Epoxy

Epoxy

Epoxy is either any of the basic components or the cured end products of epoxy resins, as well as a colloquial name for the epoxide functional group. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. 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 acid anhydrides), phenols, alcohols and thiols. 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 high mechanical properties, temperature and chemical resistance. Epoxy has a wide range of applications, including metal coatings, use in electronics / electrical components/LED, high tension electrical insulators, paint brush manufacturing, fiber-reinforced plastic materials and structural adhesives.



Epoxy resin

Epoxy resins are low molecular weight pre-polymers or higher molecular weight polymers which normally contain at least two epoxide groups. The epoxide group is also sometimes referred to as a glycidyl or oxirane group.

A wide range of epoxy resins are produced industrially. 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).

Epoxy resins are polymeric or semi-polymeric materials, 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 require melting to enable processing.

An important criterion for epoxy resins is the epoxide content. This is commonly expressed as the epoxy equivalent weight, which is the number of epoxide equivalents in 1 kg of resin (Eq./kg), or as the equivalent weight, which is the weight in grammes of resin containing 1 mole equivalent of epoxide (g/mol). One measure may be simply converted to another:

Equivalent weight (g/mol) = 1000 / epoxide number (Eq./kg).

The equivalent weight or epoxide number is used to calculate the amount of co-reactant (hardener) to use when curing epoxy resins. Epoxies are typically cured with stoichiometric or near-stoichiometric quantities of curative to achieve maximum physical properties.

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 formulating.

Bisphenol A epoxy resin

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. 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 crosslinking reactions, e.g. with aminoplasts, phenoplasts and isocyanates.

Bisphenol F epoxy resin

Bisphenol F may also undergo epoxidation in a similar fashion to bisphenol A. Compared to DGEBA, bisphenol F epoxy resins have lower viscosity and a higher mean epoxy content per gramme, which (once cured) gives them increased chemical resistance.

Novolac epoxy resin

Reaction of phenols with formaldehyde and subsequent glycidylation with epichlorohydrin produces epoxidised novolacs, such as epoxy phenol novolacs (EPN) and epoxy cresol novolacs (ECN). These are highly viscous to solid resins with typical mean epoxide functionality of around 2 to 6. The high epoxide functionality of these resins forms a highly crosslinked polymer network displaying high temperature and chemical resistance, but low flexibility.

Aliphatic epoxy resin

Aliphatic epoxy resins are typically formed by glycidylation of aliphatic alcohols or polyols. The resulting resins may be monofunctional (e.g. dodecanol glycidyl ether), difunctional (butanediol diglycidyl ether), or higher functionality (e.g. trimethylolpropane triglycidyl ether). These resins typically display low viscosity at room temperature (10-200 mPa.s) and are often referred to as reactive diluents. They are rarely used alone, but are rather employed to modify (reduce) the viscosity of other epoxy resins. This has led to the term ‘modified epoxy resin’ to denote those containing viscosity-lowering reactive diluents. 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 low 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.

Glycidylamine epoxy resin

Glycidylamine epoxy resins are higher functionality epoxies which are formed when aromatic amines are reacted with epichlorohydrin. Important industrial grades are triglycidyl-p-aminophenol (functionality 3) and N,N’,N”,N”’-tetraglycidyl-bis-(4-aminophenyl)-methan (functionality 4). The resins are low to medium viscosity at room temperature, which makes them easier to process than EPN or ECN resins. This coupled with high reactivity, plus high temperature resistance and mechanical properties of the resulting cured network makes them important materials for aerospace composite applications.

Curing epoxy resins

In general, uncured epoxy resins have only poor mechanical, chemical and heat resistance properties. 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 may be achieved by reacting an epoxy with itself (homopolymerisation) or by forming a copolymer with polyfunctional curatives or hardeners. 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.

Whilst some epoxy resin/ hardener combinations will cure at ambient temperature, many require heat, with temperatures up to 150 °C being common, and up to 200 °C 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 required 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 accelerators. 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.

Homopolymerisation

Epoxy resin may be reacted with itself in the presence of an anionic catalyst (a Lewis base such as tertiary amines or imidazoles) or a cationic catalyst (a Lewis acid such as a boron trifluoride complex) to form a cured network. This process is known as catalytic homopolymerisation. The resulting network contains only ether bridges, and exhibits high thermal and chemical resistance, but is brittle and often requires elevated temperature to effect curing, so finds only niche applications industrially. Epoxy homopolymerisation is often used when there is a requirement for UV curing, since cationic UV catalysts may be employed (e.g. for UV coatings).

Amines

Polyfunctional primary amines form an important class of epoxy hardeners. Primary amines undergo an addition reaction with the epoxide group to form a hydroxyl group and a secondary amine. The secondary amine can further react with an epoxide to form a tertiary amine and an additional hydroxyl group. Kinetic studies have shown the reactivity of the primary amine to be approximately double that of the secondary amine. Use of a difunctional or polyfunctional amine forms a three-dimensional cross-linked network. Aliphatic, cycloaliphatic and aromatic amines are all employed as epoxy hardeners. Amine type will alter both the processing properties (viscosity, reactivity) and the final properties (mechanical, temperature and heat resistance) of the cured copolymer network. Thus amine structure is normally selected according to the application. Reactivity is broadly in the order aliphatic amines > cycloaliphatic amines > aromatic amines. Temperature resistance generally increases in the same order, since aromatic amines form much more rigid structures than aliphatic amines. Whilst aromatic amines were once widely used as epoxy resin hardeners due to the excellent end properties they imparted, health concerns with handling these materials means that they have now largely been replaced by safer aliphatic or cycloaliphatic alternatives.

Anhydrides

Epoxy resins may be cured with cyclic anhydrides at elevated temperatures. Reaction occurs only after opening of the anhydride ring, e.g. by secondary hydroxyl groups in the epoxy resin. A possible side reaction may also occur between the epoxide and hydroxyl groups, but this may suppressed by addition of tertiary amines. The low viscosity and high latency of anhydride hardeners makes them suitable for processing systems which require addition of mineral fillers prior to curing, e.g. for high voltage electrical insulators.

Phenols

Polyphenols, such as bisphenol A or novolacs can react with epoxy resins at elevated temperatures (130-180 °C), normally in the presence of a catalyst. The resulting material has ether linkages and displays higher chemical and oxidation resistance than typically obtained by curing with amines or anhydrides. Since many novolacs are solids, this class of hardeners is often employed for powder coatings.

Thiols

Also known as mercaptans, thiols contain a sulfur which reacts very readily with the epoxide group, even at ambient or sub-ambient temperatures. Whilst the resulting network does not typically display high temperature or chemical resistance, the high reactivity of the thiol group makes it useful for applications where heated curing is not possible, or very fast cure is required e.g. for domestic DIY adhesives and chemical rock bolt anchors. Thiols have a characteristics odour which can be detected in many of two household adhesives.

 

 

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