CN105294462A - Method for preparing 2-(dimethylamino)ethyl acrylate by ester interchange method - Google Patents
Method for preparing 2-(dimethylamino)ethyl acrylate by ester interchange method Download PDFInfo
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- CN105294462A CN105294462A CN201510778355.8A CN201510778355A CN105294462A CN 105294462 A CN105294462 A CN 105294462A CN 201510778355 A CN201510778355 A CN 201510778355A CN 105294462 A CN105294462 A CN 105294462A
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Abstract
The invention relates to a method for preparing 2-(dimethylamino)ethyl acrylate by an ester interchange method. The preparation method comprises that an organic solvent, methyl acrylate, N, N-dimethyl ethanolamine and a polymerization inhibitor are added into a reactor, the mixture undergoes a reaction in the presence of loaded zinc chloride as an ester interchange reaction catalyst at a temperature of 0-80 DEG C to produce the 2-(dimethylamino)ethyl acrylate compound. A mole ratio of the methyl acrylate raw material to the N, N-dimethyl ethanolamine raw material is 1: 1.0-1: 10. A mole ratio of the catalyst to methyl acrylate is in a range of 0.01-20%. The method realizes high efficiency and eco-friendly preparation of amino acrylate under mild conditions.
Description
Technical field
The present invention relates to ester class building-up reactions field, be specifically related to the preparation method of DMAM, in particular to the method for carrying out transesterification reaction from methyl acrylate and N, N-dimethyl ethanol amine compound and preparing DMAM compounds.
Background technology
DMAM compounds is the important fine-chemical intermediate of a class, it has active higher amido and vinyl-functional simultaneously, is widely used in the fields such as polymeric flocculant, rubber modifier, lubricating oil additive, drilling mud additives.Be subject to the extensive concern of numerous researcher in recent years.
The synthetic method report of vinylformic acid amido ethyl ester compound is more, usually with methyl acrylate and N, N-dimethylethanolamine for raw material, by ester exchange method acrylic acid synthesizing aminoethyl compounds.But there is many weak points in this compounds method of traditional synthesis.(chemistry and biotechnology, 2009,26 (4) such as Wang Yiyong, 20) reporting with tetrabutyl titanate is the method that catalyzer carries out transesterification reaction and prepares vinylformic acid diethyl aminoethyl, the method catalyzer price is higher, not easily reclaims, contaminate environment.It is catalyzer that Liu Xiangchen etc. (chemistry world, 2002,43,138 pages) have studied with organo-tin compound, is prepared the method for vinylformic acid amido ethyl ester compound by ester exchange method; It is catalyst preparing vinylformic acid aminoethyl that patent CN201080022554.1 reports with dibutyl tin acetate; It is the preparation method of catalyzer that patent CN201080022690.0 reports with Dibutyltin oxide.Organotin catalysts toxicity is comparatively large in these methods, price is higher, under the requirement that environmental protection standard improves day by day now, and unsuitable large-scale application.Therefore, research and develop a kind of easy, environmental protection, efficiently prepare the technique of DMAM compounds and become one of the study hotspot in this field current.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, propose a kind of can efficiently, environmental protection, low cost the method preparing DMAM compound.
In the reaction of acrylic acid synthesizing dimethyl amido ethyl ester compound, usually adopt the method for catalyzed transesterification.The ester-interchange method of bibliographical information prepares the method for DMAM, and conventional catalyzer is titanic acid ester, organo-tin compound etc., and these catalyst toxicities are large, price, not easily reclaim, and its application is by restriction to a certain extent.Zinc chloride is a kind of important inorganic salt product, can as catalyzer, stablizer, additive etc., and range of application is extremely wide.In this reaction process, zinc chloride is a kind of catalyzer of excellent performance, has that catalytic efficiency is high, thermostability high, is day by day subject to the attention of numerous scientific research personnel in organic synthesis.But zinc chloride solvability in this reaction system is poor, by zinc chloride load on the carriers such as gac, aluminum oxide, molecular sieve, can reduce consumption, improve its catalytic activity, be conducive to catalyst recovery.
The present invention is a kind of method that ester-interchange method prepares DMAM, comprises the following steps:
In reactor, add organic solvent, methyl acrylate, catalyzer and stopper, in reaction system, drip N, N-dimethylethanolamine, when 0 ~ 80 DEG C, react 0.5 ~ 10h, generate DMAM compound; Wherein, the mol ratio of described catalyzer and methyl acrylate is 0.01 ~ 20%; The mol ratio of raw material propylene acid methyl esters and N, N-dimethylethanolamine is 1:1.0 ~ 1:10; Described catalyzer is loading type zinc chloride.
Described catalyzer is preferably loading type zinc chloride, and carrier is the one in gac, aluminum oxide, molecular sieve.By certain density liquor zinci chloridis of carrier impregnation such as gac, aluminum oxide, molecular sieves, drying, calcination process form.
Described organic solvent is one or more solvents in acetone, butanone, toluene, chloroform, tetracol phenixin, hexane, hexanaphthene, heptane, octane, acetonitrile, tetrahydrofuran (THF), glycol dimethyl ether.
Described stopper is at least one in the compounds such as nitroxyl free radical piperidine alcohols, piperidines free radical tris phosphite, hydroquinone monomethyl ether, thiodiphenylamine, tert.-butyl phenol, Resorcinol.
In technique scheme, the mol ratio of described catalyzer and methyl acrylate is preferably 0.1% ~ 5%, and the temperature of reaction of described transesterification reaction is preferably 50 ~ 80 DEG C.
The preparation method of DMAM compound of the present invention is compared with existing preparation method; have employed loading type zinc chloride is catalyst for esterification reaction, and catalyst toxicity is little, consumption is few, is easy to reclaim; present method is more efficient, environmental protection, is suitable for large-scale production.
Embodiment
Below in conjunction with concrete example, the present invention is described in detail, but be not limited to these examples, and raw material used in the present invention is commercially available.
Embodiment 1
Be furnished with in the reactor of reaction and rectification device to 5000ml, add 1291g methyl acrylate, 600g hexanaphthene, nitroxyl free radical piperidine alcohols stopper 17.2g, the zinc chloride catalyst (charge capacity 15%) that 50g is activated carbon supported, stir, be warming up to 70 DEG C, drip 890gN, N-dimethylethanolamine, be warming up to backflow, control of reflux ratio 5:1, reaction 6h.After reaction terminates, filtering recovering catalyst, rectification under vacuum, obtains the DMAM 1230g that purity is greater than 99%.
Embodiment 2
Be furnished with in the reactor of reaction and rectification device to 5000ml, add 1205g methyl acrylate, 500g toluene, hydroquinone monomethyl ether's stopper 12.4g, the zinc chloride catalyst (charge capacity 21%) of 65g gama-alumina load, stir, be warming up to 70 DEG C, drip 890gN, N-dimethylethanolamine, be warming up to backflow, control of reflux ratio 8:1, reaction 7h.After reaction terminates, filtering recovering catalyst, rectification under vacuum, obtains the DMAM 1193g that purity is greater than 99%.
Embodiment 3
Be furnished with in the reactor of reaction and rectification device to 5000ml, add 1446g methyl acrylate, 750g heptane, piperidines free radical tris phosphite stopper 25.3g, the zinc chloride catalyst (charge capacity 16%) that 90gZSM-5 is molecular sieve carried, stir, be warming up to 70 DEG C, drip 1068gN, N-dimethylethanolamine, be warming up to backflow, control of reflux ratio 8:1, reaction 6h.After reaction terminates, filtering recovering catalyst, rectification under vacuum, obtains the DMAM 1424g that purity is greater than 99%.
Claims (4)
1. ester-interchange method prepares a method for DMAM, it is characterized in that, said method comprising the steps of:
In reactor, add organic solvent, methyl acrylate, catalyzer and stopper, in reaction system, drip N, N-dimethylethanolamine, when 0 ~ 80 DEG C, react 0.5 ~ 10h, generate DMAM compound; Wherein, the mol ratio of described catalyzer and methyl acrylate is 0.01 ~ 20%; The mol ratio of raw material propylene acid methyl esters and N, N-dimethylethanolamine is 1:1.0 ~ 1:10; Described catalyzer is loading type zinc chloride.
2. ester-interchange method according to claim 1 prepares the method for DMAM, it is characterized in that, described catalyzer is loading type zinc chloride, and carrier is the one in gac, aluminum oxide, molecular sieve.
3. ester-interchange method according to claim 1 prepares the method for DMAM, it is characterized in that, the mol ratio of described catalyzer and methyl acrylate is 0.1% ~ 5%; The temperature of reaction of described transesterification reaction is 50 ~ 80 DEG C.
4. ester-interchange method according to claim 1 prepares the method for DMAM, it is characterized in that, described stopper is at least one in the compounds such as nitroxyl free radical piperidine alcohols, piperidines free radical tris phosphite, hydroquinone monomethyl ether, thiodiphenylamine, tert.-butyl phenol, Resorcinol.
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| CN201510778355.8A CN105294462A (en) | 2015-11-13 | 2015-11-13 | Method for preparing 2-(dimethylamino)ethyl acrylate by ester interchange method |
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| CN201510778355.8A CN105294462A (en) | 2015-11-13 | 2015-11-13 | Method for preparing 2-(dimethylamino)ethyl acrylate by ester interchange method |
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| CN201510778355.8A Pending CN105294462A (en) | 2015-11-13 | 2015-11-13 | Method for preparing 2-(dimethylamino)ethyl acrylate by ester interchange method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413627A (en) * | 2021-08-25 | 2021-09-21 | 山东蓝湾新材料有限公司 | Energy-saving separation device for high-molecular polymer intermediate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3872161A (en) * | 1972-03-06 | 1975-03-18 | Nippon Catalytic Chem Ind | Process for the manufacture of alkylaminoalkyl acrylates |
| JPS62185059U (en) * | 1986-05-15 | 1987-11-25 | ||
| JP2004189650A (en) * | 2002-12-10 | 2004-07-08 | Mitsubishi Rayon Co Ltd | Method for producing (meth)acrylic ester |
| CN1312113C (en) * | 2003-05-28 | 2007-04-25 | 大野绿水株式会社 | Process for the production of n-alkylaminoalkyl (meth)acrylates |
| CN100349851C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
-
2015
- 2015-11-13 CN CN201510778355.8A patent/CN105294462A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3872161A (en) * | 1972-03-06 | 1975-03-18 | Nippon Catalytic Chem Ind | Process for the manufacture of alkylaminoalkyl acrylates |
| JPS62185059U (en) * | 1986-05-15 | 1987-11-25 | ||
| CN100349851C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
| JP2004189650A (en) * | 2002-12-10 | 2004-07-08 | Mitsubishi Rayon Co Ltd | Method for producing (meth)acrylic ester |
| CN1312113C (en) * | 2003-05-28 | 2007-04-25 | 大野绿水株式会社 | Process for the production of n-alkylaminoalkyl (meth)acrylates |
Non-Patent Citations (1)
| Title |
|---|
| 史鸿鑫: "《现代化学功能材料》", 30 June 2009, 北京：化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413627A (en) * | 2021-08-25 | 2021-09-21 | 山东蓝湾新材料有限公司 | Energy-saving separation device for high-molecular polymer intermediate |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: CHINA NATIONAL OFFSHORE OIL Corp. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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