CN101177403B - Method for preparing N-dimethylamino propyl methyl acrylamide - Google Patents
Method for preparing N-dimethylamino propyl methyl acrylamide Download PDFInfo
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- CN101177403B CN101177403B CN2007100109377A CN200710010937A CN101177403B CN 101177403 B CN101177403 B CN 101177403B CN 2007100109377 A CN2007100109377 A CN 2007100109377A CN 200710010937 A CN200710010937 A CN 200710010937A CN 101177403 B CN101177403 B CN 101177403B
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Abstract
The invention relates to a method for preparing N-dimethylamino propyl methacrylamide by catalyzing and cracking, which comprises the following technical steps: A. two incipient ingredients methyl methacrylate and N, N-dimethyl-1, 3-propane diamine are sealed in an autoclave for catalyzing and condensing, so as to generate the intermediate N-dimethylamino-Beta-dimethylamino methacrylamide; B. putting the intermediate N-dimethylamino-Beta-dimethylamino methacrylamide into a reactor with distilling apparatus and driving off the crude products of N-dimethylamino propyl methacrylamide through catalyzing and cracking; C. adding the crude products of N-dimethylamino propyl methacrylamide and polymerization inhibitor into a rectifying tower to generate the finished products. The invention has the advantages of less reaction steps, high conversion rate, small amount of byproducts, low cost for post treatment, and ability to meet application demand.
Description
Technical field
The present invention relates to the preparation method of N-dimethylamino-propyl Methacrylamide.
Background technology
N-(3-dimethylamino) propyl methyl acid amides (DMAPMA) is a kind of very important fine-chemical intermediate and monomer, by it for main intermediate synthetic polymkeric substance belong to external the 4th generation flocculation agent and third generation oil production additive, it is widely used in industries such as coating, resin, plating, printing and dyeing, water treatment flocculant, membrane technique, medicine, makeup.The global exploitation of this product sees the sixties in last century with the application beginning, but, to latter stage in last century, the application of this product still is not very extensive, after entering 21 century, external priority is successively developed the very good fine chemistry industry product innovation of a large amount of qualities with this product, comprising makeup, hair shampoo article, high-grade paint, ionic membranes etc. have caused the extensive concern of domestic and international industry circle personage to this product thus, western developed country has been gone into enough human and material resources to this, financial resources are carried out more deep research, and relevant research report is constantly delivered.China begins to see at the beginning of 21 century to the research work of this product, although up to the present, this product still end is seen the report that the suitability for industrialized production finished is arranged, the industry that sets foot in neither be very extensive, but, its research application work has obtained country and insider's great attention, wherein, be listed in national natural science fund subsidy project and state key fundamental research development program is subsidized project with copolymerization synthetic ionic membrane technology such as this product and maleic anhydride, acrylamides, therefrom we can spy on the bright prospects of this product future development.
The route of synthetic N-dimethylamino-propyl Methacrylamide mainly contains: (1) Japanese Patent J.P:0267,257 reports are with methyl methacrylate and N, N-dimethyl-1, the 3-propylene diamine is a starting raw material, through alcoholysis, ammonia separate, dealcoholysis, rectification process get product, reaction yield 63%, product purity can reach more than 99%.Reaction equation is as follows:
The shortcoming of this method is that step is many, and reaction time is long, and yield is low, and the production cost height is difficult to satisfy the market sale demand.
(2) German Patent D.E:3,128,574 reports are raw material with the Methacrylamide, with N, N-dimethyl-1,3-propylene diamine condensation single step reaction is produced product, and reaction equation is as follows:
Though this method step is short, reaction needs to carry out under High Temperature High Pressure, so produces a large amount of by products in the process, is difficult to reach its application requiring through aftertreatment.
(3) Japanese Patent J.P:59-76044 report is with methacrylic acid, N, and the N-dimethylated propyl diethylenetriamine is a raw material, and in toluene solution, in the presence of catalyzer and stopper, being heated to refluxes carries out dehydration reaction, report reaction yield: 50%.Utilization can with water azeotropic toluene as the band aqua, remove the water of reaction existence, reach the purpose that increases product yield, this method shortcoming is to use solvent toluene, and side reaction is more in the reaction process, reaction equation is as follows:
(4) Japanese Patent J.P:56-100749 reports with methyl methacrylate excessive and N, N-dimethyl-1, and the reaction of 3-propylene diamine makes product through aftertreatment.
This method advantage is that step is short, the transformation efficiency height; Shortcoming is the excessive easy polymerization of methyl methacrylate, is difficult to reclaim, and the polymkeric substance of generation not only influences quality product, and stops up conversion unit, makes the production operation difficulty.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of employing catalyzer and shortens the reaction times, can be continuously produced, and the reaction yield height, byproduct is few, and aftertreatment is simple, the method for preparing N-dimethylamino propyl methyl acrylamide that product purity is high.
The technical scheme that adopts is:
Method for preparing N-dimethylamino propyl methyl acrylamide comprises following processing step:
Comprise with methyl methacrylate and N that 1, N-dimethyl-1,3-propylene diamine are starting raw material, described two kinds of raw materials are enclosed catalyzing and condensing in the reactor, preparation intermediate N dimethylamino-β-dipropyl amino methyl acrylamide;
2, the intermediate N dimethylamino-β-dipropyl amino methyl acrylamide of preparation is inserted in the reactor that has water distilling apparatus, catalytic pyrolysis distillates N-dimethylamino-propyl Methacrylamide raw product;
3, rectifying in distilled N-dimethylamino-propyl Methacrylamide raw product and the stopper adding rectifying tower is made finished product.
Above-mentioned processing step 1 described starting raw material methyl methacrylate and N, N-dimethyl-1, the ratio of components of 3-propylene diamine is 1: 3, selecting carbonic acid gas for use is catalyzer, and with catalyzing and condensing in the reactor of carbonic acid gas feeding sealing, the feeding amount of carbonic acid gas is the 2-5% of reaction material total amount, and temperature of reaction is 90-100 ℃, and the reaction times is 6-7 hour.
Above-mentioned processing step 2, its working method is the small amount of intermediate bottoming, at cracking temperature is that 220-240 ℃, pressure are 10mmHg, drip intermediate, make product along with dripping along with cracking distillates, catalyst for cracking is the salt of calcium, barium, aluminium, boron, magnesium, and the catalyst for cracking consumption is the 5-6% of reactor product total amount.
Above-mentioned catalyst for cracking is calcium salt Ca (NO
3)
24H
2O, barium salt Bal
22H
2O, aluminium salt Al (OTS)
3, boron salt BF
3(C
2H
5)
2O, magnesium salts Mg (OCH
3)
2
Above-mentioned processing step 3, described stopper is respectively MEHQ, thiodiphenylamine, N, N-phenylbenzene two phenylenediamines, add-on accounts for the 0.2-0.5% of N-dimethylamino-propyl Methacrylamide raw product gross weight.
Above-mentioned processing step 3 is with the overhead product adding rectifying tower of step 2, collects 6mmHg, 130 ℃ product fraction, and with the raw material N that reclaims, N-dimethyl-1,3-propylene diamine are applied mechanically to processing step 1 reaction.
Advantage of the present invention is:
(1) reactions steps is short, has only two-step reaction, in cracking process, owing to improved operating method, adds catalyzer and has shortened the reaction times, makes it simple and easy to do on suitability for industrialized production.
(2) polymkeric substance is few, and production unit is easy to clean, and can carry out serialization production.And quantity of three wastes is few, belongs to cleaning procedure.
(3) yield height, step 1 and step 2 reaction yield are more than 90%; By product is few, and aftertreatment is simple, and product purity can reach more than 99%.Can satisfy its application requiring.
Embodiment
Method for preparing N-dimethylamino propyl methyl acrylamide comprises following processing step:
Comprise with methyl methacrylate and N that 1, N-dimethyl-1,3-propylene diamine are starting raw material, (raw material is commercial product), its methyl methacrylate and N, N-dimethyl-1,3-propylene diamine proportioning is 1: 3, because methyl methacrylate is easily polymerization in air, and N, N-dimethyl-1,3-propylene diamine volatile characteristic in air, make its yield very low, have only 20%.And a large amount of polymer scales is arranged at the bottom of bottle, and being difficult to carry out aftertreatment, product content is very low.In order to change this situation, the present invention encloses two kinds of raw materials in the reactor, makes its secluding air; And feed carbonic acid gas as catalyzer, and the catalyzing and condensing reaction, this reaction has prepared intermediate N dimethylamino-β-dipropyl amino methyl acrylamide for temperature reaction.
Stoped N like this, N-dimethyl-1, the volatilization of 3-propylene diamine, and do not have the polymkeric substance generation substantially, and improve like this more than the reaction yield to 90%, make aftertreatment simple and easy to do, product content reaches more than 98%.
2,4.5% place the reactor that has water distilling apparatus to feel secure the intermediate N dimethylamino-β-dipropyl amino methyl acrylamide of preparation, be warmed up to 220 ℃ and drip down intermediates being decompressed to 10mmHg, make product along with dripping along with distillating, reduced the pyritous residence time of product, make polymkeric substance so seldom, improved yield greatly.But this method reaction times is long, and operational condition is also very harsh.In order to improve speed of response, the present invention has selected the method that adds catalyzer for use, selected catalyzer and catalytic performance thereof (following cracking temperature is 220 ℃) as shown in the table:
As can be seen from the above table, Ca (NO
3)
24H
2The catalytic performance of O is best, makes rate of cleavage improve 6 times.Add before the catalyzer, the time of intermediate scission reaction is 30 hours, uses after the catalyzer, and the time is 5 hours.Shortened the reaction times so greatly, made simple to operate.Catalyst levels is 6% of a reaction solution.
3, processing step 2 distilled N-dimethylamino-propyl Methacrylamide raw product and stopper are added in the rectifying tower, collect 6mmHg, 130 ℃ product fraction, and with the raw material N that reclaims, N-dimethyl-1,3-propylene diamine are applied mechanically to processing step 1 reaction.Rectification process need add a certain amount of stopper just can make reaction carry out smoothly, because product contains two keys, is easy to polymerization and influences the quality and the yield of product in the process of intensification rectifying.Selected stopper is MEHQ, thiodiphenylamine, N, N-phenylbenzene two phenylenediamines, and its add-on accounts for 0.5% of N-dimethylamino-propyl Methacrylamide raw product gross weight.
Embodiment one
Step 1:
100 gram methyl methacrylates, 300 gram N, N-dimethyl-1, the 3-propylene diamine adds feeding 8 gram carbonic acid gas in the reactor, stirring is warming up to 100 ℃ and kept 6 hours, and then cooling decompression steams excessive N, N-dimethyl-1, the 3-propylene diamine is intermediates N-dimethylamino-propyl-β-dipropyl amino methyl acrylamide.
Step 2:
With 1 gram Ca (NO
3)
24H
2O, the above-mentioned intermediates of 18 grams add and have in the reaction flask of vacuum distillation apparatus, are decompressed to 10mmHg, and stirring when being warming up to 220 ℃ has raw material and product to distillate, with intermediates and Ca (NO
3)
24H
2O is in slowly splashing in the reaction flask, and product that cracking this moment goes out and raw material are also along with the process that drips distillates.5 hours afterreactions finish, and contain 31.1% raw material N in the overhead product, N-dimethyl-1,3-propylene diamine and 67.9% product N-dimethylamino-propyl Methacrylamide.
Step 3:
0.5 gram MEHQ and above-mentioned overhead product added have in the reaction flask of rectifying tower, collect 6mmHg, 130 ℃ product fraction, and the raw material that reclaims applied mechanically to the first step reaction.
Embodiment two
Step 1:
Feed 20 gram carbonic acid gas in reactor, stir and be warmed up to 90 ℃ of maintenances 7 hours, other are with embodiment one;
Step 2:
With 0.9 gram Ca (NO
3)
24H
2O, 18 gram intermediates add and have in the reaction flask of vacuum distillation apparatus, stir and are warming up to 240 ℃, and other are with embodiment one;
Step 3:
1.3 gram MEHQ are added in the reaction flask of rectifying tower, and other are with embodiment one.
Embodiment three
Step 1:
Feed 14 gram carbonic acid gas in reactor, stir and be warmed up to 96 ℃ of maintenances 6.5 hours, other are with embodiment one;
Step 2:
With 0.95 gram Ca (NO
3)
24H
2O, 18 gram intermediates add and have in the reaction flask of vacuum distillation apparatus, stir and are warming up to 230 ℃, and other are with embodiment one;
Step 3:
1 gram MEHQ is added in the reaction flask of rectifying tower, and other are with embodiment one.
The result of implementation total recovery can reach 70%, product content 98%.
Claims (2)
1. method for preparing N-dimethylamino propyl methyl acrylamide, its feature comprises following processing step:
A, comprise that with methyl methacrylate and N N-dimethyl-1,3-propylene diamine are starting raw material, above-mentioned two kinds of raw materials are enclosed in the reactor, methyl methacrylate and N, N-dimethyl-1, the ratio of components of 3-propylene diamine is 1: 3, selecting carbonic acid gas for use is catalyzer, and with catalyzing and condensing in the reactor of carbonic acid gas feeding sealing, the feeding amount of carbonic acid gas is the 2-5% of reaction material total amount, and temperature of reaction is 90-100 ℃, reaction times is 6-7 hour, prepares intermediate;
The intermediate of B, the preparation that takes a morsel is inserted in the reactor that has water distilling apparatus and is felt secure, at cracking temperature is that 220-240 ℃, pressure are 10mmHg, drip intermediate, make product along with dripping along with cracking distillates, get N-dimethylamino-propyl Methacrylamide raw product: catalyst for cracking is the salt of calcium, barium, aluminium, boron, magnesium, and the catalyst for cracking consumption is the 5-6% of reactor product total amount;
C, distilled N-dimethylamino-propyl Methacrylamide raw product and stopper added rectifying makes finished product in the rectifying tower, described stopper is respectively MEHQ, thiodiphenylamine, and add-on accounts for the 0.2-0.5% of N-dimethylamino-propyl Methacrylamide raw product gross weight.
2. method for preparing N-dimethylamino propyl methyl acrylamide according to claim 1, it is characterized in that described processing step C, it is overhead product adding rectifying tower with step B, collect 6mmHg, 130 ℃ product fraction, and with the raw material N that reclaims, N-dimethyl-1,3-propylene diamine are applied mechanically to processing step A reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100109377A CN101177403B (en) | 2007-04-12 | 2007-04-12 | Method for preparing N-dimethylamino propyl methyl acrylamide |
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|---|---|---|---|
| CN2007100109377A CN101177403B (en) | 2007-04-12 | 2007-04-12 | Method for preparing N-dimethylamino propyl methyl acrylamide |
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| CN101177403A CN101177403A (en) | 2008-05-14 |
| CN101177403B true CN101177403B (en) | 2011-01-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348130B (en) * | 2015-12-02 | 2017-06-06 | 天津久日新材料股份有限公司 | A kind of preparation method of N, N dimethyl propyl acrylamide |
| CN105481698B (en) * | 2015-12-28 | 2017-06-13 | 江苏富淼科技股份有限公司 | A kind of propane diamine of N, N dimethyl 1,3 reclaims the method with the propane diamine of coproduction N, N, N ', N ' tetramethyl 1,3 |
| CN105693537A (en) * | 2015-12-29 | 2016-06-22 | 四川光亚聚合物化工有限公司 | N-alkyl acrylamide intermediate and preparation method thereof and preparation method of N-alkyl acrylamide |
| CN105439890A (en) * | 2015-12-31 | 2016-03-30 | 沈阳化工研究院有限公司 | Method for preparing DMAPPA (N-(3-dimethyl aminopropyl) acrylamide) through catalytic amidation |
| CN108047057B (en) * | 2017-12-28 | 2020-06-02 | 山东铂源药业有限公司 | Synthesis method of butenafine |
| CN112608248A (en) * | 2020-12-16 | 2021-04-06 | 无锡海特圣大光电材料科技有限公司 | Method for synthesizing N, N-dimethylaminopropyl acrylamide by decarboxylation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256665A (en) * | 1979-08-31 | 1981-03-17 | Texaco Development Corporation | Preparation of β-aminopropionamides |
| US4287363A (en) * | 1980-09-02 | 1981-09-01 | Texaco Inc. | Preparation of N-(alkylaminoalkyl)acrylamides |
| EP0799821A1 (en) * | 1996-04-04 | 1997-10-08 | Richard M. Gerkin | Reactive amine catalyst for use in polyurethane synthesis |
| CN1837188A (en) * | 2006-04-21 | 2006-09-27 | 江苏飞翔化工股份有限公司 | Process for synthesizing methyl acryloyl-(N,N-dimethyl propylene diamine) and device therefor |
-
2007
- 2007-04-12 CN CN2007100109377A patent/CN101177403B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256665A (en) * | 1979-08-31 | 1981-03-17 | Texaco Development Corporation | Preparation of β-aminopropionamides |
| US4287363A (en) * | 1980-09-02 | 1981-09-01 | Texaco Inc. | Preparation of N-(alkylaminoalkyl)acrylamides |
| EP0799821A1 (en) * | 1996-04-04 | 1997-10-08 | Richard M. Gerkin | Reactive amine catalyst for use in polyurethane synthesis |
| CN1837188A (en) * | 2006-04-21 | 2006-09-27 | 江苏飞翔化工股份有限公司 | Process for synthesizing methyl acryloyl-(N,N-dimethyl propylene diamine) and device therefor |
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