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United States Patent 19 11 Patent Number: 5,503.937 Bertram Et Al

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United States Patent 19 11 Patent Number: 5,503.937 Bertram Et Al USOO5503937A United States Patent 19 11 Patent Number: 5,503.937 Bertram et al. 45) Date of Patent: Apr. 2, 1996 54 CURABLE COMPOSITION WHICH FOREIGN PATENT DOCUMENTS COMPRISESADDUCTS OF HETEROCYCLIC 0858648 12/1970 Canada .................................. 402/261 COMPOUNDS 0893191 2/1972 Canada .................................. 402/267 0239784 10/1987 European Pat. Off.. 75) Inventors: James L. Bertram, Lake Jackson; 2624981 12/1976 Germany ....................... B32B 27/38 Louis L. Walker, Clute; John W. 0073794 6/1979 Japan ..................................... 54.6/12 Muskopf, Lake Jackson, all of Tex. O127378 10/1981 Japan ..................................... 54.6/12 58-138729 8/1983 Japan ............................. CO8G 59/62 73 Assignee: The Dow Chemical Company, 0963.058 7/1964 United Kingdom. 1174124 12/1969 United Kingdom ................... 54.6/12 Midland, Mich. 2099825A 12/1982 United Kingdom. 86/OO627 1/1986 WIPO 21 Appl. No.: 192,465 8601216 2/1986 WIPO ............................ CO8G 59/02 22 Fied: Feb. 7, 1994 OTHER PUBLICATIONS Swain et al. J. Am. Chem. Soc. 75, p. 141, 1953. Related U.S. Application Data J. Org. Chem., vol. 49, pp. 1824-1825 (1984) by B. J. McBride, M. E. Garst and M. Hopkins. 60 Division of Ser. No. 894,416, Jun. 5, 1992, abandoned, and "On the thermal behaviour of some alkylammonium tet a continuation-in-part of Ser. No. 894,416, which is a rafluoroborates', Zabinska, Feroni and Sanesi, Journ. Calo division of Ser. No. 555,350, Jul. 18, 1990, Pat. No. 5,134, 239, which is a division of Ser. No. 274,227, Nov. 18, 1988, rim., Anal. Therm. Thermodyn. Chim., vol. 17, pp. 250–253 abandoned, which is a continuation-in-part of Ser. No. (1986). 155,381, Feb. 12, 1988, abandoned, which is a continuation "Proposed Mechanism for the Curing of Epoxy Resins with in-part of Ser. No. 21,837, Mar. 4, 1987, Pat. No. 4,725,652, Amine-Lewis Acid Complexes or Salts', J. J. Harris et al., J. which is a continuation-in-part of Ser. No. 849,087, Apr. 7, Ap. Pol. Sc., vol. 10, pp. 523-534 (1966). 1986, abandoned, which is a continuation-in-part of Ser. No. 716.279, Mar. 25, 1985, Pat. No. 4,594,241, which is a Akagane et al Shikizai Kyokaishi 197245(2) 69-74 Chemi continuation-in-part of Ser. No. 631,672, Jul. 17, 1984, cal Abstract vol. 77, 1972. abandoned. 1972 Abstract 12818Or, 1972. Lewis, et al. JACS. vol.43, 1921 pp. 2218-2223. (51) Int. Cl. ............................ C08G 59/62; C08G 59/14 Hawley's Condensed Chemical Dictionary 11th Ed. (Van 52 U.S. Cl. ................. 428/414; 252/182,23; 252/182,3; Nostrand Reinhold Co. New York) p. 529, 1982. 252/182.31; 428/416: 428/418; 525/482; McBride et al., "Arylation of Dialkyl Sulfides', J. Org. 525/485 Chem. 49, 1824-1825 (1984). 58 Field of Search .............................. 548/335.1, 343.5, Derwent Abstract No. 74-69862V/40, 1974. 548/405, 122, 146, 215, 304.4, 335.1, 405, Derwent Abstract No. 82-07422J/50 (abstract for EPO 066 469; 544/2, 35, 107, 224, 264, 283, 347, 543), 1982. 353, 358; 546/152, 184, 347; 549/29, 49; Derwent Abstract No. 81-50624D/28, 1981. 556/68; 252/182; 428/414, 416, 418; 525/482, Primary Examiner Yogendra N. Gupta 485 57) ABSTRACT 56 References Cited A curable composition which comprises: U.S. PATENT DOCUMENTS (1) a compound which contains on average more than 1 epoxy group per molecule; 3,048,552 8/1962 Fang ....................................... 260f28.5 3,277,050 10/1966 Pettigrew ................................. 26Of47 (2) a compound which contains on average more than 1 3,477,990 11/1969 Dante et al. .............................. 26O147 phenolic hydroxyl group per molecule; and 3,493,630 2/1970 Salensky ................................. 260/831 (3) a catalytic amount of a catalyst compound which 3,547,881 12/1970 Mueller et al. ... ... 260/47 contains: 3,565,861 2/1971 White et al. ...... , 260/47 (a) a cation containing at least one heterocyclic nitro 3,591,556 7/1971 Godfrey et al. ...... ... 260f27 gen-containing ring, and 3,687,894 9/1972 Collings et al. .. 528/104 X 3,694,407 9/1972 Krikorian ...... ... 260/47 EP (b) an anion which is a conjugate base of fluoroarsenic 3,725,341 1/1973 Kegers et al. ... 528,04X acid, fluoroantimonic acid, fluorophosphoric acid, 3,738,862 6/1973 Klarquist et al...... 52804 X chloroarsenic acid, chloroantimonic acid, chloro 3,794,619 2/1974 Hasegawa et al. ... ... 260/47 EP phosphoric acid, nitric acid, hydrofluoric acid, trif 3,859,379 1/1975 Kitamura et al...... ... 260/831 luoroacetic acid, trifluoromethane sulfonic acid, 3,899,546 8/1975 Stoy et al. .............................. 260,834 picric acid, fluoboric acid, or an acid represented by 3,919,169 11/1975 Ramsey et al. ............... ... 528/89 X the Formula: 3,947,395 3/1976 Ogata et al. ........................... 260f28 P 3,948,855 4/1976 Perry ............. ... 260/47 EP 4,026,862 5/1977 Smith et al. .......................... 528/89 X 4,069,055 1/1978 Crivello ................................ 528/92 X wherein each R is independently a hydrocarbyl or 4,136,102 1/1979 Crivello ................................ 52.2/3 X substituted hydrocarbyl group and R is a halogen, a 4,150,988 4/1979 Crivello ................................ 522/3 X hydrocarbonoxy group, a hydrocarbonamino group, 4,154,872 5/1979 Tsao et al. ............................ 522/31 X or a hydrocarbonphosphino group. 4,173,476 1/1979 Smith et al. .......................... 522/31 X (List continued on next page.) 16 Claims, No Drawings 5,503.937 Page 2 U.S. PATENT DOCUMENTS 4,440,914 4/1984 Helfand et al. ......................... 525/482 4,477,645 10/1984 Doorakian et al. ....................... 528/99 4,175,972 11/1979 Crivello ............................ 522/31 X18 4,496,709 1/1985 Doorakian et al. .. ... 528/89 4,273,668 6/1981 Crivello .. ... 522/3 X 4,503,211 3/1985 Robins ................. ... 528/92 4,318,766 3/1982 Smith ... 522/31 X 4,540,823 9/1985 Doorakian et al. .. ... 568/10 4,320,222 3/1982 Lopez ... 528/104 X 4,544,732 10/1985 Corley .............. 528/88 X 4,322,456 3/1982 Martin ..... 427/195 4,554,342 11/1985 Corley ....................................... 528/90 4,343,731 8/1982 Pucci et al. ............................. 523/427 4,581,436 4/1986 Corley ................................... 528/88 X 4,358,578 11/1982 Brownscombe .......................... 528/91 4,594,291 6/1986 Bertram et al. ....................... 528/97 X 4,366,295 12/1982 Tyler, Jr. et al. ... 525/482 4,692,504 9/1987 Frank ............... 502/164X 4,393,185 7/1983 Berner et al. .......... ... 528/27 4,725,652 2/1988 Bertram et al. ... 528/91 X 4.410,596 10/1983 Whiteside, Jr. et al. ............... 428/413 4,766,196 8/1988 Goel et al. ............................ 528/91 X 4,438,254 3/1984 Doorakian et al. ................. 528/04X 4,775,734 10/1988 Goel .......................................... 528/89 5,503,937 1. 2 CURABLE COMPOSITION WHICH acid or acid salt contained in component (2) per nitrogen, COMPRISESADDUCTS OF HETEROCYCLIC phosphorus, or sulfur-containing heterocyclic ring contained COMPOUNDS in component (1). Another aspect of the present invention pertains to an CROSSREFERENCE TO RELATED hydronium compound represented by the following formula APPLICATIONS This application is a division/continuation-in-part of Zea Xea application Ser. No. 07/894,416 filed June 5, 1992 (now abandoned), which is a division of application Ser. No. wherein X is a weak nucleophilic anion other than the anion 555,350 filed Jul. 18, 1990 (now U.S. Pat. No. 5,134,239), 10 of p-toluenesulfonic acid; Z is a cation containing at least which is a division of application serial no. 07/274,227 filed one heterocyclic nitrogen, phosphorus, or sulfur ring; and a Nov. 18, 1988 (now abandoned), which is a continuation has a value equal to the number of heterocyclic nitrogen, in-part or application Ser. No. 155,381 filed Feb. 12, 1988 phosphorus, or sulfur-containing rings in Z. (now abandoned), which is a continuation-in-part of appli The present invention also pertains to imidazolonium cation Ser. No. 021,837 filed Mar. 4, 1987 (now U.S. Pat. 5 compounds represented by the following formula I No. 4,725,652), which is a continuation-in-part of applica C-RC Formula I tion Ser. No. 849,087 filed Apr. 7, 1986 (now abandoned), Xe which is a continuation-in-part of application Ser. No. 716,279 filed Mar. 25 1985, (now U.S. Pat. No. 4,594,291), N2.21 which is a continuation-in-part of application Ser. No. 20 631,676, filed Jul. 17, 1984 (now abandoned); all of which Ra are incorporated herein by reference. wherein each R', R, R and Rare independently hydrogen or a hydrocarbyl group having from 1 to about 18 carbon FIELD OF THE INVENTION atoms or such hydrocarby groups containing an oxygen, The present invention concerns latent, curable, catalyzed 25 sulfur, cyano or halogen substituent, or R and R can mixtures of epoxy-containing compounds and aromatic combine to form a 5 or 6 membered ring with the carbon and hydroxyl-containing compounds. The present invention also nitrogen atoms from the imidazole ring to which they are concerns latent catalysts and epoxy resin compositions con attached or R and R can combine to form a 5 or 6 taining them. membered ring with the two carbon atoms from the imida 30 zole ring to which they are attached; and X is the anion BACKGROUND OF THE INVENTION portion of an acid other than p-toluenesulfonic acid having a weak nucleophilic anion. Epoxy resins have been precatalyzed with phosphonium Further, the present invention pertains to morpholinonium and other compounds to provide latent compositions which compounds represented by the following formula II wherein form advanced, higher molecular weight epoxy resins when 35 each R, R.
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