Claims
- 1. A process for the preparation of epoxy compounds which comprises reacting a molar excess of at least one epihalohydrin with at least one aromatic compound containing an active hydrogen atom reactive with an epihalohydrin in the presence of an organic solvent or mixture of organic solvents and an alkali metal hydroxide while controlling the concentration of water in the reaction mixture; the improvement which comprises
- (1) after completion of the reaction, conducting one of the following
- (a) cooling the reaction mixture to a temperature of not greater than about 30.degree. C. followed by neutralization of the reaction mixture with carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10;
- (b) neutralizing the reaction mixture with carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10 followed by cooling the reaction mixture to a temperature of not greater than about 30.degree. C.; or
- (c) simultaneously neutralizing the reaction mixture with carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10 and cooling the reaction mixture to a temperature of not greater than about 30.degree. C.;
- (2) adding a sufficient quantity of water to form an aqueous layer and an organic layer;
- (3) separating the organic layer and the aqueous layer;
- (4) subjecting the organic layer to multiple washings with water; and
- (5) recovering the epoxy resin from the resultant organic solution containing epihalohydrin, organic solvent and epoxy resin.
- 2. A process of claim 1 wherein in steps (1-a), (1-b) and (1-c) the pH is from about 8 to about 10 and said weak inorganic acid has a pK value of from about 2 to about 5.
- 3. A process of claim 1 wherein in steps (1-a), (1-b) and (1-c) the pH is from about 8 to about 9.
- 4. A process for the preparation of epoxy compounds which process comprises
- (A) continuously or incrementally adding an aqueous alkali metal hydroxide solution over a period of from about 0.5 to about 20, suitably from about 1 to about 10, more suitably from about 1 to about 6, most suitably from about 1.5 to about 3, hours to a mixture containing (1) at least one aromatic compound containing at least one active hydrogen atom reactive with an epihalohydrin, (2) at least a molar excess of at least one epihalohydrin and (3) at least one organic solvent which codistills with water and epihalohydrin at a temperature below the boiling point of the lowest boiling compound among the components in the reaction mixture at the pressure employed or at least one organic solvent which has a boiling point above the temperature at which epihalohydrin and water codistill at the temperature and pressure employed or a combination of such solvents;
- (B) conducting the reaction under a reduced pressure sufficient to provide a distillate with a boiling point of from about 35.degree. C. to about 90.degree. C. while continuously removing water by means of codistillation with epihalohydrin and solvent at a rate such that the water content in the reaction mixture is less than about 6 percent by weight;
- (C) separating the water from the distillate and returning the epihalohydrin and organic solvent to the reaction mixture;
- (D) drying the reaction mixture at conditions which do not remove substantial quantities of unreacted epihalohydrin until the concentration of water is equal to or less than about 2 percent by weight;
- (E) after drying, conducting one of the following
- (1) cooling the reaction mixture to a temperature of not greater than about 30.degree. C. followed by neutralization of the reaction mixture with carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10;
- (2) neutralizing the reaction mixture with carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10 followed by cooling the reaction mixture to a temperature of not greater than about 30.degree. C.; or
- (3) simultaneously neutralizing the reaction mixture with carbon dioxide or carbon dioxide or weak inorganic acid in a quantity such that the reaction mixture has a pH of from about 7 to about 10 and cooling the reaction mixture to a temperature of not greater than about 30.degree. C.;
- (F) adding a sufficient amount of water so as to form an aqueous layer containing dissolved alkali metal halide and an organic layer containing epoxy resin/epihalohydrin/organic solvent;
- (G) separating the organic and aqueous layers and subjecting the organic layer to multiple washings with water; and
- (H) recovering the resultant epoxy resin from the water washed organic layer containing resin/epihalohydrin/organic solvent mixture by any suitable means.
- 5. A process of claim 4 wherein
- (i) in step (A), the alkali metal hydroxide is added over a period of from about 1 to about 10 hours;
- (ii) in step (B), the reaction is conducted under vacuum at a temperature of from about 40.degree. C. to about 85.degree. C. and the water is removed at a rate such that the water content in the reaction mixture is from about 0.1 to about 4;
- (iii) in step (D), the water content is equal to or less than about 1.5 percent by weight; and
- (iv) in step (E), the pH value is from about 7 to about 10 and said inorganic acid has a pK value of from about 2 to about 2.5.
- 6. A process of claim 5 wherein
- (i) in step (A), the alkali metal hydroxide is added over a period of from about 1 to about 6 hours;
- (ii) in step (B), the reaction is conducted at a temperature of from about 45.degree. C. to about 75.degree. C. and the water is removed at a rate such that the water content in the reaction mixture is from about 0.2 to about 2;
- (iii) in step (D), the water content is equal to or less than about 1 percent by weight; and
- (iv) in step (E), the pH value is from about 8 to about 10 and said inorganic acid is selected from the group consisting of.
- 7. A process of claim 6 wherein
- (i) in step (A), the alkali metal hydroxide is added over a period of from about 1.5 to about 3 hours;
- (ii) in step (B), the reaction is conducted under a vacuum at a temperature of from about 50.degree. C. to about 70.degree. C. and the water is removed at a rate such that the water content in the reaction mixture is from about 0.2 to about 0.5;
- (iii) in step (D), the water content is equal to or less than about 0.2 percent by weight; and
- (iv) in step (E), the pH value is from about 8 to about 9.
- 8. A process of claim 1, 2 or 3 wherein the aqueous phases containing alkali metal halide and minor quantities of soluble organic compounds from steps 3 and 4 is extracted by contacting the aqueous phases, either separately or in combination, with an epihalohydrin; and subjecting the thus epihalohydrin washed product to distillation to remove water and organic materials therefrom.
- 9. A process of claims 4, 5, 6 or 7 wherein the aqueous phase and water was streams containing alkali metal halide and minor quantities of soluble organic compounds from step G is extracted by contacting the aqueous phase and water wash streams, either separately or in combination, with an epihalohydrin; and subjecting the thus epihalohydrin washed product to distillation to remove water and organic materials therefrom.
- 10. A process of claim 1, 2, 3, 4, 5, 6, or 7 wherein:
- (i) said epihalohydrin is epichlorohydrin;
- (ii) said alkali metal hydroxide is sodium hydroxide; and
- (iii) said compound containing an active hydrogen atom reactive with an epihalohydrin is a compound represented by the following formulas I, II, III, IV or V: ##STR6## wherein each A is independently a divalent hydrocarbon group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 -- or --CO--; A' is a divalent hydrocarbon group having from 1 to about 6, preferably from 1 to about 4, carbon atoms; A" is a trivalent hydrocarbon group having from 1 to about 12 carbon atoms each R is independently hydrogen, a hydrocarbyl group having from 1 to about 10 carbon atoms, a halogen atom, a hydroxyl group or an amino group; each Z is independently --OH, --NH.sub.2 or --COOH; p has a value of from about 1 to about 100; m has a value from about 1 to about 6 and n has a value of zero or 1.
- 11. A process of claim 10 wherein said compound containing an active hydrogen atom reactive with an epihalohydrin is bisphenol A, bisphenol F or bisphenol K.
- 12. A process of claim 8 wherein:
- (i) said epihalohydrin is epichlorohydrin;
- (ii) said alkali metal hydroxide is sodium hydroxide; and
- (iii) said compound containing an active hydrogen atom reactive with an epihalohydrin is a compound represented by the following formulas I, II, III, IV or V: ##STR7## wherein each A is independently a divalent hydrocarbon group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 -- or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 6, preferably from 1 to about 4, carbon atoms; A" is a trivalent hydrocarbon group having from 1 to about 12 carbon atoms each R is independently hydrogen, a hydrocarbyl group having from 1 to about 10 carbon atoms, a halogen atom, a hydroxyl group or an amino group; each Z is independently --OH, --NH.sub.2 or --COOH; p has a value of from about 1 to about 100; m has a value from about 1 to about 6 and n has a value of zero or 1.
- 13. A process of claim 12 wherein said compound containing an active hydrogen atom reactive with an epihalohydrin is bisphenol A, bisphenol F or bisphenol K.
- 14. A process of claim 9 wherein:
- (i) said epihalohydrin is epichlorohydrin;
- (ii) said alkali metal hydroxide is sodium hydroxide; and
- (iii) said compound containing an active hydrogen atom reactive with an epihalohydrin is a compound represented by the following formulas I, II, III, IV or V: ##STR8## wherein each A is independently a divalent hydrocarbon group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 -- or --CO--; A' is a divalent hydrocarbon group having from 1 to about 6, preferably from 1 to about 4, carbon atoms; A" is a trivalent hydrocarbon group having from 1 to about 12 carbon atoms each R is independently hydrogen, a hydrocarbyl group having from 1 to about 10 carbon atoms, a halogen atom, a hydroxyl group or an amino group; each Z is independently --OH, --NH.sub.2 or --COOH; p has a value of from about 1 to about 100; m has a value from about 1 to about 6 and n has a value of zero or 1.
- 15. A process of claim 14 wherein said compound containing an active hydrogen atom reactive with an epihalohydrin is bisphenol A, bisphenol F or bisphenol K.
- 16. A process of claim 1, 2, 3, 4, 5, 6 or 7 wherein neutralization is conducted with carbon dioxide.
- 17. A process of claim 8 wherein neutralization is conducted with carbon dioxide.
- 18. A process of claim 9 wherein neutralization is conducted with carbon dioxide.
- 19. A process of claim 10 wherein neutralization is conducted with carbon dioxide.
- 20. A process of claim 11 wherein neutralization is conducted with carbon dioxide.
- 21. A process of claim 12 wherein neutralization is conducted with carbon dioxide.
- 22. A process of claim 13 wherein neutralization is conducted with carbon dioxide.
- 23. A process of claim 14 wherein neutralization is conducted with carbon dioxide.
- 24. A process of claim 15 wherein neutralization is conducted with carbon dioxide.
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 190,608 filed May 5, 1988, now abandoned.
US Referenced Citations (13)
Foreign Referenced Citations (5)
Number |
Date |
Country |
173297 |
Jul 1978 |
CSX |
2056033 |
Jun 1971 |
DEX |
224040 |
Jun 1985 |
DEX |
59-209644 |
Nov 1984 |
JPX |
60-81176 |
May 1985 |
JPX |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
190608 |
May 1988 |
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