CN102952043B - Synthesis method of tert-butyl acrylamide sulfonate - Google Patents
Synthesis method of tert-butyl acrylamide sulfonate Download PDFInfo
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Abstract
The invention discloses a synthesis method of tert-butyl acrylamide sulfonate, which comprises the following steps of: providing a first solution and a second solution, wherein the first solution is obtained through contact between acrylonitrile and a first sulfonating agent at -30 to 15 DEG C, and the second solution is obtained through contact between acrylonitrile and a second sulfonating agent at -30 to 15 DEG C; at -20 to 50 DEG C, enabling the first solution to contact with isobutene accounting for 10-100% of isobutene feed and the second solution to obtain a third solution; at -20 to 50 DEG C, enabling the third solution to contact with isobutene accounting for 0-90% of the isobutene feed to obtain a paste product; and separating and purifying the paste product to obtain tert-butyl acrylamide sulfonate. Through the method disclosed by the invention, other substances are not required in a reaction system, the production cost is greatly reduced, and the purity is improved.
Description
Technical field
The present invention relates to a kind of synthetic method of N-tert-butyl acrylamide sulfonic acid.
Background technology
N-tert-butyl acrylamide sulfonic acid (acrylamido tertiary butyl sulfonic acid, hereinafter referred to as ATBS) is multifunctional water-soluble anionic monomer, and molecular structure is
because the molecular structure of ATBS has to the insensitive sulfonic group of salt with by the amide group of good protection; therefore its homopolymerization and multipolymer have much special character; have broad application prospects, can be widely used in the fields such as oilfield chemistry, water conditioner, chemical fibre, plastics, printing and dyeing, coating, tensio-active agent, static inhibitor, pottery, photograph, washing auxiliary detergent, ion exchange resin, gas separation membrane, electronic industry.
The technique of current most typical production ATBS, is with vinyl cyanide, and oleum and iso-butylene are that raw material reacts preparation ATBS under relatively mild condition.First U.S. Pat 3544597 has reported this method of preparing amide group sulfonic compound, and has obtained the higher monomer of purity, but reaction conditions is comparatively harsh.Dong chemical company of Japan (DE2904444, DE2904465) has improved aforesaid method, and has proposed to obtain the more technical scheme of high purity ATBS.Method described in this patent is that excessive vinyl cyanide is doubled as to reaction solvent, in helium atmosphere, under low temperature, adds oleum, under agitation passes into iso-butylene, make its reaction, product A TBS separates out from mixed solution, obtains muddy product, after super-dry, can obtain the thick product of ATBS.
In order to improve the yield of ATBS, CN1072406A discloses a kind of method of the ATBS of raising yield, the method is the organic acid anhydride that adds 0.5-50 % by weight in reaction process, as acetic anhydride, made the preparation method of highly purified ATBS monomer by vinyl cyanide, sulfuric acid and iso-butylene single step reaction, while using sulfuric acid, add organic acid anhydride not only can improve ATBS product yield, and the particle of product crystallization is larger.
CN101284805A discloses a kind of method of ATBS yield, in sulfuric acid, add in advance organic sulfonated bodies of 2-30 % by weight, as p-hydroxybenzenyl sulfonate, the sulfuric acid that is mixed with organic sulfonated bodies is mixed with vinyl cyanide, pass into again iso-butylene, the method not only suppresses the generation of side reaction, and product grain size number is larger, improves the yield of ATBS.
Summary of the invention
The object of the invention is a kind of method for new synthesizing tertiary butyl acrylamide sulfonic acid is provided, the method can realize without extra other components of adding that in ATBS product, by-products content is lower, purity is higher.
The present inventor is through research, be surprised to find that, in the time of synthetic ATBS, vinyl cyanide is contacted to obtained solution adition process with sulphonating agent is controlled, just can effectively reduce the sulfonation by product in reaction process without extra other reagent that add, to meet, yield and purity are had to the production of the high-quality ATBS of requirements at the higher level, thereby obtain the present invention.
The invention provides a kind of synthetic method of N-tert-butyl acrylamide sulfonic acid, wherein, the method comprises the following steps:
(1) provide the first solution and the second solution,
Described the first solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the first sulphonating agent; Described the second solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the second sulphonating agent;
(2) at-20 ℃ at 50 ℃, the first solution is contacted with the second solution with the iso-butylene of the 10-100% that accounts for isobutylene feed, obtain the 3rd solution;
(3) at-20 ℃ at 50 ℃, the 3rd solution is contacted with the iso-butylene of the 0-90% that accounts for isobutylene feed, obtain pulpous state product;
(4) pulpous state product is separated and purifying, obtain N-tert-butyl acrylamide sulfonic acid;
Wherein, described the first sulphonating agent and the second sulphonating agent are identical or different, and the concentration of respectively doing for oneself is sulfuric acid or the oleum of 98-103 % by weight; The ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.1-0.9: 1; The mol ratio of the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene is 5-25: 1: 0.8-1.2.
Compared with prior art, method provided by the invention is without introduce other materials in reaction system, only need to control vinyl cyanide in reaction process contacts separately with sulphonating agent in batches, just can effectively reduce the by product producing in reaction process, especially sulfonation by product, make the purity of the ATBS product obtaining higher, save on the one hand the expense of raw materials of buying other materials, also reduce on the other hand in reaction system and added and from reaction system, remove the step of this material, thereby greatly reduced production cost and improved purity.
Embodiment
The invention provides a kind of synthetic method of N-tert-butyl acrylamide sulfonic acid, wherein, the method comprises the following steps:
(1) provide the first solution and the second solution,
Described the first solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the first sulphonating agent; Described the second solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the second sulphonating agent;
(2) at-20 ℃ at 50 ℃, the first solution is contacted with the second solution with the iso-butylene of the 10-100% that accounts for isobutylene feed, obtain the 3rd solution;
(3) at-20 ℃ at 50 ℃, the 3rd solution is contacted with the iso-butylene of the 0-90% that accounts for isobutylene feed, obtain pulpous state product;
(4) pulpous state product is separated and purifying, obtain N-tert-butyl acrylamide sulfonic acid;
Wherein, described the first sulphonating agent and the second sulphonating agent are identical or different, and the concentration of respectively doing for oneself is sulfuric acid or the oleum of 98-103 % by weight; The ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.1-0.9: 1; The mol ratio of the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene is 5-25: 1: 0.8-1.2.
According to synthetic method of the present invention, the concentration of the concentration of described the first sulphonating agent and the second sulphonating agent can be identical or different, as long as described the first sulphonating agent and the second sulphonating agent are sulfuric acid or the oleum that concentration is 98-103 % by weight.In the present invention, the definition of the concentration of sulfuric acid or oleum is with well known in the art identical, and the concentration of sulfuric acid refers to wherein H
2sO
4weight percentage, the concentration of oleum refers to SO wherein
3be scaled H
2sO
4rear H
2sO
4weight percentage.Under preferable case, the concentration of the second sulphonating agent is lower than the concentration of the first sulphonating agent, the more preferably low 0.3-3 % by weight of concentration of concentration ratio first sulphonating agent of the second sulphonating agent, i.e. concentration (the % by weight)=0.3-3 % by weight of the concentration of the first sulphonating agent (% by weight)-second sulphonating agent.Further preferably, the concentration of the first sulphonating agent is 100-102 % by weight, and the concentration of described the second sulphonating agent is 99-102 % by weight.
According to synthetic method of the present invention, the weight of described the first sulphonating agent and the second sulphonating agent weight can there is no particular limitation.Under preferable case, the ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.1-0.9: 1, further, under preferable case, the ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.2-0.8: 1.In above-mentioned preferred proportional range, can obtain obviously higher ATBS yield, and the consumption of the higher sulfuric acid of concentration can be less.
According to synthetic method of the present invention, the weight of described vinyl cyanide and the weight of sulphonating agent can change in a big way, all can realize goal of the invention of the present invention.Under preferable case, in the first solution, the mol ratio of described vinyl cyanide and the first sulphonating agent is 5-30: 1, be preferably 8-28: 1; In the second solution, the mol ratio of described vinyl cyanide and the second sulphonating agent is 5-30: 1, be preferably 8-28: 1.
According to synthetic method of the present invention, in step (1), vinyl cyanide is contacted to the object contacting with the second sulphonating agent with vinyl cyanide with the first sulphonating agent be all the sulphuric acid soln in order to obtain vinyl cyanide, therefore, according to the present invention, there is no particular limitation for the condition that vinyl cyanide is contacted with sulphonating agent, consider that sulphonating agent is strongly-acid and the strong oxidizing property of high-concentration sulfuric acid or oleum, lower temperature is conducive to prevent the generation of side reaction and is conducive to operation, preferably, vinyl cyanide is-30 ℃ to 15 ℃ with the temperature that the first sulphonating agent contacts, time is 3-300 minute, further under preferable case, the temperature of contact is-15 ℃ to 0 ℃, time is 30-180 minute, vinyl cyanide is-30 ℃ to 15 ℃ with the temperature that the second sulphonating agent contacts, and the time is 3-300 minute, and further, under preferable case, the temperature of contact is-15 ℃ to 0 ℃, and the time is 30-180 minute.
According to synthetic method of the present invention, there is no particular limitation for the process that passes into of described iso-butylene, can all pass in the first solution in step (2), that is, the intake of iso-butylene accounts for 100% of isobutylene feed.Under preferable case, in step (2), the iso-butylene of the 10-90% that accounts for isobutylene feed can be passed in the first solution, remaining iso-butylene can pass in step (3), more preferably 20-80 % by weight, more preferably 30-70%.It should be noted that, in the step (2) intake of iso-butylene account for isobutylene feed 100% time, the present invention can not comprise step (3), after step (2), directly carries out the operation of step (4).
According to synthetic method of the present invention, in step (2), there is no particular limitation with accounting for the iso-butylene of 10-100% of isobutylene feed and the second solution contact conditions for the first solution that step (1) is obtained, vinyl cyanide is contacted with the first sulphonating agent and form after the first solution, start to heat up or do not heat up after enter step (2), the iso-butylene and the second solution that account for the 10-100% of isobutylene feed can contact in temperature-rise period or after heating up.Wherein, there is no particular limitation for the speed of described intensification, as long as arrive the required temperature of reaction of step (2).The temperature of preferred steps (2) contact is 10 ℃ to 55 ℃, and the time is 10-300 minute, and further the temperature of preferred steps (2) contact is 20-50 ℃, and the time is 30-180 minute.
According to synthetic method of the present invention, in step (2), to adding the iso-butylene of the 10-100% that accounts for isobutylene feed and the mode of the second solution in the first solution, there is no particular limitation, can first the iso-butylene of the 10-100% that accounts for isobutylene feed be passed into after the first solution, then add the second solution; Maybe iso-butylene and the second solution of the 10-100% that accounts for isobutylene feed can be joined in the first solution simultaneously.
According to synthetic method of the present invention, in step (3), remaining iso-butylene is not particularly limited with the condition that the 3rd solution contacts, can constant temperature in the temperature of reaction of step (2), usually, temperature is-10 ℃ to 50 ℃, and the time is 10-300 minute.
According to synthetic method of the present invention, there is no particular limitation for relation between the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene, it can be conventional ratio, preferably, the molar ratio of the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene is 5-25: 1: 0.8-1.2, more preferably, 7-18: 1: 0.9-1.1.
According to synthetic method of the present invention, the source of described vinyl cyanide has no particular limits.Under preferable case, the water content of described vinyl cyanide is lower than 1 % by weight, more preferably 0.2-0.7 % by weight.
According to synthetic method of the present invention, the method for described separation can be any method that can realize liquid-solid separation, as filtration method, comprises normal pressure filtration method, vacuum filtration process etc. the pulpous state product of generation being chilled to room temperature, obtains after filtering filter cake and filtrate.Filter cake is carried out to vacuum-drying, and described vacuum drying condition can be normal condition, and if drying temperature can be 50-130 ℃, drying pressure can be for being less than 30KPa, and the desciccate obtaining is ATBS crude product.
According to synthetic method of the present invention, the method for described purifying can be the method for conventional purifying ATBS crude product.Preferably, adopt the method for recrystallization to carry out purifying to ATBS crude product, the concrete operations of the method for described recrystallization comprise: the aqueous acetic acid that is 3-20 % by weight by 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 85-105 ℃ until ATBS dissolving crude product, then by cooling the mixed solution obtaining 3-5 hour, filter and vacuum-drying, described vacuum drying condition can be identical with aforementioned vacuum drying condition, after dry, can obtain ATBS sterling, sterling purity is generally greater than 99 % by weight.
Below by embodiment, method of the present invention is described further.
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, moving phase is 0.1mol/L KH
2pO
4solution, flow velocity is 1.0mL/min, UV-detector.
In the present invention, the yield of ATBS is to calculate according to the weight of the add-on of iso-butylene raw material and ATBS crude product.
Embodiment 1
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
(1) being provided with in the four-hole boiling flask of temperature regulating device, agitator, thermometer and gas feeding unit, add 220g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 34g of 103 % by weight, obtain the first solution, in reinforced process and after holding temperature be-15 ℃.
In another stirred vessel, add 110g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 27g of 103 % by weight, obtains the second solution, in reinforced process and after holding temperature for-15 ℃ and maintain whipped state.
(2) the first solution is continued to stir after 1 hour, passing into 12g iso-butylene after being warmed up to 40 ℃ reacts, and then the second solution is all joined in reaction system with the speed of 12ml/min.
(3) after the total amount of the iso-butylene adding reaches 35g, close iso-butylene valve in reaction system, be incubated after 1 hour and finish to react.Reaction solution is carried out to vacuum filtration, obtain filter cake and filtrate.Filter cake is carried out to vacuum-drying, and temperature is 60 ℃, and pressure is 10kPa, obtains dried filter cake, is ATBS crude product.The LC purity of ATBS crude product is 96.3 % by weight, and the content of single sulfonation iso-butylene is 1.2 % by weight, and through calculating, yield is 93%.
ATBS crude product is carried out to recrystallization with the aqueous acetic acid that concentration is 10 % by weight, obtain high-purity ATBS, purity is 99.42 % by weight.
Embodiment 2
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
(1) being provided with in the four-hole boiling flask of temperature regulating device, agitator, thermometer and gas feeding unit, add 180g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 25g of 103 % by weight, obtain the first solution, in reinforced process and after holding temperature be-15 ℃.
In another stirred vessel, add 150g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 36g of 101 % by weight, obtains the second solution, in reinforced process and after holding temperature for-15 ℃ and maintain whipped state.
(2) the first solution is continued to stir after 1 hour, passing into 8g iso-butylene after being warmed up to 40 ℃ reacts, and then the second solution is all joined in reaction system with the speed of 12ml/min.
(3) after the total amount of the iso-butylene adding reaches 35g, close iso-butylene valve in reaction system, be incubated after 1 hour and finish to react.Reaction solution is carried out to vacuum filtration, obtain filter cake and filtrate.Filter cake is carried out to vacuum-drying, and temperature is 60 ℃, and pressure is 10kPa, obtains dried filter cake, is ATBS crude product.The LC purity of ATBS crude product is 97.15 % by weight, and the content of single sulfonation iso-butylene is that 0.9% process is calculated, and yield is 92.5%.
ATBS crude product is carried out to recrystallization with the aqueous acetic acid that concentration is 10 % by weight, obtain high-purity ATBS, purity is 99.69 % by weight.
Embodiment 3
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
(1) being provided with in the four-hole boiling flask of temperature regulating device, agitator, thermometer and gas feeding unit, add 220g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 34g of 103 % by weight, obtain the first solution, in reinforced process and after holding temperature be-15 ℃.
In another stirred vessel, add 110g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 27g of 100 % by weight, obtains the second solution, in reinforced process and after holding temperature for-15 ℃ and maintain whipped state.
(2) the first solution is continued to stir after 1 hour, passing into 12g iso-butylene after being warmed up to 40 ℃ reacts, and then the second solution is all joined in reaction system with the speed of 12ml/min.
(3) after the total amount of the iso-butylene adding reaches 35g, close iso-butylene valve in reaction system, be incubated after 1 hour and finish to react.Reaction solution is carried out to vacuum filtration, obtain filter cake and filtrate.Filter cake is carried out to vacuum-drying, and temperature is 60 ℃, and pressure is 10kPa, obtains dried filter cake, is ATBS crude product.The LC purity of ATBS crude product is 97.21 % by weight, and single sulfonation iso-butylene content is 0.8%, and through calculating, yield is 93%.
ATBS crude product is carried out to recrystallization with the aqueous acetic acid that concentration is 10 % by weight, obtain high-purity ATBS, purity is 99.72 % by weight.
Embodiment 4
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
According to the method synthesizing tertiary butyl acrylamide sulfonic acid of embodiment 1, different, the first sulphonating agent is that concentration is the oleum of 102 % by weight, and the second sulphonating agent is that concentration is the sulfuric acid of 100 % by weight.The LC purity of the ATBS crude product obtaining is 97.52 % by weight, and single sulfonation iso-butylene content is 0.8%, and through calculating, yield is 93.5%.
ATBS crude product is carried out to recrystallization with 10% aqueous acetic acid, obtain high-purity ATBS, purity is 99.75 % by weight.
Embodiment 5
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
According to the method synthesizing tertiary butyl acrylamide sulfonic acid of embodiment 1, different, the second sulphonating agent is that concentration is the oleum of 102 % by weight.The LC purity of the ATBS crude product obtaining is 96.8 % by weight, and single sulfonation iso-butylene content is 1.1%, and through calculating, yield is 93%.
ATBS crude product is carried out to recrystallization with 10% aqueous acetic acid, obtain high-purity ATBS, purity is 99.53 % by weight.
Embodiment 6
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
According to the method synthesizing tertiary butyl acrylamide sulfonic acid of embodiment 1, different, the temperature of reaction of step (2) and step (3) is 20 ℃.The LC purity of the ATBS crude product obtaining is 97.05 % by weight, and single sulfonation iso-butylene content is 0.7%, and through calculating, yield is 91%.
ATBS crude product is carried out to recrystallization with 10% aqueous acetic acid, obtain high-purity ATBS, purity is 99.52 % by weight.
Embodiment 7
The present embodiment is for illustrating the synthetic method of N-tert-butyl acrylamide sulfonic acid provided by the invention.
According to the method synthesizing tertiary butyl acrylamide sulfonic acid of embodiment 1, different, the temperature of reaction of step (2) and step (3) is 30 ℃.The LC purity of the ATBS crude product obtaining is 97.33 % by weight, and single sulfonation iso-butylene content is 0.8%, and through calculating, yield is 93%.
ATBS crude product is carried out to recrystallization with 10% aqueous acetic acid, obtain high-purity ATBS, purity is 99.7 % by weight.
Comparative example 1
(1) being provided with in the four-hole boiling flask of temperature regulating device, agitator, thermometer and gas feeding unit, add 330g vinyl cyanide, vinyl cyanide is cooled to after-10 ℃, add the oleum 61g containing 103 % by weight, in reinforced process and after holding temperature be-10 ℃ and continue stirring 1 hour.
(2) passing into 35g iso-butylene after being warmed up to 40 ℃ reacts.
(3), after treating that iso-butylene passes into, be incubated after 1 hour and finish to react.Reaction solution is carried out to vacuum filtration, obtain filter cake and filtrate.Filter cake is carried out to vacuum-drying, and temperature is 110 ℃, and pressure is 10KPa, obtains dried filter cake, is ATBS crude product.The LC purity of ATBS crude product is 94 % by weight, and single sulfonation iso-butylene content is 1.5%, and through calculating, yield is 88%.
ATBS crude product is carried out to recrystallization with 10% aqueous acetic acid, obtain high-purity ATBS, purity is 99 % by weight.
Comparative example 2
(1) being provided with in the four-hole boiling flask of temperature regulating device, agitator, thermometer and gas feeding unit, add 220g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 12g of 104 % by weight, obtain the first solution, in reinforced process and after holding temperature be-15 ℃.
In another stirred vessel, add 110g vinyl cyanide, vinyl cyanide being cooled to after-15 ℃, add concentration is the oleum 49g of 99 % by weight, obtains the second solution, in reinforced process and after holding temperature for-15 ℃ and maintain whipped state.
(2) the first solution is continued to stir after 1 hour, passing into 12g iso-butylene after being warmed up to 40 ℃ reacts, and then the second solution is all joined in reaction system with the speed of 12ml/min.
(3) after the total amount of the iso-butylene adding reaches 35g, close iso-butylene valve in reaction system, be incubated after 1 hour and finish to react.Reaction solution is carried out to vacuum filtration, obtain filter cake and filtrate.Filter cake is carried out to vacuum-drying, and temperature is 60 ℃, and pressure is 10kPa, obtains dried filter cake, is ATBS crude product.The LC purity of ATBS crude product is 93.5 % by weight, and single sulfonation iso-butylene content is 1.3%, and through calculating, yield is 88%.
ATBS crude product is carried out to recrystallization with the aqueous acetic acid that concentration is 10 % by weight, obtain high-purity ATBS, purity is 98.8 % by weight.
Claims (8)
1. a synthetic method for N-tert-butyl acrylamide sulfonic acid, is characterized in that, the method comprises the following steps:
(1) provide the first solution and the second solution,
Described the first solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the first sulphonating agent; Described the second solution be by-30 ℃ at 15 ℃, vinyl cyanide is contacted and is obtained with the second sulphonating agent;
(2) at-20 ℃ at 50 ℃, the first solution is contacted with the second solution with the iso-butylene of the 20-80% that accounts for isobutylene feed, obtain the 3rd solution;
(3) at-20 ℃ at 50 ℃, the 3rd solution is contacted with the iso-butylene of the 20-80% that accounts for isobutylene feed, obtain pulpous state product;
(4) pulpous state product is separated and purifying, obtain N-tert-butyl acrylamide sulfonic acid;
Wherein, described the first sulphonating agent and the second sulphonating agent concentration of respectively doing for oneself is sulfuric acid or the oleum of 98-103 % by weight, the low 0.3-3 % by weight of concentration of concentration ratio first sulphonating agent of described the second sulphonating agent; The ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.1-0.9:1; The mol ratio of the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene is 5-25:1:0.8-1.2.
2. synthetic method according to claim 1, wherein, the ratio of the gross weight of the weight of the first sulphonating agent and the first sulphonating agent and the second sulphonating agent is 0.2-0.8:1.
3. synthetic method according to claim 1, wherein, in the first solution, the mol ratio of described vinyl cyanide and the first sulphonating agent is 5-30:1.
4. synthetic method according to claim 1, wherein, in the second solution, the mol ratio of described vinyl cyanide and the second sulphonating agent is 5-30:1.
5. synthetic method according to claim 1, wherein, the mol ratio of the total amount of described vinyl cyanide and the first sulphonating agent and the total amount of the second sulphonating agent and the total amount of iso-butylene is 7-18:1:0.9-1.1.
6. synthetic method according to claim 1, wherein, in step (1), is-15 ℃ to 0 ℃ by vinyl cyanide with the temperature that the first sulphonating agent contacts, and the time is 3-300 minute; Vinyl cyanide is-15 ℃ to 0 ℃ with the temperature that the second sulphonating agent contacts, and the time is 3-300 minute.
7. synthetic method according to claim 1, wherein, in step (2), is-10 ℃ to 50 ℃ with the iso-butylene of the 20-80% that accounts for isobutylene feed with the temperature that the second solution contacts by the first solution, and the time is 10-300 minute.
8. synthetic method according to claim 1, wherein, in step (3), is-10 ℃ to 50 ℃ by the 3rd solution with the temperature that the iso-butylene of 20-80% that accounts for isobutylene feed contacts, and the time is 10-300 minute.
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| CN104311455B (en) * | 2014-06-05 | 2018-02-27 | 中国石油化工集团公司 | A kind of preparation method of 2 acrylamido 2 methyl-prop (alkane) sulfonic acid |
| CN105481713A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Method and apparatus for recovering N-t-butyl acrylamide |
| CN105481714A (en) * | 2014-09-16 | 2016-04-13 | 中国石油化工股份有限公司 | Method for comprehensive utilization of 2-acrylamide-2-methylpropanesulfonic acid production process waste residue |
| 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 |
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