WO2009003746A1 - Verfahren zur herstellung von allylmethacrylat - Google Patents
Verfahren zur herstellung von allylmethacrylat Download PDFInfo
- Publication number
- WO2009003746A1 WO2009003746A1 PCT/EP2008/055669 EP2008055669W WO2009003746A1 WO 2009003746 A1 WO2009003746 A1 WO 2009003746A1 EP 2008055669 W EP2008055669 W EP 2008055669W WO 2009003746 A1 WO2009003746 A1 WO 2009003746A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- range
- allyl alcohol
- allyl
- methacrylate
- Prior art date
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Classifications
-
- 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
Definitions
- the present invention relates to processes for the preparation of allyl methacrylate.
- Allyl methacrylate serves inter alia as an intermediate for the preparation of
- Silyl group-containing methacrylates Accordingly, various methods are known to obtain this compound. These include in particular processes in which allyl alcohol is reacted with methacrylates, for example methyl methacrylate or ethyl methacrylate. To improve the yield and the selectivity of the reaction, different catalysts can be used.
- acids or bases can be used to catalyze the transesterification.
- Such reactions are set forth, for example, in CN 1410412 or DE 34 23 441.
- side reactions must be expected, such as the Michael addition, which reduces both the purity of the desired allyl methacrylate and the yield.
- Methyl methacrylate with allyl alcohol are catalyzed by titanium alcoholates.
- nitrogen-containing polymerization inhibitors are used, which are undesirable in allyl methacrylate.
- Methyl methacrylate with allyl alcohol in the presence of titanium alcoholates In this case, oxygen-containing polymerization inhibitors are used.
- the document DE 28 05 702 describes the preparation of esters of unsaturated carboxylic acids.
- compounds containing zirconium and / or calcium can be used to catalyze the reactions described.
- Particularly suitable catalysts include in particular zirconium acetylacetonate.
- the preparation of allyl methacrylate is not explicitly described. The reactions lead to high yields of about 98%, based on the alcohol used. However, it follows that the product contains considerable amounts of by-products.
- silyl group-containing methacrylates from allyl alcohol requires a very high purity of the starting materials since impurities, e.g. Allyl alcohol and water can deactivate the used for the synthesis of silane methacrylate Pt catalyst. In the same way disturb nitrogen-containing secondary components. Allyl methacrylate, which is sold commercially for this purpose as starting material, may therefore contain at most 200 ppm of allyl alcohol, with the lowest possible content of allyl alcohol is desirable. To meet these requirements, the products obtained according to the prior art must be cleaned consuming.
- allyl methacrylate in which the product is obtained with a very high purity.
- the resulting allyl methacrylate should contain only very small amounts of allyl alcohol and / or water.
- Another object of the invention was to provide a method in which allyl methacrylate can be obtained very selectively. Moreover, it was an object of the present invention to provide processes for the preparation of allyl methacrylate, which can be carried out easily and inexpensively. The product should be obtained in high yields and, if possible, with low energy consumption. In addition, the reaction should be able to be carried out in particular without nitrogen-containing polymerization inhibitors.
- the present invention accordingly provides a process for preparing allyl methacrylate, which comprises reacting allyl alcohol with an ester of methacrylic acid, the reaction being catalyzed by zirconium acetylacetonate.
- the process according to the invention enables a particularly selective preparation of allyl methacrylate. Furthermore, the inventive method can be carried out easily and inexpensively, the product can be obtained in high yields and, overall, with low energy consumption. In addition, the reaction can be carried out in particular without nitrogen-containing polymerization inhibitors.
- allyl methacrylate is produced.
- Allyl methacrylate (2-methylpropenoic propenyl ester) has long been known and has the CAS number 96-05-9.
- the CAS number of allyl alcohol is 107-18-6.
- allyl alcohol is reacted with an ester of methacrylic acid.
- methacrylates are formed in particular by alcohols having 1 to 4 carbon atoms. These include, in particular, methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol. Ethyl methacrylate or methyl methacrylate is particularly preferably used, with methyl methacrylate being very particularly preferred.
- the weight ratio of allyl alcohol to the ester of methacrylic acid is preferably in the range from 1: 1, 5 to 1:10, more preferably 1: 2.5 to 1: 5 and most preferably in the range from 1: 3 to 1: 4.
- zirconium acetylacetonate is used to catalyze the present transesterification.
- the CAS number of zirconium acetylacetonate is 17501-44-9.
- the preparation of zirconium acetylacetonate from acetylacetone (pentane-2,4-dione) and zirconium compounds is described for example in Houben-Weyl, Methods of Organic Chemistry, 4th edition, Bd. VI / 2, 1963, pages 53-55 and 58 to 61 and in AE Martell, M. Calvin, "The Chemistry of Metal Chelate Compounds" (1958).
- 0.2 to 5 mmol, more preferably 0.5 to 2 mmol zirconium acetylacetonate per mole of allyl alcohol can be used.
- the preparation of the catalyst can also be carried out in situ, the
- Starting materials can be added before or during the transesterification of the reaction mixture.
- the reaction can be carried out at overpressure or underpressure.
- the transesterification at a pressure in the range of 200 to 2000 mbar, more preferably in the range of 500 to 1300 mbar. be performed.
- the reaction temperature can also be in a wide range, in particular as a function of the pressure. According to a preferred
- the reaction is preferably carried out at a temperature in the range of 80 0 C to 120 0 C, particularly preferably 95 to 115 ° C.
- the temperature at which the reaction takes place is increased in the course of the reaction.
- the temperature at the beginning of the reaction in particular up to a conversion of 80%, preferably up to a conversion of 70%, based on the weight of the allyl alcohol used, preferably in the range of 90 0 C to 100 0 C and towards the end of the reaction, in particular after a conversion of 80%, preferably according to a conversion of 90%, based on the weight of the allyl alcohol used, in the range of 105 ° C to 115 0 C.
- the transesterification can be carried out both continuously and batchwise. It is also possible not to initially introduce part of the methacrylic acid ester used for the transesterification before the beginning of the reaction, but to meter it in during the reaction.
- the process according to the invention can be carried out in bulk, i. be carried out without the use of another solvent. If desired, an inert solvent can also be used. These include, among others, gasoline, benzene, toluene, n-hexane, cyclohexane and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK).
- the liberated alcohol can be removed by distillation, for example methanol or ethanol, optionally azeotropically with methyl methacrylate or ethyl methacrylate, from the reaction mixture.
- the water content in the allyl methacrylate is preferably at most 0.1%, more preferably at most 0.02%, based on the weight of the composition.
- the reaction times depend, among other things, on the selected parameters, such as pressure and temperature. However, they are generally in the range of 1 to 24 hours, preferably 3 to 12 hours, and most preferably 6 to 9 hours. In continuous processes, the residence times are generally in the range of 0.5 to 24 hours, preferably from 1 to 12 hours and most preferably 2 to 3 hours. Further references with regard to the reaction times can be found by the person skilled in the art in the attached examples.
- the reaction may take place with stirring, wherein the stirring speed may be more preferably in the range of 50 to 2000 rpm, most preferably in the range of 100 to 500 rpm.
- the pH can be in a wide range. Conveniently, the reaction can be carried out at a pH in the range of 5 to 9, preferably 6 to 8.
- polymerization inhibitors can be used in the reaction.
- These compounds such as hydroquinones, hydroquinone ethers such as hydroquinone monomethyl ether or di-tert-butyl catechol, phenothiazine, p-phenylenediamine, methylene blue or hindered phenols, are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially.
- the effect of the stabilizers is usually that they act as radical scavengers for the free radicals occurring during the polymerization.
- polymerization inhibitors which contain no nitrogen are particularly useful.
- phenols are preferably used as the polymerization inhibitor.
- Particularly surprising advantages can be achieved using mixtures comprising hydroquinone and hydroquinone monomethyl ether. Based on the weight of the total reaction mixture, the proportion of inhibitors individually or as a mixture can generally be 0.01-0.5% (wt / wt). It is expedient to feed not only the reaction vessel, but also the column and optionally the capacitor surfaces with inhibitors, which can be dosed for example in the column reflux.
- oxygen can be used for inhibition.
- This can be used, for example, in the form of air, wherein the amounts are advantageously metered so that the content in the gas phase above the reaction mixture remains below the explosion limit.
- Air quantities in the range from 0.05 to 0.5 l per hour and mol are particularly preferred
- a combination of oxygen with at least one phenol preferably hydroquinone and / or hydroquinone monomethyl ether.
- the alcohol released from the methacrylate used can be separated off by distillation.
- a mixture containing methyl methacrylate and methanol can advantageously be separated off.
- part of the separated mixture can advantageously be recycled to the following batch.
- the recyclable fraction of the separated mixture can be obtained at the end of the reaction, in particular after a conversion of 80%, preferably after a conversion of 90% of the allyl alcohol used.
- the proportion of recycled mixture at the beginning of the following batch may be in the range of 40 to 60%, based on the total weight of the transesterified methacrylic acid ester.
- the methanol- or ethanol-rich distillate obtained at the beginning of the reaction can likewise be recycled, for example by incorporation into a system operated in the composite for preparing the methacrylate ester to be transesterified.
- a suitable plant for carrying out the present transesterification may comprise, for example, a stirred tank reactor with stirrer, steam heating, distillation column and condenser.
- stirrer for example, a stirred tank reactor with stirrer, steam heating, distillation column and condenser.
- the size of the plant depends on the amount of allyl methacrylate to be produced, and the present process can be carried out both on a laboratory scale and on an industrial scale.
- the stirred tank reactor can accordingly have a vessel volume in the range of 1 m 3 to 20 m 3 , preferably 3 m 3 to 10 m 3 .
- the agitator of the reactor vessel may be designed in particular in the form of an anchor agitator, impeller, blade or inter-MIG stirrer.
- the task of the distillation column is to ensure that a methanol- or ethanol-rich azeotrope is removed in order to minimize the losses of inevitably discharged with Eduktester.
- the distillation column may have one, two or more separation stages.
- the number of separation stages is the number of plates in a tray column or the number of theoretical plates in the case of a packed column or a packed column.
- Examples of a multistage distillation column with trays include those such as bubble trays, sieve trays, tunnel trays, valve trays, slotted trays, sieve slotted trays, sieve trays, nozzle trays, centrifugal trays, for a multistage distillation column with packing such as Raschig rings, Lessing rings, Pall rings, Berl saddles, Intalox saddles and for a multistage distillation column with packing such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz).
- the conversion-dependent adjustment of the reflux ratio makes it possible, for example, to adjust the use of methyl methacrylate over wide ranges of the conversion of a methanol content in the distillate which is above 60%.
- suitable capacitors which may be included in the plant for carrying out the present transesterification include plate and shell and tube heat exchangers.
- the mixture obtained can be purified by known methods. Because of the tendency of the monomer to polymerize, distillation processes are recommended in which the thermal load of the substance to be distilled is minimized. Well suited are devices in which the monomer is continuously evaporated from a thin layer, such as falling film evaporator and evaporator with a rotating wiper system. Short-path evaporators can also be used. Such devices are known (Ullmann's Encyclopedia of Industrial Chemistry (6th edition), Verlag Wiley-VCH, Weinheim 2003, Volume 36, page 505).
- a distillation can be carried out in which a continuous evaporator with rotating wiper system and attached column can be used. This distillation can be carried out for example at a pressure in the range of 40 to 60 mbar and an evaporator temperature of 110 0 C to 130 0 C.
- allyl methacrylate which preferably contains less than 0.04%, more preferably less than 0.02% and most preferably less than 0.01% of allyl alcohol, based on the weight of the composition.
- the reaction is complete and it extracts excess MMA in vacuo, gradually reducing the pressure to 5 Torr. If no MMA distils off anymore, the vacuum is released.
- the contents of the vessel consist of 1780 kg of allyl methacrylate, which still contains 4000 ppm of allyl alcohol and 1700 ppm of methyl methacrylate (determined by gas chromatography).
- the reaction is complete and it extracts excess MMA in vacuo, gradually reducing the pressure to 5 Torr. If no MMA distils off anymore, the vacuum is released.
- the contents of the vessel consist of 2500 kg of allyl methacrylate, which still contains 1200 ppm of allyl alcohol and 7400 ppm of methyl methacrylate (determined by gas chromatography).
- the reaction is complete and it extracts excess MMA in vacuo, gradually reducing the pressure to 5 Torr. If no MMA distils off anymore, the vacuum is released.
- the contents of the vessel consist of 2740 kg allyl methacrylate containing only 10 ppm allyl alcohol and 4120 ppm methyl methacrylate (determined by gas chromatography).
- Composition (determined by gas chromatography) a) starting from raw material from Comparative Example 2: 99.55% allyl methacrylate, 0.37% MMA, 0.033% allyl alcohol water content (determined by Karl Fischer titration): 350 ppm b) starting from raw material from an inventive example 1: 99.71% allyl methacrylate, 0.22% MMA, 0.006% allyl alcohol water content (determined by Karl Fischer titration): 110 ppm c) starting from raw material from inventive example 3: 99.88% allyl methacrylate, 0.11% MMA, 0.005% allyl alcohol Water content (determined by Karl Fischer titration): 50 ppm
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08759458.6A EP2162420B1 (de) | 2007-07-05 | 2008-05-08 | Verfahren zur herstellung von allylmethacrylat |
US12/667,604 US8129563B2 (en) | 2007-07-05 | 2008-05-08 | Method for synthesizing allyl methacrylate |
CA2692583A CA2692583C (en) | 2007-07-05 | 2008-05-08 | Process for preparing allyl methacrylate |
ES08759458.6T ES2604256T3 (es) | 2007-07-05 | 2008-05-08 | Procedimiento para la obtención de metacrilato de alilo |
AU2008271503A AU2008271503B2 (en) | 2007-07-05 | 2008-05-08 | Method for synthesizing allyl methacrylate |
RU2010103712/04A RU2486172C2 (ru) | 2007-07-05 | 2008-05-08 | Способ получения аллилметакрилата |
JP2010513809A JP5479333B2 (ja) | 2007-07-05 | 2008-05-08 | アリルメタクリレートの製造法 |
BRPI0813788-9A BRPI0813788B1 (pt) | 2007-07-05 | 2008-05-08 | Methacrylate of alila preparation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007031468A DE102007031468A1 (de) | 2007-07-05 | 2007-07-05 | Verfahren zur Herstellung von Allylmethacrylat |
DE102007031468.1 | 2007-07-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009003746A1 true WO2009003746A1 (de) | 2009-01-08 |
Family
ID=39930484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/055669 WO2009003746A1 (de) | 2007-07-05 | 2008-05-08 | Verfahren zur herstellung von allylmethacrylat |
Country Status (13)
Country | Link |
---|---|
US (1) | US8129563B2 (de) |
EP (1) | EP2162420B1 (de) |
JP (1) | JP5479333B2 (de) |
KR (1) | KR101539122B1 (de) |
CN (1) | CN101337886B (de) |
AU (1) | AU2008271503B2 (de) |
BR (1) | BRPI0813788B1 (de) |
CA (1) | CA2692583C (de) |
DE (1) | DE102007031468A1 (de) |
ES (1) | ES2604256T3 (de) |
RU (1) | RU2486172C2 (de) |
TW (1) | TWI356818B (de) |
WO (1) | WO2009003746A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101824127A (zh) * | 2010-04-01 | 2010-09-08 | 江西科技师范学院 | 一种利用活性自由基无皂乳液聚合制备可交联嵌段共聚物的方法及其制备的化合物 |
WO2011157645A2 (en) | 2010-06-15 | 2011-12-22 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG11201605119WA (en) * | 2013-12-26 | 2016-07-28 | Dow Global Technologies Llc | Inhibitor combination for lithium salt-catalyzed transesterification process and method for removing lithium salt |
CN105294434A (zh) * | 2015-11-30 | 2016-02-03 | 抚顺东联安信化学有限公司 | 甲基丙烯酸月桂醇酯的制备方法 |
US11072688B2 (en) * | 2016-12-14 | 2021-07-27 | Rohm And Haas Company | Nontoxic catalyst for preparation of polysiloxane (meth)acrylates |
CN110452116A (zh) * | 2019-07-17 | 2019-11-15 | 江苏新东风化工科技有限公司 | 一种丙烯酸正丁酯酯化反应装置及其反应工艺 |
US20220388943A1 (en) * | 2019-10-23 | 2022-12-08 | Evonik Operations Gmbh | Process for preparing glycerol carbonate (meth)acrylate |
WO2023242257A1 (en) * | 2022-06-15 | 2023-12-21 | Evonik Operations Gmbh | Pressure enhanced (trans)esterification of (meth)acrylate compounds |
WO2023242259A1 (en) * | 2022-06-15 | 2023-12-21 | Evonik Operations Gmbh | Method for increasing reaction performance by intermediate removal of side product holdup |
Citations (2)
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US4202990A (en) * | 1977-02-10 | 1980-05-13 | Mitsubishi Rayon Company, Limited | Process for producing unsaturated carboxylic acid esters |
EP1078913A2 (de) * | 1999-08-27 | 2001-02-28 | Röhm Gmbh | Verfahren zur Herstellung von Di(meth)acrylsäureestern |
Family Cites Families (9)
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DE3423441A1 (de) | 1984-06-26 | 1986-01-02 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von estern der acryl- und methacrylsaeure durch umesterung |
FR2602229B1 (fr) * | 1986-07-31 | 1988-09-09 | Charbonnages Ste Chimique | Procede de preparation d'esters d'acides carboxyliques insatures |
JPH01258642A (ja) | 1988-04-06 | 1989-10-16 | Mitsubishi Gas Chem Co Inc | (メタ)アクリル酸エステルの製造法 |
FR2707290B1 (fr) * | 1993-07-06 | 1995-09-01 | Atochem Elf Sa | Procédé de préparation de l'acrylate ou du méthacrylate d'éthylthioéthyle à l'aide d'acétylacétonate de zirconium comme catalyseur. |
DE69714373T2 (de) * | 1996-10-17 | 2003-02-13 | Rohm & Haas | Verfahren zum Herstellen von Monomeren |
JPH11222461A (ja) | 1998-02-02 | 1999-08-17 | Mitsubishi Rayon Co Ltd | (メタ)アクリル酸エステルの製造方法 |
FR2815631B1 (fr) * | 2000-10-25 | 2003-12-19 | Atofina | Procede de fabrication de (meth)acrylates de methylcyclohexyle |
DE10145228A1 (de) * | 2001-09-13 | 2003-04-24 | Roehm Gmbh | Synthese von t-Butylaminoethylmethacrylat durch Umesterung des Alkohols mit MMA |
CN1410412A (zh) | 2001-09-28 | 2003-04-16 | 湖北武大有机硅新材料股份有限公司 | 甲基丙烯酸烯丙酯的合成方法 |
-
2007
- 2007-07-05 DE DE102007031468A patent/DE102007031468A1/de not_active Withdrawn
- 2007-09-12 CN CN200710148927XA patent/CN101337886B/zh active Active
-
2008
- 2008-05-08 KR KR1020107000020A patent/KR101539122B1/ko active IP Right Grant
- 2008-05-08 RU RU2010103712/04A patent/RU2486172C2/ru active
- 2008-05-08 BR BRPI0813788-9A patent/BRPI0813788B1/pt active IP Right Grant
- 2008-05-08 CA CA2692583A patent/CA2692583C/en active Active
- 2008-05-08 US US12/667,604 patent/US8129563B2/en active Active
- 2008-05-08 EP EP08759458.6A patent/EP2162420B1/de active Active
- 2008-05-08 JP JP2010513809A patent/JP5479333B2/ja active Active
- 2008-05-08 ES ES08759458.6T patent/ES2604256T3/es active Active
- 2008-05-08 WO PCT/EP2008/055669 patent/WO2009003746A1/de active Application Filing
- 2008-05-08 AU AU2008271503A patent/AU2008271503B2/en active Active
- 2008-07-02 TW TW097124961A patent/TWI356818B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4202990A (en) * | 1977-02-10 | 1980-05-13 | Mitsubishi Rayon Company, Limited | Process for producing unsaturated carboxylic acid esters |
EP1078913A2 (de) * | 1999-08-27 | 2001-02-28 | Röhm Gmbh | Verfahren zur Herstellung von Di(meth)acrylsäureestern |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101824127A (zh) * | 2010-04-01 | 2010-09-08 | 江西科技师范学院 | 一种利用活性自由基无皂乳液聚合制备可交联嵌段共聚物的方法及其制备的化合物 |
WO2011157645A2 (en) | 2010-06-15 | 2011-12-22 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
US8865931B2 (en) | 2010-06-15 | 2014-10-21 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
Also Published As
Publication number | Publication date |
---|---|
BRPI0813788B1 (pt) | 2017-12-26 |
JP5479333B2 (ja) | 2014-04-23 |
AU2008271503B2 (en) | 2013-12-05 |
TWI356818B (en) | 2012-01-21 |
BRPI0813788A2 (pt) | 2014-12-30 |
EP2162420A1 (de) | 2010-03-17 |
JP2010532330A (ja) | 2010-10-07 |
RU2010103712A (ru) | 2011-08-10 |
CA2692583A1 (en) | 2009-01-08 |
RU2486172C2 (ru) | 2013-06-27 |
TW200918499A (en) | 2009-05-01 |
EP2162420B1 (de) | 2016-09-07 |
AU2008271503A1 (en) | 2009-01-08 |
US8129563B2 (en) | 2012-03-06 |
CN101337886B (zh) | 2011-10-05 |
ES2604256T3 (es) | 2017-03-06 |
CN101337886A (zh) | 2009-01-07 |
CA2692583C (en) | 2015-10-13 |
KR20100036301A (ko) | 2010-04-07 |
DE102007031468A1 (de) | 2009-01-08 |
KR101539122B1 (ko) | 2015-07-23 |
US20100185009A1 (en) | 2010-07-22 |
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