CN101717340A - Method for cleanly producing high-purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride - Google Patents
Method for cleanly producing high-purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride Download PDFInfo
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- CN101717340A CN101717340A CN200910253708A CN200910253708A CN101717340A CN 101717340 A CN101717340 A CN 101717340A CN 200910253708 A CN200910253708 A CN 200910253708A CN 200910253708 A CN200910253708 A CN 200910253708A CN 101717340 A CN101717340 A CN 101717340A
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- ammonium chloride
- acryloyl ethoxy
- ethoxy benzyldimethyl
- benzyldimethyl ammonium
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Abstract
The invention provides a method for cleanly producing high-purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride. Methyl benzoate or ethyl benzoate is adopted as a reaction solvent, and iodides, such as lithium iodide, potassium iodide, tetramethyl-ammonium iodide, tetraethyl-ammonium iodide or tetrabutyl-ammonium iodide, and the like are adopted as a catalyst, and the reaction is carried out at 35-38 DEG C for 10-24 hours. The yield of one-path (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride is between 93 percent and 95 percent, a rough product is washed for three times by ethylacetate, and the analytical purity of the (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride is larger than 99 percent.
Description
Technical field
The present invention relates to the monomeric production method of a kind of quaternary ammonium salt cationic, particularly the clean preparation method of high purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride.
Technical background
Cationic polyacrylamide is a kind of multipolymer of polyacrylamide, as the flocculation agent of sewage disposal.By acrylamide monomer and cationic monomer copolymerization is the common method that obtains cationic polyacrylamide flocculant agent.Cationic monomer commonly used has dimethyl diallyl ammonium chloride (DMDAAC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC), acryloyl ethoxy benzyldimethyl ammonium chloride (DMAEABCQ), methylacryoyloxyethyl benzyl dimethyl ammonium chloride (DMAEAMCQ).Cationic monomer of the present invention all is the quaternary ammonium salt that contains unsaturated carbon-carbon double bond, and very easily the moisture absorption becomes the aqueous solution in air, so these cationic monomer commodity mostly are the quality percentage compositions at 40～80% the aqueous solution, so the transportation cost height.Described cationic monomer aqueous stability is poor simultaneously, must be stored under the lucifuge condition that is lower than 30 ℃, and stabilizer concentration wherein is higher than 2000ppm, certainly will influence follow-up polymerization process.
(be designated hereinafter simply as: (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride) industrial production technology comprises that (methyl) vinylformic acid dimethylin ethyl ester reacts with Benzyl Chloride in acetone, ether or acetonitrile solvent, and perhaps (methyl) vinylformic acid dimethylin ethyl ester reacts with Benzyl Chloride in water solvent for existing acryloyl ethoxy benzyldimethyl ammonium chloride and methylacryoyloxyethyl benzyl dimethyl ammonium chloride.Instruct us to use the patent of this production technology that EP0250325, WO8907588, JP52148017, JP59016859 or CN01814012 are arranged.(methyl) vinylformic acid dimethylin ethyl ester is fast with the Benzyl Chloride speed of response in acetone, ether or acetonitrile solvent, feed stock conversion height, product yield height, but acetone, ether or acetonitrile solvent belong to low boiling point organic solvent, volatile, inflammable and explosive, steam toxicity is big.Therefore, existing industrial production seldom adopts organic solvents such as acetone, ether or acetonitrile.It is fast with the Benzyl Chloride speed of response in water that WO8907588 and CN01814012 disclose (methyl) vinylformic acid dimethylin ethyl ester.Water is as solvent, and the production security height is with low cost.(but methyl) vinylformic acid dimethylin ethyl ester and the hydrolytic side reactions of Benzyl Chloride in water solvent are serious, and are that inevitably the cationic monomer aqueous solution purity of being produced is low, the raw material consumption height.
At the problem that exists in the above existing industrial production technology, the present invention proposes the clean preparation method of high purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride.
Summary of the invention
One of skill in the art knows (methyl) vinylformic acid dimethylin ethyl ester and react feed stock conversion height, gained cationic monomer purity height, product yield height with Benzyl Chloride in strong polar non-proton organic solvent such as acetone, ether or acetonitrile.But acetone, ether or acetonitrile equal solvent belong to low boiling point organic solvent, and be volatile, inflammable and explosive, and steam toxicity is big.For this reason, the inventor thinks that high boiling nontoxic methyl benzoate of use or ethyl benzoate etc. are as strong polar aprotic solvent, iodide such as lithium iodide, potassiumiodide, Tetramethylammonium iodide, tetraethyl ammonium iodide or tetrabutylammonium iodide are as catalyzer, ethyl acetate is as cleaning solvent, be fast, the preferred method of high purity, high yield, synthetic (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride cationic monomer of clean and effective production.
Result of study of the present invention shows that methyl benzoate or ethyl benzoate are as reaction solvent, iodide such as lithium iodide, potassiumiodide, Tetramethylammonium iodide, tetraethyl ammonium iodide or tetrabutylammonium iodide are as catalyzer, 35～38 ℃ of temperature controls, 10～24 hours reaction times, one way (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride yield 93～95%, ethyl acetate is washed thick product three times, and (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride product purity is greater than 99%.
The clean preparation method of high purity of the present invention (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, concrete steps are as follows:
Step 1 reaction process
(methyl) vinylformic acid dimethylin ethyl ester, Benzyl Chloride, catalyzer and reaction solvent together drop in the reactor, blast N
2After ten minutes, 35～38 ℃ of temperature controls, in 10～24 hours reaction times, after reaction finished, temperature of charge was reduced to 10～15 ℃, filtered, and made (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product.The reaction mother liquor that leaches (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product is added (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride and is entered next circulation after gas chromatographic analysis.
The mass ratio of (methyl) of the present invention vinylformic acid dimethylin ethyl ester and Benzyl Chloride is 1: 1～1.3.
Catalyzer of the present invention is selected from one or more in lithium iodide, potassiumiodide, Tetramethylammonium iodide, tetraethyl ammonium iodide or the tetrabutylammonium iodide, and its consumption is 0.05～1.5% of a Benzyl Chloride quality.
Reaction solvent of the present invention is selected from one or both mixtures in methyl benzoate or the ethyl benzoate, and its consumption is 100～500% of (methyl) vinylformic acid dimethylin ethyl ester and a Benzyl Chloride quality.
The washing process of step 2 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product
(methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product that step 1 makes is sent in the washing still, dropped into the ethyl acetate of 1～2 times of relative (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product quality, blast N
2After ten minutes, heat up 35～50 ℃, stir after 30 minutes, cool to 10～15 ℃, filtering ethyl acetate washings drops into ethyl acetate again and carries out the second time and washing for the third time respectively, makes the wet product of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride.
The drying process of the wet product of step 3 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride
The wet product of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride that step 2 makes are sent into moisture eliminator, and 35～50 ℃ of dryings of temperature control 3～4 hours make (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride product, and reclaim ethyl acetate.
The distinguishing feature of the clean preparation method of high purity provided by the invention (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride is:
1. methyl benzoate or ethyl benzoate have the boiling point height as the organic solvent of (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride reaction, its vapour pressure of controlling under the temperature of reaction little, volatility is low, reaction process is not lost.
2. reaction process of the present invention remains in (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride raw material in methyl benzoate or the ethyl benzoate solvent after finishing, and can recycle.
3. (methyl) of the present invention acryloyl ethoxy benzyldimethyl ammonium chloride crude product is sent in the washing still of built-in filter net type, behind ethyl acetate washing (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product, directly enter the ethyl acetate withdrawing can and recycle, thereby the loss of the ethyl acetate in the washing process is little from washing still bottom baiting valve.
4. reaction solvent, (methyl) vinylformic acid dimethylin ethyl ester and the Benzyl Chloride that (methyl) of the present invention acryloyl ethoxy benzyldimethyl ammonium chloride crude product is carried secretly enters in the ethyl acetate washings after the ethyl acetate washing.Ethyl acetate is reclaimed in distillation, recycles after residual reaction solvent, (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride reclaims in the still kettle.
5. (methyl) of the present invention vinylformic acid dimethylin ethyl ester and Benzyl Chloride do not have hydrolytic side reactions to take place in methyl benzoate or ethyl benzoate solvent.Gained (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride product crude product washs through ethyl acetate again, can remove reaction solvent, (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride fully, and after the wet product drying of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride of only carrying ethyl acetate secretly, (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride product purity is up to 99%, and solid phase prod transports and excellent storage stability.
6. after the wet product of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride in the moisture eliminator sent into were heated, its ethyl acetate of carrying secretly becomes gaseous volatilization overflowed, and cease of ethyl-acetate gas recovery after the icy salt solution cooling recycles, and the rate of recovery is higher than 80%.
In sum, the production method of high purity provided by the invention (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride belongs to the clean preparation method of the few three wastes of no by-product.
Embodiment 1
Open the stirrer of 1000 liter reactors, drop into 0.3 kilogram of 600 kilograms of methyl benzoate, 200 kilograms of vinylformic acid dimethylin ethyl esters, 200 kilograms of Benzyl Chlorides and potassiumiodide under the room temperature, blast N
2After the deoxygenation 10 minutes, heat temperature raising is kept 35～38 ℃ of material in reactor temperature, reacts 12 hours.Finish reaction.The material in reactor temperature is reduced to 10～15 ℃, filters, and makes 412 kilograms of acryloyl ethoxy benzyldimethyl ammonium chloride crude products.The reaction mother liquor that leaches the acryloyl ethoxy benzyldimethyl ammonium chloride crude product is added (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride and is entered next working cycle after gas chromatographic analysis.
Open the stirrer of 1000 liters washing still, under the room temperature, drop into 412 kilograms of 600 kilograms of ethyl acetate and acryloyl ethoxy benzyldimethyl ammonium chloride crude products in the washing still, blast N
2After the deoxygenation 10 minutes, keep 45～50 ℃ of the interior temperature of charge of washing still, continue to stir 1 hour.After the cooling, elimination ethyl acetate washings is added 600 kilograms of ethyl acetate, repeated washing 2 times.Filter, make 378 kilograms of the wet product of acryloyl ethoxy benzyldimethyl ammonium chloride.The wet product of 378 kilograms of acryloyl ethoxy benzyldimethyl ammonium chlorides are sent in the drying machine, 45～50 ℃ of dryings of temperature control 3 hours make 355 kilograms of acryloyl ethoxy benzyldimethyl ammonium chlorides, product yield 94.4%, analyze its purity 99.4%, and reclaim 20 kilograms of ethyl acetate.
Embodiment 2
Reaction mother liquor among the embodiment 1 is sent in the 1000 liter reactors, add 0.1 kilogram of 200 kilograms of vinylformic acid dimethylin ethyl esters, 190 kilograms of Benzyl Chlorides and potassiumiodide, processing method and step according to embodiment 1, make 370 kilograms of acryloyl ethoxy benzyldimethyl ammonium chlorides, product yield 98.4% is analyzed its purity 99.2%.
Embodiment 3
Processing method and step according to embodiment 1, with 200 kilograms of wherein vinylformic acid dimethylin ethyl esters and 0.3 kilogram of change of potassiumiodide is 0.6 kilogram of 200 kilograms of Dimethylaminoethyl Methacrylate and tetraethyl ammonium iodide, make 335 kilograms of methylacryoyloxyethyl benzyl dimethyl ammonium chlorides, product yield 93.1% is analyzed its purity 99.6%.Reaction mother liquor recycles 6 times, and methylacryoyloxyethyl benzyl dimethyl ammonium chloride product average yield is 96.12%.
Claims (3)
1. the clean preparation method of a high purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, with lithium iodide, potassiumiodide, Tetramethylammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide or their mixture is catalyzer, reaction by (methyl) vinylformic acid dimethylin ethyl ester and Benzyl Chloride makes (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, it is characterized in that this reaction carries out in methyl benzoate or ethyl benzoate.
2. according to the clean preparation method of the described high purity of claim 1 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, it is characterized in that described methyl benzoate or ethyl benzoate as reaction solvent, its consumption is 100～500% of (methyl) vinylformic acid dimethylin ethyl ester and a Benzyl Chloride quality.
3. according to the clean preparation method of the described high purity of claim 1 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride, it is characterized in that realizing by following step:
Step 1 reaction process
(methyl) vinylformic acid dimethylin ethyl ester, Benzyl Chloride, catalyzer and reaction solvent together drop in the reactor, blast N
2After ten minutes, 35～38 ℃ of temperature controls, in 10～24 hours reaction times, after reaction finished, temperature of charge was reduced to 10～15 ℃, filtered, and made (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product.
The mass ratio of (methyl) of the present invention vinylformic acid dimethylin ethyl ester and Benzyl Chloride is 1: 1～1.3.
Catalyzer of the present invention is selected from one or more in lithium iodide, potassiumiodide, Tetramethylammonium iodide, tetraethyl ammonium iodide or the tetrabutylammonium iodide, and its consumption is 0.05～1.5% of a Benzyl Chloride quality.
Reaction solvent of the present invention is selected from one or both mixtures in methyl benzoate or the ethyl benzoate, and its consumption is 100～500% of (methyl) vinylformic acid dimethylin ethyl ester and a Benzyl Chloride quality.
The washing process of step 2 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product
(methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product that step 1 makes is sent in the washing still, dropped into the ethyl acetate of 1～2 times of relative (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride crude product quality, blast N
2After ten minutes, heat up 35～50 ℃, stir after 30 minutes, temperature of charge is reduced to 10～15 ℃ in the washing still, filtering ethyl acetate washings drops into ethyl acetate again and carries out the second time and washing for the third time respectively, makes the wet product of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride.
The drying process of the wet product of step 3 (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride
The wet product of (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride that step 2 makes are sent into moisture eliminator, and 35～50 ℃ of dryings of temperature control 3～4 hours make (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride product, and reclaim ethyl acetate.
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| CN2009102537087A CN101717340B (en) | 2009-12-10 | 2009-12-10 | Method for cleanly producing high-purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride |
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| CN2009102537087A CN101717340B (en) | 2009-12-10 | 2009-12-10 | Method for cleanly producing high-purity (methyl) acryloyl ethoxy benzyldimethyl ammonium chloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516452A (en) * | 2011-10-28 | 2012-06-27 | 淮海工学院 | Preparation method of copolymer porous resin ball containing quaternary ammonium group and salicylaldehyde |
| CN106220522A (en) * | 2016-08-09 | 2016-12-14 | 陕西科技大学 | A kind of Mannich base quarternary ammonium salt compound and preparation method thereof |
| CN106835699A (en) * | 2017-02-07 | 2017-06-13 | 广东泰宝医疗器械技术研究院有限公司 | A kind of antibacterial hemostatic gauze and preparation method thereof |
| CN106916071A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | The synthetic method of benzalkonium chloride mixture |
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| US4929267A (en) * | 1985-07-26 | 1990-05-29 | Mitsubishi Gas Chemical Company | Plant growth promotion |
| US5800809A (en) * | 1992-01-14 | 1998-09-01 | Hisamitsu Pharmaceutical Co, Inc | Non-crosslinked acrylic polymers and non-crosslinked anion exchange resins |
| CN1384095A (en) * | 2001-04-27 | 2002-12-11 | 阿托菲纳公司 | Prepn of water solution of unsaturated quaternary ammonium salt |
| US20040024242A1 (en) * | 2000-08-11 | 2004-02-05 | Alain Riondel | Method for making aqueous solutions of (meth)acryloyloxyethylbenzyldimethylammonium chlorides |
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Patent Citations (4)
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| US5800809A (en) * | 1992-01-14 | 1998-09-01 | Hisamitsu Pharmaceutical Co, Inc | Non-crosslinked acrylic polymers and non-crosslinked anion exchange resins |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516452A (en) * | 2011-10-28 | 2012-06-27 | 淮海工学院 | Preparation method of copolymer porous resin ball containing quaternary ammonium group and salicylaldehyde |
| CN102516452B (en) * | 2011-10-28 | 2013-12-25 | 淮海工学院 | Preparation method of copolymer porous resin ball containing quaternary ammonium group and salicylaldehyde |
| CN106220522A (en) * | 2016-08-09 | 2016-12-14 | 陕西科技大学 | A kind of Mannich base quarternary ammonium salt compound and preparation method thereof |
| CN106835699A (en) * | 2017-02-07 | 2017-06-13 | 广东泰宝医疗器械技术研究院有限公司 | A kind of antibacterial hemostatic gauze and preparation method thereof |
| CN106916071A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | The synthetic method of benzalkonium chloride mixture |
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| CN101717340B (en) | 2012-10-31 |
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