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US3980679A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for the manufacture of glycidyl ethers of monohydric or polyhydric phenols, having improved properties

Assignee: Hoechst AG
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Filing: 1974-01-17
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Granted: 1976-09-14
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Expires: 1994-01-17
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Abstract

Abstract The invention relates to a process for the manufacture of glycidyl ethers of monohydric or polyhydric phenols with excess epichlorohydrin, wherein the monohydric or polyhydric phenols are reacted with excess epichlorohydrin, based on the phenolic hydroxyl group, in the presence of a catalyst specific for the formation of chlorohydrin ethers from phenols and epichlorohydrin, and of 0.2 to 8 % by weight of water, based on the reaction medium, until the conversion to chlorohydrin ethers is at least 10 %, preferably 50 - 90 %, based on the phenolic hydroxyl groups, and are then reacted by heating with 0.9 to 1.15 equivalents of a solid alkali metal hydroxide per phenolic hydroxyl group to give glycidyl ethers.

Inventors

  • 👤 Wilhelm Becker

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 15:30
CPC Classifications
C; C07; C07D; C07D303/00; C07D303/02; C07D303/12; C07D303/18; C07D303/20; C07D303/22; C07D303/24; C08; C08G; C08G59/00; C08G59/02; C08G59/04; C08G59/06; C08G59/063

Claims Analysis

Total Claims: 9
Claim 1
Independent Claim 301 words
In a process for manufacturing glycidyl ethers from monohydric or polyhydric phenols and excess epichlorohydrin, relative to the amount of phenolic hydroxyl groups, in the presence of a catalyst which is specific for the formation of chlorohydrin ethers from the phenol and epichlorohydrin and from 0.2 to 8 percent by weight of water, based upon the weight of the reaction medium, and then the chlorohydrin is reacted by heating with 0.9 to 1.15 equivalent of solid alkali metal hydroxide per phenolic hydroxyl group to give glycidyl ethers in the presence of 0.001 to 5 percent by weight, based on the amount of phenol employed, of a divalent tin compound, the improvement which comprises a. in the first stage, conducting the reaction between phenol and the excess epichlorohydrin in the presence of the catalyst specific to the formation of the chlorohydrin in an alkali-free medium at from 50° to 100°C for from 1 to 4 hours, until 50 to 90 percent, based on the phenolic hydroxyl groups, of the chlorohydrin is formed, and thereafter b. in a second stage, adding to the reaction mixture from stage (a) from 10 to 90 percent by weight of the solid alkali metal hydroxide over the course of 18 to 90 percent of the total time of addition of the solid alkali metal hydroxide, which time is 30 to 300 minutes, while removing the heat of reaction by cooling the mixture or distillation under reflux under reduced pressure in the presence of water of reaction or added water, and thereafter c. in a third stage, adding the remainder of the solid alkali metal hydroxide, with removal of the heat of reaction and water of reaction or added water from the mixture by azeotropic distillation, and thereafter d. distilling the excess epichlorohydrin from the glycidyl ether product.
Claim 2
Dependent Claim 301 words
In a process for manufacturing glycidyl ethers from monohydric or polyhydric phenols and excess epichlorohydrin, relative to the amount of phenolic hydroxyl groups, in the presence of a catalyst which is specific for the formation of chlorohydrin ethers from the phenol and epichlorohydrin and from 0.2 to 8 percent by weight of water, based upon the weight of the reaction medium, and then the chlorohydrin is reacted by heating with 0.9 to 1.15 equivalent of solid alkali metal hydroxide per phenolic hydroxyl group to give glycidyl ethers in the presence of 0.001 to 5 percent by weight, based on the amount of phenol employed, of a divalent tin compound, the improvement which comprises a. in the first stage, conducting the reaction between phenol and the excess epichlorohydrin in the presence of the catalyst specific to the formation of the chlorohydrin in an alkali-free medium at from 50° to 100°C for from 1 to 4 hours, until 50 to 90 percent, based on the phenolic hydroxyl groups, of the chlorohydrin is formed, and thereafter b. in a second stage, adding to the reaction mixture from stage (a) from 10 to 90 percent by weight of the solid alkali metal hydroxide over the course of 18 to 90 percent of the total time of addition of the solid alkali metal hydroxide, which time is 30 to 300 minutes, while removing the heat of reaction by cooling the mixture or distillation under reflux under reduced pressure in the presence of water of reaction or added water, and thereafter c. in a third stage, adding the remainder of the solid alkali metal hydroxide, with removal of the heat of reaction and water of reaction or added water from the mixture by azeotropic distillation, and thereafter d. distilling the excess epichlorohydrin from the glycidyl ether product.
Claim 3
Dependent Claim 33 words
Method according to claim 1, characterized in that in stage (c) the azeotropic distillation is carried out by recycling the phase containing epichlorohydrin, which had been freed from water, to the reaction mixture.
Claim 4
Dependent Claim 106 words
Method according to claim 1, characterized in that as divalent tin-compounds forming stannites (Me I 2 [Sn(OH) 4 ] or Me I [Sn(OH) 3 ]) with alkalis, such as SnCl 2 , Me I [SnCl 3 ], SnCl 2 .sup.. 2H 2 O, SnF 2 , SnBr 2 , SnJ 2 , Sn(OH) 2 , SnSO 4 , Sn(NO 3 ) 2 , Sn(SCN) 2 , SnC 2 O 4 (oxalate) and salts of divalent tin with organic acids, of the formula Sn(OOCR) 2 , wherein --R can be an alkyl or iso-alkyl radical with 1 to 12 carbon atoms, or the stannites themselves are employed.
Claim 5
Dependent Claim 26 words
Method according to claim 1, characterized in that in the reaction 3 to 15, preferably 4 to 12 mols epichlorohydrin are used per phenolic hydroxyl group.
Claim 6
Dependent Claim 28 words
Method according to claim 1, characterized in that as catalyst specific for the formation of chlorohydrin ethers choline or choline salts or/and further quaternary ammonium salts are employed.
Claim 7
Dependent Claim 25 words
Method according to claim 1, characterized in that the liquid glycidyl ether is freed from the organic solvents by steam distillation at 100° to 160°C.
Claim 8
Dependent Claim 62 words
The method according to claim 1 characterized in that volatile components are removed from the liquid glycidyl ether by heating the mixture to from 100°C to 180°C and by adding from 1 to 10 percent by weight, relative to the glycidyl ether, of aqueous hydrogen peroxide solution containing from 1 to 20 percent by weight of hydrogen peroxide, while stirring the mixture.
Claim 9
Dependent Claim 40 words
The method according to claim 1 characterized in that in stage (c) the azeotropic distillation is carried out without recycling water of reaction, added water, unreacted epichlorohydrin or the liquid phase containing epichlorohydrin which has been freed from the water.

References Cited (Backward Citations)

US2995583A Cited
NL6908790A Cited
DE2108207A1 Cited
US3766221A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1979-09-14 1980-03-15 1980-09-14 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1983-09-14 1984-03-15 1984-09-14 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1987-09-14 1988-03-15 1988-09-14 $7700.00 Window Closed / Lapsed

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