The Polymeric Materials Encyclopedia 1996 CRC Press, Inc

EPOXY RESINS (Overview)

M. S. Bhatnagar Retired Epoxy resins are polyether resins containing more than one epoxy group capable of being converted into the thermoset form. These resins, on curing, do not create volatile products in spite of the presence of a volatile solvent. The epoxies may be named as oxides, such as ethylene oxides (epoxy ethane), or 1,2-epoxide. The epoxy group also known as oxirane contains an oxygen atom bonded with two carbon atoms, which in their turn are bound by separate bonds as in Scheme I:

The simplest epoxy resin is prepared by the reaction of bisphenol A (BPA) (80-05-7) with epichlorohydrine (ECH) (106-89-8) (Scheme II). The value of n varies from 0 to 25. This determines the end-use applications of the resin.

II

Apart from innumerable patents, several books, 1-4 review articles, 5-18 and technical bulletins have been published on various aspects of epoxy resins. Applications for epoxy resins are extensive: adhesives, bonding, construction materials (flooring, paving, and aggregates), composites, laminates, coatings, molding, and textile finishing. They have recently found uses in the air- and spacecraft industries.

EPOXIDATION
There are three important methods of producing epoxides. First is catalytic epoxidation. Here the oxidation of olefins is carried out by directly oxidizing them in the vapor phase in the presence of a catalyst such as silver.

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Second is epoxidation by organic peroxides and their esters. Unsaturated compounds such as hydrocarbon fatty acids and their esters are epoxidized by peroxyacetic acid. 19 Third is epoxidation by inorganic peroxides and inorganic peroxy-acids. Sodium peroxide or tungstic acid deposited on a inert surface is used for the epoxidation of olefins by hydrogen peroxide.

CHEMISTRY
Epoxy resins are prepared by the reaction of active hydrogen-containing compounds with epichlorohydrin followed by dehydro-halogenation. Bisphenol A (BPA) (80-05-7), on reaction with epichlorohydrin (ECH) (106-89-8) in the presence of caustic soda, produces diglycidyl ether of bisphenol A (DGEBPA) (1675-54-3). Here n is nearly zero (0.2). The resin is liquid when n < 1 and solid when n > 2.

Curing
The curing of the epoxy group takes place either between the epoxide molecules themselves or by the reaction between the epoxy group and other reactive molecules with or without the help of the catalyst. 20-24 The former is known as homopolymerization, or corrective curing; and the latter is an addition or catalytic curing reaction. Both reactions result in coupling as well as crosslinking (Scheme III).

III

Curing of DGEBPA with a diamine occurs in three stages: propagation of the linear chain, formation of a branched structure, and crosslinking. Primary and secondary amines are widely used to cure epoxy resins. The reaction between the oxirane group of the epoxy resin with primary amines is shown in Scheme IV.

IV

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Tertiary amines also are used to bring about catalytic polymerization of epoxy resin and the mechanism given in Scheme V.

To suit the requirements of the end products, other nitrogen compounds used for curing are triamines (DETA, TETA), polyamides (two) obtained from vegetable oils, polyureas (two), polyisocyanates, dicyanamide, polyurethane, and imidazole. Polymercaptans, polyhydric alcohols, polyphenols, novalacs, and silanes also are used for epoxidations. Magnetic fields and photoinitiation also are used for polymerization. Hydantoin-based epoxy resin (15336-81-9) is used to form DGEBPA. Glycidyl esters of dimerfatty acids can also be produced from vegetable oils. Curing agents such as cyclic acid anhydrides are used. The reaction is shown in Scheme VI.

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VI

DGEBPA also is produced from aliphatic diols such as butane-1,4-diol (2425-79-8), propylene glycol (16096-30-3), hydrogenated BPA (13410-58-7), triglycidyl adduct of p-aminophenol, hetrocyclic glycidyl amides and imides, and triglycidyl isocyanurate (2451-62-9). Lewis acids such as boron trifluoride complexes are also used as curing agents. Cationic catalysts such as metal halides, coordination catalysts such as metal chelates and photoinitiation are used to bring about polymerization.

THE MANUFACTURING PROCESS

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The epoxy resins can be obtained in either liquid or solid states.

Liquid Epoxy Resins

In this process ECH and BPA are charged into a reactor in the ratio of 10:1. A solution of 20-40% caustic soda is added slowly to the reaction vessel as the solution is brought to the boiling point. The solution is kept boiling until 2 mol of caustic soda per mole of BPA have been added. The solution breaks up into two layers. Unreacted ECH is removed by vacuum distillation. An inert solvent is then added to the resin and the reaction is completed with excess of caustic soda solution. The resin separates into brine solution, which is thoroughly washed with water to obtain a clear resin. The solvent is removed by vacuum distillation.

Solid Epoxy Resin

Here ECH and BPA are added to the reactor in theoretical molar ratio with a little excess of ECH. Aqueous caustic soda is well mixed into the system. After one hour the reaction is complete and a taffylike mass is obtained. Phase separation is brought about by adding an inert solvent. Brine is withdrawn and the resin solution is thoroughly washed with water to remove traces of salts. The solid resin is obtained by removing the solvent by vacuum distillation.

Modified Epoxy Resins

Epoxy resins form adducts with vinyl, acrylic, polyester resins, phenol novolac (9003-35-7), cresol novolac (37382-79-9), bis-[4(2,3-epoxy propyoxy) phenyl] methane (2467-02-9), and phenol hydrocarbon novalac (13446-85-0).

STRUCTURE
Ethylene oxide is a cyclic ether. 25 The carbon atoms in oxirane are trigonally sp hybridized. One orbital from each carbon atom overlaps with the atomic orbitals of the oxygen atom to form molecular orbital in the center of the ring. Atomic p orbitals, in the plane of the ring, overlap sideways. This explains the conjugative ability of epoxy ring, and results in a bent bond structure. Since the H-C-H bond is 116 15, the carbon will be sp hybridized. But it also shares the triangular ring, so it is possible to give the correct hybridization structure. Very often the epoxy groups deform to keep the area of the ring constant. The ring atoms do not lie along the lines of greatest electron density of the atomic orbitals from the neighboring atoms. The smaller amount of overlapping is more than offset by a decrease in the strain energy.
2 2

CHARACTERIZATION AND PROPERTIES

The end groupsepoxy, hydroxide, glycol, chlorine, and bisphenol Aare estimated by the usual chemical methods. 26, 27 Researchers have found aqueous concentrated hydrochloric acid with dioxane to be a suitable reagent for estimating epoxide content. Curing agents such as amines are characterized by refractive index and specific gravity. Thin-layer chromatography has been used for identification. The reactive dye labeling technique

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has also been used for studying the curing reaction. The epoxy resins do not soften at a specific temperature but appear to undergo a gradual and imperceptible change. The softening of epoxy resins can be empirically graded by the ring and ball method. The curing of epoxy resins is an exothermic process, resulting in the production of limited-size molecules, having molecular weights of a few thousands. Their weight is determined by the usual physical methods. The number average molecular weight (Mn is determined by gas density, and cryoscopic, ebulioscopic, and osmotic ) pressure methods. The weight average molecular weight (Mw) is estimated by viscosity and light scattering methods. Solubility parameters and critical surface tension (surface tension below which a liquid drop makes zero contact angle) have been used to find the molecular weights between the cross-links (Mc). Epoxy resins have a very wide molecular weight distribution. This can be estimated by comparing the Mw and Mn values. The greater the difference, the wider the distribution. Gel permeation chromatography has been used for finding this distribution. Liquid epoxy resins or their solids in 40% diethylene glycol solution do not behave as Newtonian liquids. The kinematic or intrinsic viscosities of epoxy resins are measured by viscometers, which can measure the dependence of viscosity on shear rate. Viscosity studies also provide information regarding the formation of networks and their aging. The linear viscoelastic response of epoxies displays the internal characteristics of tensile relaxation and fracture response. Chemorheology studies display the changes in deformation and flow properties of the resin. Continuous and intermittent stress relaxation measures the appearance of network formation. Researchers have used a variety of techniques to study the thermal and environmental stability of epoxy polymers. The effect of moisture on epoxy resins has been studied from the point of view of both absorption that brings about degradation and of sorption behavior itself. Water absorption has been found to decrease the Tg because of strong hydrogen bonds. It has been shown that in amine-cured resins, water is homogeneously distributed as a plasticizer and that water clusters are present at microcracks. The strength and toughness of epoxy resins below the glass transition temperature Tg depend on the mechanism of the movement of short segments in the solid state, and above Tg mechanical properties are influenced by cross-linking density and Mc. Epoxy resins shrink on curing. Thus both the density and refractive index increase. It is necessary to distinguish between shrinkage in the liquid stage and shrinkage in the gel or solid state. Shrinkage in the gel or solid state introduces stress. Thus gelation temperature has a direct effect on the degree of shrinkage. Refractometry or dilatometric measurements are used to measure shrinkage, which determines the cure rate. Epoxy resins are noncrystalline, and cured resin finds its structural applications below the heat distortion or glass transition temperature (Tg). Continuous and intermittent stress relaxation measures the appearance of network formation. A variety of techniques have been used to study the thermal and environmental stability of epoxy

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polymers. Several mechanical properties of epoxy resins are closely related with chemical composition and internal cohesive energy of the resin. This has been found to be true well below the transition temperature, where rotational motion related to configurational entropy and stress relaxation processes do not occur. Epoxy resins undergo alpha, beta, and gamma thermal transition through proper selection of epoxy monomers and curing agents. The temperature, location, and magnitude of these transitions directly influence the thermo-mechanical properties of the resins. These transitions also are influenced by the mechanism of crosslinking produced by amines, BF3-amine complex, and anhydride curing agents. These transitions can be studied by dynamic mechanical analysis (DMA) and nuclear magnetic resonance (NMR). Epoxy resins have good electrical insulation properties. They have a 3-6 dielectric constant, a low dissipation and loss factor, and good arc, surface, and volume resistance. These properties are affected by moisture and increase in temperature. The resins can be made conductive and semiconductive by use of suitable fillers and curing agents.

APPLICATIONS Foams
Epoxy resins are used to form rigid, lightweight, foamy structures with good insulation properties. They are particularly used for foam-in-place applications in the potting process, as well as in casting. They are produced either by chemical reaction or by incorporating a prefoamed filler in the liquid system. 28

Adhesives
The versatile properties of epoxy resins make them valuable as adhesives in civilian and military applications. 29-31 About five percent of total epoxy resin production is consumed as adhesive in a wide range of structural applications. Epoxy resin adhesives form strong bonds with almost all surfaces, with the exception of some nonpolar substrates. Very often special modifiers and curing agents must be used to produce specific properties. The formulation of epoxy adhesives into a serviceable adhesive binding system is a highly specialized technology. Adhesives based on epoxide resins are available as room-temperature-curing two-component liquids, heat-curing liquids, powders, hot-melt adhesives, films, and tapes. Adhesive formulation based on epoxy resins requires a wide variety of curing and modifying agents. Generally DGEBA and oligomers are used, but to produce some specific effects alicyclic or heterocyclic epoxides are also included. Polyvinyl modified resins are used to increase flexibility and as toughening agents. Epoxy polyurethane resins make high-strength structural adhesives. Acrylates are also used to modify epoxy adhesives. Rubber- and elastomer-modified resins have been used to produce adhesive that cures under water.

Construction
Epoxy resins are now used as binders in materials for construction. 32 Generally a two-component system

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containing liquid epoxy resin, diluents, fillers, thickening agents, and curing agents is used. They are used to bond concrete, and to produce industrial seamless thin-set tarrazzo floors. This use has been extended to the laying of roads, construction of buildings, and filling cracks in concrete structures.

MOLDING
Molding can be broadly classified as simple molding and embedding processes. 33, 34 In the simple molding process, the molding powder under certain definite conditions assumes the shape of the mold. This process can be further subdivided as compression molding, injection molding, liquid injection molding, reaction injection molding, foam reservoir molding, and transfer molding. In embedment, material is packed to protect it from a hostile environment. Embedment implies complete encasement in some uniform external shape. Encapsulation, by contrast, is a coating process in which the final surface is irregular. Embedment may be further divided into casting and potting, and impregnation. These processes are common in electrical and electronic assemblies.

Epoxy Powders
The most commonly used epoxy powders are based on B-stage resins with aromatic amines or methane diamine. Dicyanodiamide or guanidine are also used, and inert fillers include silica, clay, and calcium carbonate. These resins are also used in foundry molding. Special molds are not required for epoxy resin molding powders. For nonreinforced materials such as coil covering and electrical cases, aluminum molds are used. Epoxy-molded compounds display excellent resistance to most acids, bases, solvents, salts, and other chemicals. In addition to flexibility enhancers such as polyamide, carboxylated polymers, and polysulphides, fatty diamines and thermally and electrically conductive materials also are used.

Composites and Laminates

Composites and laminates are materials produced by reinforcing the polymers with continuous fibers. These can be fabricated into structural materials. This industry consumes 27.6% of the epoxy resins produced. 35, 36

Laminates
Laminated epoxy insulations are largely used as sheets, rods, and tubes. Sheets of woven glass, paper, and polyaramid fabric or cotton prepregnated with the B-stage epoxy resins are laminated in large multiple pattern presses. These are used in preparing assemblies of copper-clad glass or polyaramid fibers for printed circuit boards in the electronics industry. Laminated epoxy structures are used in building construction for concrete molds, honeycomb cores, facing for foams, wood, metal assemblies, and reinforced pipes. Both wet impregnated and dry epoxy resin systems are used in aircraft construction. Carbon and polyaramid fibers are used in the laminates. Epoxy laminates also find application in marine industries; epoxy resins are replacing polyesters in special applications in which underwater strength is important.

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Composites
The fibers that dominate the field of advanced composites are carbon, graphite, glass, aluminum, boron, and aromatic polyamides. 35, 36 These fibers possess the desirable properties of low density [1.44-2 4.27 g/cm ] and extremely high strength (80-550 GPa). When combined with the resin binder and laminated to support applied load, they provide mechanical properties.
2

Pipes
Epoxy resins are used in filament-bound, glass-reinforced pipes and tubes.

Matrix Effects
Matrices play an important role in maintaining the orientation and spacing of the fiber and in transmitting uniform shear load between the layers of the fibrous laminate. Epoxy and modified epoxy resins have been used in composite structure. The composite property in an epoxy matrix improves with increasing fiber wet-out, which can be further improved by increasing the laminating pressure. The adhesion of matrix-dot graphite fiber was increased by finishing the surface of the fiber. The glass fiber is coated with a sizing material or coupling agent (e.g., silane) to give adequate finish. Ammonia plasma has been used to improve the finish of the fibers. A mechanism has been worked out to remedy adhesion failure between matrix and the substrate. The ultimate strength of the composite depends on the flow of resin during cure, which can be improved by adding flow agents.

Failure
The most common criteria for failure are maximum stress and maximum strain. In most structures, failure originates at a point of stress concentration and at flaws. The material property that quantifies tolerance for such failure is toughness. Several workers have studied these properties in different fibers. Techniques used to fabricate advanced composites are filament winding, pultrusion, and lamination. Fatigue strength of the laminates depends on the behavior of the plies, where fibers support the principal load. Delamination during fatigue does not affect the tensile strength but reduces compressive strength. Methods have been suggested to reduce the internal stress.

COATINGS
The coatings industry is the biggest consumer of epoxy resins. These resins are used mostly as chemical and special purpose coatings. Epoxy resins provide thin-layer durable coatings having mechanical strength and good adhesion to a variety of substrates. They are resistant to chemicals, corrosion, and solutions. They find applications in washing machines and appliances, ships and bridges, pipelines and chemical plants, automobiles, farm implements, containers, and floor coatings. Epoxy coating formulations are available as liquid resins, solid resins, high molecular weight thermoplastic resins, multifunctional resins, radiation curable resins, and special purpose resins. 37-43 Aliphatic amines, aromatic amines, and ketamines are used as curing agents for package epoxy systems.

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Epoxy baking finishes are obtained by high molecular weight epoxy resins crosslinked by phenolic or amino resins. These resins are used as lining for tanks, cars, drums, pails, pipes, downhole oilfield tubing, and food cans. Epoxy acrylic systems provide excellent coatings for appliances, kitchen cabinets, outdoor furniture, aluminum siding, and other metal products. High-solid coating solution formulations attain maximum film properties (adhesion, appearance, and freedom from defects). These are based on liquid epoxy resin acrylic adducts with epoxy resins. These adducts have proved useful in automotive primers. Epoxy resins cured with aliphatic amines, polyamides, or aliphatic liquid amine adducts are used in seamless floors. Industrial floors require extra epoxy resin. Waterborne coatings are made by dispersing or emulsifying the resins with surfactants. Such coatings also have been based on emulsified liquid epoxy resins cured with emulsified polyamide resins. These formulations are used in anionic electrodeposited coatings. They provide exterior and interior coatings for underground pipes, and electrical equipment appliances reinforcement. High-solid coatings have an additional advantage, as they are useful on steel, brass, metal furniture, buildings, and miscellaneous products. Application of powders is accomplished by electrostatic spray fluidized-bed coating and electrostatic fluidized-bed coating. For marine use, epoxy resins that cure under water or are resistant to seawater have been developed.

OTHER APPLICATIONS
Epoxy resins improve the crease resistance or breaking of fibers. They are also used as intermediates for stabilizers and plasticizers.

REFERENCES
1. Lee, H.; Neville, K. HandBook of Epoxy Resins, McGraw Hill: New York, NY, 1982. Chemistry and Technology; Marcel Dekker: New York, NY, 1987. 2. May, C. A.; Tanaka, Y. Epoxy Resins 3. Adhesion Polymers, Japan Welding Society: Tokyo, 1993. 4. Bhatnagar, M. S. Epoxy Resins; Universal Book: Bombay, India, 1996. 5. Encyclopedia of Polymer Science and Technology, John Wiley & Sons: New York, NY, 1986, Vol. 6; pp 208-271; 322-382. 6. Encyclopedia of Polymer Science and Engineering, John Wiley & Sons: New York, NY, 1986, Volume 6; pp 208-271; 322-382. 7. Ullmann's Encyclopedia of Industrial Chemistry, VCH: London, United Kingdom, 1987, Volume A9. 8. Encyclopedia of Chemical Process and Design, Marcel Dekker: New York, NY, 1983, Volume 19. 9. Bhatnagar, M. S. Polym.-Plastic Techol. Eng. 1993, 32, 53. 10. Bauer, R. S. Applied Polymer Science; American Chemical Society: Washington, DC, 1985. 11. Petrosyan, V. A. et al. Arin. Khim. Zh. 1989, 42, 54. 12. Polyakov, V. A. et al. Mekh. Kompoz. Mater. 1989, 2, 218. 13. Shode, L. G. et al. Lakrokras. Mater. Ikh. Primen. 1989, 1, 60; 3, 31; 2, 48.

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14. Kharakha, Zho G. et al. Polimery 1989, 34, 204. 15. Czvikovszky, T. Kem. Kozl. 1989, 6, 4. 16. Singh, J. Paintindia 1989, 4, 1. 17. Bhatnagar, M. S. Pop. Plast. 1987, 32, 20, 29. 18. Shibalovich, V. et al. Khim. Prom. St. Rubezhok 1988; Volume 3, p 28. 19. Adam, W. et al. Angew. Chem. 1980, 92, 54. 20. Bhatnagar, M. S. Paintindia 1992, 16, May. 21. Kohjiya, S. Gummi. Kunstst. Kutsch. 1993, 46, 208. 22. Jaroslow, Z. Chemie. 1992, 45, 117. 23. Thankachan, C. J. Coat. Technol. 1989, 6139. 24. Sokolova, Yu. A. et al. Plaste. Kautsch. 1989, 27, 241. 25. Bhatnagar, M. S. Paintindia 1992, 19, August. 26. Diessner, A. et al. IEEE Conf. Publ. 1989, 239. 27. Watanabe, M. et al. Kogyo Zairyo 1989, 37, 350. 28. Kanegae, H. Nippon Setchaku Gokkaishi 1993, 29, 580. 29. Shiruishi, N. ACS Symp. Ser. 1989, 397, 488. 30. Manfred, H. Adhesion 1989, 33, 21. 31. Matsuura, M. Nippon Setchaku Gokkaishi 1994, 30, 24. 32. Hinderwaldner, R. Adhesion 1989, 33, 16. 33. Kharakhus, O. G. et al. Polimery 1989, 34, 204. 34. Kinjo, N. et al. Adv. Polym. Sci. 1989, 88, 1. 35. Czvikovozky, T. Kem. Kozl. 1989, 69, 45. 36. Wyatt, B. S. Australian Corrosion Association; Wavehampton, Australia, 1993. 37. Puranik, V. V. Paintindia 1989, 39, 21. 38. Kochenova, Z. A. et al. Lakrokras. Mater. Ikh. Primen 1989, 2, 82. 39. Pesat, V. Kowze. Ochz. Mater. 1989, 33, 1. 40. Klien, D. et al. Verfkromik 1989, 62, 140. 41. Thankachan, C. J. Coat. Technol. 1989, 61, 39. 42. Hashim, A. S. Kompoz. Polim. Mater. 1991, 48, 16. 43. Hudrlik, F. P.; Hudrlik, M. A. Adv. Silicon Chem. 1993, 2, 1.

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