WO2003022796A1 - Synthese von alkylaminoalkyl (meth) acrylat durch umesterung - Google Patents
Synthese von alkylaminoalkyl (meth) acrylat durch umesterungInfo
- Publication number
- WO2003022796A1 WO2003022796A1 PCT/EP2002/009197 EP0209197W WO03022796A1 WO 2003022796 A1 WO2003022796 A1 WO 2003022796A1 EP 0209197 W EP0209197 W EP 0209197W WO 03022796 A1 WO03022796 A1 WO 03022796A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transesterification
- catalyst
- synthesis
- butyl
- catalysis
- Prior art date
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
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02762451A EP1423354A1 (de) | 2001-09-13 | 2002-08-16 | Synthese von alkylaminoalkyl(meth)acrylat durch umesterung |
JP2003526874A JP4146339B2 (ja) | 2001-09-13 | 2002-08-16 | エステル交換反応によるアルキルアミノアルキル(メタ)アクリレートの合成 |
US10/486,351 US7071351B2 (en) | 2001-09-13 | 2002-08-16 | Synthesis of alkylaminoalkyl (meth)acrylate by transesterification |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10145228.4 | 2001-09-13 | ||
DE10145228A DE10145228A1 (de) | 2001-09-13 | 2001-09-13 | Synthese von t-Butylaminoethylmethacrylat durch Umesterung des Alkohols mit MMA |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003022796A1 true WO2003022796A1 (de) | 2003-03-20 |
Family
ID=7698956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/009197 WO2003022796A1 (de) | 2001-09-13 | 2002-08-16 | Synthese von alkylaminoalkyl (meth) acrylat durch umesterung |
Country Status (5)
Country | Link |
---|---|
US (1) | US7071351B2 (de) |
EP (1) | EP1423354A1 (de) |
JP (1) | JP4146339B2 (de) |
DE (1) | DE10145228A1 (de) |
WO (1) | WO2003022796A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005058862A2 (de) * | 2003-11-26 | 2005-06-30 | Röhm GmbH & Co. KG | Verfahren zur herstellung von glycerincarbonatmethacrylat |
WO2012038459A1 (de) | 2010-09-23 | 2012-03-29 | Basf Se | Verfahren zur herstellung von (meth)acrylsäureestern von n,n-substituierten aminoalkoholen |
CN102798688A (zh) * | 2012-08-09 | 2012-11-28 | 北京旭阳化工技术研究院有限公司 | 气相色谱内标法测定丙酸甲酯、甲基丙烯酸甲酯和丙酸含量的方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2876375B1 (fr) * | 2004-10-12 | 2007-02-02 | Arkema Sa | Procede de preparation d'esters ou d'anydrides (meth) acryliques |
DE102007031468A1 (de) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Allylmethacrylat |
GB201009969D0 (en) | 2010-06-15 | 2010-07-21 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
FR2968659B1 (fr) * | 2010-12-08 | 2013-04-26 | Arkema France | Procede de preparation de (meth)acrylates d'alkylaminoalkyle |
US9670134B2 (en) * | 2013-03-28 | 2017-06-06 | Angus Chemical Company | Synthesis of (2-nitro)alkyl (meth)acrylates via transesterification of (meth)acrylate esters |
WO2018111458A1 (en) * | 2016-12-14 | 2018-06-21 | Rohm And Haas Company | Nontoxic catalyst for preparation of polysiloxane (meth)acrylates |
FI3778554T3 (fi) | 2018-04-12 | 2024-02-27 | Snf Group | Menetelmä 2-dimetyyliaminoetyyli(met)akrylaatin valmistamiseksi |
FR3086658B1 (fr) * | 2018-10-02 | 2021-10-15 | Arkema France | Stabilisation de (meth)acrylates d'aminoalkyle |
JP7346942B2 (ja) | 2019-07-02 | 2023-09-20 | 株式会社アイシン | 脱臭装置および便座装置 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0217155A (ja) * | 1988-07-06 | 1990-01-22 | Toagosei Chem Ind Co Ltd | ジアルキルアミノアルキル(メタ)アクリレートの製造方法 |
JPH0259546A (ja) * | 1988-08-24 | 1990-02-28 | Toagosei Chem Ind Co Ltd | ジアルキルアミノアルキル(メタ)アクリレートの製造方法 |
JPH03181449A (ja) * | 1989-12-08 | 1991-08-07 | Mitsui Toatsu Chem Inc | アクリル酸またはメタクリル酸のアルキルアミノアルキルエステルの製造方法 |
FR2747675A1 (fr) * | 1996-04-19 | 1997-10-24 | Atochem Elf Sa | Procede de preparation de (meth)acrylates |
EP0837049A1 (de) * | 1996-10-17 | 1998-04-22 | Rohm And Haas Company | Verfahren zum Herstellen von Monomeren |
EP1078913A2 (de) * | 1999-08-27 | 2001-02-28 | Röhm Gmbh | Verfahren zur Herstellung von Di(meth)acrylsäureestern |
EP1201640A1 (de) * | 2000-10-25 | 2002-05-02 | Atofina | Verfahren zur Herstellung von (Meth)acrylsäuremethylcyclohexylestern |
Family Cites Families (4)
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 (ja) * | 1986-04-01 | 1994-07-06 | 三井東圧化学株式会社 | アクリル酸またはメタクリル酸のアルキルアミノアルキルエステルの製造方法 |
DE10127939A1 (de) * | 2001-06-08 | 2002-05-29 | Basf Ag | Verfahren zur Herstellung von (Meth)acrylsäureestern |
-
2001
- 2001-09-13 DE DE10145228A patent/DE10145228A1/de not_active Withdrawn
-
2002
- 2002-08-16 EP EP02762451A patent/EP1423354A1/de not_active Withdrawn
- 2002-08-16 JP JP2003526874A patent/JP4146339B2/ja not_active Expired - Fee Related
- 2002-08-16 US US10/486,351 patent/US7071351B2/en not_active Expired - Fee Related
- 2002-08-16 WO PCT/EP2002/009197 patent/WO2003022796A1/de active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0217155A (ja) * | 1988-07-06 | 1990-01-22 | Toagosei Chem Ind Co Ltd | ジアルキルアミノアルキル(メタ)アクリレートの製造方法 |
JPH0259546A (ja) * | 1988-08-24 | 1990-02-28 | Toagosei Chem Ind Co Ltd | ジアルキルアミノアルキル(メタ)アクリレートの製造方法 |
JPH03181449A (ja) * | 1989-12-08 | 1991-08-07 | Mitsui Toatsu Chem Inc | アクリル酸またはメタクリル酸のアルキルアミノアルキルエステルの製造方法 |
FR2747675A1 (fr) * | 1996-04-19 | 1997-10-24 | Atochem Elf Sa | Procede de preparation de (meth)acrylates |
EP0837049A1 (de) * | 1996-10-17 | 1998-04-22 | Rohm And Haas Company | Verfahren zum Herstellen von Monomeren |
EP1078913A2 (de) * | 1999-08-27 | 2001-02-28 | Röhm Gmbh | Verfahren zur Herstellung von Di(meth)acrylsäureestern |
EP1201640A1 (de) * | 2000-10-25 | 2002-05-02 | Atofina | Verfahren zur Herstellung von (Meth)acrylsäuremethylcyclohexylestern |
Non-Patent Citations (3)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 014, no. 146 (C - 0704) 20 March 1990 (1990-03-20) * |
PATENT ABSTRACTS OF JAPAN vol. 014, no. 236 (C - 0720) 18 May 1990 (1990-05-18) * |
PATENT ABSTRACTS OF JAPAN vol. 015, no. 431 (C - 0881) 5 November 1991 (1991-11-05) * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005058862A2 (de) * | 2003-11-26 | 2005-06-30 | Röhm GmbH & Co. KG | Verfahren zur herstellung von glycerincarbonatmethacrylat |
WO2005058862A3 (de) * | 2003-11-26 | 2006-05-04 | Roehm Gmbh | Verfahren zur herstellung von glycerincarbonatmethacrylat |
US7414147B2 (en) | 2003-11-26 | 2008-08-19 | Roehm Gmbh & Co. Kg | Method for producing glycerol carbonate methacrylate |
WO2012038459A1 (de) | 2010-09-23 | 2012-03-29 | Basf Se | Verfahren zur herstellung von (meth)acrylsäureestern von n,n-substituierten aminoalkoholen |
CN102798688A (zh) * | 2012-08-09 | 2012-11-28 | 北京旭阳化工技术研究院有限公司 | 气相色谱内标法测定丙酸甲酯、甲基丙烯酸甲酯和丙酸含量的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE10145228A1 (de) | 2003-04-24 |
EP1423354A1 (de) | 2004-06-02 |
JP2005502698A (ja) | 2005-01-27 |
US7071351B2 (en) | 2006-07-04 |
US20040249191A1 (en) | 2004-12-09 |
JP4146339B2 (ja) | 2008-09-10 |
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