WO1994024083A1 - Procede de production d'acide adipique - Google Patents
Procede de production d'acide adipique Download PDFInfo
- Publication number
- WO1994024083A1 WO1994024083A1 PCT/JP1993/000457 JP9300457W WO9424083A1 WO 1994024083 A1 WO1994024083 A1 WO 1994024083A1 JP 9300457 W JP9300457 W JP 9300457W WO 9424083 A1 WO9424083 A1 WO 9424083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nitric acid
- dihydroxycyclohexane
- formula
- group
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
-
- 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
Definitions
- the present invention relates to a conventional technique for producing adipic acid from cyclohexenoxide.
- Netherlands Patent Application No. 6601148 describes a method for producing adipic acid by oxidizing a 1,2-dioxycyclohexane compound in a nitric acid aqueous solution containing a water-soluble vanadium salt.
- adipic acid by nitric acid oxidation of cyclohexanol and / or cyclohexanone, the advantage is that nitric acid is less consumed in the form of nitrogen and nitrous oxide. Proposals have been made as an effective method.
- Example 1 describes an example using cyclohexene oxide as a raw material.However, despite the reaction using nitric acid having a high concentration of 70%, the yield of adipic acid is low. At 94%, 0.16 mol of nitric acid per mol of organic raw material was consumed in the form of nitrous oxide and nitrogen. In Example 4, 1,2-dihydroxycyclohexane was used as a raw material. Although the reaction was also performed using nitric acid at a high concentration of 70%, the yield of adipic acid was 92%, and 0.12 mole of the organic raw material was 0.12 mole. Nitric acid is consumed in the form of nitrous oxide and nitrogen, and although the effect is improved, it is not always satisfactory.
- a first object of the present invention is to overcome the disadvantages of the above-mentioned Netherlands Patent Application No. 6601148, increase the yield of adipic acid, suppress the production of nitrous oxide and nitrogen, and It is to establish a production method of adipic acid which is highly valuable.
- the present inventors have conducted intensive studies and have accomplished the present invention. That is, the method comprises the following steps (a) and (b) for producing adipic acid from cyclohexene oxide.
- the present inventors have conducted intensive studies on the oxidation of 1,2-dihydroxycyclohexane, and have found that, together with vanadium, metals belonging to Group IB, Group EB, Group IV, Group V, Group VIB, Group HB, and Group Corb.
- adipic acid By oxidizing the diol in an aqueous solution of nitric acid containing one or more of the above, adipic acid can be obtained in high yield, and surprisingly, the production of nitrous oxide and nitrogen is substantially reduced. And found that it could be suppressed to a negligible amount.
- Examples of the metal used together with vanadium in the present invention include, for example, Cu, Ag and the like as the I group, Zn. Group IV, Sn, Pb, Ti, Zr, etc., Group V, Sb, Pb, Nb, Ta, etc., Group VIB, Cr, Mo, etc., Group WB, Mn etc. Can be exemplified.
- the metal may be in any form as long as it is soluble in nitric acid, such as simple metals, inorganic salts, organic acid salts, and complexes.
- the amount of the catalyst used is relatively wide, and the total weight of the metals used can range from 0.01% by weight of the nitric acid aqueous solution used to the reaction to the saturation solubility, but is usually used in the range of 5% by weight or less. .
- these oligomers of formula (1) are easily oxidized by nitric acid to produce adipic acid in high yield, and in addition to the conventional nitric acid oxidation of cyclohexanol and cyclohexanone.
- the number n of the oligomer of the formula (1) is particularly preferably in the range of 1 to 5 on average, and if it is larger than this range, the yield of adipic acid is deteriorated.
- the oxidation of the oligomer of formula (1) with a mixture of 1,2-dihydroxycyclohexane in an aqueous nitric acid solution reduces the nitric acid consumption and increases the amount of adipic acid.
- the reason is not clear, but it is better to oxidize a mixture of the oligomer of the formula (1) and 1,2-dihydroxycyclohexane in an aqueous nitric acid solution.
- the amount of generated nitrous oxide is reduced and the adipic acid yield is improved as compared with the arithmetic average value when the reaction is performed alone.
- the effect is strong at an arbitrary mixing ratio.
- the weight ratio of the oligomer of the formula (1) to 1,2-dihydroxycyclohexane is 60:40 to 1:99.
- the range is remarkable.
- the oligomer of the formula (1) is formed in the step (a) of hydrating cyclohexenoxide, there is no problem with the addition of 1,2-dihydroxycyclohexane or the like.
- oxidizing nitric acid to nitric acid a technology was established that could convert it to adipic acid in an extremely high yield and minimize the amount of nitric acid that would be lost at that time.
- the 1,2-dihydroxycyclohexane to be mixed may be either a cis-form or a trans-form, or may be a mixture.
- the ratio can be arbitrarily set.
- nitric acid oxidation is carried out by mixing the oligomer of the formula (1) or the oligomer of the formula (1) with 1,2-dihydroxycyclohexane, vanadium or vanadium and a group IB are used as catalysts. It is further preferred to use one or more of the metals H, HB, m, W, V, VIB, ⁇ MB and II.
- the metal may be in any form as long as it is soluble in nitric acid, such as simple metals, inorganic salts, organic acid salts, and complexes.
- the amount of catalyst used is relatively wide, and The total weight can be from 0.1% by weight of the nitric acid aqueous solution used for the reaction to the saturation solubility, but is usually used in the range of 5% by weight or less.
- the oxidation method with less generation of nitrogen and nitrous oxide has a big advantage such as lower consumption of nitric acid, but there are slight inconveniences in industrial implementation. Need to be considered.
- NOX NO or NO 2
- the gas volume will increase significantly and large equipment will be required for its recovery.
- the present inventors have conducted intensive studies on this point, and have studied the reaction of adipic acid by oxidizing 1,2-dihydroxycyclohexane and Z or the oligomer represented by the formula (1) with nitric acid. It has been found that distilling NOx out of the reaction system can be suppressed by reacting while blowing oxygen or an oxygen-containing gas into the system. Further, it was also found that the adipic acid yield was improved at this time.
- the amount of water to be used may be not less than the theoretical amount, but usually the range of 0.25 to 10 times the weight of cyclohexene oxide is applied. If it is smaller than this range, the reaction will be extremely slow. If it is larger than this range, a large amount of energy will be required to separate the excessively used water.
- a catalyst that promotes the reaction of hydration of cyclohexenoxide may be used, and a general acid or base catalyst (for example, US Pat. No. 3,576,890, German Patent 1,793,244) No. 7, etc.) and inorganic solid acids such as zeolite and montmorillonite (US Pat. No. 4,011,278, Japanese Patent Application Laid-Open No. 414,449, etc.) Zion exchange resin ( BC Ranu and R. Chakraborty, Synthetic Consicat ions, 20 (12), 1751-1767 (1990), etc.
- a catalyst having the ability to hydrate epoxides can be used.
- the amount used depends on the type and conditions of the catalyst, but usually, an amount of 0.1 mol% or more of cyclohexene oxide is used as the acid or base.
- the temperature of the hydration reaction is not particularly limited, it is usually carried out in the range of normal temperature to 200 ° C.
- the conversion is usually carried out in a conversion range of 50% or more, more preferably 70% or more.
- step (a) when the conversion rate of the hexoxenoxide is not 100%, 1,2-dihydroxycyclohexane and the oligomer represented by the formula (1) as well as the cyclohexenoxide can be used. It is obtained as a mixture containing According to the study by the present inventors, even when a mixture of the oligomer of the formula (1), 1,2-dihydroxycyclohexane and cyclohexenoxide is oxidized in an aqueous nitric acid solution, the oligomer of the formula (1) is oxidized.
- the reaction temperature in the step (b) is low, the reaction rate is slow, and when it is too high, the side reaction increases, so that it is 20 to 120 ° C, and more preferably 30 to 90 ° C.
- the nitric acid used in the step (b) can be used in a wide range of 10 to 80% by weight, but is more preferably in a range of 30 to 70% by weight.
- the molar ratio of the cyclo ring and nitric acid in the raw materials used is usually 2 or more, and more preferably 3 or more.
- the reaction solution obtained in the step (a) can be directly fed into the step (b).
- excess water in the step (a) is evaporated. And then concentrated and used in step (b).
- the separated 1,2-dihydroxycyclohexane is separated. Separation residues containing mouth hexane and Z or cyclohexenoxide (1) oligomers
- by-products other than the oligomer of formula (1) formed in the step (a) for example, 1,2-dihydroxycyclohexane, which is formed by hydration with nitric acid, are used.
- 1,2-dihydroxycyclohexane and / or cyclohexene oxide and / or the formula (1) may be used in the step (b) as long as the effects of the present invention are not significantly impaired.
- reaction is carried out by adding a solvent inert to the reaction such as water to the mixture of the raw material of the oligomer (1) of the formula (1) and Z or 1,2-dihydroxycyclohexane and di- or cyclohexenoxide. You can also.
- a solvent inert such as water
- the oligomer represented by the formula (1) 1,2-dihydroxycyclohexane, which is produced by a method other than the hydration of cyclohexene oxide, may be added.
- other methods for preparing the oligomer of the formula (1) include dehydration condensation of 1,2-dihydroxycyclohexane, ring-opening polymerization of cyclohexene oxide, and 1,2-dihydroxycyclohexane and cycle
- Addition of xenoxide, substitution reaction with OH group such as di (2-chlorocyclohexyl) ether, and hydrogenation of catechol are examples of other methods for producing 2-dihydroxycyclohexane.
- the reaction can be applied in either a batch system or a continuous system.
- a type conventionally performed with cyclohexanol and cyclohexanone can be suitably used.
- the yield of adipic acid in the Examples and Comparative Examples is based on the amount of the silicone contained in the mixture of the oligomer of the formula (1), 1,2-dihydroxycyclohexane and cyclohexenoxide in the raw materials used. It is shown in molar yield based on the ring.
- Example 1 Hydration of cyclohexenoxide> 100 g of water, 1 g of cation exchange resin (Mitsubishi Kasei, Daiaion SK1BH) 1 O gr is charged into the reactor, and the mixture is stirred at 80 ° C. gr was dropped over about 30 minutes, and then stirring was continued for 30 minutes.
- ⁇ Oxidation with nitric acid aqueous solution Of this solution obtained by concentrating water to 20% by weight under reduced pressure, 30.Ogr is contained, and 0.230% by weight of ammonium metavanadate is contained. It was added over 30 minutes to 250 gr of 60% nitric acid held in C. After that, the reaction was continued at 80 ° C. for 30 minutes, and the reaction products and released gas components were analyzed. Adipic acid was obtained in a yield of 95.7%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.039 Kg per 1 Kg of adipic acid produced. Amount. The amount of released NOX was 3.3 times the number of moles of cyclocycle in the raw materials used.
- Example 2 In the oxidation with a nitric acid aqueous solution, the reaction was carried out in the same manner as in Example 2 except that 60% nitric acid containing only 0.230% by weight of ammonium metavanadate was used. Adipic acid was obtained in a yield of 95.8%, and the amount of nitric acid lost as nitrogen and nitrous oxide was 0.080 kg per 1 kg of adipic acid produced. there were. The amount of released NOX was 3.0 times the number of moles of cyclo ring in the raw materials used.
- cyclohexenoxide 2 is used as a raw material.
- Example 2 In the oxidation with an aqueous nitric acid solution, a method similar to that of Example 2 was used except that air was blown into the aqueous nitric acid solution at a rate of 70 N liters / hour through a thin tube at the same time as the addition of 1,2-dihydroxycyclohexane. Was used to carry out the reaction.
- Adipic acid was obtained in a yield of 96.6%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.045 kg per 1 kg of adipic acid produced. Amount. Also, the amount of released NO X was equivalent to 1.9 times the number of moles of the cyclo ring in the raw materials used.
- Adipic acid was obtained in a yield of 94.8%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.051 Kg for 1 Kg of adipic acid produced Amount.
- the amount of released NOX was 3.2 times the number of moles of the cyclo ring in the raw materials used.
- the reaction was carried out in the same manner as in Example 28 except that air was blown into the aqueous nitric acid solution at a rate of 70 N liter / hour through a thin tube.
- Adipic acid was obtained in a yield of 95.2%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.052 Kg for 1 Kg of adipic acid produced. Amount.
- the amount of released NOX was 1.7 times the number of moles of cyclo ring in the raw materials used.
- the reaction was carried out in the same manner as in Example 33 except that air was blown into the nitric acid aqueous solution at a rate of 70 N liter / hour through a thin tube.
- Adipic acid was obtained in a yield of 95.9%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.052 Kg for 1 Kg of adipic acid produced. Amount.
- the amount of released NOX was equivalent to 1.8 times the number of moles of cyclo ring in the raw materials used.
- the reaction was carried out in the same manner as in Example 43 except that air was blown into the aqueous nitric acid solution at a rate of 70 N liter / hour through a thin tube.
- Adipic acid is obtained in a yield of 91.4%, and the amount of nitric acid lost as nitrogen and nitrous oxide is equivalent to 0.096 Kg for 1 Kg of adipic acid produced Quantity.
- the amount of released NOx was 1.8 times the number of moles of the cyclo ring in the raw materials used.
- the reaction was carried out in the same manner as in Example 1 except that the reaction temperature for oxidation in a nitric acid aqueous solution was 60. Adipic acid was obtained in a yield of 96.6%, and the amount of nitric acid lost as nitrogen and nitrous oxide was 0.038 Kg for 1 Kg of adipic acid produced. there were. The amount of released NOX was 3.3 times the number of moles of the cyclo ring in the raw materials used.
- the reaction was carried out in the same manner as in Example 2 except that the reaction temperature for oxidation in a nitric acid aqueous solution was 60. Adipic acid was obtained in a yield of 97.2%, and the amount of nitric acid lost as nitrogen and nitrous oxide was equivalent to 0.038 Kg for 1 Kg of adipic acid produced. Amount. The amount of released NOX was 3.4 times the number of moles of the cyclo ring in the raw materials used. Industrial applicability
- adipic acid can be obtained in a high yield from cyclohexenoxide, the amount of nitric acid consumed at that time can be extremely small, and inexpensive adipic acid can be produced.
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Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93908073A EP0645363B1 (en) | 1993-04-09 | 1993-04-09 | Process for producing adipic acid |
DE69319343T DE69319343T2 (de) | 1993-04-09 | 1993-04-09 | Verfahren zur herstellung von adipinsäure |
PCT/JP1993/000457 WO1994024083A1 (fr) | 1993-04-09 | 1993-04-09 | Procede de production d'acide adipique |
US08/190,195 US5455375A (en) | 1993-04-09 | 1993-04-09 | Process for preparing adipic acid |
CA002114635A CA2114635C (en) | 1993-04-09 | 1993-04-09 | Process for preparing adipic acid |
KR1019940700366A KR0127337B1 (ko) | 1993-04-09 | 1993-04-09 | 아디프산의 제조 방법 |
KR1019940700366A KR950700870A (ko) | 1993-04-09 | 1994-02-03 | 아디핀산의 제조 방법(process for preparing adipic acid) |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP1993/000457 WO1994024083A1 (fr) | 1993-04-09 | 1993-04-09 | Procede de production d'acide adipique |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994024083A1 true WO1994024083A1 (fr) | 1994-10-27 |
Family
ID=14070217
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1993/000457 WO1994024083A1 (fr) | 1993-04-09 | 1993-04-09 | Procede de production d'acide adipique |
Country Status (6)
Country | Link |
---|---|
US (1) | US5455375A (ja) |
EP (1) | EP0645363B1 (ja) |
KR (2) | KR0127337B1 (ja) |
CA (1) | CA2114635C (ja) |
DE (1) | DE69319343T2 (ja) |
WO (1) | WO1994024083A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006241001A (ja) * | 2005-02-28 | 2006-09-14 | Nof Corp | グリセリンモノ(メタ)アクリレートの製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235932B1 (en) | 1999-06-18 | 2001-05-22 | Chemintel (India) Private Ltd. | Process for preparation of adipic acid |
CN102464579B (zh) * | 2010-11-05 | 2014-03-12 | 中国石油化学工业开发股份有限公司 | 自环己烷氧化副产物制备己二酸的方法 |
CN113563176B (zh) * | 2021-08-25 | 2022-12-20 | 浙江工业大学 | 一种Cu(II)/硝酸二元催化体系催化O2氧化环己烯一步合成己二酸的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60239438A (ja) * | 1984-05-15 | 1985-11-28 | Asahi Chem Ind Co Ltd | アジピン酸の製造方法 |
JPS61501630A (ja) * | 1984-03-28 | 1986-08-07 | ユニオン、カ−バイド、コ−ポレ−シヨン | メタレ−ト含有固形物を使用するアルキレングリコ−ルの製造方法 |
JPH03236337A (ja) * | 1990-02-13 | 1991-10-22 | Daicel Chem Ind Ltd | 1,2―シクロヘキサンジオールの製造方法 |
JPH0446133A (ja) * | 1990-06-12 | 1992-02-17 | Daicel Chem Ind Ltd | シクロヘキサン―1,2―ジオールの製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1518242A1 (de) * | 1962-01-24 | 1969-02-13 | Vickers Zimmer Ag | Verfahren zur Herstellung von aliphatischen Dicarbonsaeuren |
NL6601148A (ja) * | 1965-03-26 | 1966-04-25 | ||
BE757061A (fr) * | 1969-10-06 | 1971-04-05 | Rhone Poulenc Sa | Procede d'obtention d'acide adipique |
US4254283A (en) * | 1979-06-07 | 1981-03-03 | Monsanto Company | Process for preparing adipic acid with recovery of glutaric and succinic acids |
US4605790A (en) * | 1985-05-21 | 1986-08-12 | E. I. Du Pont De Nemours And Company | Phenol from coal and biomass |
JP2562150B2 (ja) * | 1986-10-23 | 1996-12-11 | バスフ アクチェンゲゼルシャフト | シクロヘキシルヒドロペルオキシドを含有する反応混合物の後処理法 |
JPH0441449A (ja) * | 1990-06-07 | 1992-02-12 | Daicel Chem Ind Ltd | シクロヘキサン―1,2―ジオールの製造方法 |
US5321157A (en) * | 1992-09-25 | 1994-06-14 | Redox Technologies Inc. | Process for the preparation of adipic acid and other aliphatic dibasic acids |
-
1993
- 1993-04-09 CA CA002114635A patent/CA2114635C/en not_active Expired - Lifetime
- 1993-04-09 KR KR1019940700366A patent/KR0127337B1/ko active
- 1993-04-09 DE DE69319343T patent/DE69319343T2/de not_active Expired - Lifetime
- 1993-04-09 WO PCT/JP1993/000457 patent/WO1994024083A1/ja active IP Right Grant
- 1993-04-09 US US08/190,195 patent/US5455375A/en not_active Expired - Lifetime
- 1993-04-09 EP EP93908073A patent/EP0645363B1/en not_active Expired - Lifetime
-
1994
- 1994-02-03 KR KR1019940700366A patent/KR950700870A/ko not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61501630A (ja) * | 1984-03-28 | 1986-08-07 | ユニオン、カ−バイド、コ−ポレ−シヨン | メタレ−ト含有固形物を使用するアルキレングリコ−ルの製造方法 |
JPS60239438A (ja) * | 1984-05-15 | 1985-11-28 | Asahi Chem Ind Co Ltd | アジピン酸の製造方法 |
JPH03236337A (ja) * | 1990-02-13 | 1991-10-22 | Daicel Chem Ind Ltd | 1,2―シクロヘキサンジオールの製造方法 |
JPH0446133A (ja) * | 1990-06-12 | 1992-02-17 | Daicel Chem Ind Ltd | シクロヘキサン―1,2―ジオールの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0645363A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006241001A (ja) * | 2005-02-28 | 2006-09-14 | Nof Corp | グリセリンモノ(メタ)アクリレートの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69319343T2 (de) | 1999-03-25 |
EP0645363B1 (en) | 1998-06-24 |
US5455375A (en) | 1995-10-03 |
CA2114635A1 (en) | 1994-04-26 |
DE69319343D1 (de) | 1998-07-30 |
EP0645363A4 (en) | 1995-11-02 |
KR950700870A (ko) | 1995-02-20 |
CA2114635C (en) | 2000-05-23 |
EP0645363A1 (en) | 1995-03-29 |
KR0127337B1 (ko) | 1998-04-01 |
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