CN1114646A - Method for preparation of substituted amido-alkyl sulfonic acids - Google Patents
Method for preparation of substituted amido-alkyl sulfonic acids Download PDFInfo
- Publication number
- CN1114646A CN1114646A CN 94107673 CN94107673A CN1114646A CN 1114646 A CN1114646 A CN 1114646A CN 94107673 CN94107673 CN 94107673 CN 94107673 A CN94107673 A CN 94107673A CN 1114646 A CN1114646 A CN 1114646A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- sulfonic acids
- alkyl sulfonic
- substituted amido
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
`he present invention discloses a method or preparation of substituted amido alkyl sulfonic acids by using tert-butyl alcohol as raw material. In the concrete, to methylene dichloride solvent the correspondent reaction materials of glacial acetic acid, fuming sulfuric acid, tert-butyl alcohol and water and acrylonitriles compound are added in turn, and its technological condition and materials-adding sequence are cotnrolled so as to make their reaction complete. The solvent and excessive raw materials are removed by conventional vacuum distillation and then in the absolute ethyl alcohol the crude product is separated from mother liquor. Said invention provides a new recrystallization refining method so as to greatly simplify technological process. Said product is applicable to oil production, paper-making and textile fabrics, etc..
Description
The present invention relates to a kind of preparation method of substituted amido-alkyl sulfonic acids compound, compound is represented by following formula:
R represents low alkyl group, low-grade alkenyl in the formula; R
1, R
2Represent H, low alkyl group, aromatic base.Especially particularly in the formula (I)
(1) R is CH
2=CH-, R
1, R
2Be CH
3-, compound
Its name is called 2-acrylamido-2-methyl propane sulfonic acid, and MPPA be abbreviated as in its code name;
(2) R is
, R
1, R
2Be CH
3-, compound
Its name is called 2-(2-methyl)-acrylamido-2-methyl propane sulfonic acid, and MMPPA be abbreviated as in its code name, above-mentioned (II) and (III) preparation method of two materials.
Nineteen sixty-five Dieter Arit report has been obtained since the MPPA (document GB1090779) by vinyl cyanide, iso-butylene and chlorsulfonic acid or oleum reaction, MPPA is referred to as AMPS in U.S. Lu Bisuo company (Lubrizol Corp.), up to now its synthesis method is all based on Ritter Reaction (Ritter reaction) principle [J.Am.Chem.Soc.70,4045 (1948); Org.Reactions, 17,213 (1969)].By the raw material difference of using, synthesis method has simultaneously: 1. iso-butylene method (GB1090779, US3544597, US3506707, DE2105030, DE2523616, Res.Disc.159,62 (1977); 242,265 (1984), JP02-96559, JP03-145455, JP03-77859, JP04-74159).2. trimethyl carbinol method have only a document EP 170485 reports so far, and the reactions steps of report is not quite clear, and post-treating method is not clear; 3. isobutenyl sodium sulfonate method (JP56-103145).4. hydroxy alkyl sulfonic acid method (WO84-0165).
Use the trimethyl carbinol to be the raw material method, based on the Ritter reaction principle, the present invention proposes reaction formula first and is expressed as follows: the formation reaction of the first step carbonium ion
Q represents H, CH herein
3Me is a methyl.
In fact, if reaction is to carry out in methylene dichloride and Glacial acetic acid mixed solvent, methylene dichloride is the inert solvent, and Glacial acetic acid will be participated in the generation that reaction helps carbonium ion:
Me
2C
-CH
2SO
3H+HSO
4 In hydrolysis reaction, still there is simultaneously following reaction:
Ac represents ethanoyl herein.Net reaction is: Me
3COH+2H
2SO
4XSO
a 
Prior art with the trimethyl carbinol is being raw material when making MPPA and MMPPA, has some shortcomings: 1. Japanese Patent JP61-47458 does not have clear and definite post-treating method; 2. the pretty method of the clay fertilizer of Japanese Patent JP54-163524 is operated repeatedly when separating out product, and final product still needs recrystallizing and refining; 3. acetate seriously corroded and smell are big, ask minimizing at the production upper stress; 4. do not use stopper, decompose and/or (being total to) polymerization, cause byproduct to increase because MPPA and vinyl cyanide can cause 〉=50 ℃ of following long-time heating; If 5. order of addition(of ingredients) is unreasonable, what can cause another kind of Ritter reaction, and obtain the byproduct N-tertiary butyl-acrylamide.
In order to improve the purity of thick product MPPA or MMPPA, the technology of previous thick product recrystallizing and refining has as follows:
1. Lubrizol Corp. (Lu Bisuo company) method, in methyl alcohol, temperature is 175～180 (80.5 ± 1.7 ℃) pressurization thermosol and remove by filter insolubles down, crystallisation by cooling gets pure product (US4650614).2. the pretty method of clay fertilizer: with 3. Medtronic Inc. method of moisture 10% acetate recrystallization (JP54-106427): in methyl alcohol, dissolve 80% crude product, 40 ℃ were heated 2 hours in nitrogen atmosphere, filter 25～70 ℃ of (best 50 ℃)/1mmHg (133.322Pa) of rotation vacuum-drying 3 hours.Dehydrated alcohol or Virahol can replace methyl alcohol, and meltage is 25～35% (US4650614); 4. refine day and learn industrial's method: with hot acetic acid extraction (JP03-77860), stablizer has urea, acetic anhydride and amino urea class in the presence of stablizer.Above prior art shortcoming: 1. acetate corrodibility is big, and drying is difficult to remove tart flavour again.2. methyl alcohol toxicity is big.3. use the C1-3 lower alcohols to add and depress the recrystallization operational difficulty in boiling.4. be unfavorable for purified product preservation steady in a long-term.
Solvent title temperature (℃) solubleness (gram/100 gram solvents)
H2O 25 150
Methyl alcohol 30 8.7
Ethanol 78 (boiling point) 10
Virahol 82 (boiling point) 6
Acetate 25＜10
Prior art be reported in add in the reaction stablizer (stopper) have acrylamide (JP02-96559), amino urea class (JP03-77859), organic acid anhydride class, particularly acetic anhydride (JP03-77859, JP04-74159).
The reported in literature of comprehensive above-mentioned prior art is the method for raw material production substituted amido-alkyl sulfonic acids with the trimethyl carbinol, and the concrete grammar step is indeterminate, the post-treating method complexity, and thick product yield is low, and method for recrystallizing and refining is performance difficulty in suitability for industrialized production.
The purpose of this invention is to provide a kind of is raw material with the trimethyl carbinol, improves the control of order of addition(of ingredients) and processing condition, to prepare the method for substituted amido-alkyl sulfonic acids.
The object of the present invention is achieved like this, prepares the method for substituted amido-alkyl sulfonic acids, and its charging capacity proportioning (mol ratio) is: the trimethyl carbinol: vinyl cyanide: oleum: pure water=1: 1.1～2.0: 2.2～2.5: 10～20; Reaction in turn includes the following steps:
(1) at dichloromethane solvent and accounting in the Glacial acetic acid mixture of Glacial acetic acid total amount 1/3, stir and cooling under slowly add account for the oleum of oleum total amount 2/3 after, remaining Glacial acetic acid and oleum are all added simultaneously;
(2) above-mentioned reactant is chilled to-8～-12 ℃, keeps and slowly add the trimethyl carbinol under this temperature, kept this thermotonus after adding again 2 hours;
(3) in above-mentioned reaction mixture, add pure water and the acrylonitrile compound that accounts for pure water total amount 1/4 successively, slowly heat up 40～60 ℃, kept this thermotonus 6～10 hours;
(4) above-mentioned mixture adds remaining pure water again, reacts half an hour;
(5) methylene chloride and excessive propene nitrile compounds are removed in air distillation;
(6) excessive water and acetate are removed in above-mentioned mixed solution underpressure distillation;
(7) be cooled to room temperature after, add the dehydrated alcohol dilution, the abundant wash rice of thick product is gone out;
(8) centrifuging, an amount of absolute ethanol washing, vacuum-drying gets thick product:
(9) thick product carries out recrystallizing and refining and gets straight product.
The present invention can also be in the 3rd step of above-mentioned reaction, behind the pure water that adds 1/4 amount, add again and account for the stopper that the reaction mixture total amount is 30～50ppm, to prevent the product polymerization, be beneficial to the long-term preservation of product, the poly-agent of sun is generally p methoxy phenol, Resorcinol etc.
Reactant vinyl cyanide in the above-mentioned reaction can be vinyl cyanide or methacrylonitrile.
In order to improve the purity of thick product, except with the method for known references, the invention provides following method for recrystallizing and refining, its method comprises successively:
Thick product with the less water dissolving, heats half an hour under 40 ℃ of temperature earlier, remove by filter insolubles after, use lower alcohol, particularly dehydrated alcohol adds, and the whole wash rices of crystal are gone out, filtration, vacuum-drying.The also available methyl alcohol of the solvent of recrystallization, Virahol, Glacial acetic acid or mixed solvent such as ethanol-Glacial acetic acid, methyl alcohol-Glacial acetic acid, Virahol-Glacial acetic acid etc.; When specifically using single solvent, adopt following steps recrystallizing and refining process:
(1) thick product MPPA or MMPPA are by weight being dissolved under 40 ℃ in 100 parts of pure water with 100～300 parts
(2) filter, filtrate can add that to account for solution weight be 30～50ppm stopper p methoxy phenol or Resorcinol, also can not add stopper, adds stopper and can not cause product auto-polymerization reaction and reduce purity, just is beneficial to the product prolonged preservation.
(3) get above-mentioned solution, handle with 0.5～1.0 volume lower alcohol by 1 volume solution, this lower alcohol is generally best with dehydrated alcohol, and this moment, wash rice went out the white plates crystal, centrifuging, and with above-mentioned lower alcohol washing, vacuum-drying promptly gets straight product MPPA or MMPPA.
If use mixed solvent, be the example explanation with ethanol-acetate, then first, second step of re-crystallization step is with above-mentioned, the different the 3rd go on foot and be:
(3) get above-mentioned solution, by volume, the 1 volume aqueous solution is chilled to room temperature after adding 0.4～0.6 volume Glacial acetic acid, the dehydrated alcohol that slowly adds 05～1.6 volume more by volume, after fully wash rice goes out crystal, centrifuging, dehydrated alcohol is washed, and vacuum-drying promptly gets pure product; Above-mentioned dehydrated alcohol, also available anhydrous methanol, Virahol replace.
The present invention has been owing to adopted proper preparation method, as reactant use atmospheric and vacuum distillation to remove to desolvate and excess raw material after, be chilled to room temperature, add dehydrated alcohol dilution and wash rice and go out thick product; Used the dehydrated alcohol processing, thereby avoided serious corrosion and smell, it is easy to reclaim product simultaneously from mother liquor, makes not have thick product MPPA or MMPPA in the raffinate substantially; The present invention improves order of addition(of ingredients) and processing condition control, can reduce the generation of by product N tert butyl acrylamide to greatest extent, and manufacturing process of the present invention is compared with prior art simplified greatly.The present invention goes back in addition owing to the recrystallization solvent of the mixed solvent that has adopted lower alcohol or lower alcohol and acetate as thick product, thereby the step of recrystallization is simplified and the yield height greatly.The product that the present invention produces has extensive use, in fields such as oil production, fiber and textiles, papermaking, coating, wastewater treatment, tensio-active agent, inhibition scale remover, mechanical cutting, medical treatment product, plating and makeups use is arranged all.
Describe the present invention below in conjunction with embodiment and chart:
Accompanying drawing is the infrared spectrogram of embodiment one gained purified product MPPA (lot number 93-06) and embodiment six products obtained therefroms.Embodiment one
In 1000 milliliters of four-hole boiling flasks with agitator, thermometer, reflux exchanger and feeder, add methylene dichloride 129 grams and Glacial acetic acid 45 grams, under the water-bath cooling, slowly stir, 252 grams are contained free SO
3Be that 50% oleum adds in batches, when about 2/3 quantity of add-on, begin to drip into simultaneously with other 76.2 gram Glacial acetic acid, add the back mixture and under agitation be chilled to-8～-12 ℃ (temperature is low more good more) with the cryosel bath, be added dropwise to the trimethyl carbinol 55.6 grams approximately within an hour, reaction is heat release, reactant should maintain between-8～-12 ℃ when reinforced, keeps this temperature after adding and continues reaction 2 hours, and this moment, reactant was by the colourless golden yellow that transfers to.Add distilled water 45 grams and vinyl cyanide 79.6 grams then, the reactant heating slowly rises to and keeps reaction 8 hours about 50 ℃, and reactant transfers rose earlier to and transfers brown again at this moment.Slowly add 135 gram distilled water again, continue stirring reaction half an hour.After reflux exchanger changes water distilling apparatus into, continue to heat up, methylene dichloride is removed in elder generation's air distillation and the excessive propene nitrile (is bathed 80 ℃ of temperature, 50 ℃ of recovered temperatures) need 1 hour approximately, underpressure distillation removes and anhydrates and acetate (120 ℃ of bath temperature again, 58～70 ℃ of recovered temperatures, vacuum tightness 200～730mmHg (26662.2Pa～97324.1Pa) needs 2 hours approximately, and residue is the viscosity brown liquid, be chilled to room temperature after, add 500 milliliters of dehydrated alcohols, stirring makes it dilution, vacuum or centrifuging, and dehydrated alcohol is washed, get white plates crystal MPPA, the repeated experiment result is as follows:
| Lot number | Thick product (containing ethanol) (gram) | Must measure after the recrystallizing and refining product drying | |
| Weight (gram) | Yield (%) | ||
| 93-06 | 160 | 112 | 72.3 |
| 93-08 | 139 | 91 | 60.0 |
| 93-09 | 157 | 107 | 69.0 |
| 93-13 | 170 | 138 | 87.9 |
| On average | 112 | 72.25 | |
Thick product is with moisture 10% acetate recrystallizing and refining, and dehydrated alcohol is washed, and 50 ℃ of oven dry obtain white flakey crystal, and four batches of recrystallizing and refining average yields are 71.6%.Four batches of highly finished product average yields are 72.25%.
196 ℃ of 93-06 highly finished product fusing points (part is decomposed) wherein, infrared spectra is shown in 93-06 dotted line in the accompanying drawing.
Embodiment two
Press embodiment one way.But after adding distilled water 45 gram back elder generation adding stopper p methoxy phenol 0.8 grams, add vinyl cyanide 79.6 grams again.Obtain product MPPA equally.
Embodiment three
In glass-lined reactor, add 6.45Kg methylene dichloride and 2.25Kg Glacial acetic acid successively, after beginning stirring and cooling, slowly add when the oleum 12.4Kg that contains 50% free SO3 measures to about 2/3 and begin slowly to add simultaneously with the 3.81Kg Glacial acetic acid, when adding back continuation stirring and being chilled to reaction mixture for-10 ℃, in about 1 hour, slowly add the 2.78Kg trimethyl carbinol, be thermopositive reaction, temperature of charge should maintain between-8～-10 ℃ when reinforced, maintain after adding about-10 ℃ and reacted 2 hours, add distilled water 2.25Kg and vinyl cyanide 3.98Kg again, in about 1 hour, rise to then 40～60 ℃ and keep the reaction 6～10 hours, add distilled water 6.75Kg again, after slightly stirring, after stopping freezing and changing reflux exchanger into water distilling apparatus, begin to introduce steam heating, methylene dichloride and excessive propene nitrile (80 ℃ of temperature of charges are removed in elder generation's air distillation, recovered temperature≤50 ℃) need 1 hour approximately, excessive water and acetate (temperature of charge≤100 ℃ are removed in vacuum distilling again, pressure 0.04～0.07MPa) needs 2 hours approximately, after continuation is stirred and is chilled to room temperature after having steamed, add dehydrated alcohol 15Kg, dilution back discharging, leave standstill the back centrifugation, dehydrated alcohol is washed, and gets thick product MPPA.
Embodiment four
Press embodiment three ways.But after adding 2.25Kg distilled water, add 0.0398Kg (be vinyl cyanide amount 1%) p methoxy phenol earlier, add vinyl cyanide 3.98Kg again.Equally slightly produced MPPA, but the yield height.
Embodiment five
With the thick product of embodiment three gained, the ratio that is dissolved in distilled water 100 grams in thick MPPA200 gram is dissolved as the aqueous solution, 40 ℃ were heated about 0.5 hour, after removing by filter insolubles, add 1788～2682ml Glacial acetic acid with in 4470 milliliters of this aqueous solution, little heat release, after being chilled to room temperature, slowly add dehydrated alcohol 2235～6705ml, attached make it abundant wash rice and go out crystal with stirring after, centrifuging, vacuum-drying (50 ℃/1mmHg (133.322Pa) about 3 hours) obtains pure product MPPA, the white plates crystal, 194～196 ℃ of fusing points (part is decomposed).
Embodiment six
With the thick product of embodiment three gained, be dissolved in distilled water 100 grams by thick MPPA300 gram, 40 ℃ were heated about 0.5 hour, after removing by filter insolubles, 500 milliliters of (or more more) dehydrated alcohols of 1000 milliliters of usefulness of this aqueous solution slowly add, attachedly make it abundant wash rice with stirring and go out crystal, centrifuging, obtain pure product MPPA, vacuum-drying (50 ℃/1mmHg (133.322Pa) about 3 hours), the white plates crystal, 196 ℃ of fusing points (part is decomposed) (being numbered P-2), infrared spectra are seen in the accompanying drawing shown in the P-2 solid line.
Embodiment seven
The thick MPPA of 200 grams restrains dissolved in distilled water with 100, and 40 ℃ of heating remove by filter insolubles after about 0.5 hour, and proportion is 1.3, PH0.5～0.8, volume are 230.8 milliliters, add the equal-volume Virahol in this solution, attachedly make it abundant wash rice with stirring and go out crystal, filter, vacuum-drying obtains pure MPPA.
Replace Virahol with methyl alcohol, come to the same thing.
Embodiment eight
Embodiment four gained slightly produce MPPA, press embodiment five, six or seven method recrystallizations, obtain pure MPPA equally.
Embodiment nine
Embodiment three or example four thick product MPPA press embodiment five, six or seven methods, and after water dissolution, about 0.5 hour after-filtration of 40 ℃ of heating is removed insolubles, adds 30～50ppm p methoxy phenol by this aqueous solution gross weight, dissolving back normal temperature C
1-3Lower alcohol slowly adds attachedly the abundant wash rice of crystal to stir, filter, vacuum-drying, the pure MPPA of white plates crystal, but have micro-p methoxy phenol.
Embodiment ten
Replacing vinyl cyanide with identical molar weight methacrylonitrile is that embodiment one to embodiment nine described experimental technique and consumption also can make thick product or straight product MMPPA with above-mentioned experimental procedure.
Claims (8)
1, a kind of method for preparing substituted amido-alkyl sulfonic acids, the charge ratio of reactant is counted with mole: the trimethyl carbinol: vinyl cyanide: oleum: pure water=1: 1.1～2.0: 2.2～2.5: 10～20; Reaction in turn includes the following steps:
(1) at dichloromethane solvent and accounting in the Glacial acetic acid mixture of Glacial acetic acid total amount 1/3, stir and cooling under slowly add account for the oleum of oleum total amount 2/3 after, remaining Glacial acetic acid and oleum are all added simultaneously;
(2) above-mentioned reactant is chilled to-8～-12 ℃, keeps and slowly add the trimethyl carbinol under this temperature, kept this thermotonus after adding again 2 hours;
(3) in above-mentioned reaction mixture, add pure water and the acrylonitrile compound that accounts for pure water total amount 1/4 successively, slowly be warming up to 40～60 ℃, kept this thermotonus 6～10 hours;
(4) above-mentioned mixture adds remaining pure water again, reacts half an hour;
(5) methylene chloride and excessive propene nitrile compounds are removed in air distillation;
(6) excessive water and acetate are removed in above-mentioned mixed solution underpressure distillation;
(7) be cooled to room temperature after, add the dehydrated alcohol dilution, the abundant wash rice of thick product is gone out;
(8) an amount of absolute ethanol washing is used in centrifuging, and vacuum-drying gets thick product;
(9) thick product carries out recrystallizing and refining and gets straight product.
2, the method for preparing substituted amido-alkyl sulfonic acids according to claim 1 is characterized in that in above-mentioned the 3rd step of reaction, added to account for the stopper that the reaction mixture total amount is 30～50ppm behind the pure water that adds 1/4 amount again.
3, the method for preparing substituted amido-alkyl sulfonic acids according to claim 1 is characterized in that the vinyl cyanide described in above-mentioned the 3rd step of reaction is vinyl cyanide or methacrylonitrile.
4, the method for preparing substituted amido-alkyl sulfonic acids according to claim 1 is characterized in that above-mentioned described thick product recrystallizing and refining of the 9th step of reaction, in turn includes the following steps:
(1) thick product is by weight being dissolved under 40 ℃ in 100 parts of pure water with 100～300 parts;
(2) filter to get filtrate;
(3) get above-mentioned solution, handle with the anhydrous lower alcohol of 0.5～1.0 volume by 1 volume solution, wash rice goes out the white plates crystal, centrifuging, and with above-mentioned lower alcohol washing, vacuum-drying promptly gets straight product.
5, the method for preparing substituted amido-alkyl sulfonic acids according to claim 4 is characterized in that above-mentioned refining the 2nd step, and after filtering to get filtrate, it is 30～50ppm stopper that adding accounts for the solution total amount.
6,, it is characterized in that described stopper is p methoxy phenol or Resorcinol according to claim 2 or the 5 described methods that prepare substituted amido-alkyl sulfonic acids.
7, according to claim 4 or the 5 or 6 described methods that prepare substituted amido-alkyl sulfonic acids, it is characterized in that filtrate by volume, after getting 1 volume aqueous solution adding, 0.4～0.6 volume Glacial acetic acid, be chilled to room temperature, slowly add the anhydrous lower alcohol of 0.5～1.6 volume again, after fully wash rice goes out crystal, filter, with an amount of anhydrous lower alcohol washing, vacuum-drying promptly gets purified product.
8, the method for preparing substituted amido-alkyl sulfonic acids according to claim 7 is characterized in that lower alcohol is anhydrous methanol, dehydrated alcohol or anhydrous isopropyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107673 CN1114646A (en) | 1994-07-06 | 1994-07-06 | Method for preparation of substituted amido-alkyl sulfonic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107673 CN1114646A (en) | 1994-07-06 | 1994-07-06 | Method for preparation of substituted amido-alkyl sulfonic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114646A true CN1114646A (en) | 1996-01-10 |
Family
ID=5033169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94107673 Pending CN1114646A (en) | 1994-07-06 | 1994-07-06 | Method for preparation of substituted amido-alkyl sulfonic acids |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114646A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452965A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Method for removing polymerization inhibitor in AMPS raw material |
| CN102952050A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN102952051A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN102952049A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN110857279A (en) * | 2018-08-22 | 2020-03-03 | 潍坊金石环保科技有限公司 | Preparation method of 2-acrylamide-2-methylpropanesulfonic acid |
| CN110857277A (en) * | 2018-08-22 | 2020-03-03 | 潍坊金石环保科技有限公司 | Synthesis method of 2-acrylamide-2-methylpropanesulfonic acid |
-
1994
- 1994-07-06 CN CN 94107673 patent/CN1114646A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452965A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Method for removing polymerization inhibitor in AMPS raw material |
| CN102452965B (en) * | 2010-10-22 | 2013-08-14 | 中国石油化工股份有限公司 | Method for removing polymerization inhibitor in AMPS (2-acrylamide-2-methyl propanesulfonic acid) raw material |
| CN102952050A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN102952051A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN102952049A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and refining method thereof |
| CN110857279A (en) * | 2018-08-22 | 2020-03-03 | 潍坊金石环保科技有限公司 | Preparation method of 2-acrylamide-2-methylpropanesulfonic acid |
| CN110857277A (en) * | 2018-08-22 | 2020-03-03 | 潍坊金石环保科技有限公司 | Synthesis method of 2-acrylamide-2-methylpropanesulfonic acid |
| CN110857277B (en) * | 2018-08-22 | 2022-05-10 | 潍坊金石环保科技有限公司 | Synthesis method of 2-acrylamide-2-methylpropanesulfonic acid |
| CN110857279B (en) * | 2018-08-22 | 2022-06-03 | 潍坊金石环保科技有限公司 | Preparation method of 2-acrylamide-2-methylpropanesulfonic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114195661B (en) | Preparation method of milobalin benzenesulfonate | |
| CN113880903A (en) | Preparation method of monabivir | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN1114646A (en) | Method for preparation of substituted amido-alkyl sulfonic acids | |
| CN1218935C (en) | Substituted benzoyl urea insect growth regulator synthesizing method | |
| CN110818560A (en) | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate | |
| US6504050B1 (en) | Process for the preparation of 2-acrylamido-2-methyl-1-propanesulfonic acid | |
| CN113773182B (en) | Method for synthesizing 6, 8-dichloro octanoate | |
| CN114790219B (en) | Preparation method of lithium bis (oxalato) borate | |
| CN1217879A (en) | Larva of snout moth killing tablets and production thereof | |
| CN1336359A (en) | Three-phase phase-transfer catalytic synthesis process of 9,9-dimethoxyl methyl) fluorene | |
| CN1059662C (en) | Chloroacetic acid producing process | |
| CN111269149B (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
| CN114292172A (en) | Preparation method of 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone | |
| CN113527119A (en) | Preparation method of Barosavir intermediate | |
| JP2594826B2 (en) | Method for producing p- or m-hydroxyphenethyl alcohol | |
| CN115448869B (en) | Preparation method of intermediate for synthesizing spirotetramat | |
| CN113121532B (en) | Preparation method of dye intermediate | |
| CN114409532B (en) | Continuous synthesis method of methyl cardiac pavilion | |
| CN117510367B (en) | Preparation method of cefixime side chain open-loop acid | |
| CN112279805B (en) | Process for preparing 1- (3-methoxypyridin-2-yl) -2-propanone | |
| SU162536A1 (en) | ||
| CN114989092A (en) | Preparation method of 1, 2-dimethyl imidazole-5-sulfonyl chloride | |
| SU196809A1 (en) | ||
| CN113511979A (en) | Synthesis method and application of propranolol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |