GB1572438A - Production of dimethylaminoethyl methacrylate - Google Patents
Production of dimethylaminoethyl methacrylate Download PDFInfo
- Publication number
- GB1572438A GB1572438A GB34005/77A GB3400577A GB1572438A GB 1572438 A GB1572438 A GB 1572438A GB 34005/77 A GB34005/77 A GB 34005/77A GB 3400577 A GB3400577 A GB 3400577A GB 1572438 A GB1572438 A GB 1572438A
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- Prior art keywords
- bis
- dibutyltin
- maleate
- tributyltin
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) IMPROVEMENTS IN OR RELATING TO THE
PRODUCTION OF DIMETHYLAMINOETHYL METHACRYLATE
(71) We, NITTO CHEMICAL CO., LTD., of 5-1 Marunouchi-1-Chome,
Chiyoda-Ku, Tokyo, Japan, a corporation organised under the laws of Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the production of dimethylaminoethyl methacrylate by the known process in which methyl methacrylate and dimethylaminoethanol are subjected to transesterification. This process proceeds according to the following reaction scheme:
catalyst CH2 = CCH,COOCH3 + HOCH,CH2N(CH3)2 CH2 = CCH,COOCH,CH,N(CH,)2 + CH,()H It is generally known, in this transesterification reaction, to use as a catalyst an alkali metal alkoxide, such as sodium methoxide (NaOCH3). However, if the reaction is performed in the presence of an alkali metal alkoxide, the activity of the catalyst is reduced during the reaction and so must be replenished many times during the reaction.
This phenomenon is very troublesome.
Also, alkali metal alkoxide catalysts have the disadvantage that they cause a side reaction in which dimethylaminoethanol or methanol becomes added to the double bond in the methyl methacrylate or in the desired product.
As an alternative, the use of a titanium alkoxide as a catalyst has been proposed.
This catalyst is expensive and its activity is lost if even a very small amount of moisture is present in the reaction system. Therefore, moisture must be previously removed completely from the reaction apparatus when this catalyst is used.
Further, the use of di-n-butyltin oxide as a catalyst is proposed in U.K. Patent
Specification 1 244 576. The activity of this catalyst is also lost if a small amount of moisture is present in the reaction system. Also, the reaction velocity cannot be increased, since the catalyst is slow in developing its activity.
It has now been discovered that dimethylaminoethyl methacrylate can be produced more advantageously than by prior art processes, by the transesterification of methyl methacrylate and dimethylaminoethanol, by the use of a catalyst which does not have the above-mentioned defects of prior art catalysts.
According to the process of the present invention, the transesterification is carried out in the presence of a catalyst consisting solely of one or more organo-tin compounds selected from: compounds represented by the formula:
wherein R1, R2, R, and R4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, compounds represented by the formula:
wherein Rl, R3 and R, are the same or different and each is as defined above and n is -H, -Cl, -OR1, -SR1, S(CH2)nCOOR1 (where n is 1 or 2), -OCOR1 or -OCOCH=CHCOOR1, compounds represented by the formula:
wherein Rl and R2 are the same or different and each is as defined above, X1 is as defined above and X2 has the same definition as X,, compounds represented by the formulae:
wherein R1 and R2 are the same or different and each is as defined above and A is -COCH=CHOC-, -CH20C- or -CH2CH2-, A' is -COCH=CHOC-, -CH2O or -CH2CH20C-, and compounds represented by the formula:
wherein R1, R,, R3 and R4 are the same or different and each is as defined above, X, and X4 are the same or different and each represents -H, R1, -OR1, -SR1, -S(CH2)nCOORi (where n is 1 or 2), -OCOR1 or -OCOCH=CHCOOR1, and B is -OCOCH=CHCOO-, -#OCH2CH2#O-, -SCH2COOCH,CH2OCOCH2S- (where n is 1 or 2) or -O-
By operating in accordance with the present invention, side reactions such as the addition of dimethylaminoethanol or methanol to the double bond in methyl methacrylate or the desired product substantially do not occur during the entire process.
It is therefore possible to obtain the desired product in a high yield.
Also, the catalysts used in the process of the present invention do not lose their activity during the reaction. Therefore, the catalysts may be added to the reaction system at once when the reaction is started. Thus, the operation is simple.
Further, the catalysts used in accordance with the present invention are less affected by the presence of a very small amount of moisture in the reaction system than prior art catalysts. Therefore, it is unnecessary to remove moisture completely from the reaction system prior to the reaction.
Many of the catalysts which can be used in carrying out the present invention are also used as stabilizers for polyvinyl chloride resin or pesticides or as raw materials for their production. Therefore, they are usually commercially available.
There are many examples of the compounds represented by formula (I), but the catalyst used, according to a preferred embodiment of the process of the invention, is at least one compound selected from tetramethyl tin, tetraethyl tin, tetrabutyl tin, tetraoctyl tin and tetraphenyl tin.
Examples of preferred compounds according to formula (II) include triphenyltin methoxide, triphenyltin ethoxide, triphenyltin butoxide, triphenyltin acetate, triphenyltin hydride, tributyltin methoxide, tributyltin ethoxide, tributyltin butoxide, tributyltin hydride, triphenyltin chloride, tributyltin acetate, tributyltin chloride, trioctyltin hydride, trioctyltin methoxide, trioctyltin ethoxide, trioctyltin butoxide and trioctyltin acetate.
Examples of preferred compounds according to formula (III) include dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dibutyltin dihydride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, dioctyltin dihydride, doctyltin diacetate and dioctyltin dilaurate.
According to the preferred embodiment of the process using compounds according to formula (IVa), the catalyst is at least one compound selected from dibutyltin maleate, dioctyltin maleate, dibutyltin ethylenealkoxide and dioctyltin ethylenealkoxide.
According to another preferred embodiment, dealing with compounds according to formula (IVb), the catalyst is at least one compound selected from dibutyltin mercaptoacetate, dibutyltin ss-mercaptopropionate, dioctyltin mercaptoacetate and dioctyltin ss- mercaptopropionate. The structural formulae are given below.
According to yet another preferred embodiment of the process of the invention, compounds according to formula (V) are used, selected from his- (tributyltin) maleate, bis(tributyltin) oxide, bis(tributyltin) ethylenealkoxide, ethylene bis(tributyltin mercaptoacetate), bis(dibutylmethoxytin) maleate, bis(dibutylmethoxytin) oxide, bis(dibutylmethoxytin) ethylenealkoxide, ethylene bis (dibutylmethoxytin mercaptoacetate), bis(dibutylethoxytin) maleate, bis(dibutyl- ethoxytin) oxide, bis(dibutylethoxytin) ethylenealkoxide, ethylene bis(dibutylethoxytin mercaptoacetate), bis(dibutylbutoxytin) maleate, bis( dibutyllauroxytin) maleate, bis (dibutylbutoxytin) oxide, bis(dibutylbutoxytin) ethylenealkoxide, ethylene bis(dibutoxytin mercaptoacetate, bis(trioctyltin) maleate, bis(trioctyltin) oxide, bis(trioctyl- tin) ethylenealkoxide, ethylene bis ( trioctyltin mercaptoaceate), bis( dioctyl-methoxytin) malate, bis(dioctylmethoxytin) oxide, bis(dioctylmethoxytin) ethylenealkoxide, ethylene bis-(dioctylmethoxytin mercaptoacetate), and bis(dioctyl-lauroxytin) maleate. The structural formulae of some of these compounds are given below.
Structural Formulae
(1) Dibutyltin mercaptoacetate and
(2) Dioctyltin mercaptoacetate (Formula IVb):
where A is butyl (1) or octyl (2); these compounds are prepared by reacting the corresponding dialkyltin dichloride with mercaptoacetic acid under conditions evolving 2 molecules of HCl per molecule of the dialkyltin dichloride.
(3) Dibutyltin fi-mercaptopropionate and
(4) Dioctyltin fi-mercaptopropionate (Formula IVb):
where A again is butyl (3) or octyl (4); these compounds are made by essentially the same reaction; the corresponding dialkyltin dichloride being reacted with p-mercapto- propionic acid.
(5) Ethylene bis(tributyltin-mercaptoacetate) and
(6) Ethylene bis(trioctyltin-mercaptoacetate) (Formula V):
where A again is butyl (5) or octyl (6); these compounds are made by reacting mercaptoacetic acid (2 mols), ethylene oxide (1 mol) and the corresponding trialkyltin chloride (2 mols) under conditions yielding HCI (2 mols) and H20 (1 mol).
(7) Ethylene bis( dibutylmethoxytin-mercaptoacetate), (8) Ethylene bis( dibutylethoxytin-mercaptoacetate ) and
(9) Ethylene bis(dioctylmethoxyltin-mercaptoaceate) Formula V):
where A is butyl (7) and (8) and octyl (9) and RO- is methoxy (7) and (9) or ethoxy (8); these compounds are made in the same way as (5) and (6), using the corresponding dialkylolkoxytin chloride.
The molar amount of catalyst used in carrying out the process of the invention is usually 0.1% to 5%, preferably 0.25 to 2.5%, based on the amount of dimethylaminoethanol employed as starting material. The catalysts used in the process are generally soluble in the reactants. Development of their catalytic activity is therefore rapid and the velocity of the reaction between methyl methacrylate and dimethylaminoethanol can be increased.
The amount of methyl methacrylate used is preferably and usually 1.2 to 3.5 moles per mole of dimethylaminoethanol.
in carrymg out the reaction, a polymerization inhibitor is advantageously added,
to prevent polymerization of the methyl acrylate and the dimethylaminoethyl meth
acrylate. Polymerization inhibitors generally used include phenothiazine and hydro
quinone monomethyl ether.
The reaction temperature is usually 80" to 1300 C. At a temperature less than 800C, the activity of the catalysts is low. A reaction temperature above 1300C is generally not desired, because side reactions, e.g. polymerization, are liable to occur.
Although the reaction may be conducted under atmospheric presure, it is preferable to carry out the reaction under a slightly reduced pressure, so that the methanol formed as a by-product can then be rapidly distilled off from the reaction system.
In carrying out the reaction, it is unnecessary to supply the catalyst in portions and the required amount of catalyst can simply be added at the start of the reaction
A reaction solvent is generally not required, but may be used. Examples of such solvents include benzene, toluene and hexane.
The methanol formed as a by-product in the reaction exhibits azeotropy with the unreacted methyl methacrylate. During the reaction, therefore, an azeotropic mixture of methanol and methyl methacrylate is desirably refluxed to the reaction system, at a suitable reflux ratio, using a distillation column, while a part of the mixture is withdrawn from the reaction system. The reflux ratio usually employed is in the range from 1:1 to 10:1.
The conditions generally used in carrying out the process of the invention will be explained and then the process illustrated by the subsequent Examples.
First of all, appropriate amounts of the starting materials, a catalyst, a polymerization inhibitor and, optionally, a solvent are charged into and heated in a reactor equipped with a thermometer and a distillation column. The mixture is reacted for some time under complete reflux, the temperature of the liquid being about 1000 C.
At the point where reflux becomes violent, part of an azeotropic mixture of methanol and methyl methacrylate is withdrawn from the system at a reflux ratio of about 5:1.
During the reaction, the temperature at the top of the distillation column is kept at 55" to 700C.
As the reaction progresses, the temperature at the top of the column and the temperature of the reaction mixture increase. In order to prevent side reactions and the formation of polymers, it is desirable to keep the temperature of the reaction mixture at 1300C or less.
The reaction time varies according to the molar ratio of the starting materials, the reaction temperature, the reflux ratio and other factors, but is usually 6 hours or less. When the reaction approaches the end, the temperature at the top of the distillation column increases suddenly.
The state of the reaction may be checked by measuring the conversion of dimethylaminoethanol in the reaction liquid by gas chromatography.
After completion of the reaction, the reaction mixture is distilled under reduced pressure according to the usual method. The unreacted methyl methacrylate is first distilled off and then the desired product, dimethylaminoethyl methacrylate, is distilled off.
Dimethylaminoethyl methacrylate, the product of the process of the invention, is useful as a raw material for the production of cationic polymers which may be used, for instance, as antistatic agents, soil-improving agents, electroconductive processing agents, paper treating agents and flocculants.
Example 1.
187 g of methyl methacrylate, 66.8 g of dimethylaminoethanol, 1.5 g of phenothiazine as a polymerization inhibitor and 3.5 g of dibutyltin diethoxide as a catalyst were charged into a flask equipped with a stirrer, a thermometer and a packed distillation column. The mixture was heated to boiling, while the pressure of the reaction system was kept constant at 560 mm Hg.
The resultant azeotropic mixture of the methanol formed and methyl methacrylate was subjected to complete reflux for about 5 minutes. Then, the reaction was continued while part of the azeotropic mixture was removed from the system at a reflux ratio of 5:1. During the reaction, the temperature at the top of the distillation column was kept at 560 to 600C. The transesterification reaction was completed in 3 hours.
After completing the reaction, the reaction mixture was distilled under reduced pressure to obtain 114.1 g of a fraction boiling in the range from 72"C at 18 mm Hg to 63.30C at 5 mm Hg.
By analysis of this fraction by gas chromatography, infrared spectroscopic analysis and nuclear magnetic resonance, it was confirmed that the fraction is dimethylaminoethyl methacrylate. The yield of dimethylaminoethyl methacrylate was 96.8%, based on the starting dimethylaminoethanol.
Example 2.
760 g of methyl methacrylate, 268 g of dimethylaminoethanol, 6.2 g of phenothiazine as a polymerization inhibitor and 20.8 g of dibutyltin maleate as a catalyst were charged into a reactor equipped with a stirrer, a thermometer and a distillation column. The mixture was heated to boiling with stirring.
The resultant azeotropic mixture of the methanol formed and methyl methacrylate was subjected to complete reflux for about 5 minutes. The reaction was then continued while part of the azeotropic mixture was removed fr9m the system at a reflux ratio of 5:1. During the reaction, the temperature at the top of the distillation column was kept at 65" to 700C.
After completing the reaction, the reaction mixture was distilled under reduced pressure in the same manner as in Example 1 to obtain 438 g of dimethylaminoethyl methacrylate, namely a yield of 92.6% based on the dimethylaminoethanol used.
Examples 3-10.
Dimethylaminoethyl methacrylate was prepared in the same manner as in
Example 1, except that tetrabutyltin, triphenyltin ethoxide, dibutyltin dihydride, dibutyltin dilaurate, dibutyltin di- (methoxycarbonylmethylmercaptide), bis(dibutyllauroxytin) maleate, bis(tributyltin) oxide and dibutyltin dichloride alone were respectively used as the catalyst.
The results obtained are shown in the following Table, where "Yield of desired product" indicates the yield of dimethylaminoethyl methacrylate obtained, based on the starting dimethylaminoethanol.
TABLE
Catalyst used Yield of Reaction Reaction desired dAmount(g) time (g) product Example Compound Amount (g) (hours) (%) 3 Tetrabutyltin 5 5 95.0 .4 Triphenyltin 5 6 88.8 ethoxide 5 Dibutyltin 5 4 96.3 dihydride 6 Dibutyltin 6 5.5 89.9 dilaurate 7 Dibutyltin di- 6 5 69.3 (methoxycarbonyl methylmercaptide) 8 Bis(dibutyl- 6 6 87.6 lauroxytin) maleate 9 Bis(tributyltin) 5 5 90.2 oxide 10 Dibutyltin 2.3 4 54.4 di chloride The catalysts used in Examples 3, 4, 5, 8 and 9 were synthesized according to known processes. The other catalysts used are commercially available.
Comparative Example.
Dimethylaminoethyl methacrylate was prepared in the same manner as in
Example 1, except that 0.8 g of sodium methoxide was used as a catalyst The reaction
time was 1.5 hours.
After completing the reaction, the reaction mixture was distilled under reduced
pressure. Analysis of the reaction product showed that the conversion of the starting
dimethylaminoethanol was 92.4%, but the yield of dimethylaminoethyl methacrylate was only 58.7% based on the starting dimethylaminoethanol. Further, a considerable
amount of by-products, including methoxy-iso-butyric acid methyl ester, methoxy-isobutyric acid dimethylaminoethyl ester, dimethylaminoethoxy-iso-butyric acid dimethyl
aminoethyl ester and sodium methacrylate, were produced.
WHAT WE CLAIM IS:- 1. A process for producing dimethylaminoethyl methacrylate, which comprises subjecting methyl methacrylate and dimethylaminoethanol to transesterification in the presence of a catalyst consisting solely of one or more organo-tin compounds selected from: compounds represented by the formula:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (9)
1. A process for producing dimethylaminoethyl methacrylate, which comprises subjecting methyl methacrylate and dimethylaminoethanol to transesterification in the presence of a catalyst consisting solely of one or more organo-tin compounds selected from: compounds represented by the formula:
wherein R1, R2, R3 and R4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, compounds represented by the formula:
wherein R1, R2 and R1 are the same or different and each is as defined above and X1 is -H, Cl, -OR1, -SR1, S(CH2)nCOOR1 (where n is 1 or 2), -OCOR1 or -OCOCH= CHCOOR1, compounds represented by the formula:
wherein R, and R2 are the same or different and each is as defined above, X1 is as defined above and X2 has the same definition as X1, compounds represented by the formulae:
wherein R1 and R2 are the same or different and each is as defined above and A is -COCH=CHOC-, -CH10C- or -CH1CH1-, A' is -COCH=CHOC-, -CH2OC- or -CH2CH2OC-, and compounds represented by the formula:
wherein R1, R2, R, and R4 are the same or different and each is as defined above,
X3 and X4 are the same or different and each represents -H, R1, -OR1, SR1, S(CH2),COOR1 (where n is 1 or 2), -OCOR1 or -OCOCH=CHCOOR1, and B is -OCOCH=CHCOO-, #OCH2CH2#O-, -SCH2CO#OCH2CH2#OCOCH2S- (where n is 1 or 2) or-O-.
2. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (I) selected from tetramethyltin, tetraethyltin, tetrabutyltin, tetraoctyltin and tetraphenyltin.
3. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (II), selected from triphenyltin methoxide, triphenyltin ethoxide, triphenyltin butoxide, triphenyitin acetate, triphenyltin hydride, tributyltin methoxide, tributyltin ethoxide, tributyltin butoxide, tribuyltin hydride, triphenyltin chloride, tributyltin acetate, tributyltin chloride, trioctyltin hydride, trioctyltin methoxide, trioctyltin ethoxide, trioctyltin butoxide and trioctyltin acetate.
4. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (III), selected from dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dibutyltin dihydride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichioride, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, dioctyltin dihydride, doctyltin diacetate and dioctyltin dilaurate.
5. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (IVa), selected from dibutyltin maleate, dioctyltin maleate, dibutyltin ethylenealkoxide and dioctyltin ethylenealkoxide.
6. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (IVb), selected from dibutyltin mercaptoacetate, dibutyltin fi-mercaptopropionate, dioctyltin mercaptoacetate and dioctyltin fi-mercapto- propionate.
7. A process according to claim 1, wherein the catalyst comprises at least one compound according to formula (V), selected from bis(tributyltin) maleate, bis (tributyltin) oxide, bis (tributyltin) ethylenealkoxide, ethylene bis (tributyltin mercaptoacetate), bis ( dibutylmethoxytin) maleate, bis (dibutylmethoxytin) oxide, bis ( dibutyl- methoxytin) ethylenealkoxide, ethylene bis( dibutylmethoxytin mercaptoacetate), bis (dibutylethoxytin) maleate, bis(dibutylethoxytin) oxide, bis(dibutylethoxytin) ethylenealkoxide, ethylene bis (dibutylethoxytin mercaptoacetate), bis (dibutylbutoxytin) maleate, bis(dibutyllauroxytin) maleate, bis(dibutylbutoxytin) oxide, bis(dibutylbutoxytin) ethylenealkoxide, ethylene bis(dibutoxytin mercaptoacetate), bis (trioctyltin) maleate, bis( trioctyltin) oxide, bis ( trioctyltin) ethylenealkoxide, ethylene bis ( trioctyl- tin mercaptoacetate), bi3(dioctylmethoxytin) maleate, bis(dioctylmethoxytin) oxide, bis(dioctylmethoxytin) ethylenealkoxide, ethylene bis(dioctylmethoxytin mercaptoacetate) and bis(dioctyllauroxytin) maleate.
8. A process for producing dimethylaminoethyl methacrylate according to claim 1, substantially as herein described with reference to the foregoing examples.
9. Dimethylaminoethyl methacrylate, when produced by a process according to any preceding claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB34005/77A GB1572438A (en) | 1977-08-12 | 1977-08-12 | Production of dimethylaminoethyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB34005/77A GB1572438A (en) | 1977-08-12 | 1977-08-12 | Production of dimethylaminoethyl methacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1572438A true GB1572438A (en) | 1980-07-30 |
Family
ID=10360176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB34005/77A Expired GB1572438A (en) | 1977-08-12 | 1977-08-12 | Production of dimethylaminoethyl methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1572438A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0118639A1 (en) * | 1982-10-26 | 1984-09-19 | Ciba Specialty Chemicals Water Treatments Limited | Synthesis of acrylic or methacrylic acid esters |
| WO2007057120A1 (en) * | 2005-11-16 | 2007-05-24 | Ciba Holding Inc. | Manufacture of esters |
-
1977
- 1977-08-12 GB GB34005/77A patent/GB1572438A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0118639A1 (en) * | 1982-10-26 | 1984-09-19 | Ciba Specialty Chemicals Water Treatments Limited | Synthesis of acrylic or methacrylic acid esters |
| WO2007057120A1 (en) * | 2005-11-16 | 2007-05-24 | Ciba Holding Inc. | Manufacture of esters |
| US7999131B2 (en) | 2005-11-16 | 2011-08-16 | Basf Se | Manufacture of esters |
| AU2006314805B2 (en) * | 2005-11-16 | 2012-02-02 | Basf Se | Manufacture of esters |
| US8309755B2 (en) | 2005-11-16 | 2012-11-13 | Basf Se | Manufacture of esters |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940812 |