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Epoxy is the family of basic components or cured end products of epoxy Resin. Epoxy resins, also known as polyepoxides, are a class of reactive and which contain epoxide groups. The epoxide functional group is also collectively called epoxy. The IUPAC name for an epoxide group is an oxirane.
Epoxy resins may be reacted (cross-linked) either with themselves through catalytic homopolymerisation, or with a wide range of co-reactants including polyfunctional amines, acids (and ), phenols, alcohols and thiols (sometimes called mercaptans). These co-reactants are often referred to as hardeners or curatives, and the cross-linking reaction is commonly referred to as curing.
Reaction of polyepoxides with themselves or with polyfunctional hardeners forms a thermosetting polymer, often with favorable mechanical properties and high thermal and chemical resistance. Epoxy has a wide range of applications, including , composites, use in electronics, electrical components (e.g. for chips on board), LEDs, high-tension electrical insulators, paint brush manufacturing, fiber-reinforced plastic materials, and for structural and other purposes.
The health risks associated with exposure to epoxy resin compounds include contact dermatitis and allergic reactions, as well as respiratory problems from breathing vapor and sanding dust, especially from compounds not fully cured.
The other production route for epoxy resins is the conversion of aliphatic or cycloaliphatic alkenes with :Kaiser, Wolfgang (2011) Kunststoffchemie für Ingenieure. Vol. 3. Hanser, Munich. pp. 437 ff. . In contrast to glycidyl-based epoxy resins, this production of such epoxy monomers does not require an acidic hydrogen atom but an aliphatic double bond.
The epoxide group is also sometimes referred to as an oxirane group.
In this two-stage reaction, epichlorohydrin is first added to bisphenol A (bis(3-chloro-2-hydroxy-propoxy)bisphenol A is formed), then a bisepoxide is formed in a condensation reaction with a stoichiometric amount of sodium hydroxide. The chlorine atom is released as sodium chloride (NaCl) and the hydrogen atom as water.
Higher molecular weight diglycidyl ethers (n ≥ 1) are formed by the reaction of the bisphenol A diglycidyl ether formed with further bisphenol A, this is called prepolymerization:
A product comprising a few repeat units ( n = 1 to 2) is a viscous, clear liquid; this is called a liquid epoxy resin. A product comprising more repeating units ( n = 2 to 30) is at room temperature a colourless solid, which is correspondingly referred to as solid epoxy resin.
Instead of bisphenol A, other bisphenols (especially bisphenol F) or brominated bisphenols (e. g. tetrabromobisphenol A) can be used for the said epoxidation and prepolymerisation. Bisphenol F may undergo epoxy resin formation in a similar fashion to bisphenol A. These resins typically have lower viscosity and a higher mean epoxy content per gram than bisphenol A resins, which (once cured) gives them increased chemical resistance.
Important epoxy resins are produced from combining epichlorohydrin and bisphenol A to give bisphenol A diglycidyl ethers.
Increasing the ratio of bisphenol A to epichlorohydrin during manufacture produces higher molecular weight linear polyethers with glycidyl end groups, which are semi-solid to hard crystalline materials at room temperature depending on the molecular weight achieved. This route of synthesis is known as the "taffy" process. The usual route to higher molecular weight epoxy resins is to start with liquid epoxy resin (LER) and add a calculated amount of bisphenol A and then a catalyst is added and the reaction heated to circa . This process is known as "advancement".Hofer, Arnold; Schneider, Hildegard, and Siegenthaler, Nikolaus (1996) "Epoxy resin mixtures containing advancement catalysts", . As the molecular weight of the resin increases, the epoxide content reduces and the material behaves more and more like a thermoplastic. Very high molecular weight polycondensates (ca. 30,000–70,000 g/mol) form a class known as phenoxy resins and contain virtually no epoxide groups (since the terminal epoxy groups are insignificant compared to the total size of the molecule). These resins do however contain hydroxyl groups throughout the backbone, which may also undergo other cross-linking reactions, e.g. with aminoplasts, phenoplasts and .
Epoxy resins are polymeric or semi-polymeric materials or an oligomer, and as such rarely exist as pure substances, since variable chain length results from the polymerisation reaction used to produce them. High purity grades can be produced for certain applications, e.g. using a distillation purification process. One downside of high purity liquid grades is their tendency to form crystalline solids due to their highly regular structure, which then require melting to enable processing.
An important criterion for epoxy resins is the Epoxy value which is connected to the epoxide group content. This is expressed as the " epoxide equivalent weight", which is the ratio between the molecular weight of the monomer and the number of epoxide groups. This parameter is used to calculate the mass of co-reactant (hardener) to use when curing epoxy resins. Epoxies are typically cured with stoichiometry or near-stoichiometric quantities of hardener to achieve the best physical properties.
Cycloaliphatic epoxides contain one or more aliphatic rings in the molecule on which the oxirane ring is contained (e.g. 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate). They are produced by the reaction of a cyclic alkene with a peracid (see above).Hammerton, L. (1996) Recent Developments in Epoxy Resins. Ed.: Rebecca Dolbey. RAPRA Review Reports. p. 8. . Cycloaliphatic epoxides are characterised by their aliphatic structure, high oxirane content and the absence of chlorine, which results in low viscosity and (once cured) good weather resistance, low dielectric constants and high Glass transition. However, aliphatic epoxy resins polymerize very slowly at room temperature, so higher temperatures and suitable accelerators are usually required. Because aliphatic epoxies have a lower electron density than aromatics, cycloaliphatic epoxies react less readily with nucleophiles than bisphenol A-based epoxy resins (which have aromatic ether groups). This means that conventional nucleophilic hardeners such as amines are hardly suitable for crosslinking. Cycloaliphatic epoxides are therefore usually homopolymerized thermally or UV-initiated in an electrophilic or cationic reaction. Due to the low dielectric constants and the absence of chlorine, cycloaliphatic epoxides are often used to encapsulate electronic systems, such as microchips or LEDs. They are also used for radiation-cured paints and varnishes. Due to their high price, however, their use has so far been limited to such applications.
Epoxidized vegetable oils are formed by epoxidation of unsaturated fatty acids by reaction with peracids. In this case, the peracids can also be formed in situ by reacting carboxylic acids with hydrogen peroxide. Compared with LERs (liquid epoxy resins) they have very low viscosities. If, however, they are used in larger proportions as , this often leads to reduced chemical and thermal resistance and to poorer mechanical properties of the cured epoxides. Large scale epoxidized vegetable oils such as epoxidized soy and lens oils are used to a large extent as secondary plasticizers and cost stabilizers for PVC.
Aliphatic glycidyl epoxy resins of low molar mass (mono-, bi- or polyfunctional) are formed by the reaction of epichlorohydrin with aliphatic alcohols or polyols (glycidyl ethers are formed) or with aliphatic carboxylic acids (glycidyl esters are formed). The reaction is carried out in the presence of a base such as sodium hydroxide, analogous to the formation of bisphenol A-diglycidyl ether. Also aliphatic glycidyl epoxy resins usually have a low viscosity compared to aromatic epoxy resins. They are therefore added to other epoxy resins as reactive diluents or as adhesion promoters. Epoxy resins made of (long-chain) polyols are also added to improve tensile strength and impact strength.
A related class is cycloaliphatic epoxy resin, which contains one or more cycloaliphatic rings in the molecule (e.g. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate). This class also displays lower viscosity at room temperature, but offers significantly higher temperature resistance than the aliphatic epoxy diluents. However, reactivity is rather low compared to other classes of epoxy resin, and high temperature curing using suitable accelerators is normally required. As aromaticity is not present in these materials as it is in Bisphenol A and F resins, the UV stability is considerably improved.
Brominated bisphenol A is used when flame retardant properties are required, such as in some electrical applications (e.g. printed circuit boards). The tetrabrominated bisphenol A (TBBPA, 2,2-bis(3,5-dibromophenyl)propane) or its diglycidyl ether, 2,2-bis3,5-dibromo-4-(2,3-epoxypropoxy)phenylpropane, can be added to the epoxy formulation. The formulation may then be reacted in the same way as pure bisphenol A. Some (non-crosslinked) epoxy resins with very high molar mass are added to engineering thermoplastics, again to achieve flame retardant properties.
Fluorinated epoxy resins have been investigated for some high performance applications, such as the fluorinated diglycidether 5-heptafluoropropyl-1,3-bis2-(2,3-epoxypropoxy)hexafluoro-2-propylbenzene. As it has a low surface tension, it is added as a wetting agent (surfactant) for contact with glass fibres. Its reactivity to hardeners is comparable to that of bisphenol A. When cured, the epoxy resin leads to a thermosetting plastic with high chemical resistance and low water absorption. However, the commercial use of fluorinated epoxy resins is limited by their high cost and low Tg.
In general, uncured epoxy resins have only poor mechanical, chemical and heat resistance properties. (1989). 9780080967011 ISBN 9780080967011 However, good properties are obtained by reacting the linear epoxy resin with suitable curatives to form three-dimensional cross-linked thermoset structures. This process is commonly referred to as curing or gelation process. Curing of epoxy resins is an exothermic reaction and in some cases produces sufficient heat to cause thermal degradation if not controlled. Curing does induce residual stress in epoxy systems which have been studied. The induced stresses may be alleviated with flexibilisers.
Curing may be achieved by reacting an epoxy with itself (homopolymerisation) or by forming a copolymer with polyfunctional curatives or hardeners. This curing is what produces the qualities of the substance such as resistance, durability, versatility, and adhesion. In principle, any molecule containing a reactive hydrogen may react with the epoxide groups of the epoxy resin. Common classes of hardeners for epoxy resins include amines, acids, acid anhydrides, phenols, alcohols and thiols. Relative reactivity (lowest first) is approximately in the order: phenol < anhydride < aromatic amine < cycloaliphatic amine < aliphatic amine < thiol.
While some epoxy resin/ hardener combinations will cure at ambient temperature, many require heat, with temperatures up to being common, and up to for some specialist systems. Insufficient heat during cure will result in a network with incomplete polymerisation, and thus reduced mechanical, chemical and heat resistance. Cure temperature should typically attain the glass transition temperature (Tg) of the fully cured network in order to achieve maximum properties. Temperature is sometimes increased in a step-wise fashion to control the rate of curing and prevent excessive heat build-up from the exothermic reaction.
Hardeners which show only low or limited reactivity at ambient temperature, but which react with epoxy resins at elevated temperature are referred to as latent hardeners. When using latent hardeners, the epoxy resin and hardener may be mixed and stored for some time prior to use, which is advantageous for many industrial processes. Very latent hardeners enable one-component (1K) products to be produced, whereby the resin and hardener are supplied pre-mixed to the end user and only require heat to initiate curing. One-component products generally have shorter shelf-lives than standard 2-component systems, and products may require cooled storage and transport.
The epoxy curing reaction may be accelerated by addition of small quantities of accelerant. Tertiary amines, carboxylic acids and alcohols (especially phenols) are effective accelerators. Bisphenol A is a highly effective and widely used accelerator, but is now increasingly replaced due to health concerns with this substance. The most widely used accelerator is 2,4,6-Tris(dimethylaminomethyl)phenol.
As with other classes of thermoset polymer materials, blending different grades of epoxy resin, as well as use of additives, plasticizers or fillers is common to achieve the desired processing or final properties, or to reduce cost. Use of blending, additives and fillers is often referred to as formulation.
All quantities of mix generate their own heat because the reaction is exothermic. Large quantities will generate more heat and thus greatly increase the rate of the reaction and so reduce working time (pot-life). So it is good practice to mix smaller amounts which can be used quickly to avoid waste and to be safer. There are various methods of toughening them, as they can be brittle. Rubber toughening is a key technology used for toughening.
Epoxy coatings are often used in industrial and automotive applications since they are more heat resistant than latex-based and alkyd-based paints. Epoxy paints tend to deteriorate, known as "chalking out", due to UV exposure. Epoxy coatings have also been used in drinking water applications. Epoxy coatings find much use to protect mild and other steels due to their excellent protective properties.
Change in color, known as yellowing, is a common phenomenon for epoxy materials and is often of concern in art and conservation applications. Epoxy resins yellow with time, even when not exposed to UV radiation. Significant advances in understanding yellowing of epoxies were achieved by Down first in 1984 (natural dark aging) and later in 1986 (high-intensity light aging). Down investigated various room-temperature-cure epoxy resin adhesives suitable for use in glass conservation, testing their tendency to yellow. A fundamental molecular understanding of epoxy yellowing was achieved, when Krauklis and Echtermeyer discovered the mechanistic origin of yellowing in a commonly used amine epoxy resin, published in 2018. They found that the molecular reason for epoxy yellowing was a thermo-oxidative evolution of carbonyl groups in the polymeric carbon–carbon backbone via a nucleophilic radical attack.
Polyester epoxies are used as for washers, driers and other "white goods". Fusion Bonded Epoxy Powder Coatings (FBE) are extensively used for corrosion protection of steel pipes and fittings used in the oil and gas industry, potable water transmission pipelines (steel), and concrete reinforcing rebar. Epoxy coatings are also widely used as primers to improve the adhesion of automotive and marine paints especially on metal surfaces where corrosion (rusting) resistance is important. Metal cans and containers are often coated with epoxy to prevent rusting, especially for foods like tomatoes that are . Epoxy resins are also used for decorative flooring applications such as terrazzo flooring, chip flooring, and colored aggregate flooring.
Epoxies have been modified in a variety of ways, including reacting with fatty acids derived from oils to yield epoxy esters, which were cured the same way as alkyds. Typical ones were L8 (80% linseed) and D4 (40% dehydrated castor oil). These were often reacted with styrene to make styrenated epoxy esters, used as primers. Curing with phenolics to make drum linings, curing esters with amine resins and pre-curing epoxies with amino resins to make resistant top coats. Organic chains maybe used to hydrophobically modify epoxy resins and change their properties. The effect of chain length of the modifiers has been studied.
Some epoxies are cured by exposure to ultraviolet light. Such epoxies are commonly used in optics, optical fiber, and optoelectronics.
Flexible epoxy resins are used for potting transformers and inductors. By using vacuum impregnation on uncured epoxy, winding-to-winding, winding-to-core, and winding-to-insulator air voids are eliminated. The cured epoxy is an electrical insulator and a much better conductor of heat than air. Transformer and inductor hot spots are greatly reduced, giving the component a stable and longer life than unpotted product.
Epoxy resins are applied using the technology of resin dispensing.
There are two main areas of marine use. Because of the better mechanical properties relative to the more common polyester resins, epoxies are used for commercial manufacture of components where a high strength/weight ratio is required. The second area is that their strength, gap filling properties and excellent adhesion to many materials including timber have created a boom in amateur building projects including aircraft and boats.
Normal gelcoat formulated for use with polyester resins and vinylester resins does not adhere to epoxy surfaces, though epoxy adheres very well if applied to polyester resin surfaces. "Flocoat" that is normally used to coat the interior of polyester fibreglass yachts is also compatible with epoxies.
Epoxy materials tend to harden somewhat more gradually, while polyester materials tend to harden quickly, particularly if a lot of catalyst is used.Hakiki, F., Nuraeni, N., Salam, D.D., Aditya, W., Akbari, A., Mazrad, Z.A.I. and Siregar, S. Preliminary Study on Epoxy-Based Polymer for Water Shut-Off Application. Paper IPA15-SE-025. Proceeding of The 39th IPA Conference and Exhibition, Jakarta, Indonesia, May 2015. The chemical reactions in both cases are exothermic.
While it is common to associate polyester resins and epoxy resins, their properties are sufficiently different that they are properly treated as distinct materials. Polyester resins are typically low strength unless used with a reinforcing material like glass fibre, are relatively brittle unless reinforced, and have low adhesion. Epoxies, by contrast, are inherently strong, somewhat flexible and have excellent adhesion. However, polyester resins are much cheaper.
Epoxy resins typically require a precise mix of two components which form a third chemical to get the stated properties. Depending on the properties required, the ratio may be anything from 1:1 or over 10:1, but in usually they must be mixed exactly. The final product is then a precise thermoset plastic. Until they are mixed the two elements are relatively inert, although the 'hardeners' tend to be more chemically active and should be protected from the atmosphere and moisture. The rate of the reaction can be changed by using different hardeners, which may change the nature of the final product, or by controlling the temperature.
By contrast, polyester resins are usually made available in a 'promoted' form, such that the progress of previously-mixed resins from liquid to solid is already underway, albeit very slowly. The only variable available to the user is to change the rate of this process using a catalyst, often Methyl-Ethyl-Ketone-Peroxide (MEKP), which is very toxic. The presence of the catalyst in the final product actually detracts from the desirable properties, so that small amounts of catalyst are preferable, so long as the hardening proceeds at an acceptable pace. The rate of cure of polyesters can therefore be controlled by the amount and type of catalyst as well as by the temperature.
As adhesives, epoxies bond in three ways: a) Mechanically, because the bonding surfaces are roughened; b) by proximity, because the cured resins are physically so close to the bonding surfaces that they are hard to separate; c) ionically, because the epoxy resins form ionic bonds at an atomic level with the bonding surfaces. This last is substantially the strongest of the three. By contrast, polyester resins can only bond using the first two of these, which greatly reduces their utility as adhesives and in marine repair.
These commodity epoxy Manufacturing mentioned above typically do not sell epoxy resins in a form usable to smaller end users, so there is another group of companies that purchases epoxy raw materials from the major producers and then compounds (blends, modifies, or otherwise customizes) epoxy systems from these . These companies are known as "formulators". The majority of the epoxy systems sold are produced by these formulators and they comprise over 60% of the dollar value of the epoxy market. There are hundreds of ways that these formulators can modify epoxies—by adding mineral fillers (talc, silica, alumina, etc.), by adding flexibilizers, viscosity reducers, , thickeners, accelerators, adhesion promoters, etc. These modifications are made to reduce costs, to improve performance, and to improve processing convenience. As a result, a typical formulator sells dozens or even thousands of formulations—each tailored to the requirements of a particular application or market.
The raw materials for epoxy resin production are today largely petroleum derived, although some plant derived sources are now becoming commercially available (e.g. plant derived glycerol used to make epichlorohydrin).
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