CN101293880B - Synthesizing method for preparing N-acryloyl morpholine - Google Patents
Synthesizing method for preparing N-acryloyl morpholine Download PDFInfo
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- CN101293880B CN101293880B CN2007100988853A CN200710098885A CN101293880B CN 101293880 B CN101293880 B CN 101293880B CN 2007100988853 A CN2007100988853 A CN 2007100988853A CN 200710098885 A CN200710098885 A CN 200710098885A CN 101293880 B CN101293880 B CN 101293880B
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Abstract
The invention relates to a method for synthesizing high-purity N-acryloyl-morpholine, comprising the steps of: dropwise mixing acrylic acid and phosphorus trichloride within 0.5-1 hours, and allowing reaction at 40-45DEG C for 3-4 hours under stirring speed of 80-100rpm to obtain acryloyl chloride; and dropwise mixing morpholine, an acid-binding agent and a solvent within 3-4 hours to obtain a mixed liquid, allowing reaction at 0-5DEG C for 3 hours under stirring speed of 80-100rpm, collecting supernatant, and distilling in the presence of a compound polymerization inhibitor under reduced pressure to obtain an N-acryloyl-morpholine product with purity over 99%, wherein the molar ratio of phosphorus trichloride and acrylic acid is 1:(3-3.5), the molar ratio of acryloyl chloride and morpholine is 1:(1-1.5), the addition amount of the acid-binding agent is 50-150 wt% of morpholine, the solvent addition amount is 100-200 wt% of morpholine, and the addition amount of the compound polymerization inhibitor is 0.1-1 wt% of morpholine.
Description
Technical field
The present invention relates to a kind of is the synthetic method of feedstock production high purity N-acryloyl morpholine with phosphorus trichloride and vinylformic acid.
Background technology
The N-acryloyl morpholine is the good auxiliary agent and the properties-correcting agent of synthetic resins, is used for the reaction diluent of ultraviolet curable resin, is effective properties-correcting agent of acrylate resin and gelatin simultaneously.With it is many acryloyl morpholines polymerization product of raw material, is applied to fields such as oilfield additive, ink addition agent, paper making additive and tackiness agent.Because acryloyl morpholine is nontoxic as monomer itself, has excellent biological compatibility, so gather around at water treatment field and medical field and to have broad application prospects.
Early stage acryloyl morpholine synthetic technology, the thermo-cracking that report adopts alkyl to replace the propionyl morpholine obtains.Japanese Patent JP111000375 has reported by morpholinyl propionyl morpholine route (4-morpholinyl propionyl morpholine) and under the effect of an acidic catalyst, has carried out vacuum thermal cracking, synthetic N-acryloyl morpholine, and yield is up to 29%.Reaction equation is as follows:
This method raw material is difficult to obtain, and heat scission reaction is wayward, and the hot polymerization phenomenon appears in acryloyl morpholine easily.
Summary of the invention
The purpose of this invention is to provide a kind of reaction conditions gentleness, constant product quality is not prone to the polymerism of the two keys of product, the yield height, and what cost was low is the method that raw material synthesizes the N-acryloyl morpholine with phosphorus trichloride and vinylformic acid.
The objective of the invention is to be achieved by the following technical programs:
Vinylformic acid is added in the reactor, start agitator, heat temperature raising to 30 ℃ drips phosphorus trichloride then, and rate of addition was controlled at 0.5～1 hour, was added dropwise to complete the back insulation, and the reaction times was controlled at 3～4 hours; Temperature of reaction is controlled at 40～45 ℃, and stirring velocity is 80-100 rev/min; Separate supernatant liquid then, carry out rectification and purification, the intermediates acrylate chloride directly is collected in the container that solvent is housed;
Morpholine, acid binding agent are added in the aforesaid reaction vessel, and the reactor emptying increases device for absorbing tail gas, starts agitator, be cooled to 0 ℃, drip the mixed liquid of solvation acrylate chloride then, rate of addition is controlled at and dropwised in 3～4 hours, and temperature of reaction is controlled between 0～5 ℃, kept 3 hours, stirring velocity is 80-100 rev/min, inhales then and considers supernatant liquid, carries out rectification under vacuum under composite polymerzation inhibitor, solvent recuperation is applied mechanically, and finally can obtain the N-acryloyl morpholine product more than 99%;
Wherein, phosphorus trichloride and acrylic acid mol ratio are 1: 3～3.5; The mol ratio of acrylate chloride and morpholine is 1: 1～1.5; The acid binding agent add-on is 50～150% of a morpholine weight; Solvent adding amount is 100～200% of a morpholine weight; The composite polymerzation inhibitor add-on is 0.1～1% of a morpholine weight.
Its acid binding agent can be selected from aliphatics liquid tertiary amines organic bases, mainly is triethylamine, tripropyl amine, three octyl tertiary amines etc.; First-selected triethylamine.
Its described acid binding agent can be selected from water-free mineral alkali, mainly is sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate etc.; First-selected carbonate.
It is tetracol phenixin, trichloromethane, hexanaphthene etc. that its described solvent can be selected from.
Its described composite polymerization inhibitor can be selected from active fixed stopper (as: Resorcinol, MEHQ), thermo-sensitivity stopper (as: tert-butyl catechol, phenothiazine) and micro-mantoquita etc. the weight mixture;
The mixture of first-selected MEHQ, phenothiazine and micro-mantoquita.
The mechanism of action of the present invention is: phosphorus trichloride and vinylformic acid drop in the reactor by 1:3～3.5mol; under 40～45 ℃ of conditions, carry out acylation reaction; separate then and obtain the acrylate chloride intermediate; because acrylate chloride instability; can directly be blended in the solvent and preserve, make acrylate chloride intermediates solvation.In order to the next step.
Under the acid binding agent effect, the acrylate chloride of solvation and morpholine drop in the reactor by 1:1～1.5mol, carry out acylation reaction under 0～5 ℃ of condition, synthetic N-acryloyl morpholine product.Its chemical reaction is as follows:
Just as described abovely in proportion phosphorus trichloride is added dropwise in the vinylformic acid, carries out acylation reaction under 40～45 ℃ of conditions, crude product carries out simple rectifying, and the acrylate chloride intermediates that obtain add in the solvent, makes it solvation and preserves stable.Acrylate chloride is very strong acylation reaction reagent, and the acrylate chloride of solvation drops in the morpholine solution in proportion, and acylation reaction is steadily carried out, and avoids the hot polymerization phenomenon of product N-acryloyl morpholine.In reaction process, add acid binding agent and can neutralize the hydrochloric acid gas that reaction generates rapidly, react fully and carry out.The crude product acryloyl morpholine that obtains carries out rectification under vacuum under composite polymerzation inhibitor, obtain purpose product N-acryloyl morpholine.
The present invention has following significant effect:
(1) to adopt phosphorus trichloride, vinylformic acid be the synthetic N-acryloyl morpholine of raw material in the present invention, has that raw material is easy to get, reaction conditions gentleness, operation be easy to control, constant product quality, low cost and other advantages, is easy to realize industrial production.
(2) the present invention is a raw material with phosphorus trichloride, vinylformic acid, and at first the synthesizing propylene acyl chlorides mixes the chloride reagent that makes it to become the solubilized stable thinner with solvent again, and intermediates are convenient to preserve like this, and easy to use.
(3) the present invention has used the acrylate chloride of solvation, with the morpholine acylation reaction in reacting balance, acryloyl morpholine hot polymerization phenomenon does not appear in reaction.
(4) the present invention adopts the solvation acrylate chloride to be added drop-wise in the morpholine solution, and the mole of control raw material is temperature of reaction when, and reacting balance is carried out, and side reaction is few, and acrylate chloride is transformed fully.
(5) in N-acryloyl morpholine acylation reaction, select suitable acid binding agent can make to be swift in response and carry out, react fully to the positive reaction direction.
(6) composite polymerzation inhibitor is adopted in the rectifying of N-acryloyl morpholine crude product; well carried out the protection of two keys, easy to operate, be easy to control, the product polymerization is few, is that the product yield of benchmark surpasses 72% with the acrylate chloride; product purity is more than 99%, and look is number less than No. 50 (platinum-cobalt).
Embodiment
Embodiment 1
In the 500ml reactor that stirring of slurry formula and water bath with thermostatic control are housed, add vinylformic acid 134 grams, start stirring, stirring velocity is controlled at 80 rev/mins, be warming up to 30～35 ℃, in 0.5～1 hour, drip 86 gram phosphorus trichlorides (mass content 95%) with constant pressure funnel then, temperature can slowly rise in the dropping process, and the control rate of addition makes the dropping process temperature be no more than 45 ℃.Dropwise the back at 40～45 ℃, kept 3 hours.Separate supernatant liquid, carry out rectifying with rectifying tower then, the intermediates acrylate chloride is directly collected in the tetracol phenixin constant pressure funnel that 200 gram solvents are housed standby.
121 gram morpholines, acid binding agent yellow soda ash pressed powder 90 grams are added successively and have in the 1L reactor of low temperature water-bath, and device for absorbing tail gas is installed in the reactor emptying additional.Start agitator, stirring velocity is controlled at 100 rev/mins, is cooled to 0 ℃, drips the acrylate chloride of solvation then by constant pressure funnel, is added dropwise to complete at 3～3.5 hours, keeps 3 hours again; The entire reaction course controlled temperature filters supernatant liquid then between 0～5 ℃.Clear liquid after filtering joined 0.5 gram composite polymerzation inhibitor (MEHQ 30% is housed; Phenothiazine 30%; Cuprous chloride 40%) rectifying in the rectification under vacuum tower, the N-acryloyl morpholine product 127.1 that finally obtains look number No. 10 (platinum-cobalts) restrains purity 99.30%.
Embodiment 2
The preparation of intermediates solvation acrylate chloride is with embodiment 1
121 gram morpholines, acid binding agent tripropyl amine 125 grams are added successively and have in the 1L reactor of low temperature water-bath, and device for absorbing tail gas is installed in the reactor emptying additional.Start agitator, stirring velocity is controlled at 100 rev/mins, is cooled to 0 ℃, drips the acrylate chloride of solvation then by constant pressure funnel, is added dropwise to complete at 3～3.5 hours, keeps 3 hours again; The entire reaction course controlled temperature filters supernatant liquid then between 0～5 ℃.Clear liquid after filtering joined 0.5 gram composite polymerzation inhibitor (MEHQ 25% is housed; Resorcinol 25%; Cuprous chloride 50%) rectifying in the rectification under vacuum tower, the N-acryloyl morpholine product 124.7 that finally obtains look number No. 20 (platinum-cobalts) restrains purity 99.42%.
Embodiment 3
In the 1L reactor that stirring of slurry formula and water bath with thermostatic control are housed, add vinylformic acid 335 grams, start stirring, stirring velocity is controlled at 80 rev/mins, be warming up to 30～35 ℃, in 0.5～1 hour, drip 215 gram phosphorus trichlorides (mass content 95%) with constant pressure funnel then, temperature can slowly rise in the dropping process, and the control rate of addition makes the dropping process temperature be no more than 45 ℃.Dropwising the back kept 3 hours between 40～45 ℃.Separate supernatant liquid, carry out rectifying with rectifying tower then, the intermediates acrylate chloride is directly collected in the trichloromethane constant pressure funnel that 450 gram solvents are housed standby.
302 gram morpholines, acid binding agent sodium bicarbonate solid powder 350 grams are added successively and have in the 2L reactor of low temperature water-bath, and the reactor emptying increases device for absorbing tail gas.Start agitator, stirring velocity is controlled at 100 rev/mins, is cooled to 0 ℃, drips the acrylate chloride of solvation then by constant pressure funnel, is added dropwise to complete at 3～3.5 hours, keeps 3 hours again; The entire reaction course controlled temperature filters supernatant liquid then between 0～5 ℃.Clear liquid after filtering joined 0.8 gram composite polymerzation inhibitor (MEHQ 30% is housed; Phenothiazine 30%; Cuprous chloride 40%) rectifying in the rectification under vacuum tower, the N-acryloyl morpholine product 320.7 that finally obtains look number No. 10 (platinum-cobalts) restrains purity 99.57%.
Embodiment 4
The acrylate chloride preparation of intermediates solvation is with embodiment 3
302 gram morpholines, acid binding agent sodium hydrate solid powder 170 grams are added successively and have in the 2L reactor of low temperature water-bath, and the reactor emptying increases device for absorbing tail gas.Start agitator, stirring velocity is controlled at 100 rev/mins, is cooled to 0 ℃, drips the acrylate chloride of solvation then by constant pressure funnel, is added dropwise to complete at 3～3.5 hours, keeps 3 hours again; The entire reaction course controlled temperature filters supernatant liquid then between 0～5 ℃.Clear liquid after filtering joined 0.8 gram composite polymerzation inhibitor (MEHQ 30% is housed; Phenothiazine 30%; Cuprous chloride 40%) rectifying in the rectification under vacuum tower, the N-acryloyl morpholine product 304.2 that finally obtains look number No. 20 (platinum-cobalts) restrains purity 99.62%.
Embodiment 5
In the 1L reactor that stirring of slurry formula and water bath with thermostatic control are housed, add vinylformic acid 335 grams, start stirring, stirring velocity is controlled at 80 rev/mins, be warming up to 30～35 ℃, in 0.5～1 hour, drip 215 gram phosphorus trichlorides (mass content 95%) with constant pressure funnel then, temperature can slowly rise in the dropping process, and the control rate of addition makes the dropping process temperature be no more than 45 ℃.Dropwise the back at 40～45 ℃, kept 3 hours.Separate supernatant liquid, carry out rectifying with rectifying tower then, the intermediates acrylate chloride is directly collected in the hexanaphthene constant pressure funnel that 550 gram solvents are housed standby.
302 gram morpholines, acid binding agent triethylamine 300 grams are added successively and have in the 2L reactor of low temperature water-bath, and the reactor emptying increases device for absorbing tail gas.Start agitator, stirring velocity is controlled at 100 rev/mins, is cooled to 0 ℃, drips the acrylate chloride of solvation then by constant pressure funnel, is added dropwise to complete at 3～3.5 hours, keeps 3 hours again; The entire reaction course controlled temperature filters supernatant liquid then between 0～5 ℃.Clear liquid after filtering joined 1.0 gram composite polymerzation inhibitor (MEHQ 25% are housed; Resorcinol 25%; Cuprous chloride 50%) rectifying in the rectification under vacuum tower, the N-acryloyl morpholine product 316.6 that finally obtains look number No. 40 (platinum-cobalts) restrains purity 99.07%.
Claims (1)
1. synthetic method for preparing the N-acryloyl morpholine is characterized in that:
Vinylformic acid is added in the reactor, start agitator, heat temperature raising to 30 ℃ drips phosphorus trichloride then, and rate of addition was controlled at 0.5～1 hour, was added dropwise to complete the back insulation, and the reaction times was controlled at 3～4 hours; Temperature of reaction is controlled at 40～45 ℃, and stirring velocity is 80-100 rev/min; Separate supernatant liquid then, carry out rectification and purification, the intermediates acrylate chloride directly is collected in the container that solvent is housed;
Morpholine, acid binding agent are added in the aforesaid reaction vessel, and the reactor emptying increases device for absorbing tail gas, starts agitator, be cooled to 0 ℃, drip the mixed liquid of solvation acrylate chloride then, rate of addition is controlled at and dropwised in 3～4 hours, and temperature of reaction is controlled between 0～5 ℃, kept 3 hours, stirring velocity is 80-100 rev/min, inhales then and considers supernatant liquid, carries out rectification under vacuum under composite polymerzation inhibitor, solvent recuperation is applied mechanically, and finally can obtain the N-acryloyl morpholine product more than 99%;
Wherein, phosphorus trichloride and acrylic acid mol ratio are 1: 3～3.5; The mol ratio of acrylate chloride and morpholine is 1: 1～1.5; The acid binding agent add-on is 50～150% of a morpholine weight; Solvent adding amount is 100～200% of a morpholine weight; The composite polymerzation inhibitor add-on is 0.1～1% of a morpholine weight;
Described acid binding agent is sodium hydroxide, potassium hydroxide, yellow soda ash or sodium bicarbonate;
Described composite polymerzation inhibitor is the mixture of MEHQ, phenothiazine and cuprous chloride;
Described solvent is tetracol phenixin, trichloromethane or hexanaphthene.
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| CN2007100988853A CN101293880B (en) | 2007-04-28 | 2007-04-28 | Synthesizing method for preparing N-acryloyl morpholine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993126A (en) * | 2012-12-27 | 2013-03-27 | 山东瑞博龙化工科技股份有限公司 | Cracking control device of acryloylmorpholine |
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| EP2664611A1 (en) | 2009-05-01 | 2013-11-20 | Idemitsu Kosan Co., Ltd | Method for producing alpha,beta-unsaturated carboxylic acid-N,N-disubstituted amide and method for producing 3-alkoxycarboxylic acid-N,N-disubstituted amide |
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| CN104610197B (en) * | 2015-01-30 | 2016-08-24 | 无锡海特圣大光电材料科技有限公司 | A kind of method based on acid anhydrides synthesizing propylene morpholide |
| CN104628678B (en) * | 2015-01-30 | 2016-06-15 | 无锡海特圣大光电材料科技有限公司 | A kind of method based on 2-halogen propionyl chloride synthesizing propylene morpholide |
| CN105315232B (en) * | 2015-11-17 | 2018-01-05 | 天津久日新材料股份有限公司 | A kind of preparation method of acryloyl morpholine |
| CN109665971A (en) * | 2017-10-17 | 2019-04-23 | 无锡海特圣大光电材料科技有限公司 | A kind of method for preparing monomer of temperature sensitive type monomer n-isopropyl acrylamide |
| CN113024485A (en) * | 2019-12-24 | 2021-06-25 | 南通沃兰化工有限公司 | Synthesis method of 4-acryloyl morpholine |
| CN112831380A (en) * | 2020-03-18 | 2021-05-25 | 铭钜新材料科技(上海)有限公司 | Efficient environment-friendly odor-free cleaning agent |
| CN115925652A (en) * | 2022-12-08 | 2023-04-07 | 南通沃兰化工有限公司 | Preparation method of acryloyl morpholine |
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Cited By (1)
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| CN102993126A (en) * | 2012-12-27 | 2013-03-27 | 山东瑞博龙化工科技股份有限公司 | Cracking control device of acryloylmorpholine |
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