CN104250219B - A kind of production method of tert-butyl acrylamide sulfonate - Google Patents
A kind of production method of tert-butyl acrylamide sulfonate Download PDFInfo
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- CN104250219B CN104250219B CN201310269847.5A CN201310269847A CN104250219B CN 104250219 B CN104250219 B CN 104250219B CN 201310269847 A CN201310269847 A CN 201310269847A CN 104250219 B CN104250219 B CN 104250219B
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Abstract
The present invention relates to the production method of a kind of tert-butyl acrylamide sulfonate, the method comprises the following steps: 1) mixed with sulfonating agent by acrylonitrile, forms the acrylonitrile solution containing sulfonating agent；2) provide Horizontal stirring reactor, and step 1) is obtained mixed solution be passed through continuously in described Horizontal stirring reactor and contact with isobutene, formation pulpous state product；3) described pulpous state product continuous print from Horizontal stirring reactor flows out and through being filtrated to get the filter cake containing tert-butyl acrylamide sulfonate；4) filter cake obtaining step 3) is dried, and obtains the tert-butyl acrylamide sulfonate crude product that mass content is more than 96.0%.
Description
Technical field
The present invention relates to the production method of a kind of organic compound, be specifically related to a kind of tert-butyl acrylamide sulfonate
Production method.
Background technology
Tert-butyl acrylamide sulfonate (Acrylamido Tertiary Butyl Sulfonic Acid, hereinafter referred to as
ATBS) it is multifunctional water-soluble anionic monomer, owing to molecular structure has carbon-carbon double bond and insensitive to salt
Sulfonic group, be thus susceptible to polymerization, and its homopolymerization and copolymer have much special character, have wide
Application prospect, can be widely applied to oilfield chemistry, water treatment agent, chemical fibre, plastics, printing and dyeing, coating, surface
Activating agent, antistatic additive, pottery, photograph, washing assisant, ion exchange resin, gas separation membrane, electronics
The fields such as industry.
The technique of current most typical production ATBS, is to exist with acrylonitrile, oleum and isobutene for raw material
Reaction preparation ATBS is carried out under the conditions of relatively mild.US3544597 first reported and this prepares amide groups sulphur
The method of acid compounds, and obtained the monomer that purity is higher, but reaction condition is the harshest.
At present in technology, prepare the method for ATBS usually: acrylonitrile, sulfuric acid are contacted with isobutene, raw
After pulp product, filter this pulpous state product, obtain the filter cake containing ATBS.This route yield and purity are higher,
It it is the main method producing ATBS at present.In industrialized production, the step reactor of main use is carried out
Producing, production efficiency is low, and constant product quality is poor.
US6448347 (2002) proposes the method using continuity method to produce ATBS copolymer, in this method
Middle ATBS synthesis is also the production method of serialization.US6504050 (2003) the most also company of refer to
Continuous metaplasia produces the example of ATBS.These technology are to improve on the basis of intermittent operation, and then realize
The continuous prodution of ATBS, but there is also certain technological deficiency.These technology generally use stirring of routine
Mix still charging discharging or several stirred tank is connected to realize continuous operation, thus cause material in a kettle.
The non-constant width of residence time destribution, some material can stop the most in a kettle., and in reaction mass, bag
Including acrylonitrile, the chemical property of ATBS is the most active, it is easy to polymerization or side reaction occur.The most above-mentioned technology
Cannot well solve the continuous prodution of ATBS synthesis.
Summary of the invention
The invention aims to overcome material residence time destribution in a kettle. in prior art wide
Problem, it is provided that the synthesis technique of a kind of tert-butyl acrylamide sulfonate continuity method.
It was found by the inventors of the present invention that use Horizontal stirring reactor can realize laminar flow operation, it is prevented effectively from
The situation that residence time of material is uneven, it is adaptable to produce the continuous operation of tert-butyl acrylamide sulfonate.
In the production technology of the tert-butyl acrylamide sulfonate of the present invention, use acrylonitrile, sulfuric acid with isobutene are
Primary raw material, production technology is broadly divided into following components: (1) acrylonitrile contacts at low temperatures with sulfuric acid；
(2) at a temperature of 10 DEG C～45 DEG C in the reactor with isobutene haptoreaction；(3) pulpous state generated is produced
Thing separates, and is dried, obtains the thick product of ATBS；(4) ATBS is purified, obtains high-purity ATBS.
The invention provides the production method of a kind of tert-butyl acrylamide sulfonate, the method comprises the following steps:
1) acrylonitrile is mixed with sulfonating agent, form the acrylonitrile solution containing sulfonating agent；
2) provide Horizontal stirring reactor, and step 1) is obtained mixed solution be passed through described horizontal stir continuously
Mix in reactor and contact with isobutene, form pulpous state product；
3) described pulpous state product continuous print from Horizontal stirring reactor flows out and through being filtrated to get containing the tert-butyl group third
The filter cake of acrylamide sulfonic acid；
4) filter cake obtaining step 3) is dried, and obtains the tert-butyl group third that mass content is more than 96.0%
Acrylamide sulfonic acid crude product.
In a preferred embodiment of the method for the present invention, described method farther includes:
5) using aqueous acetic acid to be purified tert-butyl acrylamide sulfonate crude product, obtaining content is
The pure tert-butyl acrylamide sulfonate of 98.3-99.8%.
In a preferred embodiment of the method for the present invention, step 2) described in horizontal reactor include:
Kettle；
Chuck, outside described chuck parcel and kettle, for controlling the temperature within kettle；
Agitator, described agitator is arranged at inside kettle, for being mixed by reactant；And
Annex, described annex is arranged at kettle inside side walls.
In one preferred embodiment of horizontal reactor in the method for the invention, described kettle draw ratio is
1.5～10, preferred draw ratio is 3～7.
In one preferred embodiment of horizontal reactor in the method for the invention, the sidewall of described kettle
Axial distribution has vent line, is used for isobutene after vaporization through through being passed through described kettle.It addition, at reactor
Two ends have charging aperture and discharging opening respectively, and can realize continuous operation.
In one preferred embodiment of horizontal reactor in the method for the invention, described reacting kettle jacketing can
To use hot water or cooling water as heat-carrying agent, under some design condition, such as can not meet operating mode, can be built-in
Cooling coil.
In one preferred embodiment of horizontal reactor in the method for the invention, described agitator includes:
Driving means, for providing power for agitator；
It is arranged at the shaft of axial direction in still, the axial direction of described shaft is at least fixed with one group radially
Paddle, each paddle at least two panels blade.
Described paddle group number can be different according to the change of the draw ratio of kettle, generally 2～10 groups, blade
While being 2～6.
In one preferred embodiment of horizontal reactor in the method for the invention, the horizontal reacting used
The normally used material of device is the material of corrosion resistance, such as stainless steel, enamel or glass.
It addition, in a preferred embodiment of horizontal reactor in the method for the present invention, described annex includes
Thermocouple and/or Pressure gauge.May also include the annex with other functions if desired.
In a preferred embodiment of the present invention, described method may further comprise:
5) the tert-butyl acrylamide sulfonate crude product using aqueous acetic acid to obtain step 4) is purified,
Obtain the tert-butyl acrylamide sulfonate that mass content is more than 99.3%.
In the method for the invention, the purpose that acrylonitrile mixes with sulfonating agent is to obtain sulphur by step 1)
The acrylonitrile solution of agent, therefore, the temperature mixed described acrylonitrile with sulfonating agent is not particularly limited,
Being generally of as highly acid and the sulfuric acid of strong oxidizing property or oleum in view of sulfonating agent, relatively low temperature has
It is beneficial to reaction and operation.The most in a preferred embodiment of the present invention, acrylonitrile described in step 1)
The temperature mixed with sulfonating agent is-15 DEG C to 10 DEG C, preferably-10-0 DEG C.When reaching stable operation, acrylonitrile
It is 5-25:1 with the mol ratio of sulfuric acid.Acrylonitrile water content should be 0.1%～0.7 mass %.
In a preferred embodiment of the method for the present invention, by step 2) in material join Horizontal counter
Answering in still, isobutene is passed through in molar rate and step 1) the ratio of the molar rate adding sulfonating agent and is
1:1～1.3:1.
In a preferred embodiment of the method for the present invention, the temperature in described horizontal reactor exists
10～45 DEG C.
In a preferred embodiment of the method for the present invention, the slurries obtained are carried out solid-liquid by step 3)
Separating, method used can be various in prior art to cross the filter method realizing separation of solid and liquid, including normal
Press filtration method, vacuum filtration process etc., be cooled to the pulpous state product of generation room temperature, obtain containing ATBS after filtering
Filter cake and filtrate.
In a preferred embodiment of the method for the present invention, step 4) uses vacuum drying method to obtaining
To filter cake be dried.
In a preferred embodiment of the method for the present invention, permissible according to the method purified described in step 5)
For conventional ATBS purification process, the method as disclosed in US4337215.Specifically, the method include by
ATBS crude product mixes with the aqueous acetic acid that water content is 3-20 weight %, described ATBS crude product and acetic acid water
The weight ratio of solution is 1:10-1:4, heat the mixture to 85 DEG C-105 DEG C until ATBS dissolving crude product,
Then being cooled down 3-5 hour by the mixed liquor obtained, filter and be vacuum dried, described vacuum drying condition is permissible
The condition being dried with aforementioned vacuum is identical, the most i.e. can get ATBS sterling, and sterling purity is generally higher than 99
Quality %.In recrystallization process, after ATBS dissolving crude product, part can be distilled out by decompression distillation
Water and acetic acid, it is possible to increase the yield of recrystallization process.
Beneficial effects of the present invention:
The production method using the present invention carries out ATBS production, it is possible to achieve the continuous prodution of ATBS, carries
High efficiency.Additionally, the method using the present invention, it is also possible to the ATBS yield significantly improved, and improve
Product stability.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but the scope of the present invention is not limited to following enforcement
Example.
The purity of ATBS product is determined by liquid-phase chromatographic analysis (LC analysis).The analysis condition of liquid chromatogram
For: Zorbax SAX chromatographic column, flowing is 0.1mol/L KH mutually2PO4Solution, flow velocity is 1.0mL/min,
UV-detector.
Embodiment 1
The production method of the ATBS that the present embodiment provides for the present invention is described.
(1) add the acrylonitrile 496g of aqueous 0.25 mass % in a mixer, and temperature be reduced to-5 DEG C,
It is subsequently adding 73.6g SO3The oleum that mass content is 3%, after stirring, enter steady state operation.
Method particularly includes: the acrylonitrile by aqueous 0.25% is added by flowmeter with the flow velocity of 248.0g/h by measuring pump
In above-mentioned blender, being simultaneously introduced oleum, wherein dissociate SO3Mass content is 3%, by measuring pump
Added by quantifier with 36.8g/h flow velocity, obtain mixed liquor.
(2) in the middle part of the blended device of mixed liquor, overfall continuously flows in horizontal reactor, and horizontal reactor has three
Individual isobutene air inlet pipeline, after being vaporized by isobutene, is added continuously to horizontal reactor with overall flow rate 11.5g/h
In, controlling reactor temperature is 37～38 DEG C.Reaction gained white slurries are by the overflow of horizontal reactor right part
Mouth enters in the flask of 1000ml bottom opening, and continuous 3 lab scales collect product slurry 590g, by centrifugation,
Obtain white crystalline powder shape product 151.0g after drying, in terms of oleum, after liquid chromatography detection, produce
Product purity is 98.5%(mass), product synthesis yield is 96.6%(mass).
Product thick to ATBS uses the aqueous acetic acid of 10% to recrystallize, and obtains high-purity ATBS, purity
For 99.5%(mass).
Embodiment 2
ATBS, except for the difference that, SO in oleum is synthesized according to the method for embodiment 13Content is 5%.?
The thick product of ATBS arrived is after liquid chromatography detects, and product purity is 98.2%(mass), product synthesizes
Yield is 96.7%(mass).
Product thick to ATBS uses the aqueous acetic acid of 10% to recrystallize, and obtains high-purity ATBS, purity
For 99.5%(mass).
Embodiment 3
Synthesizing ATBS according to the method for embodiment 1, except for the difference that, reaction temperature is 30～32 DEG C.Obtain
After the detection of ATBS thick product liquid chromatography, product purity is 97.6%(mass), product synthesis yield is
96.0%(mass).
Product thick to ATBS uses the aqueous acetic acid of 10% to recrystallize, and obtains high-purity ATBS, purity
For 99.4%(mass).
Embodiment 4
Synthesizing ATBS according to the method for embodiment 1, except for the difference that, reaction temperature is 20～22 DEG C.Obtain
After the detection of ATBS thick product liquid chromatography, product purity is 96.6%(mass), product synthesis yield is
95.2%(mass).
Product thick to ATBS use 10%(volume) aqueous acetic acid recrystallize, obtain high-purity ATBS,
Purity is 99.3%(mass).
Comparative example 1
This comparative example is for illustrating the technique that batch process produces ATBS.
To being provided with temperature regulating device, agitator, in the reactor of thermometer and gas feed arrangement, add 330g
Analyze pure acrylonitrile (wherein the content of acrylonitrile is 99.7 mass %, and surplus is water), acrylonitrile is cooled to
-10 DEG C, it is slowly added to containing 2 mass %SO361g oleum, then the temperature of reaction system is adjusted to
40 DEG C, it is slowly introducing 35g isobutene and reacts, treat that isobutene is passed through complete, terminate anti-after being incubated one hour
Should, reactant liquor is carried out vacuum filtration.Obtain filter cake and filtrate after filtration, filter cake is vacuum dried, dry
Dry temperature is 100 DEG C, and drying pressure is 10KPa, obtains dried filter cake.
This dried filter cake is ATBS crude product, is 95.5%(mass through liquid chromatography detection purity),
Through calculating, ATBS yield is 91.5%(mass).
Product thick to ATBS uses the aqueous acetic acid of 10% to recrystallize, and obtains high-purity ATBS, purity
For 98.7%(mass).
Embodiment and comparative example 1 are compared it can be seen that the method using the present invention to provide synthesizes ATBS,
Product yield can be effectively improved, and realize high-purity and produce high efficiency.
Claims (5)
1. a production method for tert-butyl acrylamide sulfonate, the method comprises the following steps:
1) acrylonitrile is mixed at-15 DEG C to 10 DEG C with sulfonating agent, form the acrylonitrile solution containing sulfonating agent；
2) Horizontal stirring reactor is provided, and by step 1) obtain mixed solution and be passed through described horizontal stir continuously
Mixing in reactor and contact with isobutene, form pulpous state product, wherein, isobutene is passed through molar rate and step 1)
The ratio of the molar rate of middle addition sulfonating agent is 1:1～1.3:1, and the temperature in described Horizontal stirring reactor exists
10～45 DEG C, described Horizontal stirring reactor includes:
Kettle, the axial distribution of the sidewall of described kettle has vent line, for being led to by isobutene after vaporization
Entering described kettle, wherein said kettle draw ratio is 1.5～10；
Chuck, described chuck is wrapped in the outside of kettle, for controlling the temperature within kettle；
Agitator, described agitator is arranged at inside kettle, for being mixed by reactant, wherein said stirs
Mix device and include driving means, for providing power for agitator；Be arranged at the shaft of axial direction in still,
One group of paddle radially, each paddle at least two panels oar at least it is fixed with in the axial direction of described shaft
Leaf；And
Annex, described annex is arranged at kettle inside side walls；
3) described pulpous state product continuous print from Horizontal stirring reactor flows out and through being filtrated to get containing the tert-butyl group third
The filter cake of acrylamide sulfonic acid；
4) to step 3) filter cake that obtains is dried, and obtains the tert-butyl group third that mass content is more than 96.0%
Acrylamide sulfonic acid crude product.
Method the most according to claim 1, it is characterised in that described kettle draw ratio is 3～7.
Method the most according to claim 1, it is characterised in that described annex includes thermocouple and/or pressure
Power table.
Method the most according to claim 1, it is characterised in that described method farther includes:
5) aqueous acetic acid is used to step 4) the tert-butyl acrylamide sulfonate crude product that obtains is purified,
Obtain the tert-butyl acrylamide sulfonate that mass content is more than 99.3%.
Method the most according to claim 1, it is characterised in that step 1) described in acrylonitrile and sulfonation
The temperature of agent mixing is-10-0 DEG C.
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| 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 |
| 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 |
| 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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| 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 |
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| 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 |
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2013
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| 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 |
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