CN104250219A - Production method of acrylamido tertiary butyl sulfonic acid - Google Patents
Production method of acrylamido tertiary butyl sulfonic acid Download PDFInfo
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- CN104250219A CN104250219A CN201310269847.5A CN201310269847A CN104250219A CN 104250219 A CN104250219 A CN 104250219A CN 201310269847 A CN201310269847 A CN 201310269847A CN 104250219 A CN104250219 A CN 104250219A
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Abstract
The invention relates to a production method of acrylamido tertiary butyl sulfonic acid. The production method comprises the following steps of 1, mixing acrylonitrile and a sulfonating agent to obtain a sulfonating agent-containing acrylonitrile solution, 2, providing a horizontal stirring reactor, and continuously feeding the mixed solution obtained by the step into the horizontal stirring reactor so that the mixed solution contacts with isobutene and product slurry is formed, 3, continuously discharging the product slurry from the horizontal stirring reactor, and filtering the product slurry to obtain acrylamido tertiary butyl sulfonic acid-containing filter cake, and 4, drying the filter cake obtained by the step 3 to obtain an acrylamido tertiary butyl sulfonic acid crude product having mass content more than 96.0%.
Description
Technical field
The present invention relates to a kind of production method of organic compound, be specifically related to a kind of production method of tert-butyl acrylamide sulfonate.
Background technology
Tert-butyl acrylamide sulfonate (Acrylamido Tertiary Butyl Sulfonic Acid, hereinafter referred to as ATBS) be multifunctional water-soluble anionic monomer, because molecular structure has carbon-carbon double bond and to the insensitive sulfonic group of salt, therefore polymerization is easy to, and its homopolymerization and multipolymer have much special character, have broad application prospects, oilfield chemistry can be widely used in, water conditioner, chemical fibre, plastics, printing and dyeing, coating, tensio-active agent, static inhibitor, pottery, take a picture, washing auxiliary detergent, ion exchange resin, gas separation membrane, the fields such as electronic industry.
The technique of current most typical production ATBS is for raw material carries out reaction preparation ATBS under relatively mild condition with vinyl cyanide, oleum and iso-butylene.US3544597 first reported this method preparing amidosulfonic acid compounds, and obtains the higher monomer of purity, but reaction conditions is comparatively harsh.
In current technology, the method preparing ATBS is generally: vinyl cyanide, sulfuric acid are contacted with iso-butylene, after generating pulpous state product, filters this pulpous state product, obtains the filter cake containing ATBS.This route yield and purity higher, be the main method of producing ATBS at present.In suitability for industrialized production, the step reactor of main use is produced, and production efficiency is low, and constant product quality is poor.
US6448347 (2002) proposes the method using continuous processing to produce ATBS multipolymer, and ATBS synthesis is also the production method of serialization in this approach.US6504050 (2003) also refer to the example of continuous prodution ATBS in an embodiment.These technology improve on the basis of batch operation, and then achieve the continuous prodution of ATBS, but also there is certain technological deficiency.These technology use conventional stirring tank to feed in raw material discharging or the series connection of several stirring tank to realize continuous operation usually, so just cause the non-constant width of material residence time destribution in a kettle., some material can stop for a long time in a kettle., and in reaction mass, comprise vinyl cyanide, the chemical property of ATBS is all very active, is easy to polymerization or side reaction occur.Therefore above-mentioned technology well cannot solve the continuous prodution of ATBS synthesis.
Summary of the invention
The object of the invention is, in order to overcome the problem that in prior art, material residence time destribution is in a kettle. wide, to provide a kind of synthesis technique of tert-butyl acrylamide sulfonate continuous processing.
The present inventor finds, uses Horizontal stirring reactor can realize plug flow operation, effectively avoids the situation of residence time of material inequality, be applicable to the continuous operation of production tert-butyl acrylamide sulfonate.
In the production technique of tert-butyl acrylamide sulfonate of the present invention, use vinyl cyanide, sulfuric acid and iso-butylene to be main raw material, production technique is mainly divided into following components: (1) vinyl cyanide contacts at low temperatures with sulfuric acid; (2) at 10 DEG C ~ 45 DEG C temperature in the reactor with iso-butylene contact reacts; (3) the pulpous state product separation will generated, dry, obtain the thick product of ATBS; (4) ATBS is carried out purifying, obtain high purity ATBS.
The invention provides a kind of production method of tert-butyl acrylamide sulfonate, the method comprises the following steps:
1) vinyl cyanide is mixed with sulphonating agent, form the acrylonitrile solution containing sulphonating agent;
2) Horizontal stirring reactor is provided, and step 1) is obtained mixing solutions and pass into continuously in described Horizontal stirring reactor and contact with iso-butylene, form pulpous state product;
3) described pulpous state product continuous print from Horizontal stirring reactor flows out and obtains the filter cake containing tert-butyl acrylamide sulfonate after filtration;
4) drying is carried out to the filter cake that step 3) obtains, obtain the tert-butyl acrylamide sulfonate crude product that mass content is more than 96.0%.
In a preferred implementation of method of the present invention, described method comprises further:
5) use aqueous acetic acid to carry out purifying to tert-butyl acrylamide sulfonate crude product, obtain the pure tert-butyl acrylamide sulfonate that content is 98.3-99.8%.
In a preferred implementation of method of the present invention, step 2) described in horizontal reactor comprise:
Kettle;
Chuck, outside described chuck parcel and kettle, for controlling the temperature of kettle inside;
Agitator, described agitator is arranged at kettle inside, for being mixed by reactant; And
Annex, described annex is arranged at kettle inside side walls.
In a preferred implementation of horizontal reactor in the method for the invention, described kettle length-to-diameter ratio is 1.5 ~ 10, and preferred length-to-diameter ratio is 3 ~ 7.
In a preferred implementation of horizontal reactor in the method for the invention, the axial distribution of the sidewall of described kettle has vent line, for by iso-butylene after vaporization through through passing into described kettle.In addition, there are opening for feed and discharge port respectively at reactor two ends, and can continuous operation be realized.
In a preferred implementation of horizontal reactor in the method for the invention, described reacting kettle jacketing can use hot water or water coolant to be heating agent, as can not operating mode be met under some design conditions, and can built-in spiral coil cooling tube.
In a preferred implementation of horizontal reactor in the method for the invention, described agitator comprises:
Drive unit, for providing power for agitator;
Be arranged at the stir shaft of axial direction due in still, the stirring rake being axially at least fixed with one group of radial direction of described stir shaft, each stirring rake has two panels blade at least.
Described stirring rake group number can be different according to the change of the length-to-diameter ratio of kettle, and be generally 2 ~ 10 groups, blade is 2 ~ 6.
In a preferred implementation of horizontal reactor in the method for the invention, the material that the normally used material of the horizontal reactor used is erosion resistance, as stainless steel, enamel or glass.
In addition, in a preferred implementation of the horizontal reactor in method of the present invention, described annex comprises thermopair and/or tensimeter.Also can comprise the annex with other functions if desired.
In a preferred embodiment of the present invention, described method also comprises further:
5) use aqueous acetic acid to carry out purifying to the tert-butyl acrylamide sulfonate crude product that step 4) obtains, obtain the tert-butyl acrylamide sulfonate that mass content is more than 99.3%.
In the method for the invention, the acrylonitrile solution in order to obtain sulphonating agent by the object that vinyl cyanide mixes with sulphonating agent in step 1), therefore, the temperature that described vinyl cyanide mixes with sulphonating agent is not particularly limited, consider that sulphonating agent has sulfuric acid for strongly-acid and strong oxidizing property or oleum usually, lower temperature is conducive to reaction and operation.Therefore in a preferred embodiment of the present invention, the temperature that vinyl cyanide described in step 1) mixes with sulphonating agent is-15 DEG C to 10 DEG C, preferably-10-0 DEG C.When reaching stable operation, the mol ratio of vinyl cyanide and sulfuric acid is 5-25:1.Vinyl cyanide water content should at 0.1% ~ 0.7 quality %.
In a preferred implementation of method of the present invention, by step 2) in material join in horizontal reacting still, the ratio that iso-butylene passes into the molar rate adding sulphonating agent in molar rate and step 1) is 1:1 ~ 1.3:1.
In a preferred implementation of method of the present invention, the temperature in described horizontal reactor is at 10 ~ 45 DEG C.
In a preferred implementation of method of the present invention, obtained slurries are carried out solid-liquid separation by step 3), method used can be the various filter method realizing solid-liquid separation of crossing in prior art, comprise natural filtration method, vacuum filtration process etc., the pulpous state product of generation is chilled to room temperature, obtains the filter cake containing ATBS and filtrate after filtering.
In a preferred implementation of method of the present invention, step 4) uses vacuum drying method to carry out drying to the filter cake obtained.
In a preferred implementation of method of the present invention, can be conventional ATBS purification process according to the method for purifying described in step 5), method disclosed in US4337215.Particularly, the aqueous acetic acid that it is 3-20 % by weight that the method comprises ATBS crude product and water content mixes, the weight ratio of described ATBS crude product and aqueous acetic acid is 1:10-1:4, mixture is heated to 85 DEG C-105 DEG C until ATBS dissolving crude product, then the mixed solution cooling 3-5 hour will obtained, filter and vacuum-drying, described vacuum drying condition can be identical with the condition of aforementioned vacuum drying, can obtain ATBS sterling after drying, sterling purity is generally greater than 99 quality %.In recrystallization process, after ATBS dissolving crude product, part water and acetic acid can be distilled out by underpressure distillation, the yield of recrystallization process can be improved.
Beneficial effect of the present invention:
Use production method of the present invention to carry out ATBS production, the continuous prodution of ATBS can be realized, enhance productivity.In addition, adopt method of the present invention, the ATBS yield that can also significantly improve, and improve product stability.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, but scope of the present invention is not limited to following examples.
The purity of ATBS product is determined by liquid-phase chromatographic analysis (LC analysis).The analysis condition of liquid chromatography is: Zorbax SAX chromatographic column, and moving phase is 0.1mol/L KH
2pO
4solution, flow velocity is 1.0mL/min, UV-detector.
Embodiment 1
The present embodiment is for illustration of the production method of ATBS provided by the invention.
(1) add the vinyl cyanide 496g of moisture 0.25 quality % in a mixer, and temperature is reduced to-5 DEG C, then add 73.6g SO
3mass content be the oleum of 3%, after stirring, enter steady state operation.Concrete grammar is: joined in above-mentioned mixing tank by under meter with the flow velocity of 248.0g/h by volume pump by the vinyl cyanide of moisture 0.25%, add oleum simultaneously, wherein free SO
3mass content is 3%, is added, obtain mixed solution by volume pump with 36.8g/h flow velocity by quantifier.
(2) mixed solution overflow port in the middle part of mixing tank continuously flows in horizontal reactor, horizontal reactor has three iso-butylene admission passages, after being vaporized by iso-butylene, join continuously in horizontal reactor with overall flow rate 11.5g/h, controlling reactor temperature is 37 ~ 38 DEG C.Reaction gained white slurries are entered by the overflow port of horizontal reactor right part in the flask of 1000ml bottom opening, continuous 3 lab scales collect product slurry 590g, through centrifugal, white crystalline powder shape product 151.0g is obtained after drying, in oleum, after liquid phase chromatography detects, product purity is 98.5%(quality), product synthesis yield is 96.6%(quality).
Use the aqueous acetic acid of 10% to carry out recrystallization to the thick product of ATBS, obtain high-purity ATBS, purity is 99.5%(quality).
Embodiment 2
According to the method synthesis ATBS of embodiment 1, unlike, SO in oleum
3content is 5%.The thick product of the ATBS obtained is after liquid phase chromatography detects, and product purity is 98.2%(quality), product synthesis yield is 96.7%(quality).
Use the aqueous acetic acid of 10% to carry out recrystallization to the thick product of ATBS, obtain high-purity ATBS, purity is 99.5%(quality).
Embodiment 3
According to the method synthesis ATBS of embodiment 1, unlike, temperature of reaction is 30 ~ 32 DEG C.After the thick product liquid phase chromatography of the ATBS obtained detects, product purity is 97.6%(quality), product synthesis yield is 96.0%(quality).
Use the aqueous acetic acid of 10% to carry out recrystallization to the thick product of ATBS, obtain high-purity ATBS, purity is 99.4%(quality).
Embodiment 4
According to the method synthesis ATBS of embodiment 1, unlike, temperature of reaction is 20 ~ 22 DEG C.After the thick product liquid phase chromatography of the ATBS obtained detects, product purity is 96.6%(quality), product synthesis yield is 95.2%(quality).
10%(volume is used to the thick product of ATBS) aqueous acetic acid carry out recrystallization, obtain high-purity ATBS, purity is 99.3%(quality).
Comparative example 1
This comparative example produces the technique of ATBS for illustration of interrupter method.
To being provided with temperature regulating device, agitator, in the reactor of thermometer and gas feeding unit, adding 330g analytical pure vinyl cyanide (wherein the content of vinyl cyanide is 99.7 quality %, and surplus is water), vinyl cyanide being cooled to-10 DEG C, slowly adding containing 2 quality %SO
361g oleum, then the temperature of reaction system is adjusted to 40 DEG C, slowly passes into 35g iso-butylene and react, treat that iso-butylene passes into complete, be incubated after one hour terminate reaction, reaction solution is carried out vacuum filtration.Obtain filter cake and filtrate after filtration, carry out vacuum-drying to filter cake, drying temperature is 100 DEG C, and drying pressure is 10KPa, obtains dried filter cake.
This dried filter cake is ATBS crude product, and detecting purity through liquid phase chromatography is 95.5%(quality), through calculating, ATBS yield is 91.5%(quality).
Use the aqueous acetic acid of 10% to carry out recrystallization to the thick product of ATBS, obtain high-purity ATBS, purity is 98.7%(quality).
Embodiment and comparative example 1 are compared and can find out, adopts method provided by the invention to synthesize ATBS, effectively can improve product yield, and realize high purity and production high-level efficiency.
Claims (10)
1. a production method for tert-butyl acrylamide sulfonate, the method comprises the following steps:
1) vinyl cyanide is mixed with sulphonating agent, form the acrylonitrile solution containing sulphonating agent;
2) Horizontal stirring reactor is provided, and step 1) is obtained mixing solutions and pass into continuously in described Horizontal stirring reactor and contact with iso-butylene, form pulpous state product;
3) described pulpous state product continuous print from Horizontal stirring reactor flows out and obtains the filter cake containing tert-butyl acrylamide sulfonate after filtration;
4) drying is carried out to the filter cake that step 3) obtains, obtain the tert-butyl acrylamide sulfonate crude product that mass content is more than 96.0%.
2. method according to claim 1, is characterized in that, step 2) described in horizontal reactor comprise:
Kettle;
Chuck, described chuck is wrapped in the outside of kettle, for controlling the temperature of kettle inside;
Agitator, described agitator is arranged at kettle inside, for being mixed by reactant; And
Annex, described annex is arranged at kettle inside side walls.
3. method according to claim 2, is characterized in that, described kettle length-to-diameter ratio is 1.5 ~ 10, and preferred length-to-diameter ratio is 3 ~ 7.
4. method according to claim 2, is characterized in that, the axial distribution of the sidewall of described kettle has vent line, for iso-butylene after vaporization is passed into described kettle.
5. method according to claim 2, is characterized in that, described agitator comprises:
Drive unit, for providing power for agitator;
Be arranged at the stir shaft of axial direction due in still, the stirring rake being axially at least fixed with one group of radial direction of described stir shaft, each stirring rake has two panels blade at least.
6. method according to claim 2, is characterized in that, described annex comprises thermopair and/or tensimeter.
7. method according to any one of claim 1-6, is characterized in that, described method comprises further:
5) use aqueous acetic acid to carry out purifying to the tert-butyl acrylamide sulfonate crude product that step 4) obtains, obtain the tert-butyl acrylamide sulfonate that mass content is more than 99.3%.
8. method according to any one of claim 1-6, is characterized in that, the temperature that vinyl cyanide described in step 1) mixes with sulphonating agent is-15 DEG C to 10 DEG C, preferably-10-0 DEG C.
9. method according to any one of claim 1-6, is characterized in that, by step 2) in material join in horizontal reacting still, the ratio that iso-butylene passes into the molar rate adding sulphonating agent in molar rate and step 1) is 1:1 ~ 1.3:1.
10. method according to any one of claim 1-6, is characterized in that, the temperature in described horizontal reactor is at 10 ~ 45 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003067A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of production method of tert-butyl acrylamide sulfonate |
| CN108017562A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of production method of tert-butyl acrylamide sulfonate |
| CN112679390A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Production device and production method of tert-butyl acrylamide sulfonic acid |
| WO2023118975A1 (en) * | 2021-12-24 | 2023-06-29 | Vinati Organics Limited | An oleum reactor in acrylamido tertiary butyl sulfonic acid synthesis and process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219498A (en) * | 1978-06-12 | 1980-08-26 | Nitto Chemical Industry Co., Ltd. | Process for preparing highly pure-2-acrylamido-2-methylpropanesulfonic acid |
| US6448347B1 (en) * | 1998-12-11 | 2002-09-10 | The Lubrizol Corporation | Continuous production of 2-acrylamido-2-methylpropane-sulfonic acid in a small reactor integrated with acrylic polymer fiber production |
| CN101066940A (en) * | 2007-06-06 | 2007-11-07 | 厦门长天企业有限公司 | Prepn process of 2-acryl amido-2-methyl propane sulfonic acid |
| CN102351744A (en) * | 2011-08-25 | 2012-02-15 | 潍坊泉鑫化工有限公司 | Synthesis process for 2-acrylamido-2-methyl propane sulfonic acid through continuous method |
| CN202322675U (en) * | 2011-12-07 | 2012-07-11 | 黑龙江省科学院石油化学研究院 | 2-acrylamide-2-methylacrylsulfonate continuous synthesis reaction device |
-
2013
- 2013-06-28 CN CN201310269847.5A patent/CN104250219B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219498A (en) * | 1978-06-12 | 1980-08-26 | Nitto Chemical Industry Co., Ltd. | Process for preparing highly pure-2-acrylamido-2-methylpropanesulfonic acid |
| US6448347B1 (en) * | 1998-12-11 | 2002-09-10 | The Lubrizol Corporation | Continuous production of 2-acrylamido-2-methylpropane-sulfonic acid in a small reactor integrated with acrylic polymer fiber production |
| CN101066940A (en) * | 2007-06-06 | 2007-11-07 | 厦门长天企业有限公司 | Prepn process of 2-acryl amido-2-methyl propane sulfonic acid |
| CN102351744A (en) * | 2011-08-25 | 2012-02-15 | 潍坊泉鑫化工有限公司 | Synthesis process for 2-acrylamido-2-methyl propane sulfonic acid through continuous method |
| CN202322675U (en) * | 2011-12-07 | 2012-07-11 | 黑龙江省科学院石油化学研究院 | 2-acrylamide-2-methylacrylsulfonate continuous synthesis reaction device |
Non-Patent Citations (1)
| Title |
|---|
| 张瑞志: "《高分子材料生产加工设备》", 30 April 1999, 北京:中国纺织出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003067A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of production method of tert-butyl acrylamide sulfonate |
| CN108017562A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of production method of tert-butyl acrylamide sulfonate |
| CN112679390A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Production device and production method of tert-butyl acrylamide sulfonic acid |
| WO2023118975A1 (en) * | 2021-12-24 | 2023-06-29 | Vinati Organics Limited | An oleum reactor in acrylamido tertiary butyl sulfonic acid synthesis and process thereof |
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