CN107245039A - A kind of method for preparing N hydroxyethyl acrylamides - Google Patents
A kind of method for preparing N hydroxyethyl acrylamides Download PDFInfo
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- CN107245039A CN107245039A CN201710442438.9A CN201710442438A CN107245039A CN 107245039 A CN107245039 A CN 107245039A CN 201710442438 A CN201710442438 A CN 201710442438A CN 107245039 A CN107245039 A CN 107245039A
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- Prior art keywords
- preparing
- hydroxyethyl acrylamides
- ethylaminoethanol
- hydroxyethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Abstract
The invention discloses a kind of method for preparing N hydroxyethyl acrylamides.Gently reacted with ethylaminoethanol at low temperature using acrylic anhydride.The acrylic acid produced as accessory substance is separated by distillation mode with product.The N hydroxyethyl acrylamides purity that the inventive method is obtained is high, and high income, simple production process is easy to get.
Description
Technical field
The present invention relates to acid amides synthesis technical field, more particularly to a kind of method for preparing N- hydroxyethyl acrylamides.
Background technology
N- hydroxyethyl acrylamides (HEAA) molecular formula is C5H9NO2, it is colourless transparent liquid, the double bond of itself can be with
Polymerisation occurs for the monomer of acrylate or methyl acrylic ester, meanwhile, after moisture evaporation ,-N hydroxyethyl groups can
To occur self-crosslinking reaction, extraordinary water-fast, scrub performance is obtained.
Generally, the method for synthesizing amide, can directly be reacted using carboxylic acid and amine and prepared, can also by ester-interchange method,
Ester interchange preparation occurs under certain condition with carboxylate methyl ester and amine, but the side reaction of both approaches is more, instead
It should be difficult to control to, yield is low.Furthermore it is also possible to using chloride method, i.e., using the high reaction activity of acyl chlorides, acyl be prepared with amine reaction
Amine.Although chloride method reaction condition is gentle, yield is also higher, and the byproduct hydrogen chloride that the method is produced needs alkaline matter to inhale
Receive, easily cause equipment corrosion and environmental pollution, and acyl chlorides is poisonous, is not suitable for commercial Application.
US5587515 discloses a kind of method for preparing N- hydroxyethyl acrylamides, this method first using di-n-propylamine with
The Michael addition reaction of methyl acrylate removes double bond, then under the catalytic action of sodium methoxide, and acyl is carried out with ethylaminoethanol
Aminating reaction, obtained compound finally carries out high temperature pyrolysis, sloughs di-n-propylamine, obtains target product N- hydroxylethyl acyls
Amine.Due to the high activity of N- hydroxyethyl acrylamides, N- hydroxyethyl acrylamides easily occur during Pintsch process for this method
Polymerisation, product yield is relatively low.
The content of the invention
The present invention provides a kind of method for preparing N- hydroxyethyl acrylamides aiming at above-mentioned defect.Using
The high reaction activity of acrylic anhydride, can gently be reacted with ethylaminoethanol at low temperature.The propylene produced as accessory substance
Acid can be separated by distillation mode with product.The N- hydroxyethyl acrylamides purity that the inventive method is obtained is high, yield
Height, simple production process is easy to get.
The method and technology scheme for preparing N- hydroxyethyl acrylamides of the present invention is, anti-with ethylaminoethanol using acrylic anhydride
Should, after separating by-products, obtain N- hydroxyethyl acrylamides.
Acrylic anhydride reacts with ethylaminoethanol under atent solvent or condition of no solvent.
The mode of separating by-products purifies for vacuum distillation.
Into ethylaminoethanol or ethylaminoethanol, solvent, the mixed liquor of polymerization inhibitor, acrylic anhydride is slowly added dropwise, process is added dropwise
0~35 DEG C of reacting liquid temperature is kept, rear reaction temperature is dripped and rises to 35~70 DEG C, continues to react 2~6 hours；
Reaction carries out vacuum distillation after terminating, take out accessory substance acrylic acid, finally obtain product N- hydroxyethyl acrylamides.
Described solvent is inert organic solvents.
Described solvent is toluene, acetonitrile, 1,4- dioxane, dimethylbenzene, tetrahydrofuran, acetone, N, N- dimethyl methyls
One kind in acid amides.
The polymerization inhibitor is hydroquinones, 1,4-benzoquinone, MEHQ, 2- TBHQs, the tertiary fourths of 2,5- bis-
Base hydroquinones, 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals (TEMPO), phenthazine, dibutyl dithio ammonia
At least two in the base copper formate polymerization inhibitors being composited.
The mol ratio of the described method for preparing N- hydroxyethyl acrylamides, raw material propylene acid anhydrides and ethylaminoethanol is 0.8
~1.2:1.
Beneficial effects of the present invention are：The present invention using acrylic anhydride high reaction activity, can at low temperature with amino
Ethanol is gently reacted.The acrylic acid produced as accessory substance can be separated by distillation mode with product.The present invention
The N- hydroxyethyl acrylamides purity that method is obtained is high, and high income, simple production process is easy to get.
Embodiment：
For a better understanding of the present invention, technical scheme is described in detail with instantiation below, but originally
Invention is not limited thereto.
Embodiment 1
The preparation of N- hydroxyethyl acrylamides
Reaction bulb adds monoethanolamine 45.8g (0.75mol), tetrahydrofuran 100mL, phenthazine 0.3g and TEMPO 0.15g,
Electric stirring is opened, cold water cooling controls rate of addition, acrylic anhydride 94.5g (0.75mol) is slowly added dropwise, keeps reaction solution
25~35 DEG C of temperature.Completion of dropping, is heated to 50 DEG C of insulations and continues to react 2h.First air-distillation, removes solvents tetrahydrofurane, so
After carry out vacuum distillation, obtain N- hydroxyethyl acrylamide 63g, yield 73%, purity 95% (GC detected values).1H NMR
(300MHz, CDCl3)：δ (ppm)=6.8 (m, 1H ,-NH-), 6.5 (m, 1H ,-C=C-H, cis), 6.3 (m, 1H ,-CH=
C-, mode), 5.7 (m, 1H ,-C=C-H, trans), 4.3 (m, 1H ,-OH), 3.7 (m, 2H ,-OCH2-), 3.3 (m, 2H ,-
NCH2-)。
Embodiment 2
The preparation of N- hydroxyethyl acrylamides
Reaction bulb adds monoethanolamine 45.8g (0.75mol), acetonitrile 100mL, phenthazine 0.3g and TEMPO 0.15g, opens
Electric stirring, cold water cooling, controls rate of addition, and acrylic anhydride 94.5g (0.75mol) is slowly added dropwise, and keeps reacting liquid temperature
25~35 DEG C.Completion of dropping, is heated to 50 DEG C of insulations and continues to react 2h.First air-distillation, removes solvent acetonitrile, is then subtracted
Pressure distillation, obtains N- hydroxyethyl acrylamide 65.5g, yield 76%, purity 97% (GC detected values).
Claims (8)
1. a kind of method for preparing N- hydroxyethyl acrylamides, it is characterised in that acrylic anhydride reacts with ethylaminoethanol, separation is secondary
After product, N- hydroxyethyl acrylamides are obtained.
2. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 1, it is characterised in that acrylic anhydride with
Ethylaminoethanol reacts under atent solvent or condition of no solvent.
3. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 1, it is characterised in that separating by-products
Mode be vacuum distillation purification.
4. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 1, it is characterised in that to ethylaminoethanol
Or in the mixed liquor of ethylaminoethanol, solvent, polymerization inhibitor, acrylic anhydride is slowly added dropwise, process is added dropwise and keeps reacting liquid temperature 0~35
DEG C, drip rear reaction temperature and rise to 35~70 DEG C, continue to react 2~6 hours；
Reaction carries out vacuum distillation after terminating, take out accessory substance acrylic acid, finally obtain product N- hydroxyethyl acrylamides.
5. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 4, it is characterised in that described solvent
For inert organic solvents.
6. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 4, it is characterised in that described solvent
For one kind in toluene, acetonitrile, 1,4- dioxane, dimethylbenzene, tetrahydrofuran, acetone, N,N-dimethylformamide.
7. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 4, it is characterised in that the polymerization inhibitor
For hydroquinones, 1,4-benzoquinone, MEHQ, 2- TBHQs, 2,5 di tert butyl hydroquinone, 4- hydroxyls-
In 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, phenthazine, copper dibutyldithiocarbamate at least two it is compound and
Into polymerization inhibitor.
8. a kind of method for preparing N- hydroxyethyl acrylamides according to claim 4, it is characterised in that acrylic anhydride with
The mol ratio of ethylaminoethanol is 0.8~1.2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710442438.9A CN107245039A (en) | 2017-06-13 | 2017-06-13 | A kind of method for preparing N hydroxyethyl acrylamides |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710442438.9A CN107245039A (en) | 2017-06-13 | 2017-06-13 | A kind of method for preparing N hydroxyethyl acrylamides |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625538A (en) * | 2020-09-29 | 2021-04-09 | 四川省俊川科技有限公司 | Epoxy resin curing agent for two-component seam beautifying agent and preparation method thereof |
| CN112876377A (en) * | 2021-01-15 | 2021-06-01 | 南京红宝丽醇胺化学有限公司 | Preparation method of hydroxypropyl acrylamide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3412650A1 (en) * | 1984-04-04 | 1985-10-17 | Röhm GmbH, 6100 Darmstadt | Process for the preparation of hydroxyalkylacrylamides and -methacrylamides |
| JPS6153A (en) * | 1984-06-08 | 1986-01-06 | Mitsubishi Rayon Co Ltd | N-2-hydroxyethylacrylamide or methacrylamide |
| CN106631862A (en) * | 2008-12-15 | 2017-05-10 | 赢创罗姆有限公司 | Method for producing N-isopropyl(meth)acrylamide |
-
2017
- 2017-06-13 CN CN201710442438.9A patent/CN107245039A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3412650A1 (en) * | 1984-04-04 | 1985-10-17 | Röhm GmbH, 6100 Darmstadt | Process for the preparation of hydroxyalkylacrylamides and -methacrylamides |
| JPS6153A (en) * | 1984-06-08 | 1986-01-06 | Mitsubishi Rayon Co Ltd | N-2-hydroxyethylacrylamide or methacrylamide |
| CN106631862A (en) * | 2008-12-15 | 2017-05-10 | 赢创罗姆有限公司 | Method for producing N-isopropyl(meth)acrylamide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625538A (en) * | 2020-09-29 | 2021-04-09 | 四川省俊川科技有限公司 | Epoxy resin curing agent for two-component seam beautifying agent and preparation method thereof |
| CN112876377A (en) * | 2021-01-15 | 2021-06-01 | 南京红宝丽醇胺化学有限公司 | Preparation method of hydroxypropyl acrylamide |
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Address after: 273300 middle section of Huaxing Road, Linyi County Economic Development Zone, Dezhou, Shandong Applicant after: Shandong Ruibolong Chemical Technology Co., Ltd. Address before: 273300 Pingyi county (Economic Development Zone) of Dezhou, Shandong Province, Hua Xinglu Applicant before: Shandong Ruibolong Chemical Technology Co., Ltd. |
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Application publication date: 20171013 |