CN105523949A - Method for preparing triethanolamine acrylate compound - Google Patents
Method for preparing triethanolamine acrylate compound Download PDFInfo
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- CN105523949A CN105523949A CN201610029306.9A CN201610029306A CN105523949A CN 105523949 A CN105523949 A CN 105523949A CN 201610029306 A CN201610029306 A CN 201610029306A CN 105523949 A CN105523949 A CN 105523949A
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- methyl acrylate
- vinylformic acid
- acrylate compound
- ester compound
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a method for preparing a triethanolamine acrylate compound. The method comprises the following steps of adding an organic solvent, a catalyst, a polymerization inhibitor and a methyl acrylate compound into a reactor, dropwise adding triethanolamine into a reaction system, and carrying out a reaction for 0.5-15 hours at the temperature of 0-90 DEG C, so as to produce the triethanolamine acrylate compound, wherein the mole ratio of the catalyst to the methyl acrylate is 0.01-20%; the mole ratio of the raw materials, i.e., the triethanolamine to the methyl acrylate is (1: 3.0) to (1: 15.0); and the catalyst is supported zinc bromide, and the methyl acrylate compound is methyl acrylate and methyl methacrylate. According to the method disclosed by the invention, the triethanolamine acrylate product can be prepared in a high-efficiency and environment-friendly manner under relatively mild experimental conditions.
Description
Technical field
The present invention relates to ester class building-up reactions field, specifically relate to and carry out from methyl acrylate compound and trolamine the method that transesterification reaction prepares vinylformic acid trolamine ester compound.
Background technology
Vinylformic acid trolamine ester compound is the important fine-chemical intermediate of a class, this compounds has the higher amido of reactive behavior and vinyl Liang Zhong functional group simultaneously, can be widely used in the numerous areas such as polymeric flocculant, zwitter-ion linking agent, quaternary ammonium salt antiseptic-germicide, polycarboxylate water-reducer, cement grinding aid.Be subject to the extensive concern of the numerous researcher in various countries in recent years.
The synthetic method report of vinylformic acid trolamine ester compound is more, patent CN200910232784.X and research paper (FoodChemistry, 2015,172,56-62; Imaging science and photochemistry, 2008,26,403) reporting respectively with triethylamine is acid binding agent, acrylate chloride and methacrylic chloride react the reaction preparing vinylformic acid methyl triethanol amine ester, methacrylic acid methyl triethanolamine ester respectively with trolamine, generate triethylamine hydrochloride by product in this reaction process.In patent CN201080055967.X, methacrylic acid and trolamine carry out esterification, use methylbenzene azeotropic band water preparing product.This reaction uses a large amount of corrodibility methylsulfonic acids.Therefore, research and develop a kind of easy, environmental protection, efficiently prepare the technique of vinylformic acid trolamine ester compound 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 vinylformic acid trimethylammonium amido ethyl ester compound.
In the reaction of acrylic acid synthesizing trolamine ester compound, usually adopt the method for esterification.The method preparing vinylformic acid trolamine ester compound of bibliographical information, conventional triethylamine, mesylate compound etc., these compound amount are large, price is high, not easily reclaim, and its application is by restriction to a certain extent.Zinc bromide is the important inorganic salt product of a class, can as catalyzer, stablizer, additive etc., and range of application is extremely wide.It is the catalyzer of excellent performance in the reaction, has the features such as catalytic efficiency is high, Heat stability is good, is day by day subject to the attention of numerous scientific research personnel in organic synthesis.But zinc bromide solvability in this reaction system is poor, by its load on the carriers such as gac, aluminum oxide, silicon oxide, molecular sieve, can reduce consumption, improve its catalytic activity, be conducive to catalyst recovery.
The present invention is a kind of preparation method of vinylformic acid trolamine ester compound, and it is characterized in that, the method comprises the following steps:
In reactor, add organic solvent, catalyzer, stopper and methyl acrylate compound, in reaction system, drip trolamine, at 0 ~ 90 DEG C, react 0.5 ~ 15h, generate vinylformic acid trolamine ester compound; Wherein, the mol ratio of described catalyzer and methyl acrylate compound is 0.01 ~ 20%; The mol ratio of raw material trolamine and methyl acrylate compound is 1:3.0 ~ 1:15.0; Described catalyzer is loading type zinc bromide, and described methyl acrylate compound is methyl acrylate and methyl methacrylate.
In above-mentioned preparation method, the carrier of described loading type zinc bromide is the one in gac, aluminum oxide, silicon oxide, molecular sieve.
The mol ratio of described catalyzer and methyl acrylate compound is 0.1 ~ 5%; The temperature of described transesterification reaction is 50 ~ 90 DEG C.
Described organic solvent is preferably one or more solvents in acetone, butanone, toluene, chloroform, tetracol phenixin, hexane, hexanaphthene, heptane, octane, acetonitrile, tetrahydrofuran (THF), glycol dimethyl ether.
Described stopper is preferably 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.
The preparation method of vinylformic acid trolamine ester compound of the present invention is compared with existing preparation method, beneficial effect is: 1) the present invention adopts loading type zinc bromide to be catalyzer, make preparation feedback condition relatively gentle, and vinylformic acid trolamine ester compound can be obtained within a short period of time; 2) adopt the inventive method preparation, the cost of product propylene triethylenetetraminehexaacetic acid alkanolamine ester compounds is lower, and 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 2064g methyl acrylate, 450g hexanaphthene, nitroxyl free radical piperidine alcohols stopper 18.8g, the Zinc Bromide catalyst (charge capacity 19%) that 45.8g is activated carbon supported, open stirring, be warming up to 70 DEG C, drip 596g trolamine, be warming up to backflow, control of reflux ratio 8:1.After reaction terminates, filtering recovering catalyst, rectification under vacuum, steams low-boiling compound, obtains trolamine triacrylate 646g.
Embodiment 2
Be furnished with in the reactor of reaction and rectification device to 5000ml, add 2500g methyl methacrylate, 400g toluene, hydroquinone monomethyl ether's stopper 19.3g, the Zinc Bromide catalyst (charge capacity 15%) of 56.4g gama-alumina load, stir, be warming up to 70 DEG C, drip 596g trolamine, be warming up to backflow, control of reflux ratio 9:1.After reaction terminates, filtering recovering catalyst, rectification under vacuum, steams low-boiling compound, obtains trolamine trimethacrylate 650g.
Embodiment 3
Be furnished with in the reactor of reaction and rectification device to 5000ml, add 2580g methyl acrylate, 400g hexanaphthene, piperidines free radical tris phosphite stopper 27.6g, the Zinc Bromide catalyst (charge capacity 17%) that 54.2gZSM-5 is molecular sieve carried, stir, be warming up to 70 DEG C, drip 596g trolamine, be warming up to backflow, control of reflux ratio 9:1.After reaction terminates, filtering recovering catalyst, rectification under vacuum, steams low-boiling compound, obtains trolamine triacrylate 684g.
Claims (5)
1. a preparation method for vinylformic acid trolamine ester compound, is characterized in that, said method comprising the steps of:
In reactor, add organic solvent, catalyzer, stopper and methyl acrylate compound, in reaction system, drip trolamine, at 0 ~ 90 DEG C, react 0.5 ~ 15h, generate vinylformic acid trolamine ester compound; Wherein, the mol ratio of described catalyzer and methyl acrylate compound is 0.01 ~ 20%; The mol ratio of raw material trolamine and methyl acrylate compound is 1:3.0 ~ 1:15.0; Described catalyzer is loading type zinc bromide, and described methyl acrylate compound is methyl acrylate and methyl methacrylate.
2. the preparation method of vinylformic acid trolamine ester compound according to claim 1, is characterized in that, the carrier of described loading type zinc bromide is the one in gac, aluminum oxide, silicon oxide, molecular sieve.
3. the preparation method of vinylformic acid trolamine ester compound according to claim 1, is characterized in that, the mol ratio of described catalyzer and methyl acrylate compound is 0.1 ~ 5%; The temperature of described transesterification reaction is 50 ~ 90 DEG C.
4. the preparation method of vinylformic acid trolamine ester compound according to claim 1, it is characterized in that, 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.
5. the preparation method of vinylformic acid trolamine ester compound according to claim 1, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610029306.9A CN105523949A (en) | 2016-01-15 | 2016-01-15 | Method for preparing triethanolamine acrylate compound |
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| CN201610029306.9A CN105523949A (en) | 2016-01-15 | 2016-01-15 | Method for preparing triethanolamine acrylate compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868008A (en) * | 2017-11-22 | 2018-04-03 | 许昌学院 | A kind of formaldehyde scavenger and its synthetic method |
| KR101872164B1 (en) * | 2017-09-20 | 2018-06-27 | 동우 화인켐 주식회사 | Acrylate Compound and Photocurable Composition Comprising the Same |
| CN112175592A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Dendritic cationic polyacrylamide coating agent for water-based drilling fluid and preparation method thereof |
| CN112250831A (en) * | 2020-10-12 | 2021-01-22 | 深圳飞扬兴业科技有限公司 | UV resin and preparation method thereof |
| CN113731120A (en) * | 2021-09-22 | 2021-12-03 | 河南佳诺威木业有限公司 | MDF tail gas standard emission process |
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| DE1543279A1 (en) * | 1965-07-15 | 1969-07-31 | Nii Monomerow Dlya Sintetitsch | Process for the production of methacrylic acid esters of polyvalent amino alcohols |
| US3872161A (en) * | 1972-03-06 | 1975-03-18 | Nippon Catalytic Chem Ind | Process for the manufacture of alkylaminoalkyl acrylates |
| CN102800098A (en) * | 2012-07-19 | 2012-11-28 | 中国科学院自动化研究所 | Multi-characteristic multi-level visible light full-color and multi-spectrum high-precision registering method |
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2016
- 2016-01-15 CN CN201610029306.9A patent/CN105523949A/en active Pending
Patent Citations (3)
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| DE1543279A1 (en) * | 1965-07-15 | 1969-07-31 | Nii Monomerow Dlya Sintetitsch | Process for the production of methacrylic acid esters of polyvalent amino alcohols |
| US3872161A (en) * | 1972-03-06 | 1975-03-18 | Nippon Catalytic Chem Ind | Process for the manufacture of alkylaminoalkyl acrylates |
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Non-Patent Citations (1)
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| 汪义勇: "酯交换法合成丙烯酸二甲氨基乙酯和丙烯酰氧基乙基三甲基氯化铵", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101872164B1 (en) * | 2017-09-20 | 2018-06-27 | 동우 화인켐 주식회사 | Acrylate Compound and Photocurable Composition Comprising the Same |
| CN107868008A (en) * | 2017-11-22 | 2018-04-03 | 许昌学院 | A kind of formaldehyde scavenger and its synthetic method |
| CN112175592A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Dendritic cationic polyacrylamide coating agent for water-based drilling fluid and preparation method thereof |
| CN112175592B (en) * | 2019-07-02 | 2022-11-29 | 中石化南京化工研究院有限公司 | Dendritic cationic polyacrylamide coating agent for water-based drilling fluid and preparation method thereof |
| CN112250831A (en) * | 2020-10-12 | 2021-01-22 | 深圳飞扬兴业科技有限公司 | UV resin and preparation method thereof |
| CN113731120A (en) * | 2021-09-22 | 2021-12-03 | 河南佳诺威木业有限公司 | MDF tail gas standard emission process |
| CN113731120B (en) * | 2021-09-22 | 2024-03-26 | 河南佳诺威木业有限公司 | MDF tail gas standard emission process |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
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