CA2140304A1 - Process for transesterification of (meth)acrylic acid esters - Google Patents
Process for transesterification of (meth)acrylic acid estersInfo
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- CA2140304A1 CA2140304A1 CA002140304A CA2140304A CA2140304A1 CA 2140304 A1 CA2140304 A1 CA 2140304A1 CA 002140304 A CA002140304 A CA 002140304A CA 2140304 A CA2140304 A CA 2140304A CA 2140304 A1 CA2140304 A1 CA 2140304A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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Abstract
The transesterification of (meth)acrylic acid esters is efficiently carried out by mixing an alkyl (meth)acrylate having small alkyl residues in the ester substituent with an alcohol that has one or more esterizable hydroxyl groups in the presence of 0.01 to 10%
by weight of a mixed catalyst consisting of 5 to 95 mole %
of a diorganyl tin oxide and 95 to 5 mole % of an organyl tin trihalogenide and/or diorganyl tin dihalogenide.
by weight of a mixed catalyst consisting of 5 to 95 mole %
of a diorganyl tin oxide and 95 to 5 mole % of an organyl tin trihalogenide and/or diorganyl tin dihalogenide.
Description
TITLE OF THE lNV~:NllON
PROCESS FOR TRANSESTERIFICATION OF
(METH)ACRYLIC ACID ESTERS
BACKGROUND OF THE INVENTION
Field of the Invention:
The present invention relates to a process for the transesterification of (meth)acrylic acid esters, especially with multi-functional alkanols, using a mixed catalyst comprising a diorganyl tin oxide and an organyl tin halogenide.
Discussion of the Backqround:
The use of diorganyl tin oxides or of organyl tin halogenides, as transesterification catalysts, is known.
For example, DE-AS 1005947 describes that di- and triorgano tin compounds effectively catalyzed esterification and transesterification reactions of (meth)acrylic acid or (meth)acrylic acid esters. The advantageous effects of the catalysts described there include high catalytic effectiveness and a low tendency toward dehydration, especially of secondary alcohols, as well as high ester yields.
Special uses of such catalysts are mentioned, for example, in DE-OS 1965308, DE-OS 2816516 or EP-A 433 135.
DE-OS 1965308 describes a process for making dimethylaminoethyl methacrylate from dimethylaminoethanol and an alkyl methacrylate, catalyzed by di-n-butyl-tin oxide. In this process, first of all, the developing azeotrope is distilled from alkyl methacrylate and alkanol and, thereupon, where the reaction product dimethylaminoethyl methacrylate is distilled.
DE-OS 2816516 describes a process for making N-substituted tmeth)acrylamide by aminolysis of alkyl (meth)acrylates with aliphatic or aromatic amines, in the presence of dialkyl tin oxide catalysts. The aminolysis of the ester group is so accelerated with these catalysts that the undesirable Michael adducts of the amines to the double bonds of the (meth)acrylic acid esters appear only in minor quantities.
EP-A 433 135 describes a process for the conversion of alkyl (meth)acrylates with hydroxyalkylimidazolidin-2-ones into corresponding transesterification products, where one can employ dialkyl tin oxides, dialkoxyl tin oxides, and dialkyl tin diesters as catalysts. Just as in the case of DE-OS 2816516, one can in practice prevent the formation of the undesirable Michael adducts.
J. Otera et al describe the production of tetraorganodistannoxanes from diorganyl tin oxides and diorganyl tin dichloride (J. Org. Chem., vol. 56 (18), pp.
5307-5311 (1991) and Chem. Rev., vol. 93, pp. 1449-1470 (1993)). Such tetraorganodistannoxanes are described as being particularly effective transesterification catalysts.
2140~0~L
The preparation of mono- or multi-functional (meth)acrylic acid esters by means of the transesterification of (meth)acrylic acid esters which have lower alkyl groups in the ester group with mono- or multi-functional alcohols, as catalyzed by diorganyl tin oxidesor diorganyl tin halogenides, according to the processes conventionally used in the art, often takes place with unsatisfactorily small yields and unacceptable reaction times. This is true particularly in case of the conversion of (meth)acrylic acid esters with multi-functional alcohols.
Thus, there remains a need for an efficient method for the transesterification of (meth)acrylic acid esters.
There also remains a need for an efficient method for the transesterification of (meth)acrylic acid esters with multifunctional alcohols.
SUMMARY OF THE I~v~llON
Accordingly, it is one object of the present invention to provide a novel method for the transesterification of (meth)acrylic acid esters.
It is another object of the present invention to provide a method for the transesterification of (meth)acrylic acid esters with alcohols having two or more esterizable hydroxy groups.
21Q03~4 It is another object of the present invention to provide such methods which are efficient and afford high yield and small amounts of impurities.
These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that such transesterification reactions of (meth)acrylic acid esters with mono- or multi-functional alcohols can be carried out particularly advantageously in the presence of a mixed catalyst comprising a diorganyl tin oxide and an organyl tin halogenide. Thus, in the present method, the production of tetraorganodistannoxane, as described by Otera et al, as a catalytically effective substance, from diorgano tin oxide and diorgano tin halogenide, is not lS necessary.
In the process according to the present invention, (meth)acrylic acid esters of formula (I) R1 o H2C=C-C--O--R2 (I) wherein R1 is H or CH3 and R2 stands for an alkyl residue having l to 6 carbon atoms, are mixed with alcohols differing from them and having one or more hydroxyl groups, in the presence of 0.0l to 10% by weight, especially of 0.l to 5% by weight, based on the total weight of the reaction mixture, of a mixed catalyst, comprising:
214031~4 (a) 5 to 95 mole%, based on the total moles of the mixed catalyst, of a diorganyl tin oxide having formula (II):
R3 ~
Sn=O (II) wherein R3 and R4 are each, independently of each other, an aliphatic, aromatic, or araliphatic residue having 1 to 12 carbon atoms; and (b) 95 to 5 mole %, based on the total moles of the mixed catalyst, of an organyl tin halogenide having formulas (IIIa), (IIIb), or a mixture thereof:
\ / \ /
Sn Sn (IIIa) (IIIb) wherein R3 and R4 are as defined above, and X is Cl, Br, CN, NCO or NCS; and wherein the sum of the amounts of diorgano tin oxides (II) and the organo tin halogenides (IIIa) and (IIIb) add up to 100 mole %.
In a particularly preferred manner, the amount of diorgano tin oxide (II) is between 25 and 75 mole % and the 21~030~
amount of organo tin halogenide (IIIa) and/or (IIIb) is between 75 and 25 mole %, based on the total moles of (II), (IIIa), and (IIIb).
Preferably, the alcohols, used during the present transesterification have two or more esterizable hydroxyl groups. Suitable multifunctional alchols include difunctional alcohols of formula (IV):
HO-R'-OH (IV) wherein R' is a possibly branched aliphatic or 10araliphatic residue with 2 to 24 carbon atoms;
trifunctional alcohols of formula (V):
OH
HO-R -OH (V) wherein R" is a straight-chain or branched aliphatic or araliphatic residue with 3 to 30 carbon atoms;
as well as tetrafunctional alcohols of formula (VI):
OH
HO-R -OH (VI) wherein R"' is a straight-chain or branched aliphatic or arallphatic residue with 4 to 40 carbon atoms.
- 2140~
DETATTTn DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following can be employed, for example, as acrylic or methacrylic acid esters of formula (I): ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl methacrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, or, preferably, methyl methacrylate as well as butyl acrylate. It is to be understood that the terms "(meth)acrylic" and "(meth)acrylate" are meant to refer to "acrylic or methacrylic" and "acrylate or methacrylate", respectively.
The alcohols used for transesterification can have one or several hydroxyl groups that are capable of transesterification, in other words, they can be mono- or multi-functional. The following mono functional alcohols might be mentioned as examples out of many: ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, n-pentanol, i-pentanol, tert-pentanol, n-hexanol, n-octanol, 2-ethylhexane-1-ol, n-decanol, n-tetradecanol, n-eicosanol, cyclohexanol, 3,3,5-trimethylcyclohexane-1-ol, tetrahydrofurfuryl alcohol, and 2-phenylethanol.
The following examples are given for the difunctional alcohols of formula (IV) as representatives of the preferred alcohols with two or several hydroxyl groups:
ethyleneglycol, diethyleneglycol, triethyleneglycol, tetraethyleneglycol, 1,3-propanediol, 1,2-propanediol, 1,3-21~0304 butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-docecanediol, and cyclohexanediol-1,4.
Suitable trifunctional alcohols of formula (V) and tetrafunctional alcohols of formula (VI) are as follows, for example: trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, pentaerythritol, erythritol, and threitol.
The following might be mentioned by way of example as representatives of penta- and hexafunctional alcohols that can also be used as transesterification components:
arabinitol, ribitol, xylitol, sorbitol glucitol and mannitol, all of which are also known as sugar alcohols (see, for example, Kirk-Othmer EncvcloPedia of Chemical Technolo~y, 3rd Ed., vol. 1, pp. 7S4-789, John Wiley, New York, 1978).
The mixing of the acrylic or methacrylic esters of formula (I) with the mono- or multi-functional alcohols is carried out in the presence of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably between 0.2 to 2% by weight, based on the total weight of the reaction mixture, of a mixed catalyst, comprising 5 to 95 mole %, preferably 25 to 75 mole %, based on the total moles of the mixed catalyst, of the diorganyl tin oxide of formula (II) and 95 to 5 mole %, preferably 75 to 25 mole 214030q ~, based on the total moles of the mixed catalyst, of the organyl tin halogenide of formula (IIIa) and/or (IIIb).
The following might be mentioned as examples of formula (II) diorganyl tin oxides: dimethyl tin oxide, diethyl tin oxide, dipropyl tin oxide, dihexyl tin oxide, dicyclohexyl tin oxide, didodecyl tin oxide, diphenyl tin oxide, dibenzyl tin oxide, as well as and preferably, dibutyl tin oxide and dioctyl tin oxide.
The following may be mentioned as examples of diorganyl tin halogenides according to formula (IIIa):
dimethyl tin dichloride, dimethyl tin dibromide, diethyl tin dichloride, dibutyl tin dibromide, dihexyl tin dichloride, dihexyl tin diiodide, dioctyl tin dibromide, diphenyl tin dichloride, dibenzyl tin dichloride, as well Dec. 21,1994 ~_and preferably,, j~ 15~r a~'dibutyl tin dichloride and dioctyl tin dichloride.
The following are mentioned as examples of organo tin trihalogenides: methyl tin trichloride, methyl tin tribromide, ethyl tin trichloride, butyl tin tribromide, butyl tin triiodide, cyclohexyl tin trichloride, phenyl tin trichloride, phenyl tin tribromide, benzyl tin trichloride, as well as and preferably, butyl tin trichloride or octyl tin trichloride.
The acrylic or methacrylic acid esters according to formula (I) are mixed with the mono- or multi-functional alcohols at temperatures of between 30 and 180C, preferably between 50 and 130 in the presence of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly Dec. 21, 1994 prefer~ably from 0.2 to 2% by weight, based on the total weight of the reaction mixture, of the mixed catalyst made up of diorganyl tin oxide and organyl tin halogenide.
In formal terms, equimolar quantities of methacrylic acid esters according to formula (I) and hydroxyl groups of the mono- or multi-functional alcohols react to form the desired end products. In practice, however, it is a good Dec~ 21, 1994 reaction Gr idea, during the m; ~; ~ ~ to keep an excess of the methacrylic acid esters (I), in which connection the -methacrylic acid ester (I) is used in quantities of between 1.2 to 15 mole, preferably 2 to 10 mole, per equivalent of hydroxyl groups.
To prevent losses of yield, caused by polymerization of the methacrylic acid esters, it is practical to mix and process the reaction mixture in the presence of a polymerization inhibitor, such as, for example, dissolved oxygen, phenothiazine, or, preferably, hydroquinone monomethylether.
Dec. 21, 1994 reaction 20~r The ~:~in~ can be done at atmosphere pressure, under ' ~ superatmospheric pressure, or under subatmospheric pressure; the reaction can be controlled discontinuously or continuously. In general, the starting materials, (meth)acrylic acid ester (I) and mono- or multi-functional alcohol, are heated to reaction temperature in the presence of the mixed catalyst and, in the process, the separated 214~3~
alcohol ~OH, as well as the excess (meth)acrylic acid ester Dec. 21, 1994 as (I) are distilled off, preferably together w;l h ~
azeotrope. The reaction times generally are between 1 and 20 hours, preferably between 2 and 8 hours, and depend on the reaction temperature or on the quantity of catalyst mixture used. Furthermore, it is possible to perform the Dec. 21, 1994 reaction ~r ~ixing in the presence of inert solvent, such as, for example, toluene or cyclohexane.
D~c. 21, 1994 reaction G~ After completion of the mi~ing, the excess (meth)acrylic acid ester (I) is removed partly or preferably completely from the reaction product, for example, by distillation.
The separation of the mixed catalyst is accomplished by adding water to the reaction mixture that may still partly contain the excess methacrylic acid ester (I). To do that, one adds water in an amount of between 1 and 200 parts by weight, preferably in an amount of between 10 and 150 parts by weight, particularly preferably in an amount of between 20 and 100 parts by weight, based on 100 parts by weight of the obtained reaction mixture, preferably after the latter has cooled, particularly at temperatures between 10 and 50C. In this way, the mixed catalyst is obtained in a filterable form.
The process according to the present invention for the production of methacrylic acid esters by transesterification of methacrylic acid esters (I) with 214~3~4 mono- or multi-functional alcohols -- in particular for the Dec. 21, 1994 manufacture of multi-functional methacrylic acid esters_ --definitely provides higher yields and definitely less by-products than the conventional processes known in the art.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
ExamPle 1: Triethyleneglycol dimethyacrylate.
A 2-liter, four-neck flask, with thermometer, mechanical stirring device, air injection tube, and filler body column in place (diameter 3 cm, length 40 cm) as well as a column head with flowback divider is charged with 240 g of triethyleneglycol (1.6 mol), 880 g of methyl methacrylate (8.8 mol), and 5 g of dibutyl tin oxide (0.02 mol) and 6.1 g of dibutyl tin dichloride (0.02 mol) as the mixed catalyst, as well as 0.046 g of hydroquinone monomethylether as a polymerization inhibitor. While piping air in slowly, one heats the reaction mixture to a temperature of 100 to 114C, while a mixture of methanol and methyl methacrylate is drawn off at a flowback ratio of 1:1 to 5:1. This generates a head temperature of, initially, 70C that rises gradually. After 2.5 hours, it reaches a constant 100C, and transesterification is 2-140~
completed. One draws off the excess methyl methacrylate under vacuum and, as residue, one gets 400 g (87% yield) of triethyleneglycol dimethylacrylate, with the following gas-chromatography make-up:
97.5% triethyleneglycol dimethacrylate 0.8% triethyleneglycol monomethacrylate 1.3% methyl methacrylate Example 2: Triethyleneglycol dimethacrylate.
The same procedure as described in Example 1 was carried out, but this time using 7.1 g of dioctyl tin oxide (0.02 mol) and 4.1 g of dioctyl tin dichloride (0.01 mol) as the mixed catalyst.
One gets 407 g (89% yield) of triethyleneglycol dimethacrylate with the following gas-chromatography make-up:
97.2% triethyleneglycol dimethacrylate 1.3% triethyleneglycol monomethacrylate 1.3% methyl methacrylate Exam~le 3: Triethyleneglycol dimethacrylate.
The same procedure as described in Example 1 was carried out, but using S g (0.02 mol) of dibutyl tin oxide and 6 g (0.021 mol) of butyl tin trichloride as the mixed catalyst. Transesterification is complete after a reaction time of 3.5 hours, and the excess methyl methacrylate is drawn off under vacuum. As residue, one gets 422 g (92%
yield) of triethyleneglycol dimethacrylate with the following gas chromatography make-up:
98.2% triethyleneglycol dimethacrylate 0.9% triethyleneglycol monomethacrylate 0.5% methyl methacrylate Comparative Example 1:
Making triethyleneglycol dimethacrylate by using only dibutyl tin dichloride as the catalyst.
The procedure described in Example 1 was carried out, but using 11.2 g (0.037 mol) of dibutyl tin dichloride as the sole catalyst. No methanol was formed even after a reaction time of 3 hours, that is to say, there was no transesterification.
ExamPle 4: Ethyleneglycol dimethacrylate.
The procedure described in Example 1 was carried out, but using 173 g (2.8 mol) of ethyleneglycol, 1200 g (12 mol) of methyl methacrylate, and 6.4 g (0.018 mol) of dioctyl tin oxide and 7.3 g (0.018 mol) of dioctyl tin dichloride as the mixed catalyst, as well as 0.084 g of hydroquinone monomethylether. Transesterification is complete after 6 hours, and the excess methyl methacrylate is drawn off under vacuum. As residue, one gets 437 g (79%
21403~4 yield) of ethyleneglycol dimethacrylate with the following gas-chromatography make-up:
98 % triethyleneglycol dimethacrylate 1.5% triethyleneglycol monomethacrylate S 0.4% methyl methacrylate ComParative Example 2:
Making ethyleneglycol dimethacrylate while using only dioctyl tin oxide as the catalyst.
The procedure described in Example 1 was carried-out, but using 248 g (94.0 mol) of ethyleneglycol, 900 g (9 mol) of methyl methacrylate, 11.5 g (0.032 mol) of dioctyl tin oxide as the catalyst, as well as 0.23 g of hydroquinone monomethylether. The two-phase reaction mixture is cooled off after a reaction time of 6.5 hours and is analyzed by way of gas chromatography.
One gets the following result:
Upper Phase 1.5% ethyleneglycol dimethacrylate 12.7% ethyleneglycol monomethacrylate 4.3% ethyleneglycol 81.3% methyl methacrylate Lower Phase 0.2% ethyleneglycol dimethacrylate 15.7% ethyleneglycol monomethacrylate 63.0% ethyleneglycol 2~403~4 20.8% methyl methacrylate Comparative ExamPle 3:
Making ethyleneglycol dimethacrylate while using only butyl tin trichloride as the catalyst.
The procedure described in Example 1 was carried out, but using 124 g (2.0 mol) of ethyleneglycol, 450 g (4.5 mol) of methyl methacrylate, 5.7 g (0.02 mol) of butyl tin trichloride as catalyst, and 0.12 g of hydroquinone monomethylether. Transesterification is completed after a reaction time of 4 hours. The gas-chromatography analysis of the reaction product reveals the following make-up:
5.9% ethyleneglycol dimethacrylate 28.5% ethyleneglycol monomethacrylate 11.0% ethyleneglycol lS 52.9% methyl methacrylate Example 5: Pentaerythritol tetramethacrylate.
The procedure described in Example 1 was carried out, but using 136 g (1.0 mol) of petaerythritol, 1000 g (10.0 mol) of methyl methacrylate, and 5.0 g (0.02 mol) of dibutyl tin oxide and 6.1 g (0.02 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.57 g of hdyroquinone monomethylether. The excess methyl methacrylate is removed by vacuum after a reaction time of 214~3~4 14 hours. The 1H-NMR-spectroscopic analysis of the reaction product reveals the following make-up:
78% mol pentaerythritol tetramethacrylate 18% mol pentaerythritol trimethacrylate 3% mol pentaerythritol dimethacrylate 1% mol pentaerythritol monomethacrylate Comparative ExamPle 4:
Making pentaerythritol tetramethyacrylate while using only dibutyl tin dichloride as the catalyst.
The procedure described in Example 5 was carried out, but using 11.4 g (0.038 mol) of dibutyl tin dichloride as the catalyst. No methanol was formed even after a reaction time of 3.5 hours, that is to say, there was no transesterification.
ExamPle 6: Pentaerythritol tetraacrylate.
The procedure described in Example 3 was carried out, but using 136 g (1.0 mol) of pentaerythritol, 1262 g (10.0 mol) of butyl acrylate, and 6.3 g (0.025 mol) of dibutyl tin oxide and 7.7 g (0.025 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.7 g hydroquinone monomethylether and 0.14 g phenothiazine as polymerization inhibitors. The mixing is done at a pressure of 295 mbar.
The excess butyl acrylate is removed via vacuum after a 03~
reaction time of 8 hours. The ~H-NMR-spectroscopic analysis of the reaction product reveals the following make-up:
28% mol pentaerythritol tetramethacrylate 48% mol pentaerythritol trimethacrylate 21% mol pentaerythritol diacrylate 3% mol pentaerythritol monoacrylate Example 7: Tetrahydrofurfuryl methacrylate The procedure described in Example 1 was carried out, but using 204 g (2.0 mol) of tetrahydrofurfuryl alcohol, 500 g (5.0 mol) of methyl methacrylate, and 4.4 g (0.0175 mol) of dibutyl tin oxide and 2.7 g (0.008 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.35 g of hdyroquinone monomethylether. Transesterification is completed after a reaction time of 2.5 hours, and the excess methyl methacrylate is drawn off under a vacuum. As residue, one gets 238 g (70% yield) of tetrahydrofurfuryl methacrylate with the following gas-chromatography make-up:
94.7% tetrahydrofurfuryl methacrylate 1.5% tetrahydrofurfuryl alcohol 2.7% methyl methacrylate The present application is based on German Patent Application P 44 ol 132.6 filed January 17, 1994, and which is incorporated herein by reference in its entirety.
Obviously, numerous modifications and variations of the present invention are possible in light of the above 2l,4~3a4 teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiFed otherwise than as specifically described herein.
PROCESS FOR TRANSESTERIFICATION OF
(METH)ACRYLIC ACID ESTERS
BACKGROUND OF THE INVENTION
Field of the Invention:
The present invention relates to a process for the transesterification of (meth)acrylic acid esters, especially with multi-functional alkanols, using a mixed catalyst comprising a diorganyl tin oxide and an organyl tin halogenide.
Discussion of the Backqround:
The use of diorganyl tin oxides or of organyl tin halogenides, as transesterification catalysts, is known.
For example, DE-AS 1005947 describes that di- and triorgano tin compounds effectively catalyzed esterification and transesterification reactions of (meth)acrylic acid or (meth)acrylic acid esters. The advantageous effects of the catalysts described there include high catalytic effectiveness and a low tendency toward dehydration, especially of secondary alcohols, as well as high ester yields.
Special uses of such catalysts are mentioned, for example, in DE-OS 1965308, DE-OS 2816516 or EP-A 433 135.
DE-OS 1965308 describes a process for making dimethylaminoethyl methacrylate from dimethylaminoethanol and an alkyl methacrylate, catalyzed by di-n-butyl-tin oxide. In this process, first of all, the developing azeotrope is distilled from alkyl methacrylate and alkanol and, thereupon, where the reaction product dimethylaminoethyl methacrylate is distilled.
DE-OS 2816516 describes a process for making N-substituted tmeth)acrylamide by aminolysis of alkyl (meth)acrylates with aliphatic or aromatic amines, in the presence of dialkyl tin oxide catalysts. The aminolysis of the ester group is so accelerated with these catalysts that the undesirable Michael adducts of the amines to the double bonds of the (meth)acrylic acid esters appear only in minor quantities.
EP-A 433 135 describes a process for the conversion of alkyl (meth)acrylates with hydroxyalkylimidazolidin-2-ones into corresponding transesterification products, where one can employ dialkyl tin oxides, dialkoxyl tin oxides, and dialkyl tin diesters as catalysts. Just as in the case of DE-OS 2816516, one can in practice prevent the formation of the undesirable Michael adducts.
J. Otera et al describe the production of tetraorganodistannoxanes from diorganyl tin oxides and diorganyl tin dichloride (J. Org. Chem., vol. 56 (18), pp.
5307-5311 (1991) and Chem. Rev., vol. 93, pp. 1449-1470 (1993)). Such tetraorganodistannoxanes are described as being particularly effective transesterification catalysts.
2140~0~L
The preparation of mono- or multi-functional (meth)acrylic acid esters by means of the transesterification of (meth)acrylic acid esters which have lower alkyl groups in the ester group with mono- or multi-functional alcohols, as catalyzed by diorganyl tin oxidesor diorganyl tin halogenides, according to the processes conventionally used in the art, often takes place with unsatisfactorily small yields and unacceptable reaction times. This is true particularly in case of the conversion of (meth)acrylic acid esters with multi-functional alcohols.
Thus, there remains a need for an efficient method for the transesterification of (meth)acrylic acid esters.
There also remains a need for an efficient method for the transesterification of (meth)acrylic acid esters with multifunctional alcohols.
SUMMARY OF THE I~v~llON
Accordingly, it is one object of the present invention to provide a novel method for the transesterification of (meth)acrylic acid esters.
It is another object of the present invention to provide a method for the transesterification of (meth)acrylic acid esters with alcohols having two or more esterizable hydroxy groups.
21Q03~4 It is another object of the present invention to provide such methods which are efficient and afford high yield and small amounts of impurities.
These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that such transesterification reactions of (meth)acrylic acid esters with mono- or multi-functional alcohols can be carried out particularly advantageously in the presence of a mixed catalyst comprising a diorganyl tin oxide and an organyl tin halogenide. Thus, in the present method, the production of tetraorganodistannoxane, as described by Otera et al, as a catalytically effective substance, from diorgano tin oxide and diorgano tin halogenide, is not lS necessary.
In the process according to the present invention, (meth)acrylic acid esters of formula (I) R1 o H2C=C-C--O--R2 (I) wherein R1 is H or CH3 and R2 stands for an alkyl residue having l to 6 carbon atoms, are mixed with alcohols differing from them and having one or more hydroxyl groups, in the presence of 0.0l to 10% by weight, especially of 0.l to 5% by weight, based on the total weight of the reaction mixture, of a mixed catalyst, comprising:
214031~4 (a) 5 to 95 mole%, based on the total moles of the mixed catalyst, of a diorganyl tin oxide having formula (II):
R3 ~
Sn=O (II) wherein R3 and R4 are each, independently of each other, an aliphatic, aromatic, or araliphatic residue having 1 to 12 carbon atoms; and (b) 95 to 5 mole %, based on the total moles of the mixed catalyst, of an organyl tin halogenide having formulas (IIIa), (IIIb), or a mixture thereof:
\ / \ /
Sn Sn (IIIa) (IIIb) wherein R3 and R4 are as defined above, and X is Cl, Br, CN, NCO or NCS; and wherein the sum of the amounts of diorgano tin oxides (II) and the organo tin halogenides (IIIa) and (IIIb) add up to 100 mole %.
In a particularly preferred manner, the amount of diorgano tin oxide (II) is between 25 and 75 mole % and the 21~030~
amount of organo tin halogenide (IIIa) and/or (IIIb) is between 75 and 25 mole %, based on the total moles of (II), (IIIa), and (IIIb).
Preferably, the alcohols, used during the present transesterification have two or more esterizable hydroxyl groups. Suitable multifunctional alchols include difunctional alcohols of formula (IV):
HO-R'-OH (IV) wherein R' is a possibly branched aliphatic or 10araliphatic residue with 2 to 24 carbon atoms;
trifunctional alcohols of formula (V):
OH
HO-R -OH (V) wherein R" is a straight-chain or branched aliphatic or araliphatic residue with 3 to 30 carbon atoms;
as well as tetrafunctional alcohols of formula (VI):
OH
HO-R -OH (VI) wherein R"' is a straight-chain or branched aliphatic or arallphatic residue with 4 to 40 carbon atoms.
- 2140~
DETATTTn DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following can be employed, for example, as acrylic or methacrylic acid esters of formula (I): ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl methacrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, or, preferably, methyl methacrylate as well as butyl acrylate. It is to be understood that the terms "(meth)acrylic" and "(meth)acrylate" are meant to refer to "acrylic or methacrylic" and "acrylate or methacrylate", respectively.
The alcohols used for transesterification can have one or several hydroxyl groups that are capable of transesterification, in other words, they can be mono- or multi-functional. The following mono functional alcohols might be mentioned as examples out of many: ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, n-pentanol, i-pentanol, tert-pentanol, n-hexanol, n-octanol, 2-ethylhexane-1-ol, n-decanol, n-tetradecanol, n-eicosanol, cyclohexanol, 3,3,5-trimethylcyclohexane-1-ol, tetrahydrofurfuryl alcohol, and 2-phenylethanol.
The following examples are given for the difunctional alcohols of formula (IV) as representatives of the preferred alcohols with two or several hydroxyl groups:
ethyleneglycol, diethyleneglycol, triethyleneglycol, tetraethyleneglycol, 1,3-propanediol, 1,2-propanediol, 1,3-21~0304 butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-docecanediol, and cyclohexanediol-1,4.
Suitable trifunctional alcohols of formula (V) and tetrafunctional alcohols of formula (VI) are as follows, for example: trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, pentaerythritol, erythritol, and threitol.
The following might be mentioned by way of example as representatives of penta- and hexafunctional alcohols that can also be used as transesterification components:
arabinitol, ribitol, xylitol, sorbitol glucitol and mannitol, all of which are also known as sugar alcohols (see, for example, Kirk-Othmer EncvcloPedia of Chemical Technolo~y, 3rd Ed., vol. 1, pp. 7S4-789, John Wiley, New York, 1978).
The mixing of the acrylic or methacrylic esters of formula (I) with the mono- or multi-functional alcohols is carried out in the presence of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably between 0.2 to 2% by weight, based on the total weight of the reaction mixture, of a mixed catalyst, comprising 5 to 95 mole %, preferably 25 to 75 mole %, based on the total moles of the mixed catalyst, of the diorganyl tin oxide of formula (II) and 95 to 5 mole %, preferably 75 to 25 mole 214030q ~, based on the total moles of the mixed catalyst, of the organyl tin halogenide of formula (IIIa) and/or (IIIb).
The following might be mentioned as examples of formula (II) diorganyl tin oxides: dimethyl tin oxide, diethyl tin oxide, dipropyl tin oxide, dihexyl tin oxide, dicyclohexyl tin oxide, didodecyl tin oxide, diphenyl tin oxide, dibenzyl tin oxide, as well as and preferably, dibutyl tin oxide and dioctyl tin oxide.
The following may be mentioned as examples of diorganyl tin halogenides according to formula (IIIa):
dimethyl tin dichloride, dimethyl tin dibromide, diethyl tin dichloride, dibutyl tin dibromide, dihexyl tin dichloride, dihexyl tin diiodide, dioctyl tin dibromide, diphenyl tin dichloride, dibenzyl tin dichloride, as well Dec. 21,1994 ~_and preferably,, j~ 15~r a~'dibutyl tin dichloride and dioctyl tin dichloride.
The following are mentioned as examples of organo tin trihalogenides: methyl tin trichloride, methyl tin tribromide, ethyl tin trichloride, butyl tin tribromide, butyl tin triiodide, cyclohexyl tin trichloride, phenyl tin trichloride, phenyl tin tribromide, benzyl tin trichloride, as well as and preferably, butyl tin trichloride or octyl tin trichloride.
The acrylic or methacrylic acid esters according to formula (I) are mixed with the mono- or multi-functional alcohols at temperatures of between 30 and 180C, preferably between 50 and 130 in the presence of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly Dec. 21, 1994 prefer~ably from 0.2 to 2% by weight, based on the total weight of the reaction mixture, of the mixed catalyst made up of diorganyl tin oxide and organyl tin halogenide.
In formal terms, equimolar quantities of methacrylic acid esters according to formula (I) and hydroxyl groups of the mono- or multi-functional alcohols react to form the desired end products. In practice, however, it is a good Dec~ 21, 1994 reaction Gr idea, during the m; ~; ~ ~ to keep an excess of the methacrylic acid esters (I), in which connection the -methacrylic acid ester (I) is used in quantities of between 1.2 to 15 mole, preferably 2 to 10 mole, per equivalent of hydroxyl groups.
To prevent losses of yield, caused by polymerization of the methacrylic acid esters, it is practical to mix and process the reaction mixture in the presence of a polymerization inhibitor, such as, for example, dissolved oxygen, phenothiazine, or, preferably, hydroquinone monomethylether.
Dec. 21, 1994 reaction 20~r The ~:~in~ can be done at atmosphere pressure, under ' ~ superatmospheric pressure, or under subatmospheric pressure; the reaction can be controlled discontinuously or continuously. In general, the starting materials, (meth)acrylic acid ester (I) and mono- or multi-functional alcohol, are heated to reaction temperature in the presence of the mixed catalyst and, in the process, the separated 214~3~
alcohol ~OH, as well as the excess (meth)acrylic acid ester Dec. 21, 1994 as (I) are distilled off, preferably together w;l h ~
azeotrope. The reaction times generally are between 1 and 20 hours, preferably between 2 and 8 hours, and depend on the reaction temperature or on the quantity of catalyst mixture used. Furthermore, it is possible to perform the Dec. 21, 1994 reaction ~r ~ixing in the presence of inert solvent, such as, for example, toluene or cyclohexane.
D~c. 21, 1994 reaction G~ After completion of the mi~ing, the excess (meth)acrylic acid ester (I) is removed partly or preferably completely from the reaction product, for example, by distillation.
The separation of the mixed catalyst is accomplished by adding water to the reaction mixture that may still partly contain the excess methacrylic acid ester (I). To do that, one adds water in an amount of between 1 and 200 parts by weight, preferably in an amount of between 10 and 150 parts by weight, particularly preferably in an amount of between 20 and 100 parts by weight, based on 100 parts by weight of the obtained reaction mixture, preferably after the latter has cooled, particularly at temperatures between 10 and 50C. In this way, the mixed catalyst is obtained in a filterable form.
The process according to the present invention for the production of methacrylic acid esters by transesterification of methacrylic acid esters (I) with 214~3~4 mono- or multi-functional alcohols -- in particular for the Dec. 21, 1994 manufacture of multi-functional methacrylic acid esters_ --definitely provides higher yields and definitely less by-products than the conventional processes known in the art.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
ExamPle 1: Triethyleneglycol dimethyacrylate.
A 2-liter, four-neck flask, with thermometer, mechanical stirring device, air injection tube, and filler body column in place (diameter 3 cm, length 40 cm) as well as a column head with flowback divider is charged with 240 g of triethyleneglycol (1.6 mol), 880 g of methyl methacrylate (8.8 mol), and 5 g of dibutyl tin oxide (0.02 mol) and 6.1 g of dibutyl tin dichloride (0.02 mol) as the mixed catalyst, as well as 0.046 g of hydroquinone monomethylether as a polymerization inhibitor. While piping air in slowly, one heats the reaction mixture to a temperature of 100 to 114C, while a mixture of methanol and methyl methacrylate is drawn off at a flowback ratio of 1:1 to 5:1. This generates a head temperature of, initially, 70C that rises gradually. After 2.5 hours, it reaches a constant 100C, and transesterification is 2-140~
completed. One draws off the excess methyl methacrylate under vacuum and, as residue, one gets 400 g (87% yield) of triethyleneglycol dimethylacrylate, with the following gas-chromatography make-up:
97.5% triethyleneglycol dimethacrylate 0.8% triethyleneglycol monomethacrylate 1.3% methyl methacrylate Example 2: Triethyleneglycol dimethacrylate.
The same procedure as described in Example 1 was carried out, but this time using 7.1 g of dioctyl tin oxide (0.02 mol) and 4.1 g of dioctyl tin dichloride (0.01 mol) as the mixed catalyst.
One gets 407 g (89% yield) of triethyleneglycol dimethacrylate with the following gas-chromatography make-up:
97.2% triethyleneglycol dimethacrylate 1.3% triethyleneglycol monomethacrylate 1.3% methyl methacrylate Exam~le 3: Triethyleneglycol dimethacrylate.
The same procedure as described in Example 1 was carried out, but using S g (0.02 mol) of dibutyl tin oxide and 6 g (0.021 mol) of butyl tin trichloride as the mixed catalyst. Transesterification is complete after a reaction time of 3.5 hours, and the excess methyl methacrylate is drawn off under vacuum. As residue, one gets 422 g (92%
yield) of triethyleneglycol dimethacrylate with the following gas chromatography make-up:
98.2% triethyleneglycol dimethacrylate 0.9% triethyleneglycol monomethacrylate 0.5% methyl methacrylate Comparative Example 1:
Making triethyleneglycol dimethacrylate by using only dibutyl tin dichloride as the catalyst.
The procedure described in Example 1 was carried out, but using 11.2 g (0.037 mol) of dibutyl tin dichloride as the sole catalyst. No methanol was formed even after a reaction time of 3 hours, that is to say, there was no transesterification.
ExamPle 4: Ethyleneglycol dimethacrylate.
The procedure described in Example 1 was carried out, but using 173 g (2.8 mol) of ethyleneglycol, 1200 g (12 mol) of methyl methacrylate, and 6.4 g (0.018 mol) of dioctyl tin oxide and 7.3 g (0.018 mol) of dioctyl tin dichloride as the mixed catalyst, as well as 0.084 g of hydroquinone monomethylether. Transesterification is complete after 6 hours, and the excess methyl methacrylate is drawn off under vacuum. As residue, one gets 437 g (79%
21403~4 yield) of ethyleneglycol dimethacrylate with the following gas-chromatography make-up:
98 % triethyleneglycol dimethacrylate 1.5% triethyleneglycol monomethacrylate S 0.4% methyl methacrylate ComParative Example 2:
Making ethyleneglycol dimethacrylate while using only dioctyl tin oxide as the catalyst.
The procedure described in Example 1 was carried-out, but using 248 g (94.0 mol) of ethyleneglycol, 900 g (9 mol) of methyl methacrylate, 11.5 g (0.032 mol) of dioctyl tin oxide as the catalyst, as well as 0.23 g of hydroquinone monomethylether. The two-phase reaction mixture is cooled off after a reaction time of 6.5 hours and is analyzed by way of gas chromatography.
One gets the following result:
Upper Phase 1.5% ethyleneglycol dimethacrylate 12.7% ethyleneglycol monomethacrylate 4.3% ethyleneglycol 81.3% methyl methacrylate Lower Phase 0.2% ethyleneglycol dimethacrylate 15.7% ethyleneglycol monomethacrylate 63.0% ethyleneglycol 2~403~4 20.8% methyl methacrylate Comparative ExamPle 3:
Making ethyleneglycol dimethacrylate while using only butyl tin trichloride as the catalyst.
The procedure described in Example 1 was carried out, but using 124 g (2.0 mol) of ethyleneglycol, 450 g (4.5 mol) of methyl methacrylate, 5.7 g (0.02 mol) of butyl tin trichloride as catalyst, and 0.12 g of hydroquinone monomethylether. Transesterification is completed after a reaction time of 4 hours. The gas-chromatography analysis of the reaction product reveals the following make-up:
5.9% ethyleneglycol dimethacrylate 28.5% ethyleneglycol monomethacrylate 11.0% ethyleneglycol lS 52.9% methyl methacrylate Example 5: Pentaerythritol tetramethacrylate.
The procedure described in Example 1 was carried out, but using 136 g (1.0 mol) of petaerythritol, 1000 g (10.0 mol) of methyl methacrylate, and 5.0 g (0.02 mol) of dibutyl tin oxide and 6.1 g (0.02 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.57 g of hdyroquinone monomethylether. The excess methyl methacrylate is removed by vacuum after a reaction time of 214~3~4 14 hours. The 1H-NMR-spectroscopic analysis of the reaction product reveals the following make-up:
78% mol pentaerythritol tetramethacrylate 18% mol pentaerythritol trimethacrylate 3% mol pentaerythritol dimethacrylate 1% mol pentaerythritol monomethacrylate Comparative ExamPle 4:
Making pentaerythritol tetramethyacrylate while using only dibutyl tin dichloride as the catalyst.
The procedure described in Example 5 was carried out, but using 11.4 g (0.038 mol) of dibutyl tin dichloride as the catalyst. No methanol was formed even after a reaction time of 3.5 hours, that is to say, there was no transesterification.
ExamPle 6: Pentaerythritol tetraacrylate.
The procedure described in Example 3 was carried out, but using 136 g (1.0 mol) of pentaerythritol, 1262 g (10.0 mol) of butyl acrylate, and 6.3 g (0.025 mol) of dibutyl tin oxide and 7.7 g (0.025 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.7 g hydroquinone monomethylether and 0.14 g phenothiazine as polymerization inhibitors. The mixing is done at a pressure of 295 mbar.
The excess butyl acrylate is removed via vacuum after a 03~
reaction time of 8 hours. The ~H-NMR-spectroscopic analysis of the reaction product reveals the following make-up:
28% mol pentaerythritol tetramethacrylate 48% mol pentaerythritol trimethacrylate 21% mol pentaerythritol diacrylate 3% mol pentaerythritol monoacrylate Example 7: Tetrahydrofurfuryl methacrylate The procedure described in Example 1 was carried out, but using 204 g (2.0 mol) of tetrahydrofurfuryl alcohol, 500 g (5.0 mol) of methyl methacrylate, and 4.4 g (0.0175 mol) of dibutyl tin oxide and 2.7 g (0.008 mol) of dibutyl tin dichloride as the mixed catalyst, as well as 0.35 g of hdyroquinone monomethylether. Transesterification is completed after a reaction time of 2.5 hours, and the excess methyl methacrylate is drawn off under a vacuum. As residue, one gets 238 g (70% yield) of tetrahydrofurfuryl methacrylate with the following gas-chromatography make-up:
94.7% tetrahydrofurfuryl methacrylate 1.5% tetrahydrofurfuryl alcohol 2.7% methyl methacrylate The present application is based on German Patent Application P 44 ol 132.6 filed January 17, 1994, and which is incorporated herein by reference in its entirety.
Obviously, numerous modifications and variations of the present invention are possible in light of the above 2l,4~3a4 teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiFed otherwise than as specifically described herein.
Claims (8)
1. A process for the transesterification of a (meth)acrylic acid ester, comprising contacting a (meth)acrylic acid ester of formula (I):
(I) wherein R1 is for H or CH3, and R2 is an alkyl residue with 1 to 6 carbon atoms, with an alcohol having one or more esterizable hydroxyl groups, in the presence of 0.01 to 10%
by weight, based on the total weight of the reaction mixture, of a mixed catalyst comprising:
(a) 5 to 95 mole %, based the total moles of the mixed catalyst, of a diorganyl tin oxide according to formula (II):
(II) wherein R3 and R4 each are, independently of each other, an aliphatic, aromatic, or araliphatic residue with 1 to 12 carbon atoms, and (b) 95 to 5 mole %, based on the total moles of the mixed catalyst, of an organyl tin halogenide selected from the group consisting of formula (IIIa), formula (IIIb), and mixtures thereof:
(IIIa) (IIIb) wherein R3 and R4 are as defined above, and X is Cl, Br, I, CN, NCO, or NCS.
(I) wherein R1 is for H or CH3, and R2 is an alkyl residue with 1 to 6 carbon atoms, with an alcohol having one or more esterizable hydroxyl groups, in the presence of 0.01 to 10%
by weight, based on the total weight of the reaction mixture, of a mixed catalyst comprising:
(a) 5 to 95 mole %, based the total moles of the mixed catalyst, of a diorganyl tin oxide according to formula (II):
(II) wherein R3 and R4 each are, independently of each other, an aliphatic, aromatic, or araliphatic residue with 1 to 12 carbon atoms, and (b) 95 to 5 mole %, based on the total moles of the mixed catalyst, of an organyl tin halogenide selected from the group consisting of formula (IIIa), formula (IIIb), and mixtures thereof:
(IIIa) (IIIb) wherein R3 and R4 are as defined above, and X is Cl, Br, I, CN, NCO, or NCS.
2. The process of Claim 1, wherein said mixed catalyst is present in an amount of 0.1 to 5% by weight, based on the total weight of the reaction mixture.
3. The process of Claim 1, wherein said mixed catalyst comprises of 25 to 75 mole % of a diorganyl tin oxide according to formula (II) and 75 to 25 mole % of an organyl tin halogenide selected from the group consisting of formula (IIIa), formula (IIIb), and mixtures thereof.
4. The process of Claim 1, wherein said alcohol has two or more esterizable hydroxyl groups.
5. The process of Claim 4, wherein said alcohol is selected from the group consisting of:
(a) difunctional alcohols according to Formula IV:
HO-R'-OH (IV) wherein R' is a straight-chain or branched aliphatic or araliphatic residue with 2 to 24 carbon atoms;
(b) trifunctional alcohols according to formula (V):
(V) wherein R" is a straight-chain or branched aliphatic or araliphatic residue with 3 to 30 carbon atoms; and (c) tetrafunctional alcohols according to formula (VI):
(VI) wherein R''' is a straight-chain or branched aliphatic or araliphatic residue with 4 to 40 carbon atoms.
(a) difunctional alcohols according to Formula IV:
HO-R'-OH (IV) wherein R' is a straight-chain or branched aliphatic or araliphatic residue with 2 to 24 carbon atoms;
(b) trifunctional alcohols according to formula (V):
(V) wherein R" is a straight-chain or branched aliphatic or araliphatic residue with 3 to 30 carbon atoms; and (c) tetrafunctional alcohols according to formula (VI):
(VI) wherein R''' is a straight-chain or branched aliphatic or araliphatic residue with 4 to 40 carbon atoms.
6. The process of Claim 1, wherein said (meth)acrylic acid ester according to formula (I) is present in an amount of 1.2 to 15 mole per mole equivalent of esterizable hydroxyl groups in said alcohol.
7. The process of Claim 1, wherein said contacting is carried out at a temperature between 50 and 130°C.
8. The process of Claim 1, wherein said mixed catalyst is separated, after completion of said transesterification, by adding water in an amount of 10 to 150 parts by weight, based on 100 parts by weight of the obtained reaction mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4401132A DE4401132A1 (en) | 1994-01-17 | 1994-01-17 | Process for the transesterification of (meth) acrylic acid esters |
| DEP4401132.6 | 1994-01-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2140304A1 true CA2140304A1 (en) | 1995-07-18 |
Family
ID=6508048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002140304A Abandoned CA2140304A1 (en) | 1994-01-17 | 1995-01-16 | Process for transesterification of (meth)acrylic acid esters |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0663386B1 (en) |
| AT (1) | ATE178880T1 (en) |
| CA (1) | CA2140304A1 (en) |
| DE (2) | DE4401132A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5606103A (en) * | 1993-09-03 | 1997-02-25 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
| US5914427A (en) * | 1996-12-13 | 1999-06-22 | Basf Aktiengesellshaft | Preparation of ω-hydroxyesiers of α,β-unsaturated carboxylic acids |
| US6541656B2 (en) * | 2000-02-10 | 2003-04-01 | Nippon Shokubai Company, Ltd. | Process for producing α, β-unsaturated carboxylic acid esters and catalyst for use in such process |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10101387A1 (en) | 2001-01-13 | 2002-07-18 | Merck Patent Gmbh | Polyester with methacrylate end groups |
| FR2824062B1 (en) | 2001-04-27 | 2004-10-15 | Atofina | PROCESS FOR PRODUCING AQUEOUS SOLUTIONS OF QUATERNARY AMMONIUM UNSATURATED SALTS |
| FR2824061B1 (en) | 2001-04-26 | 2004-03-05 | Atofina | PROCESS FOR THE MANUFACTURE OF 2- (DIMETHYLAMINO) -1- (DIMETHYLAMINOMETHYL) ETHYL (METH) ACRYLATE |
| FR2824063B1 (en) | 2001-04-26 | 2004-03-05 | Atofina | PROCESS FOR THE MANUFACTURE OF 1,3-BIS ACRYLATE CHLORIDE (DIMETHYLBENZYLAMMONIUM) ISOPROPYL ALONE OR A MIXTURE OF OTHER MONOMERS AND (CO) POLYMERS THEREOF |
| DE102005044250A1 (en) | 2005-09-15 | 2007-03-29 | Röhm Gmbh | Process for the preparation of methacrylates with reactive double bonds |
| DE102007031473A1 (en) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Process for the preparation of ethylene glycol dimethacrylate |
| FR2924114A1 (en) * | 2007-11-27 | 2009-05-29 | Arkema France | PROCESS FOR THE SYNTHESIS OF ALCOXYPOLYALKYLENE GLYCOLS (METH) ACRYLATES BY TRANSESTERIFICATION |
| JP6018402B2 (en) * | 2012-04-21 | 2016-11-02 | 大阪有機化学工業株式会社 | Method for producing 4-hydroxybutyl acrylate |
| EP2860170B1 (en) * | 2012-04-21 | 2019-08-28 | Osaka Organic Chemical Ind., Ltd. | Process for preparing 4-hydroxybutyl acrylate |
| JP6008600B2 (en) * | 2012-06-13 | 2016-10-19 | 大阪有機化学工業株式会社 | Method for producing 4-hydroxybutyl acrylate |
| EP3774715A1 (en) * | 2018-04-03 | 2021-02-17 | Sirrus, Inc. | Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441814A (en) * | 1977-09-02 | 1979-04-03 | Nitto Chem Ind Co Ltd | Preparation of acrylate or methacrylate |
| JPS58170730A (en) * | 1982-03-31 | 1983-10-07 | Mitsui Toatsu Chem Inc | Preparation of acrylic or methacrylic ester |
| JPH0341051A (en) * | 1989-07-07 | 1991-02-21 | Idemitsu Petrochem Co Ltd | Preparation of acrylate or methacrylate ester |
| DE4317428C1 (en) * | 1993-05-26 | 1994-06-16 | Goldschmidt Ag Th | Mixt. of organo-tin cpds. as catalyst - used for transesterification of (meth)acrylic acid ester monomer or polymer with cpd. contg. hydroxy gps., avoiding discolouration of prod. |
| US5498751A (en) * | 1993-09-03 | 1996-03-12 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
-
1994
- 1994-01-17 DE DE4401132A patent/DE4401132A1/en not_active Withdrawn
-
1995
- 1995-01-05 DE DE59505616T patent/DE59505616D1/en not_active Expired - Fee Related
- 1995-01-05 AT AT95100110T patent/ATE178880T1/en active
- 1995-01-05 EP EP95100110A patent/EP0663386B1/en not_active Expired - Lifetime
- 1995-01-16 CA CA002140304A patent/CA2140304A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5606103A (en) * | 1993-09-03 | 1997-02-25 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
| US5914427A (en) * | 1996-12-13 | 1999-06-22 | Basf Aktiengesellshaft | Preparation of ω-hydroxyesiers of α,β-unsaturated carboxylic acids |
| US6541656B2 (en) * | 2000-02-10 | 2003-04-01 | Nippon Shokubai Company, Ltd. | Process for producing α, β-unsaturated carboxylic acid esters and catalyst for use in such process |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0663386B1 (en) | 1999-04-14 |
| DE59505616D1 (en) | 1999-05-20 |
| EP0663386A1 (en) | 1995-07-19 |
| ATE178880T1 (en) | 1999-04-15 |
| DE4401132A1 (en) | 1995-07-20 |
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