Polyester
Polyester is a category of polymers that contain the ester functional group in their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate. 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.
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.
Natural polyesters could have played a significant role in the origins of life. Long heterogeneous polyester chains and membraneless structures are known to easily form in a one-pot reaction without catalyst under simple prebiotic conditions.
Types
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. Examples of thermoset polyesters include some of the Desmophen brand from Bayer. 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.Unsaturated polyesters 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.
According to the composition of their main chain, polyesters can be:
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 and the polyethylene adipate diol. They are then used as prepolymers.
Uses and applications
woven or knitted from polyester thread or yarn are used extensively in apparel and home furnishings, from shirts and pants to jackets and hats, bed sheets, blankets, upholstered furniture and computer mouse mats. Industrial polyester fibers, yarns and ropes are used in car tire reinforcements, fabrics for conveyor belts, safety belts, coated fabrics and plastic reinforcements with high-energy absorption. Polyester fiber is used as cushioning and insulating material in pillows, comforters and upholstery padding. Polyester fabrics are highly stain-resistant—in fact, the only class of dyes which can be used to alter the color of polyester fabric are what are known as disperse dyes.Polyesters are also used to make bottles, films, tarpaulin, sails, 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.
Industry
Basics
Polyester is a synthetic polymer made of purified terephthalic acid or its dimethyl ester dimethyl terephthalate and monoethylene glycol. With 18% market share of all plastic materials produced, it ranges third after polyethylene and polypropylene.The main raw materials are described as follows:
;Purified terephthalic acid CAS-No. 100-21-0: Synonym: 1,4 benzenedicarboxylic acid,
Sum formula: C6H42, mol. weight: 166.13
;Dimethylterephthalate CAS-No. 120-61-6: Synonym: 1,4 benzenedicarboxylic acid dimethyl ester,
Sum formula: C6H42, mol. weight: 194.19
;Mono-ethylene glycol CAS No. 107-21-1: Synonym: 1,2 ethanediol,
Sum formula: C2H6O2, mol. weight: 62.07
To make a polymer of high molecular weight a catalyst is needed. The most common catalyst is antimony trioxide :
;Antimony trioxide CAS-No. 1309-64-4: mol. weight: 291.51,
Sum formula: Sb2O3
In 2008, about 10,000 tonnes Sb2O3 were used to produce around 49 million tonnes polyethylene terephthalate.
Polyester is described as follows:
;Polyethylene terephthalate CAS-No. 25038-59-9: Synonyms/abbreviations: polyester, PET, PES,
Sum formula: H--n=60–120 OH, mol. unit weight: 192.17
There are several reasons for the importance of polyester:
- The relatively easy accessible raw materials PTA or DMT and MEG
- The very well understood and described simple chemical process of polyester synthesis
- The low toxicity level of all raw materials and side products during polyester production and processing
- The possibility to produce PET in a closed loop at low emissions to the environment
- The outstanding mechanical and chemical properties of polyester
- The recyclability
- The wide variety of intermediate and final products made of polyester.
| Product type | 2002 | 2008 |
| 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 |
Raw material producer
The raw materials PTA, DMT, and MEG are mainly produced by large chemical companies which are sometimes integrated down to the crude oil refinery where p-Xylene is the base material to produce PTA and liquefied petroleum gas is the base material to produce MEG.Polyester processing
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 | Packaging |
| Staple fiber | 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 |
| 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 polyester film;
;BO-PET: Biaxial-oriented polyester film;
A comparable small market segment 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 or POY /FDY 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
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 :
Azeotrope esterification
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.
Alcoholic transesterification
Acylation (HCl method)
The acid begins as an acid chloride, and thus the polycondensation proceeds with emission of hydrochloric acid instead of water. This method can be carried out in solution or as an enamel.Acetate method (esterification)
Ring-opening polymerization
polyesters can be assembled from lactones under very mild conditions, catalyzed anionically, cationically or metallorganically.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.