WO2004085355A1 - A process for hydrolyzing water-insoluble epoxides - Google Patents
A process for hydrolyzing water-insoluble epoxides Download PDFInfo
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- WO2004085355A1 WO2004085355A1 PCT/US2004/008103 US2004008103W WO2004085355A1 WO 2004085355 A1 WO2004085355 A1 WO 2004085355A1 US 2004008103 W US2004008103 W US 2004008103W WO 2004085355 A1 WO2004085355 A1 WO 2004085355A1
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- water
- epoxide
- insoluble
- epoxides
- diol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Definitions
- FIELD OF THE INVENTION Disclosed herein is a process for hydrolyzing water-insoluble epoxides at ambient conditions to produce the corresponding diols.
- Polyesters and polyamides have excellent fiber properties, however, polyesters, especially polyester fibers are difficult to dye.
- Polyamides are not as difficult to dye as polyesters, but one or more dyeability additives are commonly incorporated into polyamides in order to selectively increase the affinity of the polyamide fibers for certain type of dyes or the resistance of the fibers to staining with certain type of staining agents.
- 3-(2- sulfoethyl) hexanedioic acid, sodium salt confers improved basic dyeability to both polyesters and polyamides.
- a precursor to SEHA is 4- vinylcyclohexane-1,2-diol (VCH diol).
- US 4, 165,440 discloses the hydrolysis of ethylene oxide to prepare ethylene glycol using acid ion exchange resin containing fluorinated alkyl sulfonic acid groups, at a temperature range of about 20°C to about 115°C.
- JP04046133 describes the preparation of cyclododecane diol using cyclohexene oxide with water in the presence of inorganic solid acid catalysts at about 70°C.
- US3062889 describes the process for purifying acetaldehyde containing olefin oxides using a cation exchange resin (Amberlite IR-120) at a temperatures of 150°F to 230°F in which the olefin oxides was converted to glycols.
- US4107221 describes the chlorinated solvent purification process of using a strong acid cation exchange resin (Dowex, H + form) in the presence of water to remove olefin oxides including propylene oxide, epichlorohydrin, glycidol, butylene oxide, cyclohexene oxide, and styrene oxide at temperatures from ambient to 165°C.
- Ri and R 2 independently are selected from the group consisting of C3 or higher saturated or unsaturated alkyl or aryl groups, which are substituted or unsubstituted, and wherein Z is C3 or higher saturated or unsaturated alkyl or aryl groups, which are substituted or unsubstituted;
- the present invention discloses a process for preparing diols from water-insoluble epoxides.
- 4-vinylcyclohexene-1,2-epoxide represented by compound 1 was hydrolyzed to prepare 4-vinylcyclohexene-1 ,2-diol ( represented by the compound 2) with cationic exchange resin or solid acidic catalyst in water at ambient conditions.
- catalyst 1 4-vinylcyclohexene-1,2-epoxide
- 4-vinylcyclohexene-1,2-diol represented by the compound 2
- the epoxides that are useful in the present invention are those C3 to C12 substrates having an epoxide moiety. These include, but are not limited to of 4-vinylcycIohexene-1,2-epoxide, 1 ,2-cyclododecane epoxide and 1,2-cyclohexane epoxide. Although these epoxides are not soluble in water, the process of the present invention can be used without solvent and at ambient conditions.
- One embodiment of the present invention is the hydrolysis of 4- vinylcyclohexene-1 ,2-epoxide to 4-vinylcyclohexene-1 ,2-diol using heterogeneous catalysts, in water, without solvent, and at ambient condition.
- the ability to carry out the process at ambient conditions reduces the production cost of diol dramatically, which in turn is used as a co-monomer for polyester and polyamide production.
- Another embodiment of the present invention is the hydrolyses of 1 ,2-cyclododecane epoxide and 1 ,2-cyclohexane epoxide to their corresponding diols.
- a vessel is charged with a solid acid catalyst or ion exchange resin, water and a water insoluble epoxide.
- the mixture is agitated, preferable vigorously, at ambient conditions.
- the solid acid catalysts that are suitable for the present invention are silica alumina and TiF4/Si ⁇ 2. It has also been discovered that inexpensive ion exchange resins that are available for water treatment can be used to hydrolyze the epoxide with high conversion and yield.
- the ion exchange resins that are suitable for the present invention are Amberlyst-15, Dowex-HGR-W2H, Dowex-M33, Dowex-MSC-1-H, Dowex M-31, and NAFION.
- the quality of the water that can be used for the present process is not significant. Untreated water may be used. Deionized water is preferred to increase the catalyst activity.
- the molar ratio of water to epoxides is in the range of 8:1 - 20:1.
- the contact time is about 5 hours.
- Catalyst A Duolite ES-26 (strong acid cation resin, sodium form) was treated with dilute sulfuric acid, followed by Dl water to neutral.
- Catalyst B Amberlyst (strong acid cation resin) was washed with Dl water to neutral.
- Catalyst C 20 g. Silica (380 m 2 / g) was dispersed in 250 ml Dl water under stirring. 0.8 g. TiF 4 was added into the suspension. The pH of the suspension was adjusted by HCI solution to 8. The mixture was stirred at ambient condition. The gel was filtered and washed with Dl water to neutral. The solid was dried in a 120°C oven.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for hydrolyzing water-insoluble epoxides, and more particularly to a process for preparing diols. Specifically disclosed is a method for preparing 4-vinylcyclohexane-1,2-diol, 1,2-cyclohexane diol and 1,2-cyclododecane diol.
Description
TITLE OF THE INVENTION A PROCESS FOR HYDROLYZING WATER-INSOLUBLE EPOXIDES
FIELD OF THE INVENTION Disclosed herein is a process for hydrolyzing water-insoluble epoxides at ambient conditions to produce the corresponding diols.
BACKGROUND OF THE INVENTION
Polyesters and polyamides have excellent fiber properties, however, polyesters, especially polyester fibers are difficult to dye. Polyamides are not as difficult to dye as polyesters, but one or more dyeability additives are commonly incorporated into polyamides in order to selectively increase the affinity of the polyamide fibers for certain type of dyes or the resistance of the fibers to staining with certain type of staining agents. Compared to conventional cationic dyeability modifiers, 3-(2- sulfoethyl) hexanedioic acid, sodium salt (SEHA) confers improved basic dyeability to both polyesters and polyamides. A precursor to SEHA is 4- vinylcyclohexane-1,2-diol (VCH diol).
US 6312,805 B1 describes a method to produce VCH diol by treating 4-vinylcyclohexene with formic acid and hydrogen peroxide and hydrolyzing the subsequent compounds with sodium hydroxide solution. It would be desirable to have a simpler and more economic process to produce VCH diol.
There have been many disclosures related to the hydration of water-soluble epoxides to prepare the corresponding diols. US 4, 165,440 discloses the hydrolysis of ethylene oxide to prepare ethylene glycol using acid ion exchange resin containing fluorinated alkyl sulfonic acid groups, at a temperature range of about 20°C to about 115°C. JP04046133 describes the preparation of cyclododecane diol using cyclohexene oxide with water in the presence of inorganic solid acid catalysts at about 70°C.
There have also been disclosures of hydroylsis of water-insoluble epoxides using exchange resin materials. For example, US 5488184 and US 5874653 disclose propylene oxide in water using anionic exchange resin. The use of cation exchange resin (KU-23) to hydrolyze 2-butene oxide to 2,3-butanediol was published in Zhurnal Prikladnoi Khimii, Vol.
57, pp 2581-2584, 1984. The reaction was carried out at 50°C with 10 mass% of KU-23, and 1 :2 molar ratio of 2-butene oxide to water.
US3062889 describes the process for purifying acetaldehyde containing olefin oxides using a cation exchange resin (Amberlite IR-120) at a temperatures of 150°F to 230°F in which the olefin oxides was converted to glycols. US4107221 describes the chlorinated solvent purification process of using a strong acid cation exchange resin (Dowex, H+ form) in the presence of water to remove olefin oxides including propylene oxide, epichlorohydrin, glycidol, butylene oxide, cyclohexene oxide, and styrene oxide at temperatures from ambient to 165°C.
Several published reports mention that the cation exchange resins are used to convert epoxides to glycols with or without solvents (Monatsh Chem. page 745, 123, 1992; Monatsh Chem. Page 152, 122, 191; J. Med. Chem. Page 1334, 30, 8, 1987; Synthesis page 902, 1996; J. Chem.Soc.Perkin Trans.1, page 742, 7, 1993; J, Chem. Soc. Perkin Trans.1 pages 1560 and 1562, 12, 1994). However, there is no prior art that discloses the hydrolysis of water-insoluble epoxides to prepare the corresponding diol, in the absence of a solvent, under ambient conditions, using a solid acid catalyst or ion exchange resin.
It would be desirable to have a process for the hydration of water- insoluble epoxides that does not require solvent, or the cost of energy to provide heat. The present invention presents such a process.
SUMMARY OF THE INVENTION This invention describes a process for hydrolyzing a water-insoluble epoxide of the general formula
or
O
/ \ HC CH
\ / Z
II
wherein, Ri and R2 independently are selected from the group consisting of C3 or higher saturated or unsaturated alkyl or aryl groups, which are substituted or unsubstituted, and wherein Z is C3 or higher saturated or unsaturated alkyl or aryl groups, which are substituted or unsubstituted;
said process comprising:
contacting the water-insoluble epoxide with water in the presence of a solid acidic catalyst or an ion exchange resin at ambient conditions for a time sufficient to produce the corresponding diol.
DETAILED DESCRIPTION OF THE INVENTION The present invention discloses a process for preparing diols from water-insoluble epoxides. 4-vinylcyclohexene-1,2-epoxide (represented by compound 1) was hydrolyzed to prepare 4-vinylcyclohexene-1 ,2-diol ( represented by the compound 2) with cationic exchange resin or solid acidic catalyst in water at ambient conditions.
catalyst
The epoxides that are useful in the present invention are those C3 to C12 substrates having an epoxide moiety. These include, but are not limited to of 4-vinylcycIohexene-1,2-epoxide, 1 ,2-cyclododecane epoxide and 1,2-cyclohexane epoxide. Although these epoxides are not soluble in water, the process of the present invention can be used without solvent and at ambient conditions.
One embodiment of the present invention is the hydrolysis of 4- vinylcyclohexene-1 ,2-epoxide to 4-vinylcyclohexene-1 ,2-diol using heterogeneous catalysts, in water, without solvent, and at ambient condition. The ability to carry out the process at ambient conditions reduces the production cost of diol dramatically, which in turn is used as a co-monomer for polyester and polyamide production.
Another embodiment of the present invention is the hydrolyses of 1 ,2-cyclododecane epoxide and 1 ,2-cyclohexane epoxide to their corresponding diols.
In the process of the present invention, a vessel is charged with a solid acid catalyst or ion exchange resin, water and a water insoluble epoxide. The mixture is agitated, preferable vigorously, at ambient conditions.
The solid acid catalysts that are suitable for the present invention are silica alumina and TiF4/Siθ2. It has also been discovered that inexpensive ion exchange resins that are available for water treatment can be used to hydrolyze the epoxide with high conversion and yield.
The ion exchange resins that are suitable for the present invention are Amberlyst-15, Dowex-HGR-W2H, Dowex-M33, Dowex-MSC-1-H, Dowex M-31, and NAFION.
Generally, the quality of the water that can be used for the present process is not significant. Untreated water may be used. Deionized water is preferred to increase the catalyst activity. The molar ratio of water to epoxides is in the range of 8:1 - 20:1. The contact time is about 5 hours.
EXAMPLES
Catalyst A: Duolite ES-26 (strong acid cation resin, sodium form) was treated with dilute sulfuric acid, followed by Dl water to neutral.
Catalyst B: Amberlyst (strong acid cation resin) was washed with Dl water to neutral.
Catalyst C: 20 g. Silica (380 m2 /g) was dispersed in 250 ml Dl water under stirring. 0.8 g. TiF4 was added into the suspension. The pH of the suspension was adjusted by HCI solution to 8. The mixture was stirred at ambient condition. The gel was filtered and washed with Dl water to neutral. The solid was dried in a 120°C oven.
Example 1: Hydrolysis of 4-Vinylcvclohexene-1 ,2-epoxide
A 250 ml slurry reactor was loaded with the catalyst (25 g; 16 wt%), deionized water (100g; 5.55 mol) and 4-vinylcyclohexene-1,2-epoxide (75g; 0.6 mol). The mixture was vigorously stirred at ambient condition for 5 hours. An end of run sample was taken for analysis by NMR. The conversion of epoxide (compound 1) was > 99%, and the yield of diol (compound 2) was >95%.
Example 2: Hydrolysis of 1 ,2-cvclohexne epoxide
1 ,2-cyclohexene epoxide (3.1g, 0.027mol), and deionized water (4g, 0.2) and Amberlyst-15 (1g, 12 wt%) were added into a 20 ml of glass vial with a magnetic stir. The mixture was stirred vigorously for 5 hours. The final product was trans-1,2-cyclohexanediol. The conversion of epoxide was > 99%, and the yield of diol was >95%.
Example 3: Hydrolysis of 1.2-cvclododecane epoxide
1 ,2-cyclododecane epoxide (3.6g, 0.02mol), and deionized water (4g, 0.2) and Nafion® SAC-13 (1g, 12 wt%) were added into a 20 ml of glass vial with a magnetic stir. The mixture was stirred vigorously for 48 hours. The final product was trans-1 ,2-cyclododecane-1 ,2-diol. The conversion of epoxide was > 50%, and the yield of diol was >95%.
Claims
1. A process for hydrolyzing a water insoluble epoxide of the general having the formula
or
O
/ \ HC CH
\ /
Z
wherein, Ri and R2 independently are selected from the group consisting of C3 or higher saturated or unsaturated alkyl or aryl groups, which are substituted or unsubstituted, and wherein Z is C3 or higher saturated or unsaturated alkyl or aryl groups, substituted or unsubstituted; said process comprising: contacting the water insoluble epoxide with water in the presence of a solid acidic catalyst or an ion exchange resin at ambient conditions for a time sufficient to produce the corresponding diol.
2. The process of claim 1 wherein said water-insoluble epoxide is selected from the group consisting of 4-vinylcyclohexene 1 ,2-epoxide, 1,2-cyclohexane epoxide, and 1 ,2-cyclododecane epoxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/396,084 US20040192976A1 (en) | 2003-03-24 | 2003-03-24 | Process for hydrolyzing water-insoluble epoxides |
| US10/396,084 | 2003-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004085355A1 true WO2004085355A1 (en) | 2004-10-07 |
Family
ID=32988721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2004/008103 Ceased WO2004085355A1 (en) | 2003-03-24 | 2004-03-16 | A process for hydrolyzing water-insoluble epoxides |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20040192976A1 (en) |
| WO (1) | WO2004085355A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807472A (en) * | 2012-08-21 | 2012-12-05 | 南京工业大学 | Novel process for synthesizing 1, 2-cyclohexanediol by hydrolyzing epoxy cyclohexane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4620044A (en) * | 1985-10-16 | 1986-10-28 | Mobil Oil Corporation | Hydrolysis of olefin oxides to glycols |
| JPH0446133A (en) * | 1990-06-12 | 1992-02-17 | Daicel Chem Ind Ltd | Production of cyclohexane-1,2-diol |
| JP2002316959A (en) * | 2001-04-16 | 2002-10-31 | Ube Ind Ltd | Method for producing vicinal diol compound |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3062889A (en) * | 1962-11-06 | Process for purifying acetaldehyde | ||
| US4165440A (en) * | 1976-10-06 | 1979-08-21 | Shell Oil Company | Catalytic hydration of ethylene oxide to ethylene glycol |
| US4107221A (en) * | 1977-07-28 | 1978-08-15 | The Dow Chemical Company | Removal of olefin oxide from chlorinated solvents |
| JPH09508136A (en) * | 1994-01-31 | 1997-08-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing alkylene glycol |
| CZ161198A3 (en) * | 1995-11-23 | 1998-09-16 | Shell Internationale Research Maatschappij B. V. | Process for preparing alkylene glycols |
| US6312805B1 (en) * | 2000-02-11 | 2001-11-06 | E.I. Du Pont De Nemours And Company | Cationic dyeability modifier for use with polyester and polyamide |
-
2003
- 2003-03-24 US US10/396,084 patent/US20040192976A1/en not_active Abandoned
-
2004
- 2004-03-16 WO PCT/US2004/008103 patent/WO2004085355A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4620044A (en) * | 1985-10-16 | 1986-10-28 | Mobil Oil Corporation | Hydrolysis of olefin oxides to glycols |
| JPH0446133A (en) * | 1990-06-12 | 1992-02-17 | Daicel Chem Ind Ltd | Production of cyclohexane-1,2-diol |
| JP2002316959A (en) * | 2001-04-16 | 2002-10-31 | Ube Ind Ltd | Method for producing vicinal diol compound |
Non-Patent Citations (6)
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| Publication number | Publication date |
|---|---|
| US20040192976A1 (en) | 2004-09-30 |
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