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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.
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.
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.
20-24 The former is known as homopolymerization. formation of a branched structure. produces diglycidyl ether of bisphenol A (DGEBPA) (1675-54-3). Inc Second is epoxidation by organic peroxides and their esters.2). Unsaturated compounds such as hydrocarbon fatty acids and their esters are epoxidized by peroxyacetic acid. CHEMISTRY Epoxy resins are prepared by the reaction of active hydrogen-containing compounds with epichlorohydrin followed by dehydro-halogenation. The resin is liquid when n < 1 and solid when n > 2. Here n is nearly zero (0. Both reactions result in coupling as well as crosslinking (Scheme III).The Polymeric Materials Encyclopedia © 1996 CRC Press. IV Page 2 . The reaction between the oxirane group of the epoxy resin with primary amines is shown in Scheme IV. or corrective curing. Sodium peroxide or tungstic acid deposited on a inert surface is used for the epoxidation of olefins by hydrogen peroxide. Primary and secondary amines are widely used to cure epoxy resins. on reaction with epichlorohydrin (ECH) (106-89-8) in the presence of caustic soda. Bisphenol A (BPA) (80-05-7). III Curing of DGEBPA with a diamine occurs in three stages: propagation of the linear chain. 19 Third is epoxidation by inorganic peroxides and inorganic peroxy-acids. 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. and crosslinking. and the latter is an addition or catalytic curing reaction.
V To suit the requirements of the end products. Page 3 . polyamides (two) obtained from vegetable oils. Magnetic fields and photoinitiation also are used for polymerization. and imidazole. polyphenols. Inc Tertiary amines also are used to bring about catalytic polymerization of epoxy resin and the mechanism given in Scheme V. Hydantoin-based epoxy resin (15336-81-9) is used to form DGEBPA. polyhydric alcohols. Polymercaptans. other nitrogen compounds used for curing are triamines (DETA. polyurethane. and silanes also are used for epoxidations. Curing agents such as cyclic acid anhydrides are used.The Polymeric Materials Encyclopedia © 1996 CRC Press. polyisocyanates. dicyanamide. The reaction is shown in Scheme VI. TETA). polyureas (two). Glycidyl esters of dimerfatty acids can also be produced from vegetable oils. novalacs.
coordination catalysts such as metal chelates and photoinitiation are used to bring about polymerization.The Polymeric Materials Encyclopedia © 1996 CRC Press. propylene glycol (16096-30-3). Cationic catalysts such as metal halides. THE MANUFACTURING PROCESS Page 4 . Lewis acids such as boron trifluoride complexes are also used as curing agents. hydrogenated BPA (13410-58-7). Inc VI DGEBPA also is produced from aliphatic diols such as butane-1. triglycidyl adduct of p-aminophenol. hetrocyclic glycidyl amides and imides.4-diol (2425-79-8). and triglycidyl isocyanurate (2451-62-9).
The solution breaks up into two layers. Atomic p orbitals. and bisphenol AÌare estimated by the usual chemical methods.3-epoxy propyoxy) phenyl] methane (2467-02-9).The Polymeric Materials Encyclopedia © 1996 CRC Press. The resin separates into brine solution. Unreacted ECH is removed by vacuum distillation. so it is possible to give the correct hybridization structure. CHARACTERIZATION AND PROPERTIES The end groupsÌepoxy. 27 Researchers have found aqueous concentrated hydrochloric acid with dioxane to be a suitable reagent for estimating epoxide content. The reactive dye labeling technique Page 5 . cresol novolac (37382-79-9). phenol novolac (9003-35-7). The smaller amount of overlapping is more than offset by a decrease in the strain energy. Modified Epoxy Resins Epoxy resins form adducts with vinyl. This explains the conjugative ability of epoxy ring. chlorine. An inert solvent is then added to the resin and the reaction is completed with excess of caustic soda solution. overlap sideways. Curing agents such as amines are characterized by refractive index and specific gravity. which is thoroughly washed with water to obtain a clear resin. STRUCTURE Ethylene oxide is a cyclic ether. 2 2 Very often the epoxy groups deform to keep the area of the ring constant. The solid resin is obtained by removing the solvent by vacuum distillation. the carbon will be sp hybridized. hydroxide. The solution is kept boiling until 2 mol of caustic soda per mole of BPA have been added. Phase separation is brought about by adding an inert solvent. glycol. The solvent is removed by vacuum distillation. bis-[4(2. After one hour the reaction is complete and a taffylike mass is obtained. and phenol hydrocarbon novalac (13446-85-0). Thin-layer chromatography has been used for identification. Solid Epoxy Resin Here ECH and BPA are added to the reactor in theoretical molar ratio with a little excess of ECH. Since the H-C-H bond is 116° 15à. acrylic. 26. 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. Aqueous caustic soda is well mixed into the system. Inc The epoxy resins can be obtained in either liquid or solid states. But it also shares the triangular ring. polyester resins. Brine is withdrawn and the resin solution is thoroughly washed with water to remove traces of salts. 25 The carbon atoms in oxirane are trigonally sp hybridized. Liquid Epoxy Resins In this process ECH and BPA are charged into a reactor in the ratio of 10:1. in the plane of the ring. and results in a bent bond structure. The ring atoms do not lie along the lines of greatest electron density of the atomic orbitals from the neighboring atoms. A solution of 20-40% caustic soda is added slowly to the reaction vessel as the solution is brought to the boiling point.
resulting in the production of limited-size molecules. The epoxy resins do not soften at a specific temperature but appear to undergo a gradual and imperceptible change. Continuous and intermittent stress relaxation measures the appearance of network formation. Epoxy resins have a very wide molecular weight distribution. Shrinkage in the gel or solid state introduces stress. The greater the difference. and cured resin finds its structural applications below the heat distortion or glass transition temperature (Tg). 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). Researchers have used a variety of techniques to study the thermal and environmental stability of epoxy polymers. The kinematic or intrinsic viscosities of epoxy resins are measured by viscometers. Water absorption has been found to decrease the Tg because of strong hydrogen bonds. 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. The number average molecular weight (Mn ) is determined by gas density. It is necessary to distinguish between shrinkage in the liquid stage and shrinkage in the gel or solid state. The weight average molecular weight (Mw) is estimated by viscosity and light scattering methods.The Polymeric Materials Encyclopedia © 1996 CRC Press. and above Tg mechanical properties are influenced by cross-linking density and Mc. which determines the cure rate. Viscosity studies also provide information regarding the formation of networks and their aging. Epoxy resins shrink on curing. and osmotic pressure methods. The linear viscoelastic response of epoxies displays the internal characteristics of tensile relaxation and fracture response. ebulioscopic. The curing of epoxy resins is an exothermic process. Epoxy resins are noncrystalline. the wider the distribution. The softening of epoxy resins can be empirically graded by the ring and ball method. Inc has also been used for studying the curing reaction. having molecular weights of a few thousands. A variety of techniques have been used to study the thermal and environmental stability of epoxy Page 6 . Continuous and intermittent stress relaxation measures the appearance of network formation. and cryoscopic. This can be estimated by comparing the Mw and Mn values. Refractometry or dilatometric measurements are used to measure shrinkage. 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. Chemorheology studies display the changes in deformation and flow properties of the resin. 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. Thus gelation temperature has a direct effect on the degree of shrinkage. which can measure the dependence of viscosity on shear rate. Their weight is determined by the usual physical methods. It has been shown that in amine-cured resins. Thus both the density and refractive index increase. water is homogeneously distributed as a plasticizer and that water clusters are present at microcracks.
Epoxy resin adhesives form strong bonds with almost all surfaces. Epoxy resins have good electrical insulation properties. lightweight. These transitions can be studied by dynamic mechanical analysis (DMA) and nuclear magnetic resonance (NMR). Very often special modifiers and curing agents must be used to produce specific properties. Epoxy resins undergo alpha. location. They are produced either by chemical reaction or by incorporating a prefoamed filler in the liquid system. Polyvinyl modified resins are used to increase flexibility and as toughening agents. where rotational motion related to configurational entropy and stress relaxation processes do not occur. Construction Epoxy resins are now used as binders in materials for construction. APPLICATIONS Foams Epoxy resins are used to form rigid. powders. 28 Adhesives The versatile properties of epoxy resins make them valuable as adhesives in civilian and military applications.and elastomer-modified resins have been used to produce adhesive that cures under water. surface. Inc polymers. Adhesives based on epoxide resins are available as room-temperature-curing two-component liquids. They are particularly used for foam-in-place applications in the “potting” process. heat-curing liquids. and volume resistance. Epoxy polyurethane resins make high-strength structural adhesives. 29-31 About five percent of total epoxy resin production is consumed as adhesive in a wide range of structural applications. foamy structures with good insulation properties. The resins can be made conductive and semiconductive by use of suitable fillers and curing agents. with the exception of some nonpolar substrates. These transitions also are influenced by the mechanism of crosslinking produced by amines. hot-melt adhesives. and anhydride curing agents. and tapes. Rubber. The formulation of epoxy adhesives into a serviceable adhesive binding system is a highly specialized technology. and magnitude of these transitions directly influence the thermo-mechanical properties of the resins. Several mechanical properties of epoxy resins are closely related with chemical composition and internal cohesive energy of the resin. Adhesive formulation based on epoxy resins requires a wide variety of curing and modifying agents. and gamma thermal transition through proper selection of epoxy monomers and curing agents. films. beta. 32 Generally a two-component system Page 7 . BF3-amine complex. The temperature. These properties are affected by moisture and increase in temperature. and good arc. but to produce some specific effects alicyclic or heterocyclic epoxides are also included. as well as in casting. They have a 3-6 dielectric constant. a low dissipation and loss factor. Generally DGEBA and oligomers are used.The Polymeric Materials Encyclopedia © 1996 CRC Press. Acrylates are also used to modify epoxy adhesives. This has been found to be true well below the transition temperature.
diluents. and curing agents is used. and to produce industrial seamless thin-set tarrazzo floors. metal assemblies. by contrast. and polysulphides. These are used in preparing assemblies of copper-clad glass or polyaramid fibers for printed circuit boards in the electronics industry. and polyaramid fabric or cotton prepregnated with the B-stage epoxy resins are laminated in large multiple pattern presses. and other chemicals. 33. carboxylated polymers. rods. Carbon and polyaramid fibers are used in the laminates. paper. Epoxy laminates also find application in marine industries. Both wet impregnated and dry epoxy resin systems are used in aircraft construction. salts. fillers. 34 In the simple molding process. For nonreinforced materials such as coil covering and electrical cases. This industry consumes 27. These can be fabricated into structural materials. Composites and Laminates Composites and laminates are materials produced by reinforcing the polymers with continuous fibers. In addition to flexibility enhancers such as polyamide. and calcium carbonate. This use has been extended to the laying of roads. They are used to bond concrete. clay. Embedment implies complete encasement in some uniform external shape. epoxy resins are replacing polyesters in special applications in which underwater strength is important. bases. reaction injection molding. fatty diamines and thermally and electrically conductive materials also are used. Laminated epoxy structures are used in building construction for concrete molds. construction of buildings. injection molding. Epoxy-molded compounds display excellent resistance to most acids. and transfer molding. Epoxy Powders The most commonly used epoxy powders are based on B-stage resins with aromatic amines or methane diamine. wood. Special molds are not required for epoxy resin molding powders. These resins are also used in foundry molding. thickening agents.The Polymeric Materials Encyclopedia © 1996 CRC Press. Sheets of woven glass. This process can be further subdivided as compression molding. liquid injection molding. Dicyanodiamide or guanidine are also used. Page 8 . In embedment. is a coating process in which the final surface is irregular. facing for foams. and inert fillers include silica. the molding powder under certain definite conditions assumes the shape of the mold. These processes are common in electrical and electronic assemblies. foam reservoir molding.6% of the epoxy resins produced. solvents. 36 Laminates Laminated epoxy insulations are largely used as sheets. material is packed to protect it from a hostile environment. 35. and filling cracks in concrete structures. Encapsulation. and tubes. MOLDING Molding can be broadly classified as simple molding and embedding processes. Embedment may be further divided into casting and potting. honeycomb cores. Inc containing liquid epoxy resin. aluminum molds are used. and impregnation. and reinforced pipes.
They find applications in washing machines and appliances. high molecular weight thermoplastic resins. Fatigue strength of the laminates depends on the behavior of the plies. 2 Pipes Epoxy resins are used in filament-bound. Methods have been suggested to reduce the internal stress. Page 9 . silane) to give adequate finish. Techniques used to fabricate advanced composites are filament winding. automobiles. Delamination during fatigue does not affect the tensile strength but reduces compressive strength. boron. The adhesion of matrix-dot graphite fiber was increased by finishing the surface of the fiber. they provide mechanical properties. Failure The most common criteria for failure are maximum stress and maximum strain. and ketamines are used as curing agents for package epoxy systems. Epoxy and modified epoxy resins have been used in composite structure. glass. graphite. solid resins. COATINGS The coatings industry is the biggest consumer of epoxy resins. 36 These fibers possess the desirable properties of low density [1. Inc Composites The fibers that dominate the field of advanced composites are carbon. farm implements. radiation curable resins. and lamination. They are resistant to chemicals. multifunctional resins. A mechanism has been worked out to remedy adhesion failure between matrix and the substrate. pultrusion. When combined with the resin binder and laminated to support applied load. The material property that quantifies tolerance for such failure is toughness. aromatic amines. Several workers have studied these properties in different fibers. which can be improved by adding flow agents. and aromatic polyamides. 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. aluminum. The glass fiber is coated with a sizing material or coupling agent (e.. and floor coatings. and solutions. failure originates at a point of stress concentration and at flaws. which can be further improved by increasing the laminating pressure. 35. glass-reinforced pipes and tubes.27 g/cm ] and extremely high strength (80-550 GPa).The Polymeric Materials Encyclopedia © 1996 CRC Press. 37-43 Aliphatic amines. where fibers support the principal load.g. In most structures. pipelines and chemical plants. containers. Epoxy coating formulations are available as liquid resins. corrosion. and special purpose resins. The ultimate strength of the composite depends on the flow of resin during cure. Epoxy resins provide thin-layer durable coatings having mechanical strength and good adhesion to a variety of substrates. Ammonia plasma has been used to improve the finish of the fibers. The composite property in an epoxy matrix improves with increasing fiber wet-out.44-2 4. These resins are used mostly as chemical and special purpose coatings. ships and bridges.
polyamides. pp 208-271. Bhatnagar. S. L. cars. 1985. pp 208-271. and food cans. C. Chemistry and Technology. Eng. et al. United Kingdom. Bauer. For marine use. 32. Ullmann's Encyclopedia of Industrial Chemistry . High-solid coating solution formulations attain maximum film properties (adhesion. Bhatnagar. 48. 6. John Wiley & Sons: New York. Applied Polymer Science. Adhesion Polymers. 6. McGraw Hill: New York. 1987. et al. Volume 19. Epoxy Resins. V. NY. Khim. Lee. and freedom from defects). 1986. 1996. and miscellaneous products. 1987. outdoor furniture. or aliphatic liquid amine adducts are used in seamless floors. Polym. Neville. Mater. Such coatings also have been based on emulsified liquid epoxy resins cured with emulsified polyamide resins. epoxy resins that cure under water or are resistant to seawater have been developed. Vol. metal furniture. John Wiley & Sons: New York. Universal Book: Bombay. These adducts have proved useful in automotive primers. 322-382. Epoxy resins cured with aliphatic amines. HandBook of Epoxy Resins. M. 53.-Plastic Techol. 1989. Epoxy acrylic systems provide excellent coatings for appliances. K. 60. R. They provide exterior and interior coatings for underground pipes. NY. G.. 7. These resins are used as lining for tanks. 10. 4. pails. NY. 54.. Arin. 1989. Zh. Petrosyan. Marcel Dekker: New York. Kompoz. H. 12. kitchen cabinets. M. Japan Welding Society: Tokyo. They are also used as intermediates for stabilizers and plasticizers. 2. These formulations are used in anionic electrodeposited coatings. Industrial floors require extra epoxy resin. 31. Inc Epoxy baking finishes are obtained by high molecular weight epoxy resins crosslinked by phenolic or amino resins. 322-382. brass. India. V. Lakrokras. 42. aluminum siding. Encyclopedia of Chemical Process and Design . A. 1986. and electrical equipment appliances reinforcement. 1983. 218. A. OTHER APPLICATIONS Epoxy resins improve the crease resistance or breaking of fibers. These are based on liquid epoxy resin acrylic adducts with epoxy resins. Epoxy ResinsÌ 3. pipes. Encyclopedia of Polymer Science and Engineering . S. 5. et al. Waterborne coatings are made by dispersing or emulsifying the resins with surfactants. downhole oilfield tubing. 8. Shode. A. Y. 2. appearance. 13. 11. 1982. Application of powders is accomplished by electrostatic spray fluidized-bed coating and electrostatic fluidized-bed coating. Mater. as they are useful on steel. DC. Tanaka. Volume 6. Page 10 . Polyakov. Volume A9. 1989. and other metal products. NY. drums. VCH: London. 3. 1993. Primen. buildings. 1. 9. NY. S. American Chemical Society: Washington. 1993. Mekh. 2. Marcel Dekker: New York.The Polymeric Materials Encyclopedia © 1996 CRC Press. High-solid coatings have an additional advantage. Encyclopedia of Polymer Science and Technology . REFERENCES 1. May. Ikh.
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