Polyester resins are synthetic resins formed by the reaction of dibasic organic acids and polyhydric alcohols. Maleic anhydride is a commonly used raw material with diacid functionality in unsaturated polyester resins. [1] Unsaturated polyester resins are used in sheet moulding compound, bulk moulding compound and the toner of laser printers. Wall panels fabricated from polyester resins reinforced with fiberglass —so-called fiberglass reinforced plastic (FRP)—are typically used in restaurants, kitchens, restrooms and other areas that require washable low-maintenance walls. They are also used extensively in cured-in-place pipe applications. Departments of Transportation in the USA also specify them for use as overlays on roads and bridges. In this application they are known AS Polyester Concrete Overlays (PCO). These are usually based on isophthalic acid and cut with styrene at high levels—usually up to 50%. [2] Polyesters are also used in anchor bolt adhesives though epoxy based materials are also used. [3] Many companies have and continue to introduce styrene free systems mainly due to odor issues, but also over concerns that styrene is a potential carcinogen. Drinking water applications also prefer styrene free. Most polyester resins are viscous, pale coloured liquids consisting of a solution of a polyester in a reactive diluent which is usually styrene, [4] but can also include vinyl toluene and various acrylates. [5] [6]
Unsaturated polyesters are condensation polymers formed by the reaction of polyols (also known as polyhydric alcohols), organic compounds with multiple alcohol or hydroxy functional groups, with unsaturated and in some cases saturated dibasic acids. Typical polyols used are glycols including ethylene glycol, propylene glycol, and diethylene glycol; typical acids used are phthalic acid, isophthalic acid, terephthalic acid, and maleic anhydride. Water, a condensation by-product of esterification reactions, is continuously removed by distillation, driving the reaction to completion via Le Chatelier's principle. Unsaturated polyesters are generally sold to parts manufacturers as a solution of resin in reactive diluent; styrene is the most common diluent and the industry standard. The diluent allows control over the viscosity of the resin, and is also a participant in the curing reaction. The initially liquid resin is converted to a solid by cross-linking chains. This is done by creating free radicals at unsaturated bonds, which propagate in a chain reaction to other unsaturated bonds in adjacent molecules, linking them in the process. Unsaturation is generally in the form of maleate and fumarate species along the polymer chain. Maleate/fumarate generally does not self-polymerize via radical reactions, but readily reacts with styrene. Maleic anhydride and styrene are known to form alternating copolymers, and are in fact the textbook case of this phenomenon. This is one reason that styrene has been so hard to displace in the market as the industry standard reactive diluent for unsaturated polyester resins, despite increasing efforts to displace the material such as California's Proposition 65. The initial free radicals are induced by adding a compound that easily decomposes into free radicals. This compound is known as the catalyst [7] within the industry, but initiator is a more appropriate term. Transition metal salts are usually added as a catalyst for the chain-growth crosslinking reaction, and in the industry this type of additive is known as a promoter; the promoter is generally understood to lower the bond dissociation energy of the radical initiator. Cobalt salts are the most common type of promoter used. Common radical initiators used are organic peroxides such as benzoyl peroxide or methyl ethyl ketone peroxide. [8]
Polyester resins are thermosetting and, as with other resins, cure exothermically. The use of excessive initiator especially with a catalyst present can, therefore, cause charring or even ignition during the curing process. Excessive catalyst may also cause the product to fracture or form a rubbery material.
Unsaturated polyesters (UPR) are utilized in many different industrially relevant markets, but in general are used as the matrix material for various types of composites. Glass fiber-reinforced composites comprise the largest segment into which UPRs are used and can be processed via SMC, BMC, pultrusion, cured-in-place pipe (known as relining in Europe), filament winding, vacuum molding, spray-up molding, resin transfer molding (RTM). Wind turbine blades also use them [9] as well as many more processes. UPRs are also used in non-reinforced applications with common examples being gel coats, shirt buttons, mine-bolts, bowling ball cores, polymer concrete, and engineered stone/cultured marble. [10]
In organic chemistry, an ester is formed as the condensation product of a carboxylic acid and an alcohol, with water formed as the condensate by-product. An ester can also be produced with an acyl halide and an alcohol, in which case the condensate by-product is a hydrogen halide.
Polyesters are a category of polymers in which ester functionality repeats within the main chain. Polyesters are a classic example of step-growth polymer, in which a difunctional (or higher order) acid or acyl halide is reacted with a difunctional (or higher order) alcohol. Polyesters are produced commercially both as saturated and unsaturated resins. The most common and highest volume produced polyester is Polyethylene terephthalate (PET), which is an example of a saturated polyester and finds utilization in such applications as fibers for clothing and carpet, food and liquid containers (such as a water/soda bottles), as well as films. [11]
In unsaturated polyester (UPR) chemistry, unsaturation sites are present along the chain, usually by incorporation of maleic anhydride, but maleic acid and fumaric acid are also used. Maleic acid and fumaric acid are isomers where maleic is the cis-isomer and fumaric is the trans-isomer. The ester forms of these two molecules are maleate and fumarate, respectively. When curing a UPR, the fumarate form is known to react more rapidly with the styrene radical, so isomerization catalysts, such as N,N-dimethylacetoacetamide (DMAA), are often employed in the synthesis process which converts the maleates into fumarates; the isomerization can also be encouraged with increased reaction time and temperature. Within the UPR industry, the classification of the resins is generally based on the primary saturated acid. For example, a resin containing primarily terephthalic acid is known as a Tere resin, a resin containing primarily phthalic anhydride is known as an Ortho resin, and a resin containing primarily isophthalic acid is known as an Iso resin. Dicyclopentadiene (DCPD) is also a common UPR raw material, and can be incorporated two different ways. In one process, the DCPD is cracked in situ to form cyclopentadiene which can then be reacted with maleate/fumarate groups along the polymer chain via a Diels-alder reaction. This type of resin is known as a Nadic resin and is referred to as a poor man's Ortho, due to sharing many similar properties of an Ortho resin along with the extremely low cost of DCPD raw material. In another process, maleic anhydride is first opened with water or another alcohol to form maleic acid and is then reacted with DCPD where an alcohol from the maleic acid reacts across one of the double bonds of the DCPD. This product is then used to end-cap the UPR resin which yields a product with unsaturation on the end-groups. This type of resin is referred to as a DCPD resin.
Ortho resins comprise the most common type of UPR, and many are known as general purpose resins. FRP composites utilizing ortho resins are found in such application as boat hulls, bath ware, and bowling ball cores.
Iso resins are generally on the higher end of UPR products, both because of the relatively higher cost of the isophthalic acid as well as the superior properties they possess. Iso resins are the primary type of resin used in gel coat applications, which is similar to a paint, but is sprayed into a mold before the FRP is molded leaving a coating on the part. Gel coat resins must have lower color (almost clear) so as to not impart additional color to the part or so that they can be dyed properly. Gel coats must also have strong resistance to UV-weathering and water blistering.
Tere resins are often used when high modulus and strength are desired, but the low color properties of an Iso resin is not necessary. Terephthalic acid is generally lower cost than isophthalic acid, but both give similar strength characteristics to a UPR product. There exists a special sub-set of Tere resins, known as PET UPR resins, which are produced by catalytically cracking PET resin in the reactor to yield a mixture of terephthalic acid and ethylene glycol. Additional acids and glycols are then added along with maleic anhydride and a new polymer is produced. The end product is functionally the same as a Tere resin, but can often be lower cost to manufacture as scrap PET can be sourced cheaply. If a glycol-modified PET (PET-G) is used, exceptional properties can be imparted to the resin due to some of the exotic materials used in PET-G production. Tere and PET-UPR resins are used in many applications including cured-in-place pipe. [12]
Lichens have been shown to deteriorate polyester resins, as can be seen in archaeological sites in the Roman city of Baelo Claudia Spain. [13]
Polyester resin offers the following advantages:
Polyester resin has the following disadvantages:
Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.
Epoxy is the family of basic components or cured end products of epoxy resins. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. The epoxide functional group is also collectively called epoxy. The IUPAC name for an epoxide group is an oxirane.
Polyethylene terephthalate (or poly(ethylene terephthalate), PET, PETE, or the obsolete PETP or PET-P), is the most common thermoplastic polymer resin of the polyester family and is used in fibres for clothing, containers for liquids and foods, and thermoforming for manufacturing, and in combination with glass fibre for engineering resins.
In materials science, a thermosetting polymer, often called a thermoset, is a polymer that is obtained by irreversibly hardening ("curing") a soft solid or viscous liquid prepolymer (resin). Curing is induced by heat or suitable radiation and may be promoted by high pressure or mixing with a catalyst. Heat is not necessarily applied externally, and is often generated by the reaction of the resin with a curing agent. Curing results in chemical reactions that create extensive cross-linking between polymer chains to produce an infusible and insoluble polymer network.
Phenol formaldehyde resins (PF) are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Used as the basis for Bakelite, PFs were the first commercial synthetic resins (plastics). They have been widely used for the production of molded products including billiard balls, laboratory countertops, and as coatings and adhesives. They were at one time the primary material used for the production of circuit boards but have been largely replaced with epoxy resins and fiberglass cloth, as with fire-resistant FR-4 circuit board materials.
Terephthalic acid is an organic compound with formula C6H4(CO2H)2. This white solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several million tons are produced annually. The common name is derived from the turpentine-producing tree Pistacia terebinthus and phthalic acid.
Isophthalic acid is an organic compound with the formula C6H4(CO2H)2. This colorless solid is an isomer of phthalic acid and terephthalic acid. The main industrial uses of purified isophthalic acid (PIA) are for the production of polyethylene terephthalate (PET) resin and for the production of unsaturated polyester resin (UPR) and other types of coating resins.
In polymer chemistry, a structural unit is a building block of a polymer chain. It is the result of a monomer which has been polymerized into a long chain.
Maleic anhydride is an organic compound with the formula C2H2(CO)2O. It is the acid anhydride of maleic acid. It is a colorless or white solid with an acrid odor. It is produced industrially on a large scale for applications in coatings and polymers.
Chlorendic acid, or 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid, is a chlorinated carboxylic acid used in the synthesis of some flame retardants and polymers. It is a common breakdown product of several organochlorine insecticides.
An alkyd is a polyester resin modified by the addition of fatty acids and other components. Alkyds are derived from polyols and organic acids including dicarboxylic acids or carboxylic acid anhydride and triglyceride oils. The term alkyd is a modification of the original name "alcid", reflecting the fact that they are derived from alcohol and organic acids. The inclusion of a fatty acid confers a tendency to form flexible coatings. Alkyds are used in paints, varnishes and in moulds for casting. They are the dominant resin or binder in most commercial oil-based coatings. Approximately 200,000 tons of alkyd resins are produced each year. The original alkyds were compounds of glycerol and phthalic acid sold under the name Glyptal. These were sold as substitutes for the darker-colored copal resins, thus creating alkyd varnishes that were much paler in colour. From these, the alkyds that are known today were developed.
Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.
Dimethyl maleate is an organic compound with the formula C6H8O4. It is the dimethyl ester of maleic acid.
A thermoset polymer matrix is a synthetic polymer reinforcement where polymers act as binder or matrix to secure in place incorporated particulates, fibres or other reinforcements. They were first developed for structural applications, such as glass-reinforced plastic radar domes on aircraft and graphite-epoxy payload bay doors on the Space Shuttle.
Resin casting is a method of plastic casting where a mold is filled with a liquid synthetic resin, which then hardens. It is primarily used for small-scale production like industrial prototypes and dentistry. It can be done by amateur hobbyists with little initial investment, and is used in the production of collectible toys, models and figures, as well as small-scale jewellery production.
Cyclohexanedimethanol (CHDM) is a mixture of isomeric organic compounds with formula C6H10(CH2OH)2. It is a colorless low-melting solid used in the production of polyester resins. Commercial samples consist of a mixture of cis and trans isomers. It is a di-substituted derivative of cyclohexane and is classified as a diol, meaning that it has two OH functional groups. Commercial CHDM typically has a cis/trans ratio of 30:70.
1,6-Hexanediol is an organic compound with the formula (CH2CH2CH2OH)2. It is a colorless water-soluble solid.
Ralph Landau was a chemical engineer and entrepreneur active in the chemical and petrochemical industries. He is considered one of the top fifty foundational chemical engineers of the first half of the 20th century, and one of the 75 most distinguished contributors to chemical enterprise. He has published extensively on chemical engineering and holds a significant number of patents.
α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals, but also carboxylic acids and the corresponding esters and amides. In these compounds the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.
Diethylene glycol diglycidyl ether (DEGDGE) is an organic chemical in the glycidyl ether family with the formula C10H18O5.. The oxirane functionality makes it useful as a reactive diluent for epoxy resin viscosity reduction.
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