EPOXY RESINS

T
INTRODUCTION

he synthesis chemistry of epoxy resins is briefly reviewed, along with a hsting of numerous references from the Uterature. The curing of an epoxy resin by reaction with a polyamine is described in the following experiment. The reaction can be followed by running either NMR or infrared spectra at periodic intervals. After standing for several hours or days, it is analyzed again to see if there was any further change. A comparison of two different but related amines is made to see how amine functionality affects the rate of reaction, all run at room temperature.

Epoxy resins are usually prepared from compounds (or polymers) containing two or more epoxy groups that have been reacted with amines, anhydrides, or other groups capable of opening the epoxy ring and forming thermosetting products. Polymers from monoepoxy compounds have already been described in Sandler and Karo [1]. Schlack [2] and Castan [3,4] are credited with the earliest U.S. patents describing epoxy resin technology. Greenlee [5] further emphasized the use of bisphenols and their reaction with epichlorohydrin to yield diepoxides capable of reaction with crude tall oil resin acids to yield resins useful for coatings. The use of diepoxide resins that are cured with amines was reported by Whittier and Lawn [6] in a U.S. patent in 1956. The introduction of epoxidation techniques for polyunsaturated natural oils by Swern and colleagues [7,8] led to industrial interest in the preparation of epoxy compounds useful for resin production [9,10]. Epoxy resin technology has been reviewed and a number of relevant references are available [7,11-16]. The applications of epoxy resins are not only used for adhesives but in the area of coatings used for appliances, automobiles, and cans. These resins have the added advantage of being solventless systems, which helps avoid air pollution

61

on prolonged contact with epoxy resins. All amine curing agents or A^-heterocyclic types should be suspect and handled with great care.4 3.9 5.2 3. 56 (1981).8 9.9 99. may develop a skin sensitization evidenced by blisters or other dermatitis conditions.7 10.6 9. ^ Includes flooring.1 3. and while working in hoods or well-ventilated areas [20].0 7. ' Data estimated for 1990 found in Mod. Plast 51.1 6. The growth in production of epoxies is up from 183 miUion pounds in 1972 [17]. Other individuals may develop an asthmahke condition. Contaminated gloves and work clothes should be changed immediately and either laundered or discarded. Dow.4 5.1 ^ > ^ 25 — 14 13 31 15 212 89 1990^ 13 12 « Data for 1972 and 1973 reprinted from Mod. SAFETY PRECAUTIONS Epoxy resins and their curing agents are considered primary skin irritants. 21.4 2.2 8. Contact with epoxy resins should only be made using gloves and face shields.9 2.9 7. Polymer Synthesis problems in plants. to an estimated sales of epoxy products of 464 million pounds in 1990 [18]. and molding Exports Other Total 1972 5. ^ Does not include reinforcements. Some individuals. Ciba-Geigy. Major producers and approximate capacities are tabulated in Table 2. 39 (1974). Some aromatic amine curing agents may be carcinogenic.9 12.1 4. Reprinted with permission of the copyright owner.6 2.2 7. The approximate epoxy resin production capacity as of 1993 was more than 800 miUion pounds per year. The pattern of consumption of epoxy resins is described in Table 1. .3 7.8 6.62 I. road coating. Copyright 1974 by Modern Plastics. and TV resins.6 83. Frequent washing of hands is advisable and strict personal hygiene must be practiced. casting. and Shell are the major producers.8 3.0 1973 5. Epoxy thermosetting resin sales in 1990 are also reported to be 499 miUion pounds [19]. and aggregates Protective coatings Appliance finishes Auto primers Can and drum coatings Pipe coatings Plant maintenance Other (including trade sales) Reinforced plastics'^ Electrical laminates Filament winding Other Tooling. Contaminated shoes should be discarded. Plast. paving.6 6. A properly cured epoxy resin system usually presents no health problems TABLE 1 Epoxy: Pattern of Consumption'* 1000 metric tons Market Bonding and adhesives^ Flooring.7 12.4 9.5 2.1 9.

Ciba-Geigy Co. the weight of resin in grams that contains a 1-g equivalent of an epoxy group.23]. The "epoxy value" designates the fractional number of epoxy groups per 100 g of epoxy resin. Epoxy Resins 63 TABLE 2 Epoxy Resin Production Producer Shell Chemical Co. August. Pyridinium chloride-pyridine is a recommended reagent for the analysis of bisphenoldiglycidyl ether resins [22. Rhone Poulenc Reichhold Chemical Co.E. see Refs. epoxy groups are determined by the reaction with hydrogen halide and back titration with a standard base. ANALYSIS OF EPOXY RESINS Epoxy resins are analyzed for epoxy or oxirane content. Stahl. Eggers and Humphrey [28] have reported on the application of gel permeation chromatography to monitor epoxy resin molecular distributions and curing. Analytically. Approximate production capacity for 1993 in million pounds per year"^ 290 265 190 15 30 12 " From W." Marketing " Research Report on Epoxy Resins. This is achieved by the use of hydrogen bromide dissolved in an anhydrous protic solvent such as glacial acetic acid [24]. Other improved analytical procedures allow direct titration of the epoxy group [23]. Union Carbide Corp. For additional safety information. The methods developed by Jay [25] and Dijkstra and Dahmen [26] using quaternary ammonium bromide or iodide in acetic and perchloric acid solutions for titration are considered the best general techniques for a wide variety of epoxides (hindered and unhindered alicycHc epoxides). More recently. Other functional groups present may cause interference problems and result in poor end points. relating to skin irritation. 16 and 21. Individuals who show sensitivity should discontinue handling epoxy compounds. 580. Dow Chemical Co. which is reported as the epoxy or oxirane equivalent or epoxy equivalent weight. "Chemical Economics Handbook.e. CONDENSATION-ELIMINATION REACTIONS Epoxy Compounds via Epichlorohydrin Epoxy resins are generally prepared by the reaction of epichlorohydrin with active hydrogen-bearing compounds: . i. The use of the halogen acid procedure fails for epoxides that undergo intramolecular rearrangement to aldehydes or ketones [27]. Percentage oxirane oxygen is used for epoxidized oils and dienes.0600A. F.. The preparation given describes an infrared spectrophotometric method to follow curing. 1994. p. as hypersensitivity will develop making it difficult even to come close to those materials without developing dermatitis or other reactions.

Copyright April.5 21 C(hr) 1.5 5. reactions catalyzed by TABLE 3 Reactivity of Amine Accelerators witli Aniiydride-Epoxy Resin Systems'* Gel time at 65°C.9 phr hexahydrophthalic anhydride: HEX anhydride 60:40. RCONH2.5 — ^ Reprinted from G.5 3. N-dimethylaniline) 2-Aminopyridine 2-Amino-3 -methylpyridine 2-Amino-4-methylpyridine 2-Amino-5-methylpyridine 2-Amino-6-methylpyridine 2.5 1 2.5 phr hexahydrophthalic anhydride: HEX anhydride 70:30.6-Diaminopyridine A(hr) 1 — 5 5 5 5 4 1 3 3 16 17 4 8 B(hr) 0. which is then treated with a base to give the resulting epoxy compound. The curing reaction can also involve homopolymerization catalyzed by Lewis acids or tertiary amines. 100-g samples^ Accelerator Pyridine Diethylamine Triethylamine Q!-Methylbenzyldimethylamine Dibutylaminopropylamine Diethylaminopropylamine Dibutylaminopropylamine acetate p. Polymer Synthesis o X = 0.5 3. CURING-POLYMERIZATION REACTIONS OF EPOXY COMPOUNDS AND RESINS Epoxy resins are cured [29] by reaction of the epoxy group with other functional groups to give linear.64 I.5 6.S R = aliphatic or aromatic o (1) CI —CH2CH—CH2 + R — X H . RNH2. 1964 by Modern Plastics. and (C) 85. Plast 42. etc. Mod. ^ Formulations: Araldite 6010 plus 2% of the indicated accelerator and (A) 102.5 2.—CHR ^Z"^—CH. Compounds Z are active hydrogen compounds such as amines. ROH. Reprinted by permission of the copyright owner.5 3.5 42 4.5 4 1 1.^ R X — C H 2 —CH—CH2 The reaction involves a chlorohydrin intermediate. In most cases.5 1. 152 (1964).5 2. anhydrides. —CH—R \ / I O ^(2) Z = R3N. or cross-linked products as described in Eq.5 9 2. Kline. Z + CH. (B) 93.5 7 3.4 phr hexahydrophthalic anhydride: HEX anhydride 50:50.5 8.p' -Methylenebis(A^.5 2 — 2. RCOOH. branched. RSH. M. and acids [30]. (RC0)20. .5 4. (2) and in Table 3.

all epoxy groups are of equal reactivity. However. they are more difficult to handle and offer poor thermal stability. Electron-attracting groups increase the rate with nucleophilic agents (amines. aromatic amines such as 4. Although aliphatic primary amines react more rapidly (triethylenetetramine cures the above epoxy resin based on bisphenol A in 30 min at room temperature and causes it to exotherm up to 200°C).E. Some of the typical curing reactions are illustrated in Scheme 1 [33-43]. The amount of curing agent. whereas electron-donating groups (methylene. With the diglycidyl derivative of bisphenol A.4'methylene dianiline or diaminodiphenyl sulfone provide good thermal stability for the final cured resin. if of the active hydrogen type. inorganic bases). is calculated as one epoxy group for each active hydrogen of the reagent. OH R R I R'0(CH2CH —0)nH or p R'0(0CH2CH—)nOH R' = alkyl or aryl R I RSCH2 — C H — R I Sb{0CH2 —CH —X)3 I O RCH—CH2 —OCR' OH II I 0=P(0CH2—CHOH)3 -* RCH —CH2NHR' OH CH2 —CH —0)n RP—CH2—CH—OH H R —CH —CHg —NHCR' OH 0 = P ( 0 C H 2 C H —Cl)3 Scheme 1 Epoxy resin-curing reactions. Tertiary amines and Lewis acids are required only in catalytic amounts such as 5-15 phr. Too much curing agent may cause embrittlement. For example. internal epoxy groups favor reaction with electrophilic curing agents [32]. The choice of the specific curing agent is based on end-use considerations with regard to desired properties of the cured resin. whereas reactions catalyzed by tertiary amines are too slow and too highly temperature and concentration dependent to make them reUable as the sole curing agent. . Anhydrides generally provide pot lives of days or months and cure usually at 100-180°C with very little exotherm. For example. Tertiary amines accelerate the time for gelation but still require the elevated temperature cure to obtain optimum properties. triethylamine appears more reactive than tributylamine or benzyldiethylamine [31]. vinyl) improve reactivity with acidic-type electrophilic) curing agents. It is interesting to note that the activity of tertiary amines toward epoxide does not always correlate with their basicity but also depends strongly on steric factors. Epoxy Resins 65 Lewis acids are too fast for practical systems. Anhydrides usually give brittle products but the addition of polyether flexibilizing groups yields more elastomeric products [44].

Bulletin P61-454. Chem.765. 94 (1956). McAdams and J. New Jersey: Van Nostrand-Rheinhold. Castan. and P. Synstra. 1 (1949). Polymer Synthesis REFERENCES 1. Chem. Marketing Research Report on Epoxy Resins. 8 (1973). W. 7 (1987). Greenspan. B. British Patent 892. Shell Chem. "Epoxy Resins. p. 8. Inc. 33 (1971). F. Knoll. 580. Abstr. Ind. Becco Chem. Karo. Ind. 1958. Vol. Pap. Anal. (4th ed). 2000 (1956). R." McGrawHill. W. E. F. New Jersey: Noyes Data Corp. pp.. M.. 1968. 9. 1955. Am. 27. 'Teracetic Acid and Derivatives. Chem. 20 (1958).0600A. Durbetaki. Castan. Chicago.114 (1940). Neville. L. H. Swiss Patent 211.S. Jones. Swern. Lee and K. 1957. August (1994). D. Meet. Handbook of Epoxy Resins.324. New York: McGraw-Hill. 28. 7..66 I. 9. Technol. New York. Symp. P. Patent 2. 48. and E. 1969. 99-115. Soc. U.. "Epon Resins.J. H. 17. 322 (1986). Schlack. Shell Chem. Skeist. 1. Bulletin 4. W. /. Patent 2. Oxford: Pergamon. 1974 Abstract ORPL. Whittier and R. Berger. Kirk-Othmer Encyclopedia of Chemical Technology. S. Princeton. E. 1980). Jr. F. Greenspan and R. 1967. 12. 667 (1964).117 (1939). Div. U. Fischer. 1666 (1957). Boston: Academic Press (1992). R. Chem. R. Ranney.S. A. Houston. P. Anal. du Pont de Nemours & Co. W. 26. Dobinson. Humphrey. 1958 Division of Paint. Eng. High Solids Coat.. 33. Lawn. 38 (1964). 730 (1994). Scanlan. Karo. 16 (Dec. I. D.493. 1962. Patent 2.. G. New York. I. P. Corp. German Patent 676. 22. Stahl. F. 16. 4. Eng. Durbetaki. F. I. W. Neville. 29. Schechter and J. 103051d (1987). Atlantic City. Bulletin A6282. 47. News 51(40). Chem. J. S. Paper No. 36. J.486 (1950). Gannon. Plastics. N. J. McGraw-Hill. 32. Modern Plastics International 21. 55. K. 321 (1960) (refer to Scheme I). 67. Soc. Texas. R. Inc. /.. 23. du Pont de Nemours & Co. A. B. Epoxy and Urethane Adhesives. Food Machinery and Chemical Corp. J. Chromatogr. 52. R. Ind. 18. 15. 2. 38 (1992). Meet. 30. Epoxy Resins. T. Oil Chem. Polym. Chem.. T. 1971. J. J.S. Swern. Polymer Syntheses. W. I.288 (1956). 1971. Their Applications and Technology. Chemical & Engineering News 70(26). U. A. Somerville and P. Am. Anal.361 (1962). Keheres. Encycl. Corp. 45. E. Dijkstra and E. Academic Press. 20. Chem. "Handbook of Epoxy Resins.. Jay. Macromol. 25. D. 2nd ed. F. Lee and K. Makromal. 168th Am. Union Carbide Chem. Chem. Abstr. U. 6. Soc. 13.. P.483 (1943).147 (1955).. New York. P. Assoc. O. P. D. Chem.) 6. Greenlee. E. Gall. Findley.. Sci. New York. 134th Am. 21." SC 62-33. 1952 (revised 1957). 14. Gannon. Darmer. 31." Technical Brochure SC 71-1. 209 (1967). Chem. Rev. /.. Dahmen. 1958. Sandler and W. Chem. Chem. Eng.. 55 (1991). 106.S." Chapter 5. D. W. Sandler and W. Nelson. L. 6. 5. Co. 5 p. Chem. 391 (1956). and Printing Ink Chemistry. The Determination of Epoxide Groups. Phillips. Patent 2. "Industrial Hygiene Bulletin on Handling Epon Resins and Auxiliary Chemicals. S. Chemical Economics Handbook (CEH). 29. 19. A. 10. . Eng. 1967. 28.131. Chim. A. 146 in the Organic Coatings and Polymer Chemistry Division (1974). Gall and F.. F.. M. 24. 3. Anal. 1954. Eggers and J. R. and B. R. Organic Functional Group Preparations. V. Stark. Lohse. Vol. 33. Fallwell." Bulletin P-58-0283. 11. J. New York. Encyclopedia of Polymer Science & Engineering (2nd ed.120 (1938). I. and J. Hercules Powder Co. Hoffmann. 412 (1945). S. H. Phillips. Acta 31. F. R.

050. Corley. O. L. Abstr. Greenspan.S. M. Oil Chem.003. L. Patent 4. E. 35. Patent 2. 35.152-172 (1964). A. 1192 (1991). 2. Fukutani. S. Greenspan and R. High Polym. O.931 (1986). Abstr. Pfohl. 42. Voskresenskaya. Wakabayashi. W. S. K.S. 34.143. W. 161. 36. Chem. P." Tech. F. Kirpichnikov. W. A. V. R. Patent 3. Greenspan. Kana.690 (1958). 107. Ltd. R.437.066 (1991). Barlow. Abstr. Patent 5. 40. P20675S (1972). 115. W. Patent 2.S. R. /. Pearce and J.671 (1969). Swedin Ser. P. A. D. M. Japan 1974. M. Am. Berg. 331 (1958). H. T. Termini. K. 34a. U. 61570 (1986). 115577d (1991). E. Chem. German Offen. Abstr. Gall and F. 41. Chem. Data taken from "Preparation of O-Type Polymer (III) Solution Copolymerization of Glycidyl Methacrylate. U. 19. Wallace. 57 (1957).071 (1972). Patent 5. F. Soc. 35. 38. 105. p. 151530x (1987). G. Japanses Patent JP62132914A2 (1987). F. ibid. Gotlib. 11. 37. J. G. Koroly. 6J12 lOOOA. U. Okamoto. Okada. Epoxy Resins 67 34. Soc. Corley. A. Bull..485. Nippon Oil & Fats Co. U.S. R. E. Canadian Patent 560. A.E. H. Am. U.S.599. and J.579. Evans and E. Wood and J.436 (1986). Abstr. L. Chem. Chem. D. Rees. 44. A 33(6).. and N. W. Abstr. Light. and P.507 (1962). F. 105. Sandler and F. 39. 108. P.581.S.S. Okamoto. Jr. Niederhauser and J. Verizhnikov. . Chem. W. /. Liakumovich. C. Shokal. Oil Chem. S. D'Addieco.160 (1949). Tokyo. ibid. 237990p (1987). 355 (1958). Patent 3. 43. J. Vysokomol.817 (1952). U. Tokizawa. U. Japanese Patent JP 62124111A2 (1987). 79939f (1986). Chadwick..

Sign up to vote on this title
UsefulNot useful