EP1423354A1 - Synthesis of alkylaminoalkyl (meth)acrylate by transesterification - Google Patents
Synthesis of alkylaminoalkyl (meth)acrylate by transesterificationInfo
- Publication number
- EP1423354A1 EP1423354A1 EP02762451A EP02762451A EP1423354A1 EP 1423354 A1 EP1423354 A1 EP 1423354A1 EP 02762451 A EP02762451 A EP 02762451A EP 02762451 A EP02762451 A EP 02762451A EP 1423354 A1 EP1423354 A1 EP 1423354A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- transesterification
- catalyst
- synthesis
- butyl
- catalysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
Definitions
- the invention relates to a process for the transesterification of esters of unsaturated carboxylic acids with reactive alcohols and a catalyst for these processes.
- R generally represents an aliphatic or aromatic group
- R ' can be, for example, methyl or ethyl
- R 'and R" can be selected so that the resulting alcohol is more volatile than the ester.
- the use of a catalyst accelerates the establishment of equilibrium.
- the present invention relates to the synthesis of t-butylaminoethyl methacrylate by transesterification of t-butylaminoethanol with methyl methacrylate (MMA).
- the transesterification is known per se.
- JP 062717517 and JP 06256271 describe the transesterification of methyl methacrylate with t-butylaminoethanol with catalysis by K 2 CO 3 . Disadvantages here are the relatively long reaction time (5 hours) and the occurrence of by-products (91% purity), so that the product has to be purified by distillation.
- JP 62185059 and JP 62175448 describe the synthesis of diethylaminoethyl methacrylates in the presence of K 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 .
- the purity achieved is greater than 95%, but the reaction still takes 5 hours.
- JP 62242652 describes the use of KHCO 3 as a catalyst.
- the disadvantage here is that the reaction also takes 5 hours and distillation is required to purify the crude product.
- alkaline catalysts increasingly lead to double bond adducts, especially in the presence of amines.
- EP 298867 describes catalysis using titanium (IV) alcoholate. It should be noted that this method also requires working up by distillation in order to obtain a purity> 98%. Ti catalysts are also sensitive to H 2 O, which causes a greater outlay in carrying out the reaction in the synthesis. JP 62230755 describes K 3 PO catalysis. The disadvantage here is again the reaction time of 5 hours with a conversion of 83.5%.
- JP 56104851 uses dibutyltin oxide as a catalyst.
- This catalyst has the disadvantage that it takes 8 hours for a conversion greater than 95%.
- Alkali metal oxides are disclosed in FR 1568382 and in GB 1174148.
- the disadvantage here is that the sales are ⁇ 95% and the yield is only slightly larger than 80%.
- EP 160427 (Allied Colloids) describes the transesterification of (meth) acrylates in the presence of an alcohol and / or in the presence of a mixture of alcoholates of the alcohol in question and / or of methanol with Ca, Mg or Ba, Ti and Zr or Al.
- the catalyst can be recycled.
- dimethylaminoethanol (DMEA) is transesterified with MMA to form DMAEA (dimethylaminoethyl methacrylate).
- DMEA dimethylaminoethanol
- EP 118639 (Allied Colloids) describes a transesterification process with catalysis by metal alcoholates of the metals Ti, Al, Zr, Ca or Mg.
- reaction must be carried out in the absence of water and reactive alcohols. The best results are achieved with calcium or magnesium as a metal component. No information is given on the by-product range.
- the object was to provide a further process for the transesterification of unsaturated carboxylic acid esters.
- the catalyst should be easy to manufacture and easy to remove.
- the invention describes a process for the transesterification of reactive alcohols with methyl methacrylate.
- Reactive alcohols are understood to be alcohols with one or more functional groups, for example hydroxyl groups, amino groups, substituted amino groups, thiol groups, epoxy groups.
- the advantage of the solution according to the invention which consists in the catalysis of the transesterification by zirconium acetylacetonate, is a methacrylic acid ester with a lower crosslinker content. The yield, based on the raw materials used, is higher, there are fewer by-products.
- R -CH2-, -CH2-CH2-, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, -CH2-CH-,
- zirconium acetylacetonate In addition to zirconium acetylacetonate, other 1,3-diketonates of zirconium, e.g. B. 1, 3 diphenylpropane-1, 3-dione can be used.
- MMA methyl methacrylate
- tBAE tert-butylaminoethanol
- tBAEMA tert-butylaminoethyl methacrylate
- EGDMA ethylene glycol dimethacrylate
- MtBMAA N, N- (methacryloyloxyethyl) tert-butyl methacrylamide
- the table shows that the amount of EGDMA is reduced by at least 50% compared to catalysis with dioctyltin oxide.
- the decrease in the high-boiling crosslinker MtBMAA to less than 0.1% is much more significant.
- the catalyst can be separated off easily by distillation.
Landscapes
- 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)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10145228 | 2001-09-13 | ||
DE10145228A DE10145228A1 (en) | 2001-09-13 | 2001-09-13 | Synthesis of t-butylaminoethyl methacrylate by transesterification of the alcohol with MMA |
PCT/EP2002/009197 WO2003022796A1 (en) | 2001-09-13 | 2002-08-16 | Synthesis of alkylaminoalkyl (meth)acrylate by transesterification |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1423354A1 true EP1423354A1 (en) | 2004-06-02 |
Family
ID=7698956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02762451A Withdrawn EP1423354A1 (en) | 2001-09-13 | 2002-08-16 | Synthesis of alkylaminoalkyl (meth)acrylate by transesterification |
Country Status (5)
Country | Link |
---|---|
US (1) | US7071351B2 (en) |
EP (1) | EP1423354A1 (en) |
JP (1) | JP4146339B2 (en) |
DE (1) | DE10145228A1 (en) |
WO (1) | WO2003022796A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10355830A1 (en) * | 2003-11-26 | 2005-06-09 | Röhm GmbH & Co. KG | Production of (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate for use e.g. in adhesives or paint, comprises transesterification of methyl methacrylate with glycerol carbonate using a metal 1,3-diketonate catalyst |
FR2876375B1 (en) * | 2004-10-12 | 2007-02-02 | Arkema Sa | PROCESS FOR THE PREPARATION OF (METH) ACRYLIC ESTERS OR ANYDRIDES |
DE102007031468A1 (en) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Process for the preparation of allyl methacrylate |
GB201009969D0 (en) | 2010-06-15 | 2010-07-21 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
BR112013006497A2 (en) | 2010-09-23 | 2016-07-12 | Basf Se | process for preparing (meth) acrylic esters of n-substituted amino alcohols |
FR2968659B1 (en) * | 2010-12-08 | 2013-04-26 | Arkema France | PROCESS FOR THE PREPARATION OF ALKYLAMINOALKYL (METH) ACRYLATES |
CN102798688B (en) * | 2012-08-09 | 2014-08-13 | 旭阳化学技术研究院有限公司 | Method for determining contents of methyl propionate, methyl methacrylate and propionic acid by gas chromatography internal standard method |
WO2014158445A1 (en) * | 2013-03-28 | 2014-10-02 | Rohm And Haas Company | Synthesis of (2-nitro)alkyl (meth)acrylates via transesterification of (meth)acrylate esters |
CN110036057B (en) * | 2016-12-14 | 2021-11-30 | 罗门哈斯公司 | Non-toxic catalyst for preparing polysiloxane (meth) acrylate |
US12091480B2 (en) | 2018-04-12 | 2024-09-17 | Snf Group | Method for producing 2-dimethylaminoethyl (meth)acrylate |
FR3086658B1 (en) * | 2018-10-02 | 2021-10-15 | Arkema France | STABILIZATION OF AMINOALKYL (METH) ACRYLATES |
JP7346942B2 (en) | 2019-07-02 | 2023-09-20 | 株式会社アイシン | Deodorizing equipment and toilet seat equipment |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4543422A (en) * | 1982-10-26 | 1985-09-24 | Allied Colloids Limited | Synthesis of vinyl esters |
GB8410497D0 (en) * | 1984-04-25 | 1984-05-31 | Allied Colloids Ltd | Synthesis of vinyl esters |
JPH0651664B2 (en) * | 1986-04-01 | 1994-07-06 | 三井東圧化学株式会社 | Process for producing alkylaminoalkyl ester of acrylic acid or methacrylic acid |
JPH0217155A (en) * | 1988-07-06 | 1990-01-22 | Toagosei Chem Ind Co Ltd | Production of dialkylaminoalkyl (meth)acrylate |
JPH0259546A (en) * | 1988-08-24 | 1990-02-28 | Toagosei Chem Ind Co Ltd | Production of dialkylaminoalkyl (meta)acrylate |
JP2702249B2 (en) * | 1989-12-08 | 1998-01-21 | 三井東圧化学株式会社 | Process for producing alkylaminoalkyl ester of acrylic acid or methacrylic acid |
FR2747675B1 (en) * | 1996-04-19 | 1998-05-22 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF (METH) ACRYLATES |
EP0837049B1 (en) * | 1996-10-17 | 2002-07-31 | Rohm And Haas Company | A process for preparing monomers |
DE19940622C1 (en) * | 1999-08-27 | 2001-05-17 | Roehm Gmbh | Process for the preparation of di (meth) acrylic acid esters |
FR2815631B1 (en) * | 2000-10-25 | 2003-12-19 | Atofina | PROCESS FOR THE MANUFACTURE OF METHYLCYCLOHEXYL (METH) ACRYLATES |
DE10127939A1 (en) * | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters, e.g. dialkylaminoethyl (meth)acrylates, by catalytic transesterification involves four-stage distillation |
-
2001
- 2001-09-13 DE DE10145228A patent/DE10145228A1/en not_active Withdrawn
-
2002
- 2002-08-16 US US10/486,351 patent/US7071351B2/en not_active Expired - Fee Related
- 2002-08-16 EP EP02762451A patent/EP1423354A1/en not_active Withdrawn
- 2002-08-16 WO PCT/EP2002/009197 patent/WO2003022796A1/en active Application Filing
- 2002-08-16 JP JP2003526874A patent/JP4146339B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO03022796A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2005502698A (en) | 2005-01-27 |
WO2003022796A1 (en) | 2003-03-20 |
US7071351B2 (en) | 2006-07-04 |
DE10145228A1 (en) | 2003-04-24 |
JP4146339B2 (en) | 2008-09-10 |
US20040249191A1 (en) | 2004-12-09 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 20040130 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ROEHM GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK ROEHM GMBH |
|
17Q | First examination report despatched |
Effective date: 20081201 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK ROEHM GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20090415 |