EP1423354A1 - Synthesis of alkylaminoalkyl (meth)acrylate by transesterification - Google Patents

Synthesis of alkylaminoalkyl (meth)acrylate by transesterification

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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Withdrawn
Application number
EP02762451A
Other languages
German (de)
French (fr)
Inventor
Bardo Schmitt
Joachim Knebel
Maik Caspari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1423354A1 publication Critical patent/EP1423354A1/en
Withdrawn legal-status Critical Current

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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.

Abstract

The invention relates to a method for transesterifying methyl methacrylate involving catalysis, particularly zirconium acetylacetonate catalysis. The obtained esters of formula (I) are characterized by having an extremely low content of cross-linking agents.

Description

Synthese von t-ButylaminoethylmethaciNlat durch UmesterungSynthesis of t-butylaminoethyl methacylate by transesterification
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Umesterung von Estern ungesättigter Carbonsäuren mit reaktiven Alkoholen und einem Katalysator für diese Verfahren.The invention relates to a process for the transesterification of esters of unsaturated carboxylic acids with reactive alcohols and a catalyst for these processes.
Stand der TechnikState of the art
Es ist bekannt, Carbonsäureester durch Umesterung herzustellen.It is known to produce carboxylic acid esters by transesterification.
R — COOR' + R,L- OH ► R — COOR" + R'— OHR - COOR '+ R , L - OH ► R - COOR "+ R'— OH
R stellt im allgemeinen eine aliphatische oder aromatische Gruppe dar, R' kann beispielsweise Methyl oder Ethyl sein, und R" ist eine Gruppe, die mehr Kohlenstoffatome als R' enthalten kann. R' und R" kann man so auswählen, dass der entstehende Alkohol leichter flüchtig als der Ester ist. Der Einsatz eines Katalysators beschleunigt die Einstellung des Gleichgewichts. R generally represents an aliphatic or aromatic group, R 'can be, for example, methyl or ethyl, and R "is a group which can contain more carbon atoms than R'. 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.
Die vorliegende Erfindung betrifft die Synthese von t- Butylaminoethylmethacrylat durch Umesterung von t-Butylaminoethanol mit Methacrylsäuremethylester (MMA). Die Umesterung ist an sich bekannt. JP 062717517 und JP 06256271 beschreiben die Umesterung von Methylmethacrylat mit t-Butylaminoethanol unter Katalyse von K2CO3. Nachteilig hierbei ist die relativ lange Reaktionszeit (5 Stunden), und das Auftreten von Nebenprodukten (91 % Reinheit), so dass das Produkt durch Destillation gereinigt werden muss.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 und JP 62175448 beschreiben die Synthese von Diethylaminoethylmethacrylaten in Gegenwart von K2CO3, Rb2Cθ3, Cs2CO3. Die erzielte Reinheit ist zwar größer 95 %, die Reaktion dauert aber immer noch 5 Stunden.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 beschreibt die Verwendung von KHCO3als Katalysator. Hierbei ist nachteilig, dass die Reaktion ebenfalls 5 Stunden dauert und eine Destillation zur Reinigung des Rohprodukts erforderlich ist. Generell kann festgehalten werden, dass alkalische Katalysatoren vermehrt zu Doppelbindungsaddukten führen, insbesondere in Gegenwart von Aminen.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. In general, it can be stated that alkaline catalysts increasingly lead to double bond adducts, especially in the presence of amines.
EP 298867 beschreibt die Katalyse mittels Titan(IV)-Alkoholat. Hierbei ist zu bemerken, dass auch mit dieser Methode eine Aufarbeitung mittels Destillation notwendig ist, um eine Reinheit > 98 % zu erhalten. Ti-Katalysatoren sind außerdem H2O empfindlich, was einen größeren Aufwand bei der Reaktionsführung der Synthese verursacht. JP 62230755 beschreibt die K3PO -Katalyse. Nachteilig hierbei ist wiederum die Reaktionszeit von 5 Stunden bei einem Umsatz von 83,5 %.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%.
In JP 56104851 wird Dibutylzinnoxid als Katalysator eingesetzt. Dieser Katalysator hat den Nachteil, dass für einen Umsatz größer 95 % 8 Stunden benötigt werden.JP 56104851 uses dibutyltin oxide as a catalyst. This catalyst has the disadvantage that it takes 8 hours for a conversion greater than 95%.
Alkalimetalloxide werden in FR 1568382 und in GB 1174148 offenbart. Nachteilig hierbei ist, dass die Umsätze < 95 % sind und die Ausbeute nur etwas größer als 80 % beträgt.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) beschreibt die Umesterung von (Meth)acrylaten in Gegenwart eines Alkohols und/oder in Gegenwart eines Gemisches aus Alkoholaten des betreffenden Alkohols und/oder von Methanol mit Ca, Mg oder Ba, Ti und Zr oder AI. Der Katalysator kann recycled werden.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.
Nach der Vorschrift wird Dimethylaminoethanol (DMEA) mit MMA zu DMAEA (Dimethylaminoethylmethacrylat) umgeestert. Nachteilig hierbei ist, dass der Alkohol zuerst in das Metallalkoholat umgewandelt werden muss, was aufwendig ist, um dann in großer Menge bei der Synthese eingesetzt zu werden (Anteil-Ligand DMEA : MMA = 3 : 4 !). EP 118639 (Allied Colloids) beschreibt ein Umesterungsverfahren unter Katalyse von Metallalkoholaten der Metalle Ti, AI, Zr, Ca oder Mg.According to the instructions, dimethylaminoethanol (DMEA) is transesterified with MMA to form DMAEA (dimethylaminoethyl methacrylate). The disadvantage here is that the alcohol first has to be converted into the metal alcoholate, which is complex, in order to be used in large amounts in the synthesis (DMEA: MMA = 3: 4!). EP 118639 (Allied Colloids) describes a transesterification process with catalysis by metal alcoholates of the metals Ti, Al, Zr, Ca or Mg.
US-PS 2,138,763 beschreibt die Umesterung von Methylmethacrylat mit unterschiedlichen Aminoalkoholen in Gegenwart von Na-Methanolat.US Pat. No. 2,138,763 describes the transesterification of methyl methacrylate with different amino alcohols in the presence of Na methanolate.
Die Reaktion muss in Abwesenheit von Wasser und reaktiven Alkoholen durchgeführt werden. Die besten Ergebnisse werden mit Calcium oder Magnesium als Metallkomponente erreicht. Über das Nebenproduktspektrum werden keine Angaben gemacht.The 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.
Aufgabetask
Es bestand die Aufgabe, ein weiteres Verfahren zur Umesterung von ungesättigten Carbonsäureestern zur Verfügung zu stellen. Der Katalysator sollte einfach herzustellen und gut abtrennbar sein.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.
Die Erfindung beschreibt ein Verfahren zur Umesterung von reaktiven Alkoholen mit Methylmethacrylat. Unter reaktiven Alkoholen werden Alkohole mit einer oder mehreren funktionellen Gruppen verstanden, beispielsweise Hydroxygruppen, Aminogrupen, substituierte Aminogruppen, Thiolgruppen, Epoxygruppen. Vorteil der erfindungsgemäßen Lösung, die in der Katalyse der Umesterung durch Zirkonacetylacetonat besteht, ist ein Methacrylsäureester mit einem niedrigerem Vernetzergehalt. Die Ausbeute, bezogen auf die eingesetzten Rohstoffe, ist höher, es fallen weniger Nebenprodukte an.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.
Lösungsolution
Gelöst werden diese sowie weitere nicht explizit genannte Aufgaben, die jedoch aus den hierin einleitend diskutierten Zusammenhängen ohne weiteres ableitbar oder erschließbar sind, durch ein Verfahren des Anspruches 1. Zweckmäßige Abwandlungen des erfindungsgemäßen Verfahrens werden in den auf Anspruch 1 rückbezogenen Unteransprüchen unter Schutz gestellt.These and other tasks which are not explicitly mentioned, but which can be derived or inferred from the contexts discussed at the outset, are solved by a method of claim 1. Appropriate modifications of the method according to the invention are protected in the subclaims referring to claim 1.
Reaktionsgleichungreaction equation
(II) (III) (I) R1 = H, CH3 R = H, CH3, CH2-CH3 (II) (III) (I) R 1 = H, CH 3 R = H, CH 3 , CH 2 -CH 3
- Propyl, Isopropyl,- propyl, isopropyl,
- Butyl, Isobutyl, t-Butyl R = CH3, CH2-CH3 - Butyl, isobutyl, t-butyl R = CH 3 , CH 2 -CH 3
- Propyl, Isopropyl- propyl, isopropyl
- Butyl, Isobutyl, t-Butyl- butyl, isobutyl, t-butyl
R = -CH2-, -CH2-CH2-, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, -CH2-CH-,R = -CH2-, -CH2-CH2-, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, -CH2-CH-,
I CH3 I CH 3
CH3 ICH 3 I
-CH2-C-CH2CH2-CH2-C
I I
Als Katalysator können neben Zirkonacetylacetonat auch andere 1 ,3-Diketonate des Zirkons, z. B. 1 ,3 Diphenylpropan-1 ,3-dion verwendet werden. In addition to zirconium acetylacetonate, other 1,3-diketonates of zirconium, e.g. B. 1, 3 diphenylpropane-1, 3-dione can be used.
BEISPIELEEXAMPLES
Allgemeine VersuchsbeschreibungGeneral description of the experiment
117,2 g (1 mol) 2-(tert.-Butylamino)ethanol, 500g (5 mol) Methylmethacrylat (MMA), Katalysator (1-2% bez. auf Ansatz, siehe Tabelle) und Stabilisator (0,62g Irganox 1076/Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat, 0,012g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl) werden im Reaktionskolben mit Kolonne und automatischem Kolonnenkopf vorgelegt und aufgeheizt. Die Umesterung wird bei einer Kopftemperatur von 70 °C unter Abzug des Methanol-MM A-Azeotrops durchgeführt. Steigt die Temperatur an, wird unter einem Rückflußverhältnis von 10:1 bis zu einer Temperatur von 100 °C Destillat abgezogen. Anschließend wird überschüssiges MMA im Vakuum abdestilliert. 117.2 g (1 mol) of 2- (tert-butylamino) ethanol, 500 g (5 mol) of methyl methacrylate (MMA), catalyst (1-2% based on the batch, see table) and stabilizer (0.62 g of Irganox 1076 / Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.012 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl) are placed in the reaction flask with a column and an automatic column head and heated. The transesterification is carried out at a top temperature of 70 ° C. with the deduction of the methanol-MM A azeotrope. If the temperature rises, the distillate is drawn off under a reflux ratio of 10: 1 to a temperature of 100.degree. Excess MMA is then distilled off in vacuo.
Tabelletable
MMA = Methylmethacrylat tBAE = tert.-Butylaminoethanol tBAEMA = tert.-ButylaminoethylmethacrylatMMA = methyl methacrylate tBAE = tert-butylaminoethanol tBAEMA = tert-butylaminoethyl methacrylate
EGDMA = EthylenglykoldimethacrylatEGDMA = ethylene glycol dimethacrylate
MtBMAA = N, N-(Methacryloyloxyethyl)-tert.-butylmethacrylamid MtBMAA = N, N- (methacryloyloxyethyl) tert-butyl methacrylamide
Die Tabelle zeigt, dass die Menge an EGDMA im Vergleich zur Katalyse mit Dioctylzinnoxyd um mindestens 50 % reduziert wird. Viel signifikanter ist jedoch die Abnahme des hochsiedenden Vernetzers MtBMAA auf unter 0,1 %. Die Abtrennung des Katalysators ist leicht durch Destillation zu erzielen. The table shows that the amount of EGDMA is reduced by at least 50% compared to catalysis with dioctyltin oxide. However, 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.

Claims

PATENTANSPRÜCHE
1. Verfahren zur Herstellung von Verbindungen der Formel1. Process for the preparation of compounds of the formula
(i)(I)
dadurch gekennzeichnet, dasscharacterized in that
man Verbindungen der Formel IIcompounds of formula II
(II)(II)
mit Verbindungen der Formel IIIwith compounds of formula III
(III)(III)
in Gegenwart eines Katalysators umsetzt, wobei gilt: R1 = H, CH3 in the presence of a catalyst, where: R 1 = H, CH 3
R = H, CH3, CH2-CH3 R = H, CH 3 , CH 2 -CH 3
R = H, CH3, CH2-CH3 R = H, CH 3 , CH 2 -CH 3
- Propyl, Isopropyl,- propyl, isopropyl,
- Butyl, Isobutyl, t-Butyl - butyl, isobutyl, t-butyl
- Propyl, Isopropyl- propyl, isopropyl
- Butyl, Isobutyl, t-Butyl- butyl, isobutyl, t-butyl
R = -CH2-, -CH2-CH2-, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, -CH2-CH-,R = -CH2-, -CH2-CH2-, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, -CH2-CH-,
I CH3 I CH 3
CH3 ICH 3 I
2. Verfahren nach Anspruch 1 ,2. The method according to claim 1,
dadurch gekennzeichnet, dasscharacterized in that
der Katalysator Zirkonacetylacetonat ist.the catalyst is zirconium acetylacetonate.
3. Verfahren nach Anspruch 1 ,3. The method according to claim 1,
dadurch gekennzeichnet, dasscharacterized in that
der Katalysator in Mengen von 0,1 - 5,0 Gew.-%, bezogen auf das Gesamtgewicht des Ansatzes, eingesetzt wird. the catalyst is used in amounts of 0.1-5.0% by weight, based on the total weight of the batch.
4. Verfahren nach Anspruch 1 ,4. The method according to claim 1,
dadurch gekennzeichnet, dasscharacterized in that
das Verfahren sowohl kontinuierlich als auch diskontinuierlich durchgeführt wird.the process is carried out both continuously and batchwise.
5. Verfahren nach Anspruch 1 ,5. The method according to claim 1,
dadurch gekennzeichnet, dasscharacterized in that
die Verbindung der Formel III t-Butylaminoethanol ist. the compound of formula III is t-butylaminoethanol.
EP02762451A 2001-09-13 2002-08-16 Synthesis of alkylaminoalkyl (meth)acrylate by transesterification Withdrawn EP1423354A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10145228A DE10145228A1 (en) 2001-09-13 2001-09-13 Synthesis of t-butylaminoethyl methacrylate by transesterification of the alcohol with MMA
DE10145228 2001-09-13
PCT/EP2002/009197 WO2003022796A1 (en) 2001-09-13 2002-08-16 Synthesis of alkylaminoalkyl (meth)acrylate by transesterification

Publications (1)

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US (1) US7071351B2 (en)
EP (1) EP1423354A1 (en)
JP (1) JP4146339B2 (en)
DE (1) DE10145228A1 (en)
WO (1) WO2003022796A1 (en)

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FR2876375B1 (en) * 2004-10-12 2007-02-02 Arkema Sa PROCESS FOR THE PREPARATION OF (METH) ACRYLIC ESTERS OR ANYDRIDES
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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
JP7163406B2 (en) 2018-04-12 2022-10-31 エスペーセーエム・エスアー 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

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US20040249191A1 (en) 2004-12-09
JP4146339B2 (en) 2008-09-10
DE10145228A1 (en) 2003-04-24
WO2003022796A1 (en) 2003-03-20
US7071351B2 (en) 2006-07-04
JP2005502698A (en) 2005-01-27

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