermoplastics can, in principle, be recycled, PET bottle recycling is more practical than many other plastic applications because of the high value of the resin and the almost exclusive use of PET for widely used water and carbonated soft drink bottling. PET has a
resin identification code The ASTM International Resin Identification Coding System, often abbreviated RIC, is a set of symbols appearing on plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingre ...

resin identification code
of 1. The prime uses for recycled PET are polyester Synthetic fiber, fiber, strapping, and non-food containers. Because of the recyclability of PET and the relative abundance of post-consumer waste in the form of bottles, PET is rapidly gaining market share as a carpet fiber. Mohawk Industries released everSTRAND in 1999, a 100% post-consumer recycled content PET fiber. Since that time, more than 17 billion bottles have been recycled into carpet fiber. Pharr Yarns, a supplier to numerous carpet manufacturers including Looptex, Dobbs Mills, and Berkshire Flooring, produces a BCF (bulk continuous filament) PET carpet fiber containing a minimum of 25% post-consumer recycled content. PET, like many plastics, is also an excellent candidate for thermal disposal (incineration), as it is composed of carbon, hydrogen, and oxygen, with only trace amounts of catalyst elements (but no sulfur). PET has the energy content of soft coal. When recycling polyethylene terephthalate or PET or polyester, in general three ways have to be differentiated: #The chemical recycling back to the initial raw materials purified
terephthalic acid Terephthalic acid is an organic compound , CH4; is among the simplest organic compounds. In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen chemical bond, bonds. Due to carbon's ability to Catenatio ...

terephthalic acid
(PTA) or
dimethyl terephthalate Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.Richard J. Sheehan "Terephth ...
(DMT) and
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
(EG) where the polymer structure is destroyed completely, or in process intermediates like #The mechanical recycling where the original polymer properties are being maintained or reconstituted. #The chemical recycling where transesterification takes place and other glycols/polyols or glycerol are added to make a polyol which may be used in other ways such as polyurethane production or PU foam production Chemical recycling of PET will become cost-efficient only applying high capacity recycling lines of more than 50,000 tons/year. Such lines could only be seen, if at all, within the production sites of very large polyester producers. Several attempts of industrial magnitude to establish such chemical recycling plants have been made in the past but without resounding success. Even the promising chemical recycling in Japan has not become an industrial breakthrough so far. The two reasons for this are: at first, the difficulty of consistent and continuous waste bottles sourcing in such a huge amount at one single site, and, at second, the steadily increased prices and price volatility of collected bottles. The prices of baled bottles increased for instance between the years 2000 and 2008 from about 50 Euro/ton to over 500 Euro/ton in 2008. Mechanical recycling or direct circulation of PET in the polymeric state is operated in most diverse variants today. These kinds of processes are typical of small and medium-size industry. Cost-efficiency can already be achieved with plant capacities within a range of 5000–20,000 tons/year. In this case, nearly all kinds of recycled-material feedback into the material circulation are possible today. These diverse recycling processes are being discussed hereafter in detail. Besides chemical contaminants and Chemical decomposition, degradation products generated during first processing and usage, mechanical impurities are representing the main part of quality depreciating impurities in the recycling stream. Recycled materials are increasingly introduced into manufacturing processes, which were originally designed for new materials only. Therefore, efficient sorting, separation and cleaning processes become most important for high quality recycled polyester. When talking about polyester recycling industry, we are concentrating mainly on recycling of PET bottles, which are meanwhile used for all kinds of liquid packaging like water, carbonated soft drinks, juices, beer, sauces, detergents, household chemicals and so on. Bottles are easy to distinguish because of shape and consistency and separate from waste plastic streams either by automatic or by hand-sorting processes. The established polyester recycling industry consists of three major sections: * PET bottle collection and waste separation: waste logistics * Production of clean bottle flakes: flake production * Conversion of PET flakes to final products: flake processing Intermediate product from the first section is baled bottle waste with a PET content greater than 90%. Most common trading form is the bale but also bricked or even loose, pre-cut bottles are common in the market. In the second section, the collected bottles are converted to clean PET bottle flakes. This step can be more or less complex and complicated depending on required final flake quality. During the third step, PET bottle flakes are processed to any kind of products like film, bottles, fiber, filament, strapping or intermediates like pellets for further processing and engineering plastics. Besides this external (post-consumer) polyester bottle recycling, numbers of internal (pre-consumer) recycling processes exist, where the wasted polymer material does not exit the production site to the free market, and instead is reused in the same production circuit. In this way, fiber waste is directly reused to produce fiber, preform waste is directly reused to produce preforms, and film waste is directly reused to produce film.


PET bottle recycling


Purification and decontamination

The success of any recycling concept is hidden in the efficiency of purification and decontamination at the right place during processing and to the necessary or desired extent. In general, the following applies: The earlier in the process foreign substances are removed, and the more thoroughly this is done, the more efficient the process is. The high plasticization temperature of PET in the range of is the reason why almost all common organic impurities such as Polyvinyl chloride, PVC, Polylactic acid, PLA, polyolefin, chemical wood-pulp and paper fibers, polyvinyl acetate, melt adhesive, coloring agents, sugar, and protein residues are transformed into colored degradation products that, in their turn, might release in addition reactive degradation products. Then, the number of defects in the polymer chain increases considerably. The particle size distribution of impurities is very wide, the big particles of 60–1000 μm—which are visible by naked eye and easy to filter—representing the lesser evil, since their total surface is relatively small and the degradation speed is therefore lower. The influence of the microscopic particles, which—because they are many—increase the frequency of defects in the polymer, is relatively greater. Besides efficient sorting, the removal of visible impurity particles by melt filtration processes plays a particular part in this case. In general, one can say that the processes to make PET bottle flakes from collected bottles are as versatile as the different waste streams are different in their composition and quality. In view of technology there is not just one way to do it. Meanwhile, there are many engineering companies that are offering flake production plants and components, and it is difficult to decide for one or other plant design. Nevertheless, there are processes that are sharing most of these principles. Depending on composition and impurity level of input material, the general following process steps are applied. #Bale opening, briquette opening #Sorting and selection for different colors, foreign polymers especially PVC, foreign matter, removal of film, paper, glass, sand, soil, stones, and metals #Pre-washing without cutting #Coarse cutting dry or combined to pre-washing #Removal of stones, glass, and metal #Air sifting to remove film, paper, and labels #Grinding, dry and / or wet #Removal of low-density polymers (bottle caps) by density differences #Hot-wash #Caustic wash, and surface etching, maintaining intrinsic viscosity and decontamination #Rinsing #Clean water rinsing #Drying #Air-sifting of flakes #Automatic flake sorting #Water circuit and water treatment technology #Flake quality control


Impurities and material defects

The number of possible impurities and material defects that accumulate in the polymeric material is increasing permanently—when processing as well as when using polymers—taking into account a growing service lifetime, growing final applications and repeated recycling. As far as recycled PET bottles are concerned, the defects mentioned can be sorted in the following groups: # Reactive polyester OH- or COOH- end groups are transformed into dead or non-reactive end groups, e.g. formation of vinyl ester end groups through dehydration or decarboxylation of terephthalate acid, reaction of the OH- or COOH- end groups with mono-functional degradation products like mono-carbonic acids or alcohols. Results are decreased reactivity during re-polycondensation or re-SSP and broadening the molecular weight distribution. # The end group proportion shifts toward the direction of the COOH end groups built up through a thermal and oxidative degradation. The results are decrease in reactivity, and increase in the acid autocatalytic decomposition during thermal treatment in presence of humidity. # Number of polyfunctional macromolecules increases. Accumulation of gels and long-chain branching defects. # Number, concentration, and variety of nonpolymer-identical organic and inorganic foreign substances are increasing. With every new thermal stress, the organic foreign substances will react by decomposition. This is causing the liberation of further degradation-supporting substances and coloring substances. # Hydroxide and peroxide groups build up at the surface of the products made of polyester in presence of air (oxygen) and humidity. This process is accelerated by ultraviolet light. During an ulterior treatment process, hydro peroxides are a source of oxygen radicals, which are source of oxidative degradation. Destruction of hydro peroxides is to happen before the first thermal treatment or during plasticization and can be supported by suitable additives like antioxidants. Taking into consideration the above-mentioned chemical defects and impurities, there is an ongoing modification of the following polymer characteristics during each recycling cycle, which are detectable by chemical and physical laboratory analysis. In particular: *Increase of COOH end-groups *Increase of color number b *Increase of haze (transparent products) *Increase of oligomer content *Reduction in filterability *Increase of by-products content such as acetaldehyde, formaldehyde *Increase of extractable foreign contaminants *Decrease in color L *Decrease of intrinsic viscosity or dynamic viscosity *Decrease of crystallization temperature and increase of crystallization speed *Decrease of the mechanical properties like tensile strength, elongation at break or elastic modulus *Broadening of molecular weight distribution The recycling of PET bottles is meanwhile an industrial standard process that is offered by a wide variety of engineering companies.


Processing examples for recycled polyester

Recycling processes with polyester are almost as varied as the manufacturing processes based on primary pellets or melt. Depending on purity of the recycled materials, polyester can be used today in most of the polyester manufacturing processes as blend with virgin polymer or increasingly as 100% recycled polymer. Some exceptions like BOPET-film of low thickness, special applications like optical film or yarns through FDY-spinning at > 6000 m/min, microfilaments, and micro-fibers are produced from virgin polyester only.


Simple re-pelletizing of bottle flakes

This process consists of transforming bottle waste into flakes, by drying and crystallizing the flakes, by plasticizing and filtering, as well as by pelletizing. Product is an amorphous re-granulate of an intrinsic viscosity in the range of 0.55–0.7 dℓ/g, depending on how complete pre-drying of PET flakes has been done. Special feature are: Acetaldehyde and oligomers are contained in the pellets at lower level; the viscosity is reduced somehow, the pellets are amorphous and have to be crystallized and dried before further processing. Processing to: *A-PET film for
thermoforming Thermoforming is a manufacturing process where a plastic Plastics are a wide range of synthetic polymers, synthetic or semi-synthetic materials that use polymers as a main ingredient. Their Plasticity (physics), plasticity makes it possible for ...
*Addition to PET virgin production *BoPET packaging film *PET Bottle resin by SSP *Carpet yarn *Engineering plastic *Filaments *Non-woven *Packaging stripes *Staple fibre. Choosing the re-pelletizing way means having an additional conversion process that is, at the one side, energy-intensive and cost-consuming, and causes thermal destruction. At the other side, the pelletizing step is providing the following advantages: *Intensive melt filtration *Intermediate quality control *Modification by additives *Product selection and separation by quality *Processing flexibility increased *Quality uniformization.


Manufacture of PET-pellets or flakes for bottles (bottle to bottle) and A-PET

This process is, in principle, similar to the one described above; however, the pellets produced are directly (continuously or discontinuously) crystallized and then subjected to a solid-state polycondensation (SSP) in a tumbling drier or a vertical tube reactor. During this processing step, the corresponding intrinsic viscosity of 0.80–0.085 dℓ/g is rebuilt again and, at the same time, the acetaldehyde content is reduced to < 1 ppm. The fact that some machine manufacturers and line builders in Europe and the United States make efforts to offer independent recycling processes, e.g. the so-called bottle-to-bottle (B-2-B) process, such as Next Generation Recycling (NGR), BePET, Starlinger, URRC or BÜHLER, aims at generally furnishing proof of the "existence" of the required extraction residues and of the removal of model contaminants according to FDA applying the so-called challenge test, which is necessary for the application of the treated polyester in the food sector. Besides this process approval it is nevertheless necessary that any user of such processes has to constantly check the FDA limits for the raw materials manufactured by themselves for their process.


Direct conversion of bottle flakes

In order to save costs, an increasing number of polyester intermediate producers like spinning mills, strapping mills, or cast film mills are working on the direct use of the PET-flakes, from the treatment of used bottles, with a view to manufacturing an increasing number of polyester intermediates. For the adjustment of the necessary viscosity, besides an efficient drying of the flakes, it is possibly necessary to also reconstitute the viscosity through
polycondensation Condensation polymers are any kind of polymers formed through a condensation reaction—where molecules join together—''losing'' small molecules as byproducts such as water or methanol. Condensation polymers are formed by polycondensation, when ...

polycondensation
in the melt phase or solid-state polycondensation of the flakes. The latest PET flake conversion processes are applying twin screw extruders, multi-screw extruders or multi-rotation systems and coincidental vacuum degassing to remove moisture and avoid flake pre-drying. These processes allow the conversion of undried PET flakes without substantial viscosity decrease caused by hydrolysis. With regard to the consumption of PET bottle flakes, the main portion of about 70% is converted to fibers and filaments. When using directly secondary materials such as bottle flakes in spinning processes, there are a few processing principles to obtain. High-speed spinning processes for the manufacture of POY normally need a viscosity of 0.62–0.64 dℓ/g. Starting from bottle flakes, the viscosity can be set via the degree of drying. The additional use of TiO2 is necessary for full dull or semi dull yarn. In order to protect the spinnerets, an efficient filtration of the melt is, in any case is necessary. For the time-being, the amount of POY made of 100% recycling polyester is rather low because this process requires high purity of spinning melt. Most of the time, a blend of virgin and recycled pellets is used. Staple fibers are spun in an intrinsic viscosity range that lies rather somewhat lower and that should be between 0.58 and 0.62 dℓ/g. In this case, too, the required viscosity can be adjusted via drying or vacuum adjustment in case of vacuum extrusion. For adjusting the viscosity, however, an addition of chain length modifier like
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
or diethylene glycol can also be used. Spinning non-woven—in the fine titer field for textile applications as well as heavy spinning non-woven as basic materials, e.g. for roof covers or in road building—can be manufactured by spinning bottle flakes. The spinning viscosity is again within a range of 0.58–0.65 dℓ/g. One field of increasing interest where recycled materials are used is the manufacture of high-tenacity packaging stripes, and monofilaments. In both cases, the initial raw material is a mainly recycled material of higher intrinsic viscosity. High-tenacity packaging stripes as well as monofilament are then manufactured in the melt spinning process.


Recycling to the monomers

Polyethylene terephthalate can be depolymerized to yield the constituent monomers. After purification, the monomers can be used to prepare new polyethylene terephthalate. The ester bonds in polyethylene terephthalate may be cleaved by hydrolysis, or by transesterification. The reactions are simply the reverse of those used #Production, in production.


Partial glycolysis

Partial glycolysis (transesterification with ethylene glycol) converts the rigid polymer into short-chained oligomers that can be melt-filtered at low temperature. Once freed of the impurities, the oligomers can be fed back into the production process for polymerization. The task consists in feeding 10–25% bottle flakes while maintaining the quality of the bottle pellets that are manufactured on the line. This aim is solved by degrading the PET bottle flakes—already during their first plasticization, which can be carried out in a single- or multi-screw extruder—to an intrinsic viscosity of about 0.30 dℓ/g by adding small quantities of ethylene glycol and by subjecting the low-viscosity melt stream to an efficient filtration directly after plasticization. Furthermore, temperature is brought to the lowest possible limit. In addition, with this way of processing, the possibility of a chemical decomposition of the hydro peroxides is possible by adding a corresponding P-stabilizer directly when plasticizing. The destruction of the hydro peroxide groups is, with other processes, already carried out during the last step of flake treatment for instance by adding H3PO3. The partially glycolyzed and finely filtered recycled material is continuously fed to the esterification or prepolycondensation reactor, the dosing quantities of the raw materials are being adjusted accordingly.


Total glycolysis, methanolysis, and hydrolysis

The treatment of polyester waste through total glycolysis to fully convert the polyester to (C6H4(CO2CH2CH2OH)2). This compound is purified by vacuum distillation, and is one of the intermediates used in polyester manufacture (see #Production, production). The reaction involved is as follows: : [(CO)C6H4(CO2CH2CH2O)]n + ''n'' HOCH2CH2OH → ''n'' C6H4(CO2CH2CH2OH)2 This recycling route has been executed on an industrial scale in Japan as experimental production. Similar to total glycolysis, methanolysis converts the polyester to
dimethyl terephthalate Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.Richard J. Sheehan "Terephth ...
(DMT), which can be filtered and vacuum distilled: : [(CO)C6H4(CO2CH2CH2O)]n + ''2n'' CH3OH → ''n'' C6H4(CO2CH3)2 Methanolysis is only rarely carried out in industry today because polyester production based on dimethyl terephthalate(DMT) has shrunk tremendously, and many dimethyl terephthalate (DMT) producers have disappeared.Fakirov, Stoyko (ed.) (2002) ''Handbook of Thermoplastic Polyesters'', Wiley-VCH, Weinheim, pp. 1223 ff, Also as above, polyethylene terephthalate can be hydrolyzed to terephthalic acid and
ethylene glycol Ethylene glycol (IUPAC name In chemical nomenclatureA chemical nomenclature is a set of rules to generate systematic names for chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecula ...

ethylene glycol
under high temperature and pressure. The resultant crude terephthalic acid can be purified by recrystallization (chemistry), recrystallization to yield material suitable for re-polymerization: : [(CO)C6H4(CO2CH2CH2O)]n + 2''n'' H2O → ''n'' C6H4(CO2H)2 + ''n'' HOCH2CH2OH This method does not appear to have been commercialized yet.


See also

* BoPET (biaxially oriented PET) * Bioplastic * PET bottle recycling * Plastic recycling * Polycyclohexylenedimethylene terephthalate—a polyester with a similar structure to PET * Polyester * Solar water disinfection—a method of disinfection, disinfecting water using only sunlight and plastic PET bottles


References


External links


American Plastics Council: PlasticInfo.org

KenPlas Industry Ltd.: "What is PET (Polyethylene Terephthalate)"

"WAVE Polymer Technology: PET (Polyethylene Terephthalate) flakes processing"

Arropol commercial producer of polyol from post-consumer PET fiber
{{DEFAULTSORT:Polyethylene Terephthalate Biomaterials Terephthalate esters Commodity chemicals English inventions Flexible electronics Household chemicals Plastics Polyesters Polymers Thermoplastics Transparent materials