CN103130688B - Preparing method of 2-acrylamide alkyl sulfonic acid - Google Patents
Preparing method of 2-acrylamide alkyl sulfonic acid Download PDFInfo
- Publication number
- CN103130688B CN103130688B CN201310052066.0A CN201310052066A CN103130688B CN 103130688 B CN103130688 B CN 103130688B CN 201310052066 A CN201310052066 A CN 201310052066A CN 103130688 B CN103130688 B CN 103130688B
- Authority
- CN
- China
- Prior art keywords
- sulfur trioxide
- alkyl sulfonic
- acrylonitrile
- acrylamide alkyl
- olefin
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparing method of 2-acrylamide alkyl sulfonic acid and belongs to the technical field of high-polymer material monomer synthesis, wherein the 2-acrylamide alkyl sulfonic acid is a polymerizable surface active agent monomer. Raw materials of the 2-acrylamide alkyl sulfonic acid are alpha-olefin, industrial grade acrylonitrile, 10%-20% of fuming sulphuric acid and sulfur trioxide. A quantity relative ratio of the raw materials is n (the alpha-olefin): n (sulfuric acid (H2SO4) +sulfur trioxide (SO3)): n (the acrylonitrile) = 1: (0.95-1.15): (5-11), wherein n (H2SO4): n (SO3) =1: (1.23-2.28). 10%-20% of the fuming sulphuric acid and the sulfur trioxide serve as sulfonating agents. The industrial grade acrylonitrile which serves as the raw material and solvent can be directly applied without dehydration. In the process of preparation, no dehydration agent is needed. In addition, the yield of target products is larger than 80%, the purity is larger than 98%, the reaction process is stable and easy to control, the post processing of the products and the solvent is simple, and the industrial production is facilitated.
Description
Technical field：
The present invention relates to a kind of preparation method of 2- acrylamide alkyl sulfonic acids, 2- acrylamide alkyl sulfonic acids are one
Polymerisable surfactant monomer is planted, belongs to macromolecular material monomer synthesis technical field.
Technical background：
Vinyl monomer with sulfonic acid group and its polymer, the not only special performance with strong acid, and to hydrolysis, temperature
Degree and bivalent cation have specific stability, and application in some aspects has become irreplaceable monomer and polymer,
Range of application such as in terms of emulsion polymerization, printing and dyeing, oil field, water treatment industry is more and more wider.
2- acrylamido -2- methyl propane sulfonic acids（AMPS）Be relatively it is early obtain heavy polymer can be obtained
Amidosulfonic acid monomer.Acrylamido chain alkyl sulfonic acid, such as 2- acrylamidos hexadecane are have developed on this basis
Sulfonic acid（AMC16S）, 2- acrylamido dodecane sulfonic acids（AMC12S）, 2- acrylamido tetradecane sulfonic acid（AMC14S）.It is such
Hydrophobic chain alkyl and hydrophilic sulfonic group, amide groups are carried in monomer molecule, is a kind of polymerisable surface active monomer.
The monomer copolymerization such as such monomer and acrylamide, can obtain the copolymer with ionic surfactant side chain, the analog copolymer
The aggregation of surface activity side chain is induced by salt and good salt-resistance is obtained, can be used for high temperature and high salinity formation condition
Under oil displacement agent and drilling fluid additive.
A kind of 1998,12 (4) the 2- acrylamido dodecane sulfonic acids for disclosing synthesis, chemical science and technology are printed during chemical industry
A kind of 2000,8 (1) the 2- acrylamido tetradecane sulfonic acid for disclosing synthesis, guizhou chemical industry 1997,4 discloses a kind of synthesis
2- acrylamido hexadecane sulfonic acid, but this kind of acrylamido chain alkyl sulfonic acid is all with acrylonitrile, length in synthesis
Olefine and oleum are raw material, and oleum used must be more than 50% oleum（It is in solid-state under room temperature）, prepare
In it is not easy to operate, and need to adopt dehydrant, bring trouble to product later-period purification.
The content of the invention：
The purpose of the present invention be exactly be overcome prior art preparation it is not easy to operate, and need to adopt dehydrant, produce
Product later-period purification and the troublesome problem of solvent recovery, there is provided a kind of preparation method of 2- acrylamide alkyl sulfonic acids.
A kind of preparation method of 2- acrylamide alkyl sulfonic acids, by with alpha-olefin and industrial level acrylonitrile, oleum
It is raw material with sulfur trioxide, is n by the amount ratio of material（Alpha-olefin）:n(H2SO4+SO3):N (acrylonitrile)=1:（0.95~
1.15）:（5~11）, wherein n (H2SO4):n(SO3)=1:(1.23~2.28) are prepared from, and comprise the following steps：
（1）Acrylonitrile, alpha-olefin are added into the reaction with stirring, thermometer, Dropping funnel, airway and condenser
In bottle, the temperature of system is down to into less than -5 DEG C with ice salt bath after stirring, was added in system in 30~60 minutes
Oleum, keeps reaction temperature to be less than 10 DEG C in adition process；
（2）After oleum is added, to step in 45~90 minutes（1）Sulfur trioxide is passed through in the system of gained,
Keep reaction temperature to be less than 15 DEG C in adition process, after sulfur trioxide amount reaches, add 2~5mL water, stir at room temperature
3~10h of reaction；
（3）By step（2）The 2- acrylamide alkyl sulfonic acids crystallization that reaction is generated is filtered with glass sand core funnel, gained
After crystal washs 2 times with acrylonitrile respectively, it is vacuum dried at 60 DEG C, obtains final product product of the present invention, filtrate is through distillation or fractional distillation
Reusable edible afterwards.
The sulfur trioxide content that dissociates in described oleum is 10%~20%, can be by 25% oleum and 98%
Concentrated sulphuric acid is according to different proportion mixed preparing.
Described alpha-olefin be hendecene -1, laurylene -1, tridecylene -1, tetradecene -1, ten pentaenes -1, hexadecene-1,
17 alkene -1, octadecylene -1 or 19 alkene -1.
Described first adds oleum, then the charging sequence of logical sulfur trioxide, or first to lead to sulfur trioxide, then add oleum
The feed way of acid.
The invention has the beneficial effects as follows：Using 10%~20% oleum and sulfur trioxide as sulfonating agent, to propylene
The water content of nitrile is directly applied as the industrial acrylonitrile of raw material and solvent without strict demand without dehydration, and in preparing not
Using dehydrant, target product yield is more than 98% more than 80%, purity, and course of reaction is steadily easily-controllable, product and solvent post processing
Simply, it is easy to industrialized production；The present invention can be used for the polymerisable surfactant of emulsion polymerization with sulfonic group and double bond,
Can be used for the conjunction of printing thickeners, the polymer oil-displacing agent of novel heatproof salt resistance, fracturing fluid gelatinizer and drilling fluid additive
Into.
Specific embodiment：
With reference to specific embodiment, the present invention will be further described.But the present invention is not limited in following embodiments.
Embodiment 1：
According to n（Alpha-olefin）:n(H2SO4+SO3):N (acrylonitrile)=1:0.95:5, n (H2SO4):n(SO3)=1:2.28
Ratio, by 265.3 grams of acrylonitrile, 196.37 grams of tetradecenes -1 add with stirring, thermometer, Dropping funnel, airway and
In the reaction bulb of condenser, the temperature of system is down to into -5 DEG C with ice salt bath after stirring, was added in system with 60 minutes
Enter 35.52 gram 20% of oleum, keep reaction temperature to be less than 10 DEG C in adition process；After oleum is added, 45 are used
Minute is passed through 45.67 grams of sulfur trioxide in system, keeps reaction temperature to be less than 15 DEG C in adition process, treats sulfur trioxide amount
After reaching, 5mL water is added, at room temperature stirring reaction 10h；The 2- acrylamide alkyl sulfonic acid crystallization glass that reaction is generated
Glass sand core funnel is filtered, and after gained crystal washs 2 times with acrylonitrile respectively, is vacuum dried at 60 DEG C, obtains 278.3 grams of products
Thing, in terms of tetradecene -1, yield 80.2%, content 99.31%, platinum-cobalt colorimetric number is 3, and filtrate is through distillation or fractional distillation Posterior circle
Utilize.
Embodiment 2：
According to n（Alpha-olefin）:n(H2SO4+SO3):N (acrylonitrile)=1:1.15:11, n (H2SO4):n(SO3)=1:1.23
Ratio, by 583.66 grams of acrylonitrile, 168.32 grams of laurylenes -1 add with stirring, thermometer, Dropping funnel, airway and
In the reaction bulb of condenser, the temperature of system is down to into -6 DEG C with ice salt bath after stirring, was added in system with 30 minutes
Enter 54.84 gram 10% of oleum, keep reaction temperature to be less than 10 DEG C in adition process；After oleum is added, 90 are used
Minute is passed through 43.86 grams of sulfur trioxide in system, keeps reaction temperature to be less than 15 DEG C in adition process, treats sulfur trioxide amount
After reaching, 2mL water is added, at room temperature stirring reaction 3h；The 2- acrylamide alkyl sulfonic acid crystallization glass that reaction is generated
Glass sand core funnel is filtered, and after gained crystal washs 2 times with acrylonitrile respectively, is vacuum dried at 60 DEG C, obtains 269.6 grams of products of institute
Thing, in terms of laurylene -1, yield 84.5%, content 98.67%, platinum-cobalt colorimetric number is 4, and filtrate is through distillation or fractional distillation Posterior circle
Utilize.
Embodiment 3：
According to n（Alpha-olefin）:n(H2SO4+SO3):N (acrylonitrile)=1:1:9, n (H2SO4):n(SO3)=1:1.84 ratio
Example, 477.54 grams of acrylonitrile, 224.43 grams of hexadecene-1s are added with stirring, thermometer, Dropping funnel, airway and cold
In the reaction bulb of condenser, the temperature of system is down to into -8 DEG C with ice salt bath after stirring, was added in system with 45 minutes
40.63 gram 15% of oleum, keeps reaction temperature to be less than 10 DEG C in adition process；After oleum is added, with 60 points
45.71 grams of sulfur trioxide are passed through in clockwise system, keep reaction temperature to be less than 15 DEG C in adition process, treat that sulfur trioxide amount reaches
After arriving, 3.5mL water is added, at room temperature stirring reaction 6h；The 2- acrylamide alkyl sulfonic acid crystallization glass that reaction is generated
Glass sand core funnel is filtered, and after gained crystal washs 2 times with 350g acrylonitrile respectively, is vacuum dried at 60 DEG C, obtains 322.9 grams of institute
Product, in terms of hexadecene-1, yield 86.1%, content 99.12%, platinum-cobalt colorimetric number is 3, and filtrate is followed after distillation or fractional distillation
Ring is utilized.
According to the method for embodiment 3, only change alpha-olefin and its consumption, the result of the test of embodiment 4~9 is shown in Table 1.
The result detail list of 1 embodiment of table 4~9
| Embodiment | 4 | 5 | 6 | 7 | 8 | 9 |
| Alpha-olefin | Hendecene -1 | Tridecylene -1 | Ten pentaenes -1 | 17 alkene -1 | Octadecylene -1 | 19 alkene -1 |
| Consumption/gram | 154.3 | 182.31 | 210.42 | 238.42 | 252.48 | 266.51 |
| Product/gram | 244.9 | 277.1 | 309.0 | 330.3 | 330.9 | 330.7 |
| Yield/% | 80.3 | 83.2 | 85.6 | 84.9 | 82.1 | 80.21 |
| Content/% | 98.09 | 99.01 | 99.14 | 99.00 | 98.62 | 98.03 |
| Platinum-cobalt colorimetric | 4 | 5 | 4 | 4 | 5 | 4 |
The yield of above-described embodiment is more than 98% more than 80%, purity, and platinum-cobalt colorimetric number value is less than or equal to 5, thus sees
Go out, the product yield of the present invention is higher, and purity is very high.
Claims (4)
1. a kind of preparation method of 2- acrylamide alkyl sulfonic acids, is characterized in that：By with alpha-olefin and industrial level acrylonitrile, send out
Cigarette sulphuric acid and sulfur trioxide are raw material, are n (alpha-olefin) by the amount ratio of material:n(H2SO4+SO3):N (acrylonitrile)=1:(0.95
~1.15):(5~11), wherein n (H2SO4):n(SO3)=1:(1.23~2.28) are prepared from；Described oleum middle reaches
It is 10%~20% from sulfur trioxide content.
2. a kind of preparation method of 2- acrylamide alkyl sulfonic acids according to claim 1, is characterized in that：Including following
Step：
(1) acrylonitrile, alpha-olefin are added into the reaction bulb with stirring, thermometer, Dropping funnel, airway and condenser
In, the temperature of system is down to into less than -5 DEG C with ice salt bath after stirring, added in system in 30~60 minutes and send out
Cigarette sulphuric acid, keeps reaction temperature to be less than 10 DEG C in adition process；
(2) after oleum is added, sulfur trioxide was passed through in the system obtained by step (1) in 45~90 minutes, is added
During keep reaction temperature to be less than 15 DEG C, after sulfur trioxide amount reaches, add 2~5mL water, at room temperature stirring reaction
3~10h；
(3) step (2) is reacted the 2- acrylamide alkyl sulfonic acids crystallization glass sand core funnel for generating to filter, gained crystal
After washing 2 times with acrylonitrile respectively, it is vacuum dried at 60 DEG C and obtains final product.
3. a kind of preparation method of 2- acrylamide alkyl sulfonic acids according to claim 1 and 2, is characterized in that：It is described
Alpha-olefin be hendecene -1, laurylene -1, tridecylene -1, tetradecene -1, ten pentaenes -1, hexadecene-1,17 alkene -1,18
Alkene -1 or 19 alkene -1.
4. a kind of preparation method of 2- acrylamide alkyl sulfonic acids according to claim 2, is characterized in that：Described elder generation
Plus oleum, then the charging sequence of logical sulfur trioxide, or first to lead to sulfur trioxide, then the feed way for adding oleum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310052066.0A CN103130688B (en) | 2013-02-17 | 2013-02-17 | Preparing method of 2-acrylamide alkyl sulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310052066.0A CN103130688B (en) | 2013-02-17 | 2013-02-17 | Preparing method of 2-acrylamide alkyl sulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103130688A CN103130688A (en) | 2013-06-05 |
| CN103130688B true CN103130688B (en) | 2017-05-17 |
Family
ID=48491193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310052066.0A Active CN103130688B (en) | 2013-02-17 | 2013-02-17 | Preparing method of 2-acrylamide alkyl sulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103130688B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104312550B (en) * | 2014-08-22 | 2018-11-06 | 中国石油化工集团公司 | A kind of anionic micro-foam drilling fluid surfactant and preparation method thereof |
| CN105461598B (en) * | 2014-09-03 | 2017-09-29 | 中国石油化工股份有限公司 | Acrylamide monomers, acrylamide based copolymer and its preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6388167A (en) * | 1986-10-01 | 1988-04-19 | Lion Corp | Production of methallylsulfonate |
| US4975482A (en) * | 1989-08-18 | 1990-12-04 | Exxon Research & Engineering Company | Viscoelastic fluids formed through the interaction of polymerizable vesicles and alkyl-containing polymers (C-2381) |
| US5036136A (en) * | 1987-12-21 | 1991-07-30 | Exxon Research And Engineering Company | Mixtures of colloidal rod-like viscoelastic fluids and anionic-alkyl containing copolymers |
| WO2000034233A1 (en) * | 1998-12-11 | 2000-06-15 | The Lubrizol Corporation | Continuous production of 2-acrylamido-2-methylpropane-sulfonic acid in a small reactor integrated with acrylic polymer fiber production |
| CN101874017A (en) * | 2007-12-06 | 2010-10-27 | 东亚合成株式会社 | 2-acrylamide-2-methylpropanesulfonic acid and process for producing the same |
| CN102452962A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Synthetic method of AMPS (2-Acrylamide-2-methylpropanesulfonic acid) |
-
2013
- 2013-02-17 CN CN201310052066.0A patent/CN103130688B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6388167A (en) * | 1986-10-01 | 1988-04-19 | Lion Corp | Production of methallylsulfonate |
| US5036136A (en) * | 1987-12-21 | 1991-07-30 | Exxon Research And Engineering Company | Mixtures of colloidal rod-like viscoelastic fluids and anionic-alkyl containing copolymers |
| US4975482A (en) * | 1989-08-18 | 1990-12-04 | Exxon Research & Engineering Company | Viscoelastic fluids formed through the interaction of polymerizable vesicles and alkyl-containing polymers (C-2381) |
| WO2000034233A1 (en) * | 1998-12-11 | 2000-06-15 | The Lubrizol Corporation | Continuous production of 2-acrylamido-2-methylpropane-sulfonic acid in a small reactor integrated with acrylic polymer fiber production |
| CN101874017A (en) * | 2007-12-06 | 2010-10-27 | 东亚合成株式会社 | 2-acrylamide-2-methylpropanesulfonic acid and process for producing the same |
| CN102452962A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Synthetic method of AMPS (2-Acrylamide-2-methylpropanesulfonic acid) |
Non-Patent Citations (2)
| Title |
|---|
| 2-丙烯酰胺基十二烷磺酸的合成与表征;王中华;《化工时刊》;19981231;第12卷(第4期);14-15 * |
| 2-丙烯酰胺基十六烷磺酸的合成与表征;王中华;《贵州化工》;19971231(第4期);30-31 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103130688A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130688B (en) | Preparing method of 2-acrylamide alkyl sulfonic acid | |
| CN107868170B (en) | Block type hydrophobic association polyacrylamide and preparation method thereof | |
| CN111234818B (en) | Method for synthesizing surface functional group modified carbon quantum dots and application of carbon quantum dots in nano oil displacement | |
| CN107033035B (en) | A kind of synthesis of high purity N-carbamylglutamic acid and its post-processing approach | |
| CN102924380B (en) | Preparation method of imidocarb | |
| CN107602475B (en) | 1-methyl-3-propylimidazole taurine ionic liquid and preparation method and application thereof | |
| CN102976282B (en) | A kind of insoluble sulfur high-efficiency stabilizing agent and preparation method thereof | |
| CN104497308B (en) | A kind of preparation method of poly- adjacent mercaptoaniline nanofiber | |
| CN103224471B (en) | A kind of synthetic method of melamine phosphate (MP) | |
| CN102001956A (en) | Preparation method for gemini surfactant with chelation capability | |
| CN102146047B (en) | Purification process of diacetone acrylamide | |
| CN101735167B (en) | Preparation method of 6-nitrosaccharin | |
| CN103450005B (en) | A kind of preparation method of clopidogrel and the alpha-brominated (2-Chlorophenyl)acetic acid of intermediate and α-thiophene ethamine base substituted acetic acid hydrochlorate | |
| CN101805275A (en) | Method for synthesizing sodium methyl allylsulfonate | |
| CN102516971A (en) | Block polyether zwitterionic heavy oil emulsified viscosity reducer and preparation method thereof | |
| CN106380601A (en) | Purifying method for polyphenylene sulfide with high molecular weight | |
| CN104449637B (en) | A kind of semi-transparent membranous type profile control and water plugging oil displacement agent and preparation method thereof | |
| CN104744365A (en) | Method for directly preparing light-emitting material 8-hydroxyquinoline copper | |
| CN106905161A (en) | A kind of synthetic method of the nitrobenzoic acid of 2 chlorine, 4 fluorine 5 | |
| CN104211622B (en) | A kind of continuous producing method of 2-acrylamide-2-methylpro panesulfonic acid | |
| CN104311455B (en) | A kind of preparation method of 2 acrylamido 2 methyl-prop (alkane) sulfonic acid | |
| CN203284212U (en) | Novel industrial-grade phosphorous acid production device | |
| CN107445864B (en) | Method for purifying long-carbon-chain cyano acid product | |
| CN111234052A (en) | Method for preparing polymer materials with different saturation degrees by emulsion reaction | |
| FR2973370B1 (en) | LOW COST PROCESS FOR THE PREPARATION OF O-ACETYLSALICYCLIC ACID AND BASIC AMINO ACID |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |