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. R. R. R. R. R. R. and R is independently admixed with an aromatic hydroxyl-containing compound hydrogen, or a hydrocarbyl group having from 1 to about 18 as disclosed by Perry in U.S. Pat. No. 3,948,855 and Can. carbon atoms or such hydrocarbyl groups containing an 893, 191; by Dante et al. in U.S. Pat. No. 3,477,9907 by oxygen, sulfur, cyano or halogen or Mueller et al. in U.S. Pat. No. 3,547,881; by Tyler, Jr. et al. in U.S. Pat. No. 4,366,2957 and by Cragar in Can. 858,648. Re Formula II. 40 "S-PS6 * SC 1 While compositions containing these catalysts and an / NRd epoxy resin are somewhat stable, such compositions which Xe also contain an aromatic hydroxyl-containing compound are Rh RC lacking in stability. & 4 31 Curable compositions containing epoxy resins and aro R 1 NN1 anRb matic hydroxyl-containing compounds and a catalyst there 45 Ra 1 YH for would be highly desirable in the preparation of storage the like substituent; and X is the anion portion of an acid stable coatings, storage stable electrical encapsulants, stor having a weak nucleophilic anion or a combination of such age stable formulations for preparing mechanical and elec acids. trical laminates and composites, storage stable one package Further, the present invention pertains to pyrrolidinonium molding compositions, storage stable curable compositions 50 compounds represented by the following formula III for use in resin transfer molding (RTM) and reaction injec tion molding (RIM) applications and the like. R R Formula III.

RiRa f i-gRe Xe SUMMARY OF THE INVENTION Sc2 sc The present invention pertains to (A) the product resulting 55 Rh 1 NN 16 NRd from contacting (1) at least one heterocyclic nitrogen, phos Rc1 NH phorus, or sulfur-containing compound other than the com wherein each R, R. R. R. R. R. R8, R and R is pound pyridine with (2) an acid other than p-toluenesulfonic independently hydrogen, or a hydrocarbyl group having acid, said acid having a weak-nucleophilic anion; and (B) suitably from 1 to about 18, more suitably from 1 to about the product resulting from contacting (1) an adduct of at 60 9, carbon atoms or such hydrocarbyl groups containing an least one acid having a relatively strong nucleophilic anion oxygen, sulfur, halogen or the like substituent with the and at least one heterocyclic nitrogen, phosphorus, or Sulfur proviso that at least one of R,R,R,R,R,R,R,R or containing compound other than the compound pyridine R is a substitutent other than hydrogen when X is the BF with (2) an acid or salt of an acid other than p-toluene anion; and X is the anion portion of an acid having a weak sulfonic acid, said acid having a weak-nucleophilic anion 65 nucleophilic anion. wherein components (1) and (2) are contacted in quantities Further, the present invention pertains to pyridinonium which provide from about 0.6 to about 1.4 equivalents of compounds represented by the following formula IV 5,503,937

Formula IV. R Formula VIII. N C-ReRa xe Xe Ra-C3 5C1 HSN, YRC Rb wherein each R, R, R, R and R is independently wherein each R, R, R, R, R and R is independently hydrogen or a hydrocarbyl group having suitably from 1 to hydrogen or a hydrocarbyl group having suitably from 1 to 10 about 18, more suitably from 1 to about 9, carbon atoms or about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, such hydrocarbyl groups containing an oxygen, sulfur, halo cyano or halogen or the like substituent; and X is the anion gen or the like substituent, and X is the anion portion of an portion of an acid having a weak nucleophilic anion. acid having a weak nucleophilic anion. Further, the present invention pertains to thiazolonium Further, the present invention pertains to pyrazolinonium 15 compounds represented by the following formula IX compounds represented by the following formula V (BN 4 C-R. Formula IX Ra-C C-Rd Formula W. H1,a - I X N , C-Ri Re-C S 3C-R HSN16 Xe 20 wherein each R', RandR is independently hydrogen or a Rb hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl wherein each R', R, R and R is independently hydrogen groups containing an oxygen, sulfur, cyano or halogen or the or a hydrocarbyl group having suitably from 1 to about 18, like substituent; and X is the anion portion of an acid having more suitably from 1 to about 9, carbon atoms or such 25 a weak nucleophilic anion. hydrocarby groups containing an oxygen, sulfur, cyano or Further, the present invention pertains to pyrrolonium halogen substituent, or R and R can combine to form a 5 compounds represented by the following formula X or 6 membered ring with the carbon and nitrogen atoms from R- 3 --R 8 Formula X. the pyrazole ring to which they are attached or RandR can 30 X combine to form a 5 or 6 membered ring with the two carbon Ra-C2 l 5C-RC atoms from the pyrazole ring to which they are attached; and HSN6 X is the anion portion of an acid having a weaknucleophilic Rh anion. wherein each R, R, R, R and R is independently Further, the present invention pertains to oxazolinonium 35 hydrogen or a hydrocarbyl group having suitably from 1 to compounds represented by the following formula VI about 18, more suitably from 1 to about 9, carbon atoms or Such hydrocarbyl groups containing an oxygen, sulfur, (BN 3 4 C-RC Formula VI. cyano or halogen or the like substituent, and X is the anion H1 2 J C C-R portion of an acid having a weak nucleophilic anion. Ra1 No1 Xe 40 Further, the present invention pertains to pyrazinonium compounds represented by the following formula XI wherein each R, R and R is independently hydrogen or a hydrocarbyl group having suitably from 1 to about 18, more N Formula XI. suitably from 1 to about 9, carbon atoms or such hydrocarbyl R-1 S-R Xe groups containing an oxygen, sulfur, cyano or halogen or the 45 R-C3 3C-Rh like substituent, and X is the anion portion of an acid having HS2 a weak nucleophilic anion. wherein each R, R, RandR is independently hydrogen, Further, the present invention pertains to imidazolidi or a hydrocarby group having suitably from 1 to about 18, nonium compounds represented by the following more suitably from 1 to about 9, carbon atoms or such formula VII 50 hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen or the like substituent, and X is the anion portion of R Formula VII. an acid having a weak nucleophilic anion. Further, the present invention pertains to pyridazinonium RaSN, i-gRe Xe compounds represented by the following formula XII Sc2 scC 55 Rb 1HSN, YRd C-Re Formula XII. Re Xe wherein each R, R,R,R,R,R, R and R is indepen Ra --CHSN1 N dently hydrogen or a hydrocarbyl group having suitably 60 wherein each R,R,R, and R is independently hydrogen, from 1 to about 18, more suitably from 1 to about 9, carbon hydrogen or a hydrocarbyl group having suitably from 1 to atoms or such hydrocarbyl groups containing an oxygen, about 18, more suitably from 1 to about 9, carbon atoms or sulfur, cyano or halogen or the like substituent; and X is the Such hydrocarbyl groups containing an oxygen, sulfur, anion portion of an acid having a weak nucleophilic anion. cyano or halogen or the like substituent, and X is the anion Further, the present invention pertains to imidazoli 65 portion of an acid having a weak nucleophilic anion. nonium compounds represented by the following Further, the present invention pertains to pyrimidinonium formula VIII compounds represented by the following formula XIII 5,503,937

g Formula XIII. R Formula XVII. C H-N R-c? 5.Ng1 Sc-Rd Xe R-CS C 3C-R wherein each R, R and R is independently hydrogen, or S1 Se a hydrocarbyl group having suitably from 1 to about 18, Ra Rb more suitably from 1 to about 9, carbon atoms or such wherein each R,R,R,R,R, R and R is independently hydrocarbyl groups containing an oxygen, sulfur, cyano or 10 hydrogen, or a hydrocarbyl group having Suitably from 1 to halogen or the like substituent; and X is the anion portion of about 18, more suitably from 1 to about 9, carbon atoms or an acid having a weak nucleophilic anion. such hydrocarbyl groups containing an oxygen, Sulfur, Further, the present invention pertains to quinoxali cyano or halogen or the like substituent, and X is the anion nonium compounds represented by the following 15 portion of an acid having a weak nucleophilic anion. formula XIV Further, the present invention pertains to purinonium R Formula XV. compounds represented by the following formula XVIII C N Rd Formula XVII. Re-c2 YC1 iSC-Rc 20 Xe R?-CSsi-NN1e C 3C-R Ra wherein each R, R. R. R. R., and R is independently 25 wherein each R, R, R and R is independently hydrogen, hydrogen, or a hydrocarbyl group having suitably from 1 to or a hydrocarbyl group having Suitably from 1 to about 18, about 18, more suitably from 1 to about 9, carbon atoms or more suitably from 1 to about 9, carbon atoms or such such hydrocarbyl groups containing an oxygen, sulfur, hydrocarby groups containing an oxygen, sulfur, cyano or cyano or halogen substituent, and X is the anion portion of 30 halogen or the like substituent; and X is the anion portion of an acid having a weak nucleophilic anion. an acid having a weak nucleophilic anion. Further, the present invention pertains to quinazolinonium Further, the present invention pertains to indazolonium compounds represented by the following formula XV compounds represented by the following formula XIX

R Formula XV. 35 R R Formula XIX. C N C H-Neb Re-C28 No1 iSC-Rc Rd-c2 NC1)N xe f 6 3 - Xe 5 R -C 5 C 4. N Re-CS,S1 C-C 40 Ra Ra Rb Rf wherein each R', R, R, R, R, and R is independently wherein each R, R. R. R, R and R? is independently hydrogen, or a hydrocarbyl group having suitably from 1 to hydrogen, or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, 45 such hydrocarby groups containing an oxygen, sulfur, cyano or halogen or the like substituent; and X is the anion cyano or halogen or the like substituent, and X is the anion portion of an acid having a weak nucleophilic anion. portion of an acid having a weak nucleophilic anion. Further, the present invention pertains to phthalazinonium Further, the present invention pertains to indolonium compounds represented by the following formula XVI 50 compounds represented by the following formula XX Rd RC Formula XVI. R R Formula XX. C C } Re-cái Ng1 SNé Re-C279HN YC1 SC-Rh 55 6 R-CS i-Y2 N R-ks.No --R Ra Rh Rg wherein each R', R, R, R, R, and R is independently wherein each R, R, R,R,R, R and R8 is independently hydrogen, or a hydrocarbyl group having suitably from 1 to 60 hydrogen, or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, Such hydrocarby groups containing an oxygen, Sulfur, cyano or halogen or the like substituent; and X is the anion cyano or halogen or the like substituent, and X is the anion portion of an acid having a weak nucleophilic anion. 65 portion of an acid having a weak nucleophilic anion. Further, the present invention pertains to quinolinonium Further, the present invention pertains to indolizinonium compounds represented by the following formula XVII compounds represented by the following formula XXI 5,503,937

Formula XXI. Formula XXV. Rd

R 4 3 Xe Rg1, C-C-Ra wherein each R', R,R,R,R, RandR is independently hydrogen, or a hydrocarbyl group having suitably from 1 to wherein each R,R,R,R,R, R and R is independently 10 about 18, more suitably from 1 to about 9, carbon atoms or hydrogen, or a hydrocarbyl group having suitably from 1 to such hydrocarbyl groups containing an oxygen, Sulfur, about 18, more suitably from 1 to about 9, carbon atoms or cyano or halogen or the like substituent; and X is the anion such hydrocarbyl groups containing an oxygen, sulfur, portion of an acid having a weak nucleophilic anion. cyano or halogen or the like substituent; and X is the anion Further, the present invention pertains to indolinonium portion of an acid having a weak nucleophilic anion. 5 compounds represented by the following formula XVI Further, the present invention pertains to phenazinonium compounds represented by the following formula XXII R Formula XXVI. C H-Neb Rd Re Rd Formula XXII. R8 -c, Nc-1. 1 Sc1 20 | | | R. Xe R-CSCNd 3c-Rh R8-C - C C 3 Ra S1 N2 se Ri k Ra wherein each R, R, R, R. R. R. R8, R' and R is 25 independently hydrogen, or a hydrocarbyl group having wherein each R, R,R,R,R,R, R and R' is indepen suitably from 1 to about 18, more suitably from 1 to about dently hydrogen, or a hydrocarbyl group having suitably 9, carbon atoms or such hydrocarbyl groups containing an from 1 to about 18, more suitably from 1 to about 9, carbon oxygen, sulfur, cyano or halogen or the like substituent, and atoms or such hydrocarbyl groups containing an oxygen, X is the anion portion of an acid having a weak nucleophilic sulfur, cyano or halogen or the like substituent, and X is the 30 anion portion of an acid having a weak nucleophilic anion. all O. Further, the present invention pertains to phenarsazi Further, the present invention pertains to piperidinonium nonium compounds represented by the following formula compounds represented by the following formula XVII XXIII Formula XXVII. Formula XXIII. 35

40 wherein each R,R,R,R,R,R, R5, R, R, R and R' is independently hydrogen, or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about wherein each R,R,R,R,R,R, R8 and R is indepen 9, carbon atoms or such hydrocarbyl groups containing an dently hydrogen, or a hydrocarbyl group having suitably oxygen, sulfur, cyano or halogen or the like substituent, and from 1 to about 18, more suitably from 1 to about 9, carbon 45 X is the anion portion of an acid having a weak nucleophilic atoms or such hydrocarbyl groups containing an oxygen, 21O. sulfur, cyano or halogen or the like substituent; and X is the Further, the present invention pertains to piperazinonium anion portion of an acid having a weak nucleophilic anion. compounds represented by the following formula XXVIII Further, the present invention pertains to phenothiazi nonium compounds represented by the following formula 8 m Y - e Formula XXVIII. XXIV 50 R itNS-R R 1. 2 NRd Formula XXIV. Ri Rc Xe C Nep C R8 -r NC10NC1 SC-Re Xe 55 wherein each R, R, R, R, R, R, R8, Rh, R and R is 3 independently hydrogen, or a hydrocarbyl group having sa-'Ns 4 suitably from 1 to about 18, more suitably from 1 to about se 9, carbon atoms or such hydrocarbyl groups containing an Ri Ra oxygen, sulfur, cyano or halogen or the like substituent; and wherein each R, R, R, R, R, R, R, R and R is 60 X is the anion portion of an acid having a weak nucleophilic independently hydrogen, or a hydrocarbyl group having 210. suitably from 1 to about 18, more suitably from 1 to about The term hydrocarbyl as employed herein refers to a 9, carbon atoms or such hydrocarbyl groups containing an monovalent aliphatic hydrocarbon group such as alkyl, oxygen, sulfur, cyano or halogen or the like substituent; and cycloalkyl, alkenyl and similar hydrocarbon groups. X is the anion portion of an acid having a weak nucleophilic The term weak-nucleophilic as employed herein means anion. 65 that the material has a nucleophilicity value “n” from greater Further, the present invention pertains to pyrrolinonium than zero to less than about 2.5, preferably from about 0.5 compounds represented by the following formula XXV to about 2, more preferably from about 1 to about 2 as 5,503.937 9 10 described by C. G. Swain and C. B. Scott in J. Am. Chem. pounds when heated to a temperature of at least about 100 Soc., Vol. 75, p. 141 (1953) which is incorporated herein by C. In most instances, the quantity of catalyst is from about reference. The term relatively strong-nucleophilic as employed 0.05 to about 50, suitably from about 0.1 to about 30, more herein means that the material has a nucleophilicity value suitably from about 0.5 to about 20, most suitably from "n" of 2.5 or greater as described by C. G. Swain and C. B. about 1 to about 10 millimoles of catalyst per epoxide Scott in J. Am. Chem. Soc., Vol. 75, p. 141 (1953) which is equivalent. incorporated herein by reference. The heterocyclic secondary and tertiary amines, nitrogen, The present invention may suitably comprise, consist of, phosphorus, or sulfur-containing compounds which can be or consist essentially of all or only a portion of the afore employed herein can contain one, two or three or more mentioned components. The components can be eliminated 10 nitrogen, phosphorus, or sulfur atoms per molecule singly or in multiples of any two or more from those components enumerated above. Suitable heterocyclic secondary and tertiary amines, The invention illustratively disclosed herein suitably can nitrogen, phosphorus, or sulfur-containing compounds also be practiced in the absence of any component which is which can be employed herein include, for example, imi not specifically disclosed or enumerated herein. 15 dazoles, imidazolidines, imidazolines, oxazoles, pyrroles, thiazoles, pyridines, pyrazines, morpholines, pyridazine, pyrimidine, pyrrolidines, pyrazoles, quinoxalines, quinazo DETAILED DESCRIPTION OF THE lines, phthalozines, quinolines, purines, indazoles, indoles, INVENTION indolazines, phenazines, phenarsines, phenothiazines, pyr Any numerical values recited herein include all values 20 rolines, indolines, piperidines, piperazines, thiophenes, ben from the lower value to the upper value in increments of one zothiophenes (thionophthenes), naphthothiophenes, thian unit provided that there is a spearation of at least 2 units threnes, phenoxathins, thienofurans, imidazothiazoles, between any lower value and any higher value. As an dithiatetrahydronaphthalenes, dithioles, oxathioles, thiaz example, if it is stated that the amount of a component is, for 25 oles, oxathiazoles, oxathiazines, thiepins, or any combina example, from 1 to 90, preferably 20 to 80, more preferably tion thereof and the like. - from 30 to 70, it is intended that values such as 15-85, 22-68, 43-51, 30-32 etc. are expressly enumerated in this Suitable imidazole compounds which can be employed specification. Usually, for values which are less than one, herein include, for example, those represented by the fol one unit is considered to be 0.1; therefore, the minimum lowing formula A separation between any lower value and any higher value is 30 0.2. These are only examples of what is specifically intended N g-r Formula A. and all possible combinations of numerical values between Ra-Cl 3C-RC the lowest value and the highest value enumerated are to be NN 1 considered to be expressly stated in this application in a similar manner. 35 The latent catalysts of the present invention are prepared wherein each R, R, R and R is independently hydrogen by simply mixing the hydronium, amine nitrogen, phospho or a hydrocarbyl group having suitably from 1 to about 18, rus, or sulfur-containing heterocyclic compound with the more suitably from 1 to about 9, carbon atoms or such acid having a weak-nucleophilic anion in the desired pro hydrocarbyl groups containing an oxygen, Sulfur, cyano or portions and stirring to insure intimate contact. The contact 40 halogen substituent, or R' and R can combine to form a 5 can be conducted at temperatures of from about 0° C. to or 6 membered ring with the carbon and nitrogen atoms from about 100° C., preferably from about 20° C. to about 60° C. for a time sufficient to complete any reaction which occurs. the imidazole ring to which they are attached or R and R' The time depends upon the temperature, but usually from can combine to form a 5 or 6 membered ring with the two about 1 to about 120, preferably from about 5 to about 60 carbon atoms from the imidazole ring to which they are minutes is sufficient. 45 attached. Particularly suitable imidazole compounds The components from which the catalysts are prepared are include, for example, 2-methylimidazole, 2-ethylimidazole, mixed in proportions which provide from about 0.6 to about 2-propylimidazole, 2-butylimidazole, 2-pentylimidazole, 1.4, suitably from about 0.75 to about 1.3, more suitably 2-hexylimidazole, 2-cyclohexylimidazole, 2-phenyl-imida from about 0.85 to about 1.2, most suitably from about 0.95 zole, 2-nonylimidazole, 2-undecylimidazole, 2-heptade to about 1.1, equivalents of acid per nitrogen, phosphorus, or 50 cylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-meth sulfur-containing heterocyclic ring. When the amount of ylimidazole, 1-benzylimidazole, 1-ethyl acid is less than about 0.6 equivalent per nitrogen-containing 2-methylbenzimidazole, 2-methyl-5,6-benzimidazole, 1-vi heterocyclic ring contained in imidazole, the catalyst is less nylimidazole, 1-allyl-2-methylimidazole, or any combina latent and begins to approach the reactivity of the original tion thereof and the like. Suitable imidazoles wherein one or imidazole prior to reaction with the acid. When the amount 55 of acid is more than about 1.4 equivalents per nitrogen more of the R", R. R., or R group contain oxygen, sulfur, containing heterocyclic ring contained in imidazole, the cyano or halogen substituents include, for example, 1-(2- catalyst becomes less latent to the point that at a ratio of hydroxypropyl)-2-methylimidazole, 2-phenyl-4,5-dimethy about 1.5:1 the catalyst becomes an accelerator as compared lolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimida to the original hydronium, amine, nitrogen, phosphorus, or 60 Zoie, 2-chloromethylbenzimidazole, sulfur-containing compound prior to reaction with the acid. 2-hydroxybenzimidazole, or any combination thereof and The latent catalysts of the present invention are useful to the like. Most particularly suitable are 2-methylimidazole, catalyze the reaction between vicinal epoxide-containing 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole and compounds and phenolic hydroxyl-containing compounds. 2-phenylimidazole. The catalysts can be employed in amounts sufficient to 65 Suitable pyrazole compounds which can be employed catalyze the reaction between the vicinal epoxide-containing herein include, for example, those represented by the fol compounds and the phenolic hydroxyl-containing com lowing formula B 5,503,937 11 12

Formula B. Rf Formula E. N C-Re | 4. / R Ra-C2 5 C wherein each R, R, R and R is independently hydrogen N1 / N or a hydrocarbyl group having suitably from 1 to about 18, N RC more suitably from 1 to about 9, carbon atoms or such k hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent, or R” and R can combine to form a 5 10 wherein each R", R, R, R, R and R is independently or 6 membered ring with the carbon and nitrogen atoms from hydrogen or a hydrocarbyl group having suitably from 1 to the pyrazole ring to which they are attached or R and R' can about 18, more suitably from 1 to about 9, carbon atoms or combine to form a 5 or 6 membered ring with the two carbon such hydrocarbyl groups containing an oxygen, sulfur, atoms from the pyrazole ring to which they are attached. cyano or halogen or the like substituent. Particularly suitable Particle suitable pyrazole compounds include, for example, 15 pyrazole, 1-methylpyrazole, 3-methylpyrazole, 4-butylpyra imidazoline compounds include, for example, imidazoline, zole, 1-methyl-3-propylpyrazole, 3-ethyl-5-methylpyrazole, 1-methylimidazolidine, 2-methylimidazolidine, 4-butylimi 1-(3-hydroxypropyl)pyrazole, 5-phenylpyrazole, 5-ben dazolidine, 1-methyl-2-propylimidazolidine, 1-ethyl-4-me zylpyrazole, l-phenyl-3-methylpyrazole, 1-cyanopyrazole, thylimidazolidine, 1-(3-hydroxypropyl)imidazolidine, 3-chloropyrazole, 4-bromo-1-methyl-pyrazole, or any com 20 2-phenylimidazolidine, 1-benzylimidazolidine, 2-phenyl-1- bination thereof and the like. methylimidazolidine, 4-cyanoimidazolidine, 5-chloroimida Suitable oxazole compounds which can be employed zolidine, 5-bromo-1-methylimidazolidine, or any combina herein include, for example, those represented by the fol tion thereof and the like. lowing formula C Suitable thiazole compounds which can be employed 25 N C-RC Formula C, herein include, for example, those represented by the fol 3. 4 lowing formula F Ra-C2 5 C-Rh 1 C-Rc O N 3 4 Formula F. Ra-C2 5 C-Rh wherein each R', RandR is independently hydrogen or a 30 1. hydrocarbyl group having suitably from 1 to about 18, more S suitably from 1 to about 9, carbonatoms or such hydrocarbyl groups containing an Oxygen, Sulfur, cyano or halogen or the wherein each R, R and R is independently hydrogen or like substituent. Particularly suitable oxazole compounds hydrocarbyl group having suitably from 1 to about 18, more include, for example, oxazole, 3-methyloxazole, 2-methy suitably from 1 to about 9, carbon atoms or such hydrocarbyl loxazole, 4-butyloxazole, 3-methyl-5-propyloxazole, 35 groups containing an oxygen, sulfur, cyano or halogen or the 2-ethyl-4-methyloxazole, 3-(3-hydroxypropyl)oxazole, like substituent. Particularly suitable thiazole compounds 4-phenyloxazole, 3-benzyloxazole, 2-phenyl-3-methylox include, for example, thiazole, 2-methylthiazole, 3-meth azole, 2-cyanooxazole, 4-chlorooxazole, 4-bromo-3-methy ylthiazole, 4-butylthiazole, 2-methyl-3-propylthiazole, loxazole, or any combination thereof and the like. 3-ethyl-5-methylthiazole, 3-(3-hydroxypropyl)thiazole, Suitable imidazolidine compounds which can be 40 employed herein include, for example, those represented by 2-phenylthiazole, 3-benzylthiazole, 4-phenyl-3-methylthi the following formula D azole, 2-cyanothiazole, 5-chlorothiazole, 5-bromo-3-meth ylthiazole, or any combination thereof and the like. R Formula D. Suitable pyrrole compounds which can be employed Rh-N C-Rf 45 herein include, for example, those represented by the fol Ra 3. 4 Re lowing formula G Y; ;5 C/ Formula G. / N1 / N Re - -R Rh N Rd Ra-C2 5 C-Rc 50 RC wherein each R, R,R,R,R,R, R and R is indepen dently hydrogen or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon wherein each R, R, R, R and R is independently atoms or such hydrocarbyl groups containing an oxygen, hydrogen or a hydrocarbyl group having suitably from 1 to sulfur, cyano or halogen or the like substituent. Particularly 55 about 18, more suitably from 1 to about 9, carbon atoms or suitable imidazolidine compounds include, for example, such hydrocarbyl groups containing an oxygen, sulfur, imidazolidine, 1-methylimidazolidine, 2-methylimidazoli cyano or halogen or the like substituent. Particularly suitable dine, 4-butylimidazolidine, 1-methyl-3-propylimidazoli pyrrole compounds include, for example, pyrrole, 1-meth dine, 1-ethyl-4-methyl-imidazolidine, 1-(3-hydroxypropy ylpyrrole, 2-methylpyrrole, 3-butylpyrrole, 1-methyl-2-pro l)imidazolidine, 2-phenylimidazolidine, 60 1-benzylimidazolidine, 2-phenyl-1-methylimidazolidine, pylpyrrole, 2-ethyl-3-methylpyrrole, 1-(3-hydroxypropy 4-cyanoimidazolidine, 4-chloroimidazolidine, 4-bromo-1- l)pyrrole, 2-phenylpyrrole, 1-benzylpyrrole, 2-phenyl-1- methylimidazolidine, or any combination thereof and the methylpyrrole, 3-cyanopyrrole, 3-chloropyrrole, 2-bromo like. 1-methylpyrrole, or any combination thereof and the like. Suitable imidazoline compounds which can be employed 65 Suitable pyridine compounds which can be employed herein include, for example, those represented by the fol herein include, for example, those represented by the fol lowing formula E lowing formula H 5,503.937 13 14

Formula H. Rh Rg Formula K. Ri- C C-Rf Ra 3. 4. Re Re-C Cr-RC N / C22 5 C Re C-Rib / N1 / N Rb N Rd wherein each R', R, R, R and R is independently Re wherein each R, R. R. R. R., R, R8, R and R is hydrogen or a hydrocarbyl group having suitably from 1 to 10 independently hydrogen, or a hydrocarbyl group having about 18, more suitably from 1 to about 9, carbon atoms or suitably from 1 to about 18, more suitably from 1 to about Such hydrocarbyl groups containing an oxygen, sulfur, 9, carbon atoms or such hydrocarbyl groups containing an cyano or halogen or the like substituent with the proviso that oxygen, sulfur, cyano or halogen or the like substituent. at least one of the R", R, R, R or R groups is other than Particularly suitable pyrrollidine compounds include, for hydrogen. Particularly suitable pyridine compounds include, 15 example, pyrrolidine, 1-methylpyrrolidine, 4-phenylpyrro for example, 2-methylpyridine, 3-methylpyridine, 4-bu lidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 1-bu tylpyridine, 2-methyl-3-propylpyridine, 3-ethyl-4-meth tylpyrrolidine, 1-methyl-2-propylpyrrolidine, 3-ethyl-4-me ylpyridine, 4-(3-hydroxypropyl)pyridine, 2-phenylpyridine, thylpyrrolidine, 2-(3-hydroxypropyl)pyrrolidine, 1-phenyl 3-benzylpyridine, 4-phenyl-2-methylpyridine, 3-cyanopyri 2-methylpyrrolidine, 2-cyanopyrrollidine, dine, 2-chloropyridine, 3-bromo-5-methylpyridine, combi 20 2-chloropyrrolidine, 2-bromo-1-methylpyrrolidine, or any nations thereof and the like. combination thereof and the like. Suitable pyrazine compounds which can be employed Suitable morpholine compounds which can be employed herein include, for example, those represented by the fol herein include, for example, those represented by the fol lowing Formula I lowing formula L 25 Rf O Re Formula L. N Formula I. N /1 N / /i N C C / 6 N R- 6 : g-R R8 Rd Ra-C5 3C-Rh Rh RC 30 wherein each R", R, R and R is independently hydrogen, or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or such Ra hydrocarbyl groups containing an oxygen, sulfur, cyano or 35 wherein is hydrogen, a hydrocarbyl group having suitably halogen or the like substituent. Particularly suitable pyrazine from 2 to about 18, more suitably from 2 to about 9, carbon compounds include, for example, pyrazine, 2-methylpyra atoms or such hydrocarbyl groups containing an oxygen, Zine, 3-methylpyrazine, 2-butylpyrazine, 2-methyl-5-pro sulfur, halogen or the like substituent; each R, R, R. R. pyl-pyrazine, 2-ethyl-6-methylpyrazine, 2-(3-hydroxy-pro R. R. R. R' and R is independently hydrogen or a pyl)pyrazine, 2-phenylpyrazine, 2-benzylpyrazine, hydrocarby group having suitably from 1 to about 18, more 2-phenyl-3-methylpyrazine, 2-cyanopyrazine, 2-chloropyra 40 Suitably from 1 to about 9, carbon atoms or such hydrocarbyl Zine, 2-bromo-5-methylpyrazine, or any combination groups containing an oxygen, sulfur, halogen or the like thereof and the like. substituent. Particularly suitable morpholine compounds Suitable pyridazine compounds which can be employed include, for example, morpholine, 4-methylmorpholine, herein include, for example, those represented by the fol 3-methylmorpholine, 4-butyl-morpholine, 4-methyl-3-pro lowing formula J 45 pylmorpholine, 2-ethyl-3-methylmorpholine, 4-(3-hydrox ypropyl)morpholine, 2-phenylmorpholine, 4-benzylmor Formula J. pholine, 3-phenyl-1-methylmorpholine, 3-cyanomorpholine, 3-chloromorpholine, 3-bromo-4-meth ylmorpholine, combinations thereof and the like. 50 Suitable pyrimidine compounds which can be employed herein include, for example, those represented by the fol lowing formula M wherein each R", R, R, and R is independently hydrogen or a hydrocarbyl group having suitably from 1 to about 18, C Formula M. more Suitably from 1 to about 9, carbon atoms or such 55 hydrocarbyl groups containing an oxygen, sulfur, cyano or Ra-C2 6 C-Rib halogen or the like substituent. Particularly suitable N / pyridazine compounds include, for example, pyridazine, N 3-methylpyridazine, 4-methylpyridazine, 3-butylpyridazine, wherein each R, R and R is independently hydrogen, or 3-methyl-4-propylpyridazine, 3-ethyl-6-methylpyridazine, 60 a hydrocarbyl group having suitably from 1 to about 18, 4-(3-hydroxypropyl)-pyridazine, 3-phenylpyridazine, more suitably from 1 to about 9, carbon atoms or such 4-benzylpyridazine, 4-phenyl-5-methylpyridazine, 4-cyan hydrocarbyl groups containing an oxygen, sulfur, cyano or opyridazine, 4-chloropyridazine, 3-bromo-5-methylpy halogen or the like substituent. Particularly suitable pyrimi ridazine, or any combination thereof and the like. dine compounds which can be employed herein include, for Suitable pyrrolidine compounds which can be employed 65 example, pyrimidine, 2-methylpyrimidine, 4-methyl-pyri herein include, for example, those represented by the fol midine, 2-butylpyrimidine, 2-methyl-4-propyl-pyrimidine, lowing formula K 4-ethyl-5-methylpyrimidine, 2-(3-hydroxypropyl)pyrimi 5,503,937 15 16 dine, 2-phenylpyrimidine, 2-benzylpyrimidine, 4-phenyl-2- cyano or halogen or the like substituent. Suitable phthala methylpyrimidine, 4-cyanopyrimidine, 2-chloropyrimidine, zine compounds include, for example, phthalazine, 1-meth 4-bromo-2-methylpyrimidine, or any combination thereof ylphthalazine, 6-methylphthalazine, 1-butylphthalazine, and the like. 1-methyl-4-propylphthalazine, 1-ethyl-6-methyl-phthala Suitable quinoxaline compounds which can be employed zine, 1-(3-hydroxypropyl)phthalazine, 5-phenylphthalazine, herein include, for example, those represented by the fol 1-benzylphthalazine, 1-phenyl-4-methylphthalazine, 1-cy lowing formula N anophthalazine, 1-chlorophthalazine, 1-bromo-4-meth ylphthalazine, or any combination thereof and the like. R Formula N. Suitable quinoline compounds which can be employed C herein include, for example, those represented by the fol /N / N 10 lowing formula Q R - , , , -R Formula Q. -C6 C 3C-Rh R N5 / M4 / C N f N M8 M /1N 15 Ra (, , , -R wherein each R, R, R, R, R, and R is independently R8-C6 C 3C C hydrogen, or a hydrocarbyl group having suitably from 1 to Ns/M4 / about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, Ra Rb cyano or halogen substituent. Particularly suitable quinoxa 20 wherein each R,R,R,R,R, R and R° is independently line compounds include, for example, quinoxaline, 2-meth hydrogen, or a hydrocarbyl group having suitably from 1 to ylquinoxaline, 5-methylquinoxaline, 2-butylquinoxaline, about t8, more suitably from 1 to about 9, carbon atoms or 2-methyl-3-propylquinoxaline, 5-ethyl-6-methylquinoxa such hydrocarbyl groups containing an oxygen, sulfur, line, 2-(3-hydroxypropyl)guinoxaline, 2-phenylquinoxaline, cyano or halogen or the like substituent. Suitable quinoline 25 compounds which can be employed herein include, for 5-benzylquinoxaline, 2-phenyl-5-methylquinoxaline, 2-cy example, quinoline, 2-methylquinoline, 3-methylquinoline, anoquinoxaline, 2-chloroquinoxaline, 2-bromo-5-meth 4-butylquinoline, 5-methyl-2-propylquinoline, 2-ethyl-3- ylquinoxaline, or any combination thereof and the like. methylguinoline, 3-(3-hydroxypropyl)guinoline, 3-phe Suitable quinazoline compounds which can be employed nylguinoline, 4-benzylquinoline, 3-phenyl-2-methylquino herein include, for example, those represented by the fol line, 3-cyanoquinoline, 4-chloroquinoline, 2-bromo-3- lowing formula O 30 methylduinoline, or any combination thereof and the like. Formula O. Suitable purine compounds which can be employed herein include, for example, those represented by the fol /\/\ lowing formula R R - , , 35 Rb Rd Formula R. N 2. N N16l, No17I yc-Ra Re-CS. to N wherein each R', R, R, R, R, and R is independently 40 hydrogen, or a hydrocarbyl group having suitably from 1 to wherein each R", R, R and R is independently hydrogen, about 18, more suitably from 1 to about 9, carbon atoms or or a hydrocarbyl group having suitably from 1 to about 18, such hydrocarbyl groups containing an oxygen, sulfur, more suitably from 1 to about 9, carbon atoms or such cyano or halogen or the like substituent. Suitable quinazo hydrocarbyl groups containing an oxygen, sulfur, cyano or line compounds include, for example, quinazoline, 2-meth 45 halogen or the like substituent. Suitable purine compounds ylquinazoline, 4-methylquinazoline, 2-butylquinazoline, include, for example, purine, 2-methylpurine, 8-methylpu 2-methyl-4-propylquinazoline, 5-ethyl-6-methyl-quinazo rine, 6-butylpurine, 2-methyl-8-propylpurine, 6-ethyl-8-me line, 2-(3-hydroxypropyl)guinazoline, 2-phenylquinazoline, thylpurine, 8-(3-hydroxypropyl)purine, 2-phenylpurine, 2-benzylquinazoline, 2-phenyl-4-methylquinazoline, 4-cy 2-benzylpurine, 6-phenyl-2-methyl-purine, 8-cyanopurine, anoquinazoline, 4-chloroquinazoline, 2-bromo-4-meth 50 2-chloropurine, 8-bromo-2-methylpurine, or any combina ylquinazoline, or any combination thereof and the like. tion thereof and the like. Suitable phthalazine compounds which can be employed Suitable indazole compounds which can be employed herein include, for example, those represented by the fol herein include, for example, those represented by the fol lowing formula P lowing formula S RC Rb Formula P. 55 Formula S. Rd-cáiC Ng1N SN R - ls&- C-R-Pa. 60 Rf wherein each R', R, R, R, R and R is independently hydrogen, or a hydrocarbyl group having suitably from 1 to wherein each R, R, R, R, R, and R is independently about 18, more suitably from 1 to about 9, carbon atoms or hydrogen, or a hydrocarbyl group having suitably from to 65 such hydrocarbyl groups containing an oxygen, sulfur, about 18, more suitably from 1 to about 9, carbon atoms or cyano or halogen or the like substituent. Suitable indazole such hydrocarbyl groups containing an oxygen, sulfur, compounds include, for example, indazole, 1-methylinda 5,503.937 17 18 zole, 3-methylindazole, 1-butylindazole, 1-methyl-3-propy include, for example, phenazine, 1-methylphenazine, 2-me lindazole, 1-ethyl-5-methylindazole, 3-(3-hydroxypropy thylphenazine, 2-butylphenazine, 1-methyl-7-propylphena Dindazole, 3-phenylindazole, 6-benzylindazole, 6-phenyl-1- zine, 1-ethyl-4-methylphenazine, 2-(3-hydroxypropy methylindazole, 3-cyanoindazole, 5-chloroindazole, l)phenazine, l-phenylphenazine, 1-benzylphenazine, 3-bromo-1-methylindazole, or any combination thereof and 1-phenyl-7-methylphenazine, 2-cyanophenazine, 1-chlo the like. rophenazine, 1-bromo-2-methylphenazine, or any combina Suitable indole compounds which can be employed herein tion thereof and the like. include, for example, those represented by the following Suitable phenarsazine compounds which can be formula T employed herein include, for example, those represented by the following formula W Rd RC Formula T. 10 Re Rd Formula W. Re-c2 C NC1N YC-Rh 2

15 4. C wherein each R, R,R,R,R, R and R is independently Ra hydrogen, or a hydrocarbyl group having suitably from 1 to wherein each R", R. R,R,R,R, R8 and R is indepen about 18, more suitably from 1 to about 9, carbon atoms or dently hydrogen, or a hydrocarbyl group having suitably Such hydrocarbyl groups containing an oxygen, Sulfur, 20 from 1 to about 18, more suitably from 1 to about 9, carbon cyano or halogen or the like substituent. Suitable indole atoms or such hydrocarby groups containing an oxygen, compounds which can be employed herein include, for sulfur, cyano or halogen or the like substituent. Suitable example, indole, 1-methylindole, 2-methylindole, 3-butyl phenarsazine compounds which can be employed herein indole, 1-methyl-2-propylindole, 2-ethyl-3-methylindole, include, for example, phenarsazine, 1-methylphenarsazine, 1-(3-hydroxypropyl)indole, 2-phenylindole, 1-benzylindole, 25 2-methylphenarsazine, 4-butylphenarsazine, 1-methyl-6- 2-phenyl-1-methylindole, 2-cyanoindole, 5-chloroindole, propylphenarsazine, 2-ethyl-3-methylphenarsazine, 1-(3- 3-bromo-1-methylindole, or any combination thereof and hydroxypropyl)phenarsazine, 4-phenylphenarsazine, 3-ben the like. zylphenarsazine, 2-phenyl-7-methylphenarsazine, Suitable indolizine compounds which can be employed 3-cyanophenarsazine, 1-chlorophenarsazine, 1-bromo-8- herein include, for example, those represented by the fol 30 methylphenarsazine, or any combination thereof and the lowing formula U like. Suitable phenothiazine compounds which can be Formula. U. employed herein include, for example, those represented by C C the following formula X Re-C2 Nc4-i 35 -R Rf Re Rd Formula V. 4. s C-Ra R-Cs: N C N C k R8 c? Nc-10Nc-1 SC-Rc Rh-C 6 C 5 C. 4., 3C-Rb wherein each R, R,R,R,R, R and R8 is independently 40 hydrogen, or a hydrocarby group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or Ri Ra such hydrocarbyl groups containing an oxygen, sulfur, wherein each R, R. R. R. R. R. R8, R and R is cyano or halogen or the like substituent. Suitable indolizine independently hydrogen, or a hydrocarbyl group having compounds include, for example, indolazine, 1-methylin suitably from 1 to about 18, more suitably from 1 to about dolizine, 2-methylindolizine, 3-butylindolizine, 5-methyl-1- 45 9, carbon atoms or such hydrocarbyl groups containing an propylindolizine, 2-ethyl-1-methylindolizine, 6-(3-hydrox oxygen, sulfur, cyano or halogen or the like substituent. ypropyl)indolizine, 3-phenylindolizine, 7-benzylindolizine, Suitable phenothiazine compounds include, for example, 2-phenyl-3-methylindolizine, 5-cyanoindolizine, 7-chlor phenothiazine, 10-methylphenothiazine, 1-methylphenothi oindolizine, 3-bromo-5-methylindolizine, or any combina azine, 2-butylphenothiazine, 10-methyl-4-propylphenothi tion thereof and the like. 50 azine, 2-ethyl-3-methyl-phenothiazine, 4-(3-hydroxypropy Suitable phenazine compounds which can be employed l)phenothiazine, 10-phenylphenothiazine, herein include, for example, those represented by the fol 1-benzylphenothiazine, 10-phenyl-4-methylphenothiazine, lowing formula V 7-cyanophenothiazine, 4-chlorophenothiazine, 4-bromo-10 methylphenothiazine, or any combination thereof and the Re Formula W. 55 like. C N C Suitable pyrroline compounds which can be employed Rf -canc16Sc1 herein include, for example, those represented by the fol lowing formula Y

60 Formula Y. wherein each R, R, R, R,R,R, R8 and R is indepen dently hydrogen, or a hydrocarbyl group having suitably from 1 to about 18, more suitably from 1 to about 9, carbon atoms or such hydrocarbyl groups containing an oxygen, 65 sulfur, cyano or halogen or the like substituent. Suitable phenazine compounds which can be employed herein 5,503.937 19 20 wherein each R', R,R,R,R,R and R8 is independently wherein each R, R,R,R,R,R,R, Rh, R and R is hydrogen, or a hydrocarbyl group having suitably from 1 to independently hydrogen, or a hydrocarby group having about 18, more suitably from 1 to about 9, carbon atoms or suitably from 1 to about 18, more suitably from 1 to about such hydrocarbyl groups containing an oxygen, sulfur, 9, carbon atoms or such hydrocarbyl groups containing an cyano or halogen or the like substituent. Suitable pyrroline oxygen, sulfur, cyano or halogen or the like substituent. compounds include, for example, pyrroline, 2-methylpyrro line, 4-methylpyrroline, 5-butylpyrroline, 5-methyl-1-pro Particularly suitable piperazine compounds which can be pylpyrroline, 1-ethyl-3-methylpyrroline, 1-(3-hydroxypro employed herein include, for example, piperazine, 1-meth pyl)pyrroline, 5-phenylpyrroline, 1-benzylpyrroline, ylpiperazine, 2-methylpiperazine, 3-butylpiperazine, 1-me 1-phenyl-4-methylpyrroline, 3-cyanopyrroline, 5-chloropy thyl-4-propylpiperazine, 1-ethyl-3-methylpiperazine, 1-(3- rroline, 2-bromo-1-methylpyrroline, or any combination O hydroxypropyl)-piperazine, 2-phenylpiperazine, thereof and the like. 1-benzylpiperazine, 1-methyl-3-phenylpiperazine, 2-cyan Suitable indoline compounds which can be employed opiperazine, 2-chloropiperazine, 1,4-dimethyl-2-bromopip herein include, for example, those represented by the fol erazine, or any combination thereof and the like. lowing formula Z The acids having a weak nucleophilic anion can contain 15 boron or be free of boron. R R Formula Z. Suitable boron containing acids include, for example, those represented by the formula HBRR' wherein each R is Rg-c27C NC1 NiSc1 Rd independently hydrogen or an aliphatic, cycloaliphatic or - 16 aromatic hydrocaron or substituted hydrocarbon group hav Rh-C3S1 C C-R 20 ing suitably from 1 to about 12, more suitably from about 1 Ra to about 6, most suitably from about 1 to about 4, carbon Ri atoms, and R is a group other than a hydrocarbyl group such as, for example, a hydrocarbonoxy, hydrocarbonamino, a wherein each R, R. R. R. R. R. R8, R and is is independently hydrogen, or a hydrocarby group having hydrocarbonphosphino, or a halogen atom, particularly fluo suitably from 1 to about 18, more suitably from 1 to about 25 rinet chlorine or bromine. The term hydrocarbon means any 9, carbon atoms or such hydrocarbyl groups containing an aliphatic, cycloaliphatic, aromatic, arylsubstituted aliphatic, oxygen, Sulfur, cyano or halogen or the like substituent. alkyl substituted aromatic groups. Particularly suitable indoline compounds include, for Fluoboric acid is sometimes referred to as fluoroboric acid example, indoline, 1-methylindoline, 2-methylindoline, or hydrogen tetrafluoroborate. Any of these expressions 3-butylindoline, 1-methyl-2-propyl-indoline, 2-ethyl-2-me 30 refer to the chemical represented by the formula HBF thylindoline, 1-(3-hydroxy-propyl)indoline, 1-phenylindo Suitable such acids containing boron include, for line, 1-benzylindoline, -phenyl-2-methylindoline, 5-cy example, hydrogen fluorotriphenylborate, hydrogen chlorot anoindoline, 7-chloroindoline, 5-bromo-1-methylindoline, riphenylborate, hydrogen fluorotributylborate, hydrogen or any combination thereof and the like. phenyltrifluoborate or chloroboric acid. Most particularly Suitable piperidine compounds which can be employed 35 suitable such acid is fluoboric acid. herein include, for example, those represented by the fol The term hydrocarbonoxy means that a hydrocarbyl group lowing formula AA as previously defined has an oxygen atom between it and the boron atom. Likewise, the term hydrocarbonamino and Formula AA. hydrocarbonphosphino mean that there is an amine or phos 40 phine group between the hydrocarbyl group and the boron atOII. 5 3C1 Particularly suitable acids which are free of boron, said Rk 1 NY n acid having a weak nucleophilic anion include, for example, Ra1 YRb R fluoarsenic acid, acid, fluophosphoric acid, chloroarsenic wherein each R, R,R,R,R,R,RS, R, R, R and Rk 45 acid, chloroantimonic acid, chlorophosphoric acid, nitric is independently hydrogen, or a hydrocarbyl group having acid, hydrofluoric acid, trifluoroacetic acid, trifluo suitably from 1 to about 18, more suitably from 1 to about romethanesulfonic acid, picric acid or any combination 9, carbon atoms or such hydrocarbyl groups containing an thereof and the like. Oxygen, Sulfur, cyano or halogen or the like substituent. Suitable metal salts of such boron-free or boron contain Suitable piperidine compounds which can be employed 50 ing acids having a weak nucleophilic anion include, for herein include, for example, piperidine, 1-methylpiperidine, example, salts containing the metals of Groups I and II of the 2-methylpiperidine, 3-butylpiperidine, 1-methyl-2-propy Periodic Table of the Elements published by Sargent-Welch lpiperidine, 2-ethyl-4-methylpiperidine, 1-(3-hydroxypro Scientific Company as catalog number S-18806. Particu pyl)piperidine, l-phenylpiperidine, 1-benzylpiperidine, larly, such salts include, for example, the sodium, potassium, 1-phenyl-2-methylpiperidine, 4-cyanopiperidine, 3-chlo 55 lithium, calcium, barium, magnesium and silver salts of such ropiperidine, 4-bromo-1-methylpiperidine, or any combina acids. tion thereof and the like. Suitable compounds having an average of more than one Suitable piperazine compounds which can be employed epoxide group per molecule which can be employed herein herein include, for example, those represented by the fol include, epoxy resins such as, for example, the glycidyl lowing formula BB 60 ethers of polyhydric phenols such as dihydroxy phenols, biphenols, bisphenols, halogenated bisphenols, alkylated Formula BB. bisphenols, trisphenols, phenolaidehyde novolac resins, sub stituted phenol-aldehyde novolac resins, phenol-hydrocar bon resins, substituted phenol-hydrocarbon resins, or any 65 combination thereof and the like. Suitable such epoxy resins include, for example, those represented by the following formulas XXIX-XXXII 5,503.937 21 22

(X)4. (X)4 Formula XXIX. O OH O / \ / N HC (-CH O o–CH-i-CH, O CH2 R R C o–CH R Formula XXX.

O OH / N HC (-CH, O (A)n o–CH-i-CH, R R

O O C (A)n C o-CH,- / N CH R / O N Formula XXXI. O CH-C CH / N CH2-C CH2 O O R / N O R th- CH2 O R A' A' C (X)4 (X)3 FF' (X)4.

(X)4 Formula XXXII. O Q' O / N / N HC (-CH, Q o-CH- CH R R O (X)4 / N O -CH- CH R wherein each A is independently a divalent hydrocarbyl 45 Substituted phenol-formaldehyde resins, phenol-hydroxy group having from 1 to about 9, preferably from 1 to about benzaldehyde resins, cresol-hydroxybenzaldehyde resins, 4, carbon atoms, -O-, -S-, -S-S-, -SO-, dicyclopentadienephenol resins, tetramethylbiphenol, tet -SO-, or -CO-; each A' is independently a divalent ramethyltetrabromobiphenol, tetramethyltribromobiphenol, hydrocarbyl group having from 1 to about 9, preferably from tetrachlorobisphenol A, or any combination thereof and the 1 to about 4 carbon atoms; Q is a hydrocarbyl group having like. from 1 to about 10 carbon atoms; Q is hydrogen or an alkyl 50 Also suitable as the epoxide compound which can be group having from 1 to about 4 carbon atoms; each R is employed in the present invention include those partially independently hydrogen or an alkyl group having from 1 to advanced epoxy resins disclosed by Bertram et al. in U.S. about 4 carbon atoms; each X is independently hydrogen, Pat. No. 4,594,291 which is incorporated herein by refer bromine, chlorine, or a hydrocarbyl group having from 1 to CCC. about 9, preferably from 1 to about 4 carbon atoms; m has 55 Also suitable as the epoxide compound are the glycidyl an average value from zero to about 12, preferably from ethers of compounds having an average of more than one about zero to about 9, most preferably from about 0.03 to aliphatic hydroxyl group per molecule such as, for example, about 3, m' has a value from about 0.01 to about 10, aliphatic diols, polyether diols, polyether triols, polyether preferably from about 0.2 to about 8, more preferably from tetrols, or any combination thereof and the like. Also suit about 0.5 to about 6, n has a value of Zero or l; and n' has able are the alkylene oxide adducts of compounds contain an average value of from zero to about 10, preferably from 60 ing an average of more than one aromatic hydroxyl group zero to about 5, most preferably from about 0.03 to about 3. per molecule such as, for example, the ethylene oxide, Also suitable are the oligomers of the epoxy resin repre propylene oxide, or butylene oxide adducts of dihydroxy sented by formula XXXII. phenols, biphenols, bisphenols, halogenated bisphenols, Particularly suitable such epoxy resins include, for alkylated bisphenols, trisphenols, phenol-aldehyde novolac example, the diglycidyl ethers of resorcinol, catechoir hyd 65 resins, halogenated phenol-aldehyde novolac resins, alky roquinone, biphenol, bisphenol A, bisphenol K, tetrabromo lated phenol-aldehyde novolac resins, hydrocarbon-phenol bisphenol A, phenol-formaldehyde novolac resins, alkyl resins, hydrocarbon-halogenated phenol resins, or hydrocar 5,503,937 23 24 bon-alkylated phenol resins, or or any combination thereof The precatalyzed compositions of the present invention and the like. can contain, if desired, pigments, fillers, dyes, diluents, Suitable aromatic hydroxyl containing compounds which solvents, stabilizers, epoxy resin curing agents, or any can be employed herein include, for example, compounds combination thereof and the like. having an average of more than one phenolic hydroxyl group per molecule. Suitable such compounds include, for Suitable stabilizer materials and curing agents which can example, dihydroxy phenols, biphenols, bisphenols, haloge be employed herein include, for example, those disclosed in nated bisphenols, alkylated bisphenols, trisphenols, phenol the aforementioned U.S. Pat. No. 4,594,291 by Bertrametal aldehyde resins, halogenated phenol-aldehyde novolac res which is incorporated herein by reference. ins, alkylated phenol-aldehyde novolac resins, The compositions of the present invention are useful in phenolhydroxybenzaldehyde resins, alkylated phenolhy O the preparation of formulations for use in the preparation of droxybenzaldehyde resins, hydrocarbon-phenol resins, electrical and structural laminates and composites, coatings, hydrocarbon-halogenated phenol resins, hydrocarbon-alky castings, moldings, encapsulants and the like. They can be employed in the conventional methods or the newer RTM lated phenol resins, or any combination thereof and the like. and RIM techniques. Particularly suitable aromatic hydroxyl-containing com The following examples are illustrative of the invention pounds include, for example, those represented by the 15 but are not to be construed as to limiting the scope thereof following formulas XXXII-XXXV in any manner. OH Formula XXXII. EXAMPLE 1. OH 20 Preparation of 2-methylimidazolium Fluoborate Complex X4 A glass flask fitted with a stirrer, thermometer, and reflux X4 X4 Formula XXXIII. condenser is charged with 15.37 grams (0.098 mole) of a 25 55.9% aqueous solution, by weight, of fluoboric acid. To this stirred solution, 8.2 grams (0.100 mole) of 2-methylimida zole are slowly added during about five minutes. The heat HO (A)n OH from the reaction warmed the solution to approximately 50° C. as the 2-methylimidazole dissolves. The solution is stirred for an additional 30 minutes as it cools to near Formula XXXIV. 30 ambient temperature. Methanol is then added, 1998 grams, OH OH OH to dilute the solution to 38.6% solids based on the weight of the 2-methylimidazole and fluoboric acid. A A The concentration of the aqueous fluoboric acid was determined by potentiometric titration to the first inflection 35 point with 0.100 N potassium hydroxide in methanol. An (X)4 (X)3 n" (X)4 MCI GT-05 automatic titrator and a combination silverd silver chloride electrode (Curtain Matheson Scientific No. (X)4 Formula XXXV. 201-947) were used to measure the pH changes during the course of the titration. g 40 EXAMPLES 2-12

C. OH PREPARATION OF 2-METHYLIMIDAZOLIUM FLUOBORATE COMPLEXES 45 (X)4 G OH The procedure described in Example 1 is repeated using (X)4 the same procedure and amount of 2-methylimidazole wherein A, A, Q, Q' X, n and m are as defined above in (2-MI), however the weight of fluoboric acid (55.9% aque formulas XII-XVI. Particularly suitable aromatic ous solution) is varied as shown in Table I. All experiments hydroxyl-containing materials include, for example, biphe 50 are diluted with methanol to 38.5% solids based on the nol, bisphenol A, bisphenol K, tetrabromobisphenol A, tet combined weights of 2-MI and fluoboric acid. The results rabromobisphenol K, resorcinol, phenol-aldehyde novolac are given in Table I. resins, cresol-aldehyde novolac resins, phenol-hydroxyben zaldehyde resins, cresol-hydroxybenzaldehyde resins, tet TABLE I ramethylbiphenol, tetramethyltribromobiphenol, tetrameth 55 2-METHYLIMDAZOLE WITH WARYING yltetrabromobiphenol, tetrachlorobisphenol A, or any RATIOS OFFLUOROBORICACD combination thereof and the like. Also suitable are the oligomers of the multifunctional phenolic compounds rep Moles of Fluoroboric Fluoroboric resented by the formula XXXV. Acid Acid Per These and other suitable aromatic hydroxyl-containing 60 Example Solution Mole of compounds are disclosed in U.S. Pat. No. 4,594,291 issued Number (grams) 2-MI Jun. 10, 1986 by Bertram et all which is incorporated herein by reference. 2 11.7 0.75 The aromatic hydroxyl-containing compounds are 3 13.7 0.84 employed in amounts which provide a ratio of aromatic 4. 13.90 0.89 65 5 1463 0.93 hydroxyl groups to epoxy groups suitably from about 0.05:1 15.37 0.98 to about 20:1, more suitably from about 0.1:1 to about 10:1, 6 16.10 1.03 most suitably from about 0.2:1 to about 5:1. 5,503,937 25 26 5.36g (0.0487 mole) of 2-ethyl-4-methylimidazole (2-E- TABLE I-continued 4-MI) 2-METHYLIMIDAZOLE WITH WARYING 7.84 g (0.0500 mole) of fluoboric acid (55.9% aqueous) RATIOS OF FLUOROBORIC ACID 11.98 g of methanol Moles of The resultant product is a clear solution containing 38.7% by Fluoroboric Fluoroboric weight of the 2-ethyl-4-methylimidazolium fluoborate Acid Acid Per adduct/complex. Example Solution Mole of Number (grams) 2-MI EXAMPLE 7 10 7 16.83 1.07 8 17.56 112 Preparation of 4,5-diphenylimidazolium fluoborate 9 1788 1.14 complex 10 18.35 1.17 11 20.39 1.30 The procedure of Example 13 is followed using the 2 2.17 1.35 5 following reagents: 4.00 g (0.0182 mole) of 4,5-diphenylimidazole (4,5-DPI) 2.92 g (0.0166 mole) of fluoboric acid (55.9% aqueous) EXAMPLE 13 7.47 g of methanol After the above reactants are added together, the mixture is Preparation of 2-phenylimidazolium Fluoborate 20 not homogeneous, therefore an additional 35.4 grams of the A glass flask fitted with a stirrer, thermometer, and reflux monomethyl ether of propylene glycol monoacetate is added condenser is charged with 15.37 grams (0,098 mole) of a to give a clear solution containing 11.3% by weight of the 55.9% aqueous solution, by weight, of fluoboric acid and 4,5-diphenyl-imidazolium fluoborate adduct/complex. 29.3 grams of methanol. To this stirred solution, 14.4 grams (0,100 mole) of 2-phenylimidazole (2-PI) are slowly added 25 EXAMPLE 18-34 during about five minutes. The heat from the reaction warms the solution to approximately 50° C. as the 2-phenylimida Imidazolium Fluoroborate Complex Catalyzed zole dissolves. The solution is stirred for an additional 30 Epoxy/phenolic Systems minutes as it cools to near ambient. The product is a clear solution containing 38.9% by weight of the 2-phenylimida 30 The catalysts described in Examples 1-17 are mixed with Zolium fluoborate adduct/complex. a 1:1 molar ratio of a diglycidyl ether of bisphenol A having an epoxy equivalent weight of 181.5 (D.E.R.TM383 Epoxy EXAMPLE 1.4 Resin commercially available from The Dow Chemical Co.) and bisphenol A (2.2-bis(4,4'-hydroxyphenyl)propane), Preparation of 4-methylimidazolium Fluoborate commercially available from The Dow Chemical Co. as Complex 35 PARABISTM) dissolved in the monomethylether of propy lene glycol monoacetate (PMA). The epoxy resin (181.5 The procedure of Example 13 is followed using the grams, 1 equiv.), bisphenol A (114 grams, 1 equiv.) and following reagents: 73.88 grams of PMA are heated between 80° C. and 100° C. 4.68 g (0.0487 mole) of 4-methylimidazole (4-MI) under a nitrogen atmosphere until homogeneous, cooled to 40 ambient temperature and the appropriate amount of catalyst 7.84 g (0.0500 mole) of fluoboric acid (55.9% aqueous) added as described in Table II. Portions of these solutions are 9.92 g of methanol then stored at 50° C. and the 25° C. viscosity monitored as The resultant product is a clear solution containing 38.5% by shown in Table III. weight of the 4-methylimidazolium fluoborate adduct/com plex. 45 TABLE II EXAMPLE 1.5 CATALYZED EPOXYIPHENOLICFORMULATIONS Example Catalyst Millimoles of Preparation of 1,2-Dimethylimidazolium Fluoborate or Comp. Solution Catalyst per Complex Expt. Catalyst Weight Equivalent of 50 No. (Ex. Number) (grams) Epoxide The procedure of Example 13 is followed using the following reagents: 18 3.92 9.0 19 2 3.47 9.0 4.68 g (0.0487 mole) of 1,2-dimethylimidazole (1,2 20 3 3.67 9.0 DMI) 21 4 3.75 9.0 55 22 5 3.82 9.0 7.84 g (0.0500 mole) of fluoboric acid (55.9% aqueous) 23 6 4.02 9.0 10.95 g of methanol 24 7 4.2 9.0 The resultant product is a clear solution containing 38.6% by 25 8 4.22 9.0 weight of the 1,2-dimethylimidazolium fluoborate adduct/ 26 9 4.24 9.0 complex. 27-k 10 431 9.0 60 28* 11 4.59 9.0 29* 2 4.67 9.0 EXAMPLE 16 30 13 5.31 9.0 3. 14 4.00 9.0 Preparation of 2-ethyl-4-methylimidazolium 32 15 4.33 9.0 Fluoborate Complex 33 16 4.65 9.0 65 34 17 24.65 9.0 The procedure of Example 13 is followed using the C. E.A* No Cat. -- - following reagents: C. E.B.'s 2-MIt 1.85 9.0 5,503.937 27 28 Resistance to methyl ethyl ketone is determined in the TABLE II-continued following manner. The ball end of a ball peen hammer weighing about 1.5 lbs. (0.6804 kg) is covered with 8 plys CATALYZED EPOXYIPHENOLICFORMULATIONS of gauze, which is then wet with methyl ethyl ketone inE SEC girlillinoles of surface(MEK). Theand ballrubbed end ofback the hammerand forth is applieduntil the to coatingthe coated is Expt. Catalyst Weight Equivalent of removed. One double rub corresponds to one back and forth No. (Ex. Number) (grams) Epoxide movement of the hammer. The number of double rubs required to remove or mar the coating is recorded. E5ask iEarl- C 3. 38 Flexibility is determined by a /8 in. wedge test using a y Gardner Falling Dart Impact Tester (available from the *Not an examplep of the ppresent invention. Gardner Laboratory,ry Inc., Bethesda, Md.) configuredgu for 0 to "C. E. is Comparative Experiment % in. ( 0 to 3,175 mm) wedge bend test. The bottom 34 in. 2-methyl imidazole alone as catalyst. (40% by wt. solution in methanol) (19.05 mm) of the panel is bent 180° over itself exposing 2-phenylimidazole alone as catalyst. (40% by wt. solution in methanol) "1,2-dimethylimidazole alone as catalyst. (40% by wi. solution in methanol) is i.e.N.E.G. the sitti completely together, they form a zero to /8 in. (0 to 3.175

TABLE III 50° C. Stability Study Nitrogen or Mol. of HBF % of Phosporus per Mol. Control Cont. of N-Cont. Initial After 1 Day After 14 Days Viscosity Ex. Or CE Compound Cmpd. Cps Pa. s. Cps Pa. s. Cps Pa. s. After 1 Day After 14 Days 18 2-MI 0.98 885 .885 1054 1054 1385 1.385 10.5 <0.7 19 2-MI 0.75 914 914 1361 1.361 N.D. N.D. 13.6 N.D. 20 2-MI 0.84 904 904 1211 1.211 24150 24.150 12. <12. 21 2-MI 0.89 891 891 144 1.144 8890 8.890 11.4 <4.4 22 2-MI 0.93 887 887 1085 1085 3120 3.120 10.8 <1.6 23 2-MI 103 877 887 1032 1.032 125 1.251 10.3 <0.6 24 2-MI 1.07 840 840 957 957 1168 1,168 9.6 <0.6 25 2-MI 12 836 836 987 987 2919 2.919 9.9 <5 26* 2-MI .4 360 1360 >200,000 200b N.D. N.D. N/A N.D. 27-k 2-MI 117 1243 1243 >200,000 >200 --- - >1999 - 28* 2-MI 1.30 1715 1.75 >200,000 >200 ---- - >1999 - 29* 2-MI 135 2000 2.000 >200,000 >200 -- - >1999 - 30 2-PI 0.98 820 820 980 .980 1404 1.404 7.0 - 31 4-MI 1.02 867 867 1020 1.020 1179 1179 - - 32 2-DMI 1.03 836 836 932 932 1260 1260 7.6 <0.6 33 2-E-4-MI 1.02 828 828 897 897 1140 - - 34 4,5-DPI 1.03 417 417 576 576 742 T42 - - A* None O 1079 1079 1081 1.081 256 1.256 - - B* 2-MI O 1006 006 10,006 10.006 -200,000 >200 -- -- C-k 2-Pic O 1042 1.042 14,000 14.000 - arr- - - D* 1,2-DMI 0 1171 17 12,228 12,228 200,000 a.200 --- m FOOTNOTES TO TABLE III *Not an example of the present invention. Examples are designated by numerals whereas comparative experiments are designated by letters. Viscosity of the composition exceeded the test method (>200,000 cps). 2-Methylimidazole, 2-phenylimidazole and 1,2-dimethylimidazole employed alone as catalyst. This value is determined by dividing the viscosity obtained in the appropriate example by the viscosity of a comparable formulation employing as the catalyst the catalyst the same nitrogen orphosphorus compound except that it has not been reacted with HBF. The viscosity is increasing during measurement.

EXAMPLE 35 mm) gap. The top plate is then impacted with the blunt end Coating Properties With 2-methyl-imidazolium of the falling dart until the panel is bent from a zero toys in. Fluoborate Catalyst (0 to 3.175 mm) wedge. The coated area over the bend is 55 then wiped for approximately one minute with a 10% The formulations described in Example 18 and Compara tive Experiment B are applied to 24 gauge BonderiteTM R90 CuSO/1N HCl solution which turns a copper-red color treated steel panels available from Parker Chemical Co. via where the coating has failed and exposed steel metal. The a wire wound steel draw down rod. The coatings are allowed percent pass value given in Table IV is calculated as the to air dry for approximately five minutes, then placed in a 60 forced air oven preset at 200° C. for 10 minutes. The panels number of inches from the /8 in. (0 to 3.175 mm) end to the are removed from the oven, cooled to ambient temperature, point of failure, as evidenced by the copper-red color, and tested as shown in Table IV. divided by the total 4 in. (101.6 mm) total length times 100. 5,503.937 29 30

TABLE IV COATING PROPERTIES OF CATALYZED SYSTEMS GARDNER FORMULATIONS FROM IMPACT /8 in. WEDGE SAMPLE NUMBER EXAMPLE OR COMPEXPT. MEKDOUBLERUBS in-bs. BEND% Pass

I 18 30-50 >180 20.34 100 lik C.E.B >100 >180 20.34 100 *Not an example of the present invention. *C.E. is Comparative Experiment.

EXAMPLE 36 15 TABLE V Clear Casting Properties With Imidazolium CLEAR CASTING PROPERTIES OF Fluoborate Catalyst CURED RESIN COMPOSITIONS Tetrabromobisphenol A 136 grams (0.5 equivalents), CATALYST 181.5 grams (1.0 equivalent) of D.E.R.TM 383, 4.3 grams 20 EXAM- FROM Glass (0.1 equivalent) of sulfanilamide, 24.8 grams (0.4 equiva PLE EXAMPLE OR Trans. lents) are stirred at 100 C-130° C. until homogeneous, NUM- COMP. Temp. Toughness Ka then 0.871 grams (2.0 millimoles) of the catalyst described in Example 1 is added. The mixture is stirred until homo BER EXPT. oC. psix in MPa. Mos geneous, degassed via evacuation for approximately one 25 36 1. 154 890 0.979 minute, then poured into preheated aluminum molds spaced 37+ 52 145 990 1.089 1/8 inch apart. The castings are cured for 16 hours at 150 C., followed by three hours at 200° C. The casting is then *Not an example of the present invention. cooled and removed from the aluminum mold for testing as shown in Table V, Example 36. 30 EXAMPLE 38 EXAMPLE 37 Preparation of Ethyltriphenylphosphonium Clear Casting Properties With Fluoborate Complex (Not An Example of Present Tetrabutylphosphonium Fluoborate Catalyst (Not Invention Described Herein) An Example of Present Invention Described 35 A glass flask fitted with a stirrer, thermometer, and reflux Herein) condenser is charged with 11.4 grams of a 71.9% methanol solution, by weighty of ethyltriphenylphosphonium acetate Example 36 is repeated using 1.84 g (2.0 millimoles) of acetic acid (ETPPA.HAc) complex (0.0200 moles). To this the catalyst described in Example 51. The testing results are stirred solution, 3.682 grams (0.0224 moles) of a 53.4% by shown in Table V, Example 37. 40 weight aqueous solution of fluoboric acid (1.12 moles per In these experiments, toughness is reported as the stress mole of ETPPA.HAc) are slowly added during about five intensification factor, K. The method for measuring K is an minutes. The heat from the reaction warms the solution to adaptation of ASTME 399-83 for plastics materials from the approximately 50° C. The solution is stirred for an additional original usage with metals. The compact tension test is now 30 minutes as it cooled to near ambient temperature. Metha widespread in usage and is described in the J. Mater. Sci., 45 nol is then added, 10.22 grams, to dilute the solution to 40% Vol., 16, 2657, 1981. An individual test piece is cut as an solids based on the weight of the ethyltriphenylphospho approximate 1 inch (25.4 mm) square from a flat casting nium fluoborate complex. usually of /s inch (3.175 mm) thickness. A dovetail notch is The weight percent of ETTPA.HAc in methanol was cut into one edge, centered, about 4 inch (6.25 mm) in determined by titration of the acetate group with 0.1006 N depth. Next, a razor blade is inserted into this notch and 50 perchloric acid (HCIO) in acetic acid to a crystal violet tapped to produce a precrack. Tow holes are then drilled endpoint (blue to green endpoint). It required 12.80 ml adjacent to the dovetail as indicated in ASTM E 399-83, (0.001280 moles) of perchloric acid solution to titrate allowing the test piece to be pinned into position in the 0.7295g of ETPPA.HAc/methanol solution dissolved in 15 Instron test machine. Extension of the sample now allows ml of dichloromethane, which calculates to 71.9 wt.% of the force required to propagate opening of the precrack to be ETPPA.HAc in methanol. measured, using a test speed of 0.02 inches/minute (0.0085 55 mm/sec.). This force is used in the equation given in ASTM EXAMPLES 39-45 E-399, along with the required sample dimensions and actual precrack length, to calculate a "stress intensification factor", K. This method is described by Lee, L. H. in Preparation of Ethyltriphenylphosphonium Physicochemical Aspects of Polymer Surfaces, K. L. Mittair 60 Fluoborate Complexes (Not an Example of Present ed., Plenum Press, New York, N.Y., 1983. Invention Described Herein) In these experiments, glass transition temperature (Tg) is The procedure described in Example 38 is repeated using measured by differential scanning calorimetry (DSC) using the same procedure and amount of ETPPA.HAc, however a calibrated DuPont Instrument (Model No. 912 with a 1090 the weight of fluoboric acid (53.4% aqueous solution) is controller). Samples are run under a nitrogen atmosphere 65 varied as shown in Table IV. All experiments are diluted with with a temperature ramp of 10° C. per minute (0.1667 methanol to 40% solids based on the combined weights of C./sec.). ETPPA. HAC and fluoboric acid. 5,503,937 31 32

TABLE IV TABLE V ETHYLTRIPHENYLPHOSPHONIUM FLUOBORATE TETRABUTYLPHOSPHONIUM FLUOBORATE COMPLEXES WITH WARYING RATIOS COMPLEXES WITH WARYINGRATIOS OF OF FLUOBORICACID FLUOBORICACD FLUOBORC MOLES FLUOBORC FLUOBORIC MOLES FLUOBORIC EXAMPLE ACID SOL ACID PERMOLE OF EXAMPLE ACID SOL. ACID PERMOLE OF NUMBER (grams) ETPPA. HAC NUMBER (grams) TBPA. HAC

39* 3.123 0.95 10 47 k 1.56 0.95 40* 3.353 1.02 48* 67 1.02 4 * 3.517 1.07 49* 1759 1.07 38% 3.682 1.12 50* 1.84 1.12 42k 3.876 1.17 51* 1923 1.17 43* 4.010 122 46* 2005 1.22 44* 4.175 1.27 52* 2.05 1.25 45k 4.339 1.32 15 53* 2.087 1.27 C.E.Ek 0.0b 0.0 54k 2.17 1.32 C.E.F. 0.0 0.0 *Not an example of the present invention. *C.E. is Comparative Experiment. *Not an example of the present invention. Ethyltriphenylphosphonium acetate acetic acid complex alone as catalyst. C.E. is Comparative Experiment. 20 Tetrabutylphosphonium acetate acetic acid complex alone as catalyst.

EXAMPLES 55-63 EXAMPLE 46 Preparation of Other Fluoborate Complexes 25 The procedure of Example 38 is followed, using a ratio of 1.02 moles of fluoboric acid per equivalent of nitrogen Preparation of Tetrabutylphosphonium Fluoborate containing compound as described in Table VI. Methanol is Complex (Not an Example of Present Invention added to bring the percent solids based on the amine Described Herein) compound-fluoborate complex to 40% by weight. 30 A glass flask fitted with a stirrer, thermometer, and reflux TABLE VI condenser is charged with 6.20 grams (0.01 moles) of a 60.9% methanol solution, by weight, of tetrabutylphospho TETRABUTYLPHOSPHONIUM FLUOBORATE COMPLEXES WITH WARYING RATIOS OF nium acetate-acetic acid complex (TBPA.HAc). To this FLUOBORICACID stirred solution, 2.00 grams (0.0122 moles) of a 53.4% by 35 weight aqueous solution of fluoboric acid (1.22 moles per EXAMPLE mole of TBPA.HAc) are slowly added during about five NUMBER NITROGEN CONTAINING COMPOUND minutes. The heat from the reaction warms the solution to 55 PYRROLIDINE approximately 50° C. The solution is stirred for an additional 56 N-METHYLMORPHOLINE 30 minutes as it cooled to near ambient temperature. Metha 40 57 MORPHOLINE 58* BUTYLAMINE nol is then added, 3,916 grams, to dilute the solution to 40% 59* DIBUTYAMINE solids based on the weight of the tetrabutylphosphonium 60* TRIBUTYLAMINE fluoborate complex. 6* DETHYLANILINE The weight percent of TBPA.HAc in methanol was deter 62 1-METHYLPYRROLIDINE mined by titration of the acetate group with 0.1006 N 45 63 PYRIDNE perchloric acid (HCIO) in acetic acid to a crystal violet *Not an example of present invention. endpoint (blue to green endpoint). It required 10.15 ml (0.001015 moles) of perchloric acid solution to titrate EXAMPLE 64 0.6301 g of TBPA.HAc/methanol dissolved in 15 ml of dichloromethane, which calculates to 60.9 wt.% TBPA.HAc 50 Fluoborate Complex Via Silver Fluoborate (Not an in methanol. Example of Present Invention Described Herein) Vacuum dried tetrabutylphosphonium chloride, 1.82 grams (0.0062 moles) is dissolved in 5.84 grams of metha EXAMPLES 47-54 nol and added dropwise to 1.20 grams (0.0062 moles) of 55 silver fluoborate dissolved in 3.46 grams of methanol. The suspension is stirred at 25°C. for 30 minutes, and the silver Preparation of Tetrabutylphosphonium Fluoborate chloride removed by filtration. The tetrabutylphosphonium Complexes (Not an Example of Present Invention fluoborate solution is concentrated to 40% solids by weight via vacuum removal of the excess methanol. Described Herein) 60 The procedure described in Example 46 is repeated using EXAMPLE 65 the same procedure and amount of tetrabutylphosphonium Fluoborate Complex Catalyzed Epoxy/phenolic acetate-acetic acid complex (TBPA.HAc), however the Systems weight of fluoboric acid (53.42% aqueous solution) is varied as shown in Table V. All experiments were diluted with 65 The catalysts described in Examples 38 to 64 are mixed methanol to 40% solids based on the combined weights of with a 1:1 molar ratio of a diglycidyl ether of bisphenol A TBPA.HAc and fluoboric acid. having an epoxy equivalent weight of 181.5 (D.E.R.TM 383 5,503,937 33 34 Epoxy Resin commercially available from The Dow Chemi What is claimed is: cal Company) and bisphenol A (2,2-bis(4,4'-hydroxyphenyl 1. A curable composition which comprises: )propane, PARABISTM commercially available from The (1) a compound which contains on average more than 1 Dow Chemical Company) dissolved in the monomethyl epoxy group per molecule, ether of propylene glycol monoacetate (PMA). The epoxy 5 - resin (181.5 grams), bisphenol A (114 grams) and 73.88 (2) to the vigore than 1 grams of PMA are heated to 80°-100° C. under a nitrogen p y yl group p atmosphere until homogeneous, cooled to ambient tempera- (3) a catalytic amount of a catalyst compound which ture and 9.0 millimoles of catalyst added to 1.00 equivalent contains: of epoxide in a manner that is described previously for (a) a cation containing at least one heterocyclic nitro Examples 18-34. Portions of these solutions are then stored gen-containing ring, and at 50° C. and the 25 C. viscosity monitored as shown in (b) an anion which is a conjugate base of fluoroarsenic Table VII. acid, fluoroantimonic acid, fluorophosphoric acid,

TABLE VII 50° C. Stability Study % of Control Phosporus Mol. of HBF Viscosity Viscosity Catalyst from Cont. per Mol. of P Initial After 1 Day After 14 Days After After Ex. Or CE Compound Cont. Cmpd. Cps Pa. s. Cps Pa s Cps Pa . s 1 Day 14 Days

39* ETPPA. HAc 0.95 364 364 460 460 - - <0.2 - 40* ETPPA. HAc 1.02 366 366 408 408 13565 13.565 <0.2 <6.8 4% ETPPA. HAC 1.07 356 356 385 385 1014 1.014 <0.2 <0.5 38* ETPPA. HAc 112 348 .348 370 370 543 543 <0.2 <0.3 42* ETPPA. HAC 1.17 348 348 391 391 623 623 <0.2 <0.3 43* ETPPA. HAC 122 436 436 749 T49 1352 1352 <0.4 <0.7 44* ETPPA. HAc 1.27 755 755 3204 3204 - --- <1.6 - 45* ETPPA. HAC 1.32 2211 2.21 10000 10,000 - - <5.0 - 47-k TBPA. HAc 0.95 401 401 570 570 - --- 1.2 - 48* TBPA. HAC 102 389 389 460 460 - - 1.0 - 49* TBPA. HAC 107 383 383 444 .444 24378 24.378 9 12.2 50k TBPA. HAC 12 377 377 430 430 6490 6.490 9 3.2 51* TBPA. HAC 1.T 387 387 407 407 733 733 9 .4 46* TBPA. HAC 122 376 376 393 393 572 572 8 3 52-k TBPA. HAC 1.25 540 0.540 1457 1.457 - - 0.7 - 53+ TBPA. HAc 1.27 385 385 462 462 841 841 1.0 .4 54-k TBPA. HAC 1.32 407 407 936 936 5900 5.900 2.0 3.0

% of Control Nitrogen Mol. of HBF Viscosity Viscosity Catalyst from Cont. per Mol. of N Initial After 1 Day After 14 Days After After Ex... or CE Compound Cont. Cmpd. Cps Pa. S Cps Pa. S Cps Pa. S 1 Day 14 Days

55 Pyrrolidine 103 830 0.830 1136 1136 1416 1416 - - 56 N-methyl 1.03 718 0.718 845 0.845 1113 1113 3.1 <5.6 morpholine 55 Morpholine 1.03 833 0.833 997 0.997 42 1.412 - 58-k Butyl amine 1.03 720 720 889 0.889 1268 1.268 --- 59* Dibutyl amine 103 602 602 684 0.684 1049 1.049 3.4 5 60* Tributyl amine 1.03 494. 494 580 0.580 849 0.849 -- C.E.I* 4-Phenyl 1.03 688 688 >2000 g >200 g - - - - morpholine 6* N,N-Diethyl- 1.03 667 667 865 0.865 - - - - 62 1-Methyl 1.03 663 663 810 810 193 1.193 - -- pyrrolidine 63* Pyridine 1.03 733 733 884 884 1484 1484 - C.E.E-k ETPPA. HAct 0 1053 1.053 >200,000 g >200 --- - w - C.E.F.k TBPA. HAc' O 898 898 47,577 47.557 >200,000 g >200 - C.E.G* Dibutylamine' O 1169 1.169 20,328 20.328 >200,000 g >200 - C.E.H-k N-Methyl- O 1330 1.330 26,999 26.999 >200,000 g >200 - - morpholine *Not an example of the present invention. Examples are designated by numerals whereas comparative experiments are disignated by letters. Ethyltriphenylphosphonium acetate acetic acid complex employed alone as catalyst. Tetrabutylphosphonium acetate acetic acid complex employed alone as catalyst. Dibutylamine employed alone as catalyst. N-methylmorpholine employed alone as catalyst. This value is determined by dividing the viscosity obtained in the appropriate example by the viscosity of a comparable formulation employing as the catalyst the same nitrogen or phosphorus compound except that it has not been reacted with HBF *Composition viscosity exceeded the test method (>200,000 cps). 5,503,937 35 36 chloroarsenic acid, chloroantimonic acid, chloro thioazole, pyrrole, pyridine, pyrazine, pyridazine, pyrroli phosphoric acid, nitric acid, hydrofluoric acid, trif dine, morpholine, pyrimidine, quinoxalin, quinazoline, luoroacetic acid, trifiuoromethane sulfonic acid, phthalazine, quinoline, purine, indazole, indole, indolizine, picric acid, fluoboric acid, or an acid represented by phenazine, phenarsazine, phenothiazine, pyrroline, indoline, the Formula: piperidine, piperazine, or combinations thereof. 8. The composition of claim 7 wherein Component (3)(a) contains a substituted or unsubstituted imidazole, pyrroli wherein each R is independently a hydrocarbyl or dine or morpholine moiety. substituted hydrocarbyl group and R is a halogen, a 9. The composition of claim 1 wherein Component (3)(b hydrocarbonoxy group, a hydrocarbonamino group, 0 ) contains essentially no boron. or a hydrocarbonphosphino group. 10. The composition of claim 1 wherein Component 2. The composition of claim 1 wherein Component (1) is (3)(b) contains boron. the glycidyl ether derivative of a polyhydric phenol. 11. The composition of claim 10 wherein Component 3. The composition of claim 2 wherein the polyhydric (3)(b) is the conjugate base of an acid represented by the phenol is selected from the group consisting of dihydrox 15 yphenols, biphenols, bisphenols, halogenated bisphenols, Formula: alkylated bisphenols, trisphenols, and novolac resins. 4. The composition of claim 1 wherein Component (2) is HBR.R. selected from the group consisting of: dihydroxyphenols, 12. The composition of claim 11 wherein each R is biphenols, bisphenols, halogenated bisphenols, alkylated 20 independently a hydrocarbon group containing from 1 to 12 bisphenols, trisphenols, phenol-aldehyde novolac resins, halogenated phenol-aldehyde novolac resins, alkylated phe carbon atoms and each R" is fluorine, chlorine or bromine. nolaldehyde novolac resins, phenol-hydroxybenzaldehyde 13. The composition of claim 10 wherein Component resins, alkylated phenol-hydroxybenzaldehyde resins, (3)(b) is the conjugate base of fluoroboric acid. hydrocarbon-phenol resins, hydrocarbon-halogenated phe 25 14. The composition of claim 1 wherein Component nol resins, hydrocarbon-alkylated phenol resin, and combi (3)(a) contains an imidazole moiety and Component (3)(b) nations thereof. contains the conjugate base of fluoroboric acid. 5. The composition of claim 1 wherein Component (2) is 15. The composition of claim 1 wherein the concentration a biphenol, a bisphenol, or a novolac resin. of catalyst is 0.05 to 50 mmol of catalyst per epoxide 6. The composition of claim 1 wherein the equivalent equivalent. ratio of aromatic hydroxyl groups to epoxy groups is from 30 16. The composition of claim 1 wherein the concentration about 0.2:1 to about 5:1. of catalyst is about 0.5 to 20 mmol of catalyst per epoxide 7. The composition of claim 1 wherein Component (3)(a) equivalent. contains at least one of the following heterocyclic moieties: imidazole, pyrazole, oxazole, imidazolidine, imidazoline,