Claims
- 1. A process for the preparation of an epoxy resin represented by the following formulas I or II ##STR5## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each R is independently hydrogen or an alkyl group having from 1 to about 3 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms or a halogen atom; Z is a group represented by the formula ##STR6## n has a value of zero or 1; n' has an average value from zero to about 20; and x and y each have a value of 1 ; which process comprises
- (1) hydrochlorinating an epoxy resin represented by the following formulas III or IV or a combination thereof ##STR7## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms; each R is independently hydrogen or an alkyl group having from 1 to about 3 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms or a halogen atom; n has a value of zero or 1; n" has an average value from zero to about 20; with a suitable hydrochlorinating agent in the presence of one or more non-reactive solvents at a temperature of from about 0.degree. C. to about 100.degree. C. at a pressure from atmospheric to superatmospheric for from about 0.5 to about 24 hours thereby producing a first chlorohydrin intermediate product;
- (2) reacting the resultant chlorohydrin product from step (1) with from about 0.01 to less than about 1 mole of of epichlorohydrin per mole of chlorohydrin in said first chlorohydrin intermediate product in the presence of one or more Lewis acid catalysts and in the presence of one or more non-reactive solvents at a temperature of from about 0.degree. C. to about 100.degree. C. and a pressure from atmospheric to superatmospheric for from about 0.5 to about 24 hours thereby producing a second chlorohydrin intermediate product;
- (3) recovering the second intermediate product formed in step (2) by any suitable means and dissolving the recovered second chlorohydrin intermediate product in one or more non-reactive solvents and dehydrochlorinating said second chlorohydrin intermediate product with one or more suitable dehydrochlorinating agents at a temperature of from about 30.degree. C. to about 90.degree. C. and a pressure from about 0.1 psia to about 14 psia for from about 0.5 to about 24 hours employing from about 0.95 to about 1.1 equivalents of dehydrochlorinating agent per mole of chlorohydrin; and
- (4) recovering the resultant aliphatic, non-hydrolyzable chlorine-containing epoxy resin product.
- 2. A process of claim 1 wherein (a) the product being prepared is represented by formula II and the epoxy resin being hydrochlorinated is represented by formula IV wherein each A is independently a divalent hydrocarbyl group having from 1 to about 6 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each R is independently hydrogen or an alkyl group having from 1 to about 3 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms, chlorine or bromine; n has a value of 1; n' has an average value from zero to about 10; and n" has an average value from zero to about 10;
- (b) step (1) conducted at a temperature of from about 30.degree. C. to about 80.degree. C., at a pressure of from about 10 psia. to about 100 psia., for from about 1 hour to about 10 hours;
- (c) step (2) is conducted at a temperature of from about 20.degree. C. to about 80.degree. C., at a pressure of from about 10 psia. to about 100 psia., for from about 1 hour to about 12 hours and the ratio of moles of epichlorohydrin to chlorohydrin is from about 0.1:1 to about 0.95:1:
- (d) dehydrohalogenation in step (3) is conducted at a temperature of from about 30.degree. C. to about 90.degree. C., at a pressure of from about 1 psia. to about 12 psia., for from about 1 hours to about 12 hours; and
- (e) the amount of dehydrochlorinating agent is from about 0.96 to about 1 mole of dehychlorinating agent per mole of chlorohydrin.
- 3. A process of claim 2 wherein
- (a) each A is independently a divalent hydrocarbyl group having from 1 to about 4 carbon atoms; each R is hydrogen; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms; n' has an average value from zero to about 5; and n" has an average value from zero to about 5;
- (b) step (1) conducted at a temperature of from about 50.degree. C. to about 70.degree. C., at a pressure of from about 10 psia. to about 100 psia., for from about 1 hour to about 10 hours;
- (c) step (2) is conducted at a temperature of from about 50.degree. C. to about 70.degree. C., at a pressure of from about 14 psia. to about 20 psia., for from about 2 hours to about 4 hours and the molar ratio of epichlorohydrin to chlorohydrin is from about 0.5 to about 0.95;
- (d) dehydrochlorination in step (3) is conducted at a temperature of from about 50.degree. C. to about 70.degree. C., at a pressure of from about 1 psia. to about 4 psia., for from about 1 hour to about 4 hours;
- (e) the amount of dehydrochlorinating agent is from about 0.98 to about 1 mole of dehychlorinating agent per mole of chlorohydrin;
- (f) the solvent employed in step 1 is an alcohol or aromatic hydrocarbon or a combination thereof;
- (g) the solvent employed in step (2) is an aromatic hydrocarbon;
- (h) the solvent employed in step (3) is a mixture of epichlorohydrin and a glycol ether; and
- (i) the dehydrochlorinating agent employed in step (3) is an alkali metal hydroxide.
- 4. A process of claim 3 wherein
- (a) in formulas II and IV, each A is an isopropylidine group and each n' and n" independently has an average value of from zero to about 3;
- (b) the hydrochlorinating agent is hydrogen chloride;
- (c) the solvent employed in the hydrochlorination step (1) is a mixture of toluene and methanol;
- (d) the coupling reaction, step (2), is conducted in the presence of stannic chloride as the catalyst;
- (e) the solvent employed in step (2) is toluene;
- (f) the solvent employed in the dehydrohalogenation reaction, step (3) is a mixture of epichlorohydrin and propylene glycol methyl ether; and
- (g) the dehydrohalogenation agent is sodium hydroxide.
Parent Case Info
This is a divisional of application Ser. No. 258,150, filed Oct. 14, 1988 , abandoned, which is incorporated herein by reference in its entirety.
US Referenced Citations (5)
Divisions (1)
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Number |
Date |
Country |
Parent |
258250 |
Oct 1988 |
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