GB2025970A - Process for preparation of glycidyl ester of acrylic acid - Google Patents
Process for preparation of glycidyl ester of acrylic acid Download PDFInfo
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- GB2025970A GB2025970A GB7925120A GB7925120A GB2025970A GB 2025970 A GB2025970 A GB 2025970A GB 7925120 A GB7925120 A GB 7925120A GB 7925120 A GB7925120 A GB 7925120A GB 2025970 A GB2025970 A GB 2025970A
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- acid
- epihalohydrin
- acrylic acid
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- alkali metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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Abstract
In the reaction of acrylic or methacrylic acid with an epihalohydrin to produce a glycidyl ester, problems have arisen with use of organic solvents and with the formation of water in the reaction medium when the starting acid has been neutralised with an alkali metal salt. These problems are counteracted by adding the starting acid gradually to a stoichiometric excess of epihalohydrin containing a stoichiometric excess of alkali metal carbonate and/or bicarbonate in suspension therein, distilling a water-epihalohydrin azeotrope as the water is formed, and then introducing a catalyst for the esterification carrying out the esterification with the residual epihalohydrin. The esterification reaction is carried out substantially anhydrously and the process is carried out without the use of an organic solvent.
Description
SPECIFICATION
Process for preparation of glycidyl ester of acrylic acid
The present invention reiates to a process for preparing a glycidyl ester of acrylic acid or methacrylic acid by reacting an alkali metal salt of acrylic acid or methacrylic acid with an epihalohydrin.
As the conventional process for the preparation of giycidyl ester of acrylic acid or methacrylic acid (hereinafter referred to as "(metha)acrylic acid"), there are known a process in which an alkali metal salt of (metha)acrylic acid is reacted with an excessive amount of epichiorohydrin in the presence of a catalyst such as a quaternary ammonium salt and a process in which (metha)acrylic acid is reacted with epichlorohydrin in the presence of a catalyst such as a quaternary ammonium salt.The former process is defective in that concentration of an aqueous solution of the alkali metal salt of (metha)- acrylic acid and drying of the alkali metal salt of (metha)acrylic acid obtained thereby requires troublesome operations and a long time, and that if the alkali metal salt of (metha) acrylic acid which is not sufficiently dried is used and reacted with epichlorohydrin, glycerin-a- dichlorohydrin is formed as a by-product and since separation of such by-product is difficult by distillation or the like, the purity and yield of the product are reduced. In the latter process, the reaction is considerably violent and there cannot be avoided a defect that a chlorohydrin ester of (metha)acrylic acid and glycerin-a-dichlorohydrin are formed in large quantities as by-products.As means for overcoming this defect, there has been proposed a process in which the chlorohydrin ester of (metha)acrylic acid or glycerin-a- dichlorohydrin is reacted with an alkali. However, in this process, the steps becomes complicated and troublesome, and the yield or purity of the resulting glycidyl ester is still insufficient.
As a modification of the former process in which the salt of (metha)acrylic acid is isolated and used for the reaction, there has been proposed a process in which (metha)acrylic acid is neutralized with an alkali in an organic solvent to form an alkali metal salt or (metha)-acrylic acid and it is then reacted with epichlorohydrin to form a glycidyl ester. For example, (metha)acrylic acid is neutralized with an alkali metal salt in N,Ndimethylformamide andes then reacted with epichlorohydrin in the presence of sodium iodide as a catalyst (see Japanese Patent Publication No.
18525/68). Futhermore, there are known a process in which (metha)acrylic acid is neutralized with an alkali metal salt in a high-boiling-point organic solvent such as sulforane or its derivative and is then reacted with epichlorohydrin (see
Japanese Patent Application Laid-Open
Specification No. 135914/74) and a process in which (metha)acrylic acid is neutralized with an aikali metal salt in an unreactive solvent such as benzene or toluene, water is removed by azeotropic distillation and the neutralized acid is then reacted with epichiorohydrin (see Japanese
Patent Publication No. 7887/65 and Japanese
Patent Publucation No. 47366/72). When (metha)-acrylic acid is neutralized with an alkali metal salt in an organic solvent such as N,Ndimethylformamide or sulforane, since water formed by neutralization is present in the reaction mixture, an undesirable side reaction takes place, resulting in reduction of the yield and purity of the glycidyl ester. Accordingly, such process is not suitable for the industrial production of the glycidyl ester.In the process where neutralization is carried out in such a solvent as benzene or toluene, though water formed by the neutralization is removed from the reaction mixture by azeotropic distillation, since the organic solvent should be used in such a large amount as 10 to 1 7 times the amount of the organic acid, the speeds of the neutralization reaction and the reaction of the alkali metal salt of (metha)acrylic acid with epichlorohydrin are drastically lowered and a long time is necessary for completion of the reaction. Moreover, steps of recovering the organic solvent used in such a large amount and separating unreacted epichlorohydrin from the organic solvent become indispensable. Therefore, this process is not preferred from the industrial viewpoint.
Under such circumstances, processes not using an organic solvent have been developed and proposed. For example there can be mentioned a process in which (metha)-acrylic acid is charged together with a large excess of epichlorohydrin and an alkali metal carbonate and reaction is carried out under heating in the presence of a catalyst (see Japanesev Patent Publication No.
24363/63) and a process in which an aqueous solution of an alkali metal salt of (metha)acrylic acid is gradually added in an excessive amount of epichlorohydrin under such conditions that azeotropic distillation of water and epichlorohydrin is caused, and water is removed from the reaction mixture by azeotropic distillation (see Japanese
Patent Application Laid-Open Specification
No. 760 12/75. According to the former process, (metha)acrylic acid is reacted with the alkali metal carbonate and also competitive reaction of addition to epichlorohydrin is caused. Accordingly, by-products such as a chlorohydrin ester of methacrylic acid and glycerin-cr-dichlorohydrin are formed in large quantities.As pointed out hereinbefore, separation of these by-products from the glycidyl ester of (metha)acrylic acid is very difficult and the overall yield and purity of the glycidyl ester of (metha)acrylic acid are reduced. In the latter process, since an alkali metal salt af (metha)acrylic acid should be separately prepared, the process steps become complicated and troublesome, and since a large quantity of water should be removed by azeotropic distillation, side reactions are readily caused and a long time is required for completion of the reaction.
The present invention relates to a process for preparing a glycidyl ester of (metha)acrylic acid by reacting an alkali metal salt of (metha)acrylic acid with an epihalohydrin, which is characterized in that neutralization of (metha)acrylic acid with an alkali compound is not carried out by using an organic solvent but in the epihalohydrin that is used as the starting substance. According to the process of the present invention, the abovementioned defects involved in the process using an organic solvent are overcome and eliminated and the intended glycidyl ester of (metha)acryiic acid can be prepared in a high yield industrially advantageously.
More specifically, in accordance with the present invention, there is provided a process for preparing a glycidyl ester of (metha)acrylic acid, which comprises suspending an alkali metal carbonate and/or bicarbonate in an amount larger than the amount equivalent to (metha)acrylic acid in an epihalohydrin, adding gradually (metha)acrylic acid to the suspension heated at a desired temperature, reacting (metha)acrylic acid with said carbonate and/or bicarbonate under such conditions that water formed by the reaction is distilled off from the reaction mixture in the form of an azeotropic mixture with the epihalohydrin, thereby to form an alkali metal salt of (metha)acrylic acid, then adding a catalyst to the reaction mixture where the neutralization has been completed, and reacting the alkali metal salt of (metha)acrylic acid with the epihalohydrin to form a glycidyl ester of (metha)acrylic acid having a high purity in a high yield.
According to the present invention, disadvantages involved in the use of an unreactive organic solvent are eliminated and furthermore, disadvantages caused by reacting (metha)acrylic acid, an alkali metal carbonate and/or bicarbonate and an epihalohydrin simultaneously are eliminated. In the process of the present invention, since an alkali metal carbonate and/or bicarbonate is suspended in an epihalohydrin and (metha)acrylic acid is gradually added to this suspension, the neutralization reaction: is - advanced slowly successively and occurrance of troubles frequentiy caused by violent neutralization, such as blowing and insufficient agitation, can be effectively prevented.Moreover, formation of a halohydrin ester of (metha)acrylic acid or a glycerin-cr-dihalohydrin as a by-product is not substantially caused at all. Still further, since water formed by the reaction is immediately removed from the reaction mixture by azeotropic distillation with the epihalohydrin, the reaction mixture is kept substantially anhydrous throughout the reaction, and there is attained an advantage that a side reaction due to the presence of water is substantially inhibited.
Still in addition, since an unreactive solvent is not used, the starting materials are not diluted at the step of the esterification reaction, and the esterification reaction is promptly advanced and is completed within a much shortened time.
Futhermore, recovery of the epihalohydrin used in an excessive amount can be accomplished very easily.
As will be apparent from the foregoing illustration, the present invention provides a practical and advantageous process for the preparation of a glycidyl ester of (metha)acrylic acid, and the above-mentioned various advantages can be attained by performing neutralization of (metha)acrylic add. in a suspension of an alkali metal carbonate and/or bicarbonate in an epihalohydrin, adding (metha)acrylic acid to this suspension gradually and adding a catalyst after completion of the neutralization to initiate the esterification reaction.
As the alkali metal carbonate and/or bicarbonate that is used in the present invention, there can be mentioned sodium carbonate, sodium hydrogencarbonate (sodium bicarbonate), potassium carbonate and potassium hydrogencarbonate (potassium bicarbonate). The carbonate and/or bicarbonate is used in an amount larger than the amount equivalent to (metha)acrylic acid.
It is ordinarily preferred that the carbonate and/or bicarbonate be used in an amount of 1.1 to 1.7 equivalents to (metha)acryiic acid.
As the epihalohydrin, epichlorohydrin is especially preferred for attaining the objects of the present invention. However, epibromohydrin and methyl epichlorohydrin can be used as well as epichlorohydrin. It is preferred that the epihalohydrin be used in such an amount that at both the neutralization and esterification steps, the epihalohydrin is present in the reaction mixture in an amount of at least 5 moles per mole of (metha)acrylic acid. If the amount of the epihalohydrin is smaller than 5 moles per mole of (metha)acrylic acid, sufficient agitation becomes difficult because of properties of a slurry of the alkali metal salt of (metha)acrylic acid formed at the neutralization step, and undesirable side reactions are readily caused.Moreover, the reaction speed is reduced at the esterification step and the reaction time is inevitably made longer,- resulting in reduction of the yield of the intended glycidyl ester.
A known catalyst can be used as the catalyst that is added to initiate the esterification reaction.
For example, there can be mentioned tertiary amines such as triethylamine, tributylamine, tr phenyl-amine, dimethylaniline and pyridine, and quaternary ammonium salts such as trimethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride, tetramethyl ammonium chloride and tetramethyl ammonium bromide.
However, catalysts that can be used in the present invention are not limited to those mentioned above. The catalyst is used in an amount customarily adopted for the reaction of this type, that is, 0.01 to 1.5 mole % based on (metha)acrylic acid.
In practising the process of the present invention, it is preferred that a polymerization inhibitor be present in the reaction mixture at the step of neutralization of (metha)acrylic acid. The polymerization inhibitor is selected from known conventional polymerization inhibitors of the quinone and copper types.
The reaction temperature adopted for the neutralization reaction should be high enough to remove water formed by neutralization by azeotropic distillation with the epihalohydrin. The removal of water by azeotropic distillation may be carried out under reduced pressure. For example, is epichlorohydrin is used as the epihalohydrin and the reaction is carried out under atmospheric pressure, the reaction temperature should be higher than 90QC. Under such temperature condition, (metha)acrylic acid is added. If (metha)acrylic acid is added at one time or at a high speed, violent neutralization reaction is caused. Accordingly, sufficient agitation becomes difficult and side reactions are readily caused.
Therefore, it is preferred that (metha)acrylic acid be gradually added. While (metha)acrylic acid is gradually added, water is distilled off in the form of an azeotropic mixture with the epihalohydrin. The epihalohydrin may be separated from the azeotropic mixture and returned to the reaction mixture. After completion of the addition of (metha)acrylic acid, the reaction is continued until water is substantially removed by azeotropic distillation.
When the neutralization has been completed, the above-mentioned catalyst is added to the reaction mixture, and the reaction of the resulting alkali metal salt of (metha)acrylic acid with the epihalohydrin is carried out at 90 to 1 200C. for 1 to 4 hours.
After completion of the reaction, the intended glycidyl ester of (metha)acrylic acid is isolated from the reaction mixture according to customary procedures. For example, the formed alkali halide and the unreacted alkali metal salt are removed by filteration or water washing, the excess of the epihalohydrin is distilled off under reduced pressure, and the glycidyl ester of (metha)acrylic acid is recovered by distillation.
The present invention will now be described in detail by reference to the following Examples.
EXAMPLE 1
A 4-neck flask having an inner capacity of 1 liter was charged with 600.0 g of epichlorohydrin, 66.2 g of anhydrous sodium carbonate and 1 g of hydroquinone monomethyl ether, and the mixture was heated to 11 20C. When the temperature was elevated to 1 120C., 86.1 g of methacrylic acid is dropped from a dropping funnel over a period of 1 hour. Just after initiation of the dropwise addition, the temperature of the reaction mixture was lowered and azeotropic.distillation of water with epichlorohydrin was initiated. When about 30 minutes had passed from the point of termination of the dropwise addition, the temperature rose to 11 20C. and azeotropic distillation was substantially stopped.The liquid obtained by azeotropic distillation comprised 125.6 g of the epichlorohydrin layer and 5.4 g of the aqueous layer. Then, 0.48 g of triethylbenzyl ammonium chloride was added as a catalyst to the reaction mixture, and the reaction was carried out at the same temperature for 2 hours. After termination of the reaction, the reaction mixture was cooled to 200C. and 200 g of water was added to the reaction mixture, and the mixture was agitated for
1 minute. The mixture was allowed to stand still for 2 hours, and the oil layer was separated from the aqueous layer. When the oil layer was analyzed by gas chromatography, it was found that glycidyl methacrylate was obtained in yield
corresponding to 93.0% of the theoretical yield.
Epichlorohydrin was recovered from the oil layer
under reduced pressure and purified glycidyl
methacrylate was then recovered by distillation in an amount corresponding to 77.9 % of the theoretical yield. A part of the formed glycidyl
methacrylate was lost at the step of distillation of
epichlorohydrin and as the preliminary distiliate fraction at the purification step. The purity of the 'product was 98.6 %.
EXAMPLE 2
A 4-neck flask having an inner capacity of 1 liter was charged with 655.0 g of epichlorohydrin,
79.5 g of anhydrous sodium carbonate and 1 g of
hydroquinone monomthyl ether, and the temperature was elevated to 1 1 OOC. When the temperature rose to 11 00C., 72 g of acrylic acid was dropped from a dropping funnel over a period of 1.5 hours. Just after initiation of the dropwise
addition, the temperature of the reaction mixture was lowered and azeotropic distillation of water
with epichlorohydrin was started. When about 20
minutes had passed from the point of termination
of the dropwise addition, the temperature rose to 11 00C. and azeotropic distillation was
substantially stopped.The liquid mixture obtained by the azeotropic distillation comprised 207.8 g of the epichlorohydrin layer and 4.4 g of the aqueous layer. Then, 0.24 g of tetramethyl ammonium chloride was added as a catalyst to the reaction mixture and the reaction was carried out for 1.5
hours at the same temperature. After termination
of the reaction, precipitates were recovered by filtration and washed with epichlorohydrin.
Epichiorohydrin was recovered from the filtrate by distillation under reduced pressure, and purified glycidyl acrylate was obtained by distillation in an
amount corresponding to 83.5 % of the theoretical yield. The purity of the product was 98.2 %.
EXAMPLE 3
A 4-neck flask having an inner capacity of 1 liter was charged with 800.0 g of epichlorohydrin, 33.1 gofanhydroussodium carbonate, 52.51 gof anhydrous sodium carbonate, 52.51 g of sodium hydrogen-carbonate and 1.0 g of hydroquinine monomethyl ether, and the mixture was heated to 1 100C. When the temperature rose to 1 1 OOC., 86.1 g of methacrylic acid was dropped from a dropping funnel over a period of 50 minutes. Just after initiation of the dropwise addition, the temperature of the reaction mixture was lowered and azeotropic distillation of water with epichlorohydrin was started.When about 30
minutes had passed from the point of termination of the dropwise addition, the temperature rose to 1 00C. and the azeotropic distillation was substantially stopped. The liquid obtained by the azeotropic distillation comprised 51.0 g of the epichlorohydrin layer and 5.0 g of the aqueous layer. Then, 0.48 g of triethylbenzyl ammonium chloride was added as a catalyst to the reaction mixture and the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was cooled to 300C., and 250 g of water was added and the mixture was agitated for 2 minutes. Then, the mixture was allowed to stand still for 2 hours and the oil layer was separated from the aqueous layer.Epichlorohydrin was recovered by distillation under reduced pressure, and purified glycidyl methacrylate was obtained by distillation in an amount corresponding to 78.3 % of the theoretical yield. The purity of the product was 98.2 %.
EXAMPLE 4
A 4-neck flask having an inner capacity of 1 liter was charged with 639 g of methyl epichlorohydrin, 66.2 g of anhydrous sodium carbonate and 1 g of hydroquinione monomethyl ether, and the mixture was heated to 1 30C.
When the temperature was elevated to 11300., 86.1 g of methacrylic acid is dropped from a dropping funnel over a period of 50 minutes. Just after initiation of the dropwise addition, the temperature of the reaction mixture was lowered and azeotropic distillation of water with methyl epichlorohydrin was initiated. the methyl epichlorohydrin layer of the azeotropic distillate was recycled to the flask through the reaction.
When about 35 minutes had passed from the point of termination of the dropwise addition, the temperature rose to 11 50C and azeotropic distillation was substantially stopped. The amount of water obtained by azeotropic distillation was 14 g. Then, 1.2 g of tetramethyl ammonium chloride was added as a catalyst to the reaction mixture, and the reaction was carried out at the same temperature for 4 hours. After termination of the reaction, the reaction mixture was cooled to 250C.
and 250 g of water was added to the reaction mixture, and the mixture was agitated for 1 minute. The mixture was allowed to stand still for 2 hours, and the oil layer was separated from the aqueous layer. When the oil layer was analysed by gas chromatography, it was found that P-methyl glycidyl methacrylate was obtained in a yield corresponding to 92.5 % of the theoretical yield.
p-Methyl epichlorohydrin was recovered frnm the oil layer under reduced pressure and purified p- methyl glycidyl methacrylate was then recovered by distillation in an amount corresponding to 75.0 % of the theoretical yield. A part of the formed p- methyl glycidyl methacrylate was lost at the step of distillation of epichlorohydrin and as the preliminary distillate fraction at the purification step. The purity of the product was 98.4 %.
EXAMPLE 5
A 4-neck flask having an inner capacity of 1 liter was charged with 655.0 g of epichlorohydrin, 110 g of anhydrous potassium carbonate and 1 g of hydroquinone monomethyl ether, and the temperature was elevated to 111 00. When the temperature rose to 111 or., 72 g of acrylic acid was dropped from a dropping funnel over a period of 70 minutes. Just after initiation of the dropwise addition, the temperature of the reaction mixture was lowered and azeotropic distillation of water with epichlorohydrin was started. When about 30 minutes had passed from the point of termination of the dropwise addition, the temperature rose to 11 50C. and azeotropic distillation was substantially stopped. The liquid mixture obtained by the azeotropic distillation comprised 98.0 g of the epochiorohydrin layer and 5.1 g of the aqueous layer. Then, 0.46 g of trimethylbenzyl ammonium chloride was added as a catalyst to the reaction mixture and the reaction was carried out for 2 hours at the same temperature. After termination of the reaction, precipitates were recovered by filtration and washed with epichlorohydrin. Epichlorohydrin was recovered from the filtrate by distillation under reduced pressure, and purified glycidyl acrylate was obtained by distillation in an amount corresponding to 73.5% of the theoretical yield.
The purity of the product was 97.8 %.
Claims (10)
1. A process for preparing a glycidyl ester of acrylic acid or methacrylic acid by reacting an alkali metal salt of acrylic acid or methacrylic acid with an epihalohydrin, characterized in that the epihalohydrin is used in an excessive amount larger than than amount equivalent to said acid, a carbonate and/or bicarbonate of an alkali metal is suspended in an amount larger than the amount equivalent to said acid in said epihalohydrin, said acid is gradually added to the suspension, said acid is reacted with said carbonate and/or bicarbonate under such conditions that water formed by reaction is distilled off from the reaction mixture in the form of an azeotropic mixture with the epihalohydrin, thereby to form an alkali metal salt of said acid, and then a catalyst is added to the reaction mixture to react the alkali metal salt of said acid with the epihalohydrin, thereby to form a glycidyl ester of said acid.
2. A process according to claim 1 whereiri the epihalohydrin is epichlorohydrin or p-methyl epichlorohydrin.
3. A process according to claim 1 or 2 wherein the epihaiohydrin is used in an amount of at least 5 moles per mole of said acid.
4. A process according to claim 1,2 or 3 wherein the carbonate and/or bicarbonate of the alkali metal is used in an amount of 1.1 to 1.7 equivalents to said acid.
5. A process according to claim 4 wherein sodium carbonate is used.
6. A process according to any preceding claim wherein as the catalyst to be added to the reaction mixture a quaternary ammonium salt is used.
7. A process according to any preceding claim wherein the reaction of the alkali metal salt of said acid with the epihalohydrin is carried out at 90 to 1200C.
8. A process according to claim 1 wherein the water is distilled off as the azeotrope as the water is formed, the esterification is carried out substantially anhydrously and the process is carried out without the use of a substantial amount of organic solvent other than the epihalohydrin itself.
9. A process according to claim 1, substantially as described in any one of the Examples.
10. An ester of acrylic or methacrylic acid when prepared by a process claimed in any preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8899078A JPS5517307A (en) | 1978-07-21 | 1978-07-21 | Preparation of glycidyl ester of acrylic or methacrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2025970A true GB2025970A (en) | 1980-01-30 |
Family
ID=13958236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7925120A Withdrawn GB2025970A (en) | 1978-07-21 | 1979-07-19 | Process for preparation of glycidyl ester of acrylic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5517307A (en) |
| GB (1) | GB2025970A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0468840A2 (en) * | 1990-07-06 | 1992-01-29 | Elf Atochem S.A. | Process for the selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates so obtained and their use in the synthesis of new polymers |
| US5207874A (en) * | 1989-12-22 | 1993-05-04 | Atochem | Process for the purification of glycidyl (meth)acrylate |
| CN103382193A (en) * | 2012-05-02 | 2013-11-06 | 三菱丽阳株式会社 | Manufacturing method of glycidyl methacrylate or glycidyl acrylate |
| CN109705061A (en) * | 2018-12-28 | 2019-05-03 | 山东广浦生物科技有限公司 | A kind of preparation method of glycidyl methacrylate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002179613A (en) * | 2000-12-08 | 2002-06-26 | Nippon Shokubai Co Ltd | Method and equipment for neutralization |
| JP5011707B2 (en) * | 2004-11-08 | 2012-08-29 | 三菱瓦斯化学株式会社 | Method for producing glycidyl methacrylate |
| JP6044264B2 (en) * | 2012-10-26 | 2016-12-14 | 三菱瓦斯化学株式会社 | Method for producing glycidyl methacrylate |
-
1978
- 1978-07-21 JP JP8899078A patent/JPS5517307A/en active Pending
-
1979
- 1979-07-19 GB GB7925120A patent/GB2025970A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5207874A (en) * | 1989-12-22 | 1993-05-04 | Atochem | Process for the purification of glycidyl (meth)acrylate |
| EP0468840A2 (en) * | 1990-07-06 | 1992-01-29 | Elf Atochem S.A. | Process for the selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates so obtained and their use in the synthesis of new polymers |
| EP0468840A3 (en) * | 1990-07-06 | 1993-10-20 | Atochem | Process for the selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates so obtained and their use in the synthesis of new polymers |
| US5283360A (en) * | 1990-07-06 | 1994-02-01 | Atochem | Selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates, and polymers thereof |
| US5510516A (en) * | 1990-07-06 | 1996-04-23 | Atochem | Process for selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates obtained and their application to the synthesis of new polymers |
| CN103382193A (en) * | 2012-05-02 | 2013-11-06 | 三菱丽阳株式会社 | Manufacturing method of glycidyl methacrylate or glycidyl acrylate |
| CN103382193B (en) * | 2012-05-02 | 2016-08-10 | 三菱丽阳株式会社 | Glycidyl methacrylate or the manufacture method of glycidyl acrylate |
| CN109705061A (en) * | 2018-12-28 | 2019-05-03 | 山东广浦生物科技有限公司 | A kind of preparation method of glycidyl methacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5517307A (en) | 1980-02-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |