CN105541625A - Method for preparing acetoacetoxy ethyl methacrylate - Google Patents
Method for preparing acetoacetoxy ethyl methacrylate Download PDFInfo
- Publication number
- CN105541625A CN105541625A CN201511007748.5A CN201511007748A CN105541625A CN 105541625 A CN105541625 A CN 105541625A CN 201511007748 A CN201511007748 A CN 201511007748A CN 105541625 A CN105541625 A CN 105541625A
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- CN
- China
- Prior art keywords
- aaem
- method preparing
- hydroxyethyl methylacrylate
- temperature condition
- ketene dimer
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a method for preparing acetoacetoxy ethyl methacrylate, which comprises the following steps: mixing hydroxyethyl methacrylate, a polymerization inhibitor, a catalyst and a solvent, and dropwisely adding ketene dimer at 30-160 DEG C; and after the dropwise addition is finished, carrying out thermal reaction under the temperature condition above until the reaction finishes; and after the thermal reaction finishes, distilling to remove the solvent, and continuing distillation to obtain the acetoacetoxy ethyl methacrylate. The method is simple in technique. The product has the advantages of high yield, high purity and stable quality.
Description
Technical field
The present invention relates to a kind of method preparing AAEM.
Background technology
AAEM (AAEM) is a kind of novel methacrylic acid aqueous functional monomer, it has low toxicity, the advantages such as easy copolymerization and good complex performance, its special molecular structure makes AAEM be polymerized in ACRYLIC EMULSION, resin based on unsaturated polyyester, the field tools such as UV photocuring have been widely used, application potential industrially constantly expands, AAEM (AAEM) is light yellow clear liquid, containing polymerizable vinyl and active acetoacetyl-functional group in molecule, be study in the world at present more, one of novel methacrylic acid monomer of the one that value ratio is larger, there is toxicity low, the features such as easy copolymerization, in Polymer Synthesizing and modification, tool has been widely used.Be commonly used to the solvent type acrylic resin of synthesis of high solid content, and synthesize self-crosslinking or normal temperature crosslinked emulsion acrylic resin.Can be used to alternative N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), hydroxyethyl methylacrylate etc., have the advantages such as reaction better controls, product performance are better, application potential industrially constantly expands.
US Patent No. 3554987, US3658878 was once disclosed the synthetic method about AAEM, hydroxyethyl methylacrylate (HEMA) and methyl aceto acetate is mostly adopted to be raw material, be that catalyzer carries out transesterification reaction with sulfuric acid, these methods are using ethyl acetate as solvent, due to methyl aceto acetate from condensation and hydrolysis, cause that side reaction is many, separation difficulty, thus yield is lower.
Summary of the invention
The object of the present invention is to provide a kind of method preparing AAEM.
The method preparing AAEM provided by the invention, comprises the following steps:
By hydroxyethyl methylacrylate, stopper, catalysts and solvents mixing, then under 30 DEG C of-160 DEG C of temperature condition, drip ketene dimer, dropwise and continue to carry out insulation reaction under said temperature condition until reaction terminates; First remove desolventizing by distillation after insulation reaction completes, then continue distillation, gained cut is AAEM.
Described stopper is Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, thiodiphenylamine, butylated hydroxytoluene, 2-Tert. Butyl Hydroquinone and 2, one or more in 5-di-tert-butyl hydroquinone, stopper consumption is the 0.1%-10% of hydroxyethyl methylacrylate quality.
Described catalyzer is triethylamine or sodium hydroxide; Catalyst levels is the 0.1%-10% of hydroxyethyl methylacrylate quality.
Described solvent is toluene, tetrahydrofuran (THF), DMF, acetone, chlorobenzene or hexanaphthene.
Described solvent and hydroxyethyl methylacrylate mol ratio are 0.1-10: 1.
The mol ratio of described methylate Hydroxyethyl acrylate and ketene dimer is 1:1-3.
The time for adding of described ketene dimer is 10 minutes to 2 hours.
The time of described insulation reaction is 1-8 hour.
In order to be greater than, 0Pa is less than or equal to 1000Pa to the pressure condition of described continuation underpressure distillation, temperature condition is 95 DEG C-135 DEG C; The cut collected under above-mentioned pressure and temperature condition is AAEM.
The present invention first goes out desolventizing by underpressure distillation, also by the mode of solvent and hydroxyethyl methylacrylate azeotropic, hydroxyethyl methylacrylate is taken out of except while desolventizing, efficiently solve the problem of hydroxyethyl methylacrylate and AAEM separation difficulty, improve product purity.
The present invention has the following advantages:
1, by preferred reaction proportioning, add catalyzer simple and easy to get and stopper, just available AAEM, not only technique is simple, and yield is up to more than 90%;
2, post processing mode is simple, and no coupling product produces.
3, by the mode of the azeotropic of solvent and hydroxyethyl methylacrylate except desolventizing, hydroxyethyl methylacrylate is taken out of simultaneously, efficiently solve the problem of hydroxyethyl methylacrylate and AAEM separation difficulty, improve product purity, the main content of product is more than 98%.
Embodiment
Embodiment 1
By 130g hydroxyethyl methylacrylate, 92g toluene, 2g sodium hydroxide is as catalyzer, 2g Resorcinol is as stopper, join after mixing in reaction flask, flask is placed in 100 DEG C of oil bath pans, when interior temperature reaches 90 DEG C-100 DEG C, 90g ketene dimer is added drop-wise in flask, time for adding is two hours, after dropwising under said temperature condition insulation reaction 6 hours, after insulation reaction terminates, distill except desolventizing under normal pressure and temperature 110 DEG C of-120 DEG C of conditions, after desolventizing, proceed underpressure distillation, collect the cut under pressure 150Pa and temperature 105 DEG C of-110 DEG C of conditions, the 202g cut obtained is AAEM, product yield is 94%, product is through chromatographic, main content is 98.5%, methacrylic acid content≤0.5%.
Embodiment 2
By 130g hydroxyethyl methylacrylate, 100gN, dinethylformamide, 2g sodium hydroxide is as catalyzer, 2g Resorcinol is as stopper, join after mixing in reaction flask, flask is placed in 100 DEG C of oil bath pans, when interior temperature reaches 90 DEG C-100 DEG C, 110g ketene dimer is added drop-wise in flask, time for adding is two hours, dropwise rear insulation reaction 6 hours, after insulation reaction terminates, except desolventizing under pressure 2000Pa and temperature 50 C-60 DEG C of conditions, after desolventizing, proceed underpressure distillation, collect the cut under pressure 200Pa and temperature 108 DEG C of-115 DEG C of conditions, the 202g cut obtained is AAEM, finished product yield is 94%, product is through chromatographic, main content is 98.6%, methacrylic acid content≤0.5%.
Embodiment 3
By 130g hydroxyethyl methylacrylate, 200g chlorobenzene, 10g triethylamine is as catalyzer, 5g thiodiphenylamine and 5g para benzoquinone are as stopper, join after mixing in reaction flask, flask is placed in 130 DEG C of oil bath pans, when interior temperature reaches 110 DEG C-130 DEG C, be added drop-wise in flask by 100g ketene dimer, time for adding is one hour, dropwises rear insulation reaction 3 hours, after insulation reaction terminates, except desolventizing under pressure 3000Pa and temperature 45 C-55 DEG C of conditions, after desolventizing, proceed underpressure distillation.Collect the cut under pressure 50Pa and temperature 100 DEG C of-105 DEG C of conditions, the 206g cut obtained is AAEM, and finished product yield is 95%, and product is through chromatographic, and main content is 98%, methacrylic acid content≤0.5%.
Embodiment 4
By 130g hydroxyethyl methylacrylate, 140g tetrahydrofuran (THF), 1g sodium hydroxide is as catalyzer, 2g thiodiphenylamine, 2g para benzoquinone and 5g MEHQ are as stopper, join after mixing in reaction flask, flask is placed in 50 DEG C of oil bath pans, when interior temperature reaches 30 DEG C-50 DEG C, 160g ketene dimer is added drop-wise in flask, time for adding is one hour, dropwise rear insulation reaction 3 hours, after insulation reaction terminates, except desolventizing under normal pressure and temperature 60 C-70 DEG C of conditions, after desolventizing, proceed underpressure distillation, collect the cut under pressure 400Pa and temperature 115 DEG C of-125 DEG C of conditions, the 205g cut obtained is AAEM, finished product yield is 95%, product is through chromatographic, main content is 98.7%, methacrylic acid content≤0.5%.
Embodiment 5
By 130g hydroxyethyl methylacrylate, 30gN, dinethylformamide, 1g triethylamine is as catalyzer, 2g MEHQ is as stopper, join after mixing in reaction flask, flask is placed in 140 DEG C of oil bath pans, when interior temperature reaches 130 DEG C-140 DEG C, 100g ketene dimer is added drop-wise in flask, time for adding is two hours, dropwise rear insulation reaction 8 hours, after insulation reaction terminates, except desolventizing under pressure 5000Pa and temperature 70 C-80 DEG C of conditions, after desolventizing, proceed underpressure distillation, collect the cut under pressure 900Pa and temperature 125 DEG C of-130 DEG C of conditions, the 203g cut obtained is AAEM, finished product yield is 94.7%, product is through chromatographic, main content is 99%, methacrylic acid content≤0.5%.
Embodiment 6
By 130g hydroxyethyl methylacrylate, 92g toluene, 2g triethylamine is as catalyzer, 2g MEHQ is as stopper, join after mixing in reaction flask, flask is placed in 100 DEG C of oil bath pans, when interior temperature reaches 80 DEG C-100 DEG C, 100g ketene dimer is added drop-wise in flask, time for adding is two hours, dropwise rear insulation reaction 8 hours, after insulation reaction terminates, except desolventizing under pressure 4000Pa and temperature 30 DEG C of-40 DEG C of conditions, after desolventizing, proceed underpressure distillation, collect the cut under pressure 20Pa and temperature 98 DEG C of-102 DEG C of conditions, the 203g cut obtained is AAEM, finished product yield is 94.7%, product is through chromatographic, main content is 99%, methacrylic acid content≤0.5%.
Claims (9)
1. prepare a method for AAEM, it is characterized in that comprising the following steps:
By hydroxyethyl methylacrylate, stopper, catalysts and solvents mixing, then under 30 DEG C of-160 DEG C of temperature condition, drip ketene dimer, dropwise and continue to carry out insulation reaction under said temperature condition until reaction terminates; First remove desolventizing by distillation after insulation reaction completes, then continue distillation, gained cut is AAEM.
2. the method preparing AAEM according to claim 1, it is characterized in that: described stopper is Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, thiodiphenylamine, butylated hydroxytoluene, 2-Tert. Butyl Hydroquinone and 2, one or more in 5-di-tert-butyl hydroquinone, stopper consumption is the 0.1%-10% of hydroxyethyl methylacrylate quality.
3. the method preparing AAEM according to claims 1, is characterized in that: described catalyzer is triethylamine or sodium hydroxide; Catalyst levels is the 0.1%-10% of hydroxyethyl methylacrylate quality.
4. the method preparing AAEM according to claims 1, is characterized in that: described solvent is toluene, tetrahydrofuran (THF), DMF, acetone, chlorobenzene or hexanaphthene.
5. the method preparing AAEM according to claims 1 or 4, is characterized in that: described solvent and hydroxyethyl methylacrylate mol ratio are 0.1-10: 1.
6. the method preparing AAEM according to claim 1, is characterized in that: the mol ratio of described methylate Hydroxyethyl acrylate and ketene dimer is 1:1-3.
7. the method preparing AAEM according to claim 1, is characterized in that: the time for adding of described ketene dimer is 10 minutes to 2 hours.
8. the method preparing AAEM according to claim 1, is characterized in that: the time of described insulation reaction is 1-8 hour.
9. a kind of method preparing AAEM according to claim 1, is characterized in that: in order to be greater than, 0Pa is less than or equal to 1000Pa to the described pressure condition continuing to distill, temperature condition is 95 DEG C-135 DEG C; The cut collected under above-mentioned pressure and temperature condition is AAEM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511007748.5A CN105541625A (en) | 2015-12-30 | 2015-12-30 | Method for preparing acetoacetoxy ethyl methacrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511007748.5A CN105541625A (en) | 2015-12-30 | 2015-12-30 | Method for preparing acetoacetoxy ethyl methacrylate |
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| CN105541625A true CN105541625A (en) | 2016-05-04 |
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| CN201511007748.5A Pending CN105541625A (en) | 2015-12-30 | 2015-12-30 | Method for preparing acetoacetoxy ethyl methacrylate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565477A (en) * | 2016-10-26 | 2017-04-19 | 潍坊科麦化工有限公司 | Preparation method of acetoacetoxy ethyl methacrylate |
| CN111995519A (en) * | 2020-09-26 | 2020-11-27 | 安徽金禾实业股份有限公司 | Preparation method of 3-methoxy methyl acrylate |
| CN114181084A (en) * | 2021-12-13 | 2022-03-15 | 山东省海洋化工科学研究院 | Method for purifying acetoacetoxy ethyl methacrylate |
| CN115490593A (en) * | 2022-09-23 | 2022-12-20 | 潍坊科麦化工有限公司 | Acetoacetoxyethyl methacrylate, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3554987A (en) * | 1965-12-20 | 1971-01-12 | Eastman Kodak Co | Novel compounds and photographic materials containing said compounds |
| US3658878A (en) * | 1965-12-20 | 1972-04-25 | Eastman Kodak Co | Ethylenically unsaturated cyano group containing compounds |
-
2015
- 2015-12-30 CN CN201511007748.5A patent/CN105541625A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3554987A (en) * | 1965-12-20 | 1971-01-12 | Eastman Kodak Co | Novel compounds and photographic materials containing said compounds |
| US3658878A (en) * | 1965-12-20 | 1972-04-25 | Eastman Kodak Co | Ethylenically unsaturated cyano group containing compounds |
Non-Patent Citations (2)
| Title |
|---|
| 司动磊等: "乙酰乙酸基甲基丙烯酸乙酯的合成", 《应用化工》 * |
| 夏宇正等: "甲基丙烯酸乙酰乙酸乙二醇双酯的制备和鉴定", 《北京化工学院学报（自然科学版）》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565477A (en) * | 2016-10-26 | 2017-04-19 | 潍坊科麦化工有限公司 | Preparation method of acetoacetoxy ethyl methacrylate |
| CN111995519A (en) * | 2020-09-26 | 2020-11-27 | 安徽金禾实业股份有限公司 | Preparation method of 3-methoxy methyl acrylate |
| CN114181084A (en) * | 2021-12-13 | 2022-03-15 | 山东省海洋化工科学研究院 | Method for purifying acetoacetoxy ethyl methacrylate |
| CN114181084B (en) * | 2021-12-13 | 2023-11-14 | 山东省海洋化工科学研究院 | Purification method of acetoacetyl ethyl methacrylate |
| CN115490593A (en) * | 2022-09-23 | 2022-12-20 | 潍坊科麦化工有限公司 | Acetoacetoxyethyl methacrylate, preparation method and application thereof |
| CN115490593B (en) * | 2022-09-23 | 2024-03-22 | 潍坊科麦化工有限公司 | Acetoacetoxyethyl methacrylate, preparation method and application thereof |
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Application publication date: 20160504 |