CN111072557A - Amide type Gemini surfactant and preparation method thereof - Google Patents
Amide type Gemini surfactant and preparation method thereof Download PDFInfo
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- CN111072557A CN111072557A CN201911254490.7A CN201911254490A CN111072557A CN 111072557 A CN111072557 A CN 111072557A CN 201911254490 A CN201911254490 A CN 201911254490A CN 111072557 A CN111072557 A CN 111072557A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Abstract
An amide Gemini surfactant and a preparation method thereof belong to the field of surfactant preparation, and the synthetic route comprises the steps of 1, reacting 2, 6-pyridinedicarboxylic acid with thionyl chloride at 55-60 ℃ to generate 2, 6-pyridinedicarboxylic acid dichloride, 2, reacting alkylamine with methyl acrylate at room temperature to generate an intermediate N-alkyl- β -sodium aminopropionate, carrying out amidation reaction on the intermediate generated by the two steps in chloroform to obtain N, N-dialkyl- β -methyl aminopropionate, and finally hydrolyzing the N, N-dialkyl- β -methyl aminopropionate under alkaline conditions to obtain a target product N, N-dialkyl- β -sodium aminopropionate.
Description
Technical Field
The invention relates to a preparation method of an amide type Gemini surfactant and measurement of related performance, and belongs to the field of preparation of surfactants.
Background
The gemini surfactant consists of two hydrophilic head groups, two hydrophobic tails and a hollow chain unit connecting the two hydrophilic heads[. Compared with the traditional monomer surfactant, the surfactant has better surface chemical properties such as: lower CMC, better emulsification, foaming, etc., and thus are receiving increasing attention.
The introduction of amido bond leads the gemini surfactant to have better mildness and better biodegradability, and has potential application in the directional transmission of drugs. Therefore, it has become a hot spot of research.
Disclosure of Invention
The invention aims to synthesize a novel amide Gemini surfactant which has lower critical micelle concentration and better emulsifying property compared with the traditional surfactant.
The invention also aims to provide a preparation method of the amide Gemini surfactant.
The technical scheme of the invention is as follows: an amide type Gemini surfactant has a specific general formula:
in the formula: r ═ C12H25、C14H29Or C16H33。
A preparation method of an amide type Gemini surfactant comprises the following steps:
1) synthesis of 2, 6-pyridinedicarboxylic acid dichloride: adding 2, 6-pyridinedicarboxylic acid into a polar solvent, then adding 2-3 drops of an acid-binding agent, and then adding thionyl chloride, wherein the mass ratio of the 2, 6-pyridinedicarboxylic acid to the thionyl chloride is 1: 5-1: 8. And then violently stirring for 12-15 h, and carrying out reduced pressure distillation to obtain a wine red intermediate, namely 2, 6-pyridine diformyl chloride.
2) Synthesizing N-alkyl- β -methyl aminopropionate, namely adding alkylamine into a polar solvent, then dropwise adding methyl acrylate, wherein the mass ratio of the alkylamine to the methyl acrylate is 1: 1.1-1: 1.5, stirring and reacting for 8-10 h, and decompressing and distilling off excessive methyl acrylate to obtain a white waxy solid, namely N-alkyl- β -methyl aminopropionate.
3) Dissolving a synthetic amide Gemini surfactant, namely 2, 6-pyridine diformyl chloride, N-alkyl- β -methyl aminopropionate and 2-3 drop acid-binding agents in a polar solvent, wherein the mass ratio of the 2, 6-pyridine diformyl chloride to the N-alkyl- β -methyl aminopropionate is 1: 2.1-1: 2.5, violently stirring for 8-12 h, washing with ice water, then removing the solvent by reduced pressure distillation, saponifying NaOH solution, and recrystallizing to obtain a white target product, namely N, N-dialkyl- β -sodium aminopropionate.
In the preparation method of the amide Gemini surfactant, the solvent in the step 1) is dichloromethane; the solvent in the step 2) is absolute methanol; the solvent in the step 3) is chloroform.
The preparation method of the amide Gemini surfactant comprises the following steps that 1) the reaction temperature is 55-60 ℃; the reaction temperature in the step 2) is 25-35 ℃; the reaction temperature in the step 3) is 25-35 ℃.
In the preparation method of the amide Gemini surface activity, the acid-binding agent used in the step 1) is N, N-dimethylformamide; the acid-binding agent used in the step 3) is triethylamine.
The preparation method of the amide Gemini surfactant is characterized by comprising the following steps: the alkylamine is dodecylamine, tetradecylamine and hexadecylamine.
The invention relates to a preparation method of an amide type Gemini surfactant, which comprises the following specific synthetic steps:
wherein R ═ C12H25、C14H29Or C16H33
The invention has the beneficial effects that:
1) the amide Gemini surfactant prepared by the invention has the advantages of easily available synthetic raw materials, low price, simple preparation process, mild reaction conditions and easy control.
2) Compared with the traditional surfactants such as Cetyl Trimethyl Ammonium Bromide (CTAB) and Sodium Dodecyl Sulfate (SDS), the amide type Gemini surfactant prepared by the invention has lower Critical Micelle Concentration (CMC) and better emulsifying property.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples. The present invention includes various alterations and modifications made by those skilled in the art based on the above technical ideas and conventional means, and is intended to be included in the scope of the present invention.
Detailed Description
Example 1
The preparation method of the amide Gemini surfactant with twelve carbon atoms comprises the following specific preparation steps:
adding a certain amount of 2, 6-pyridinedicarboxylic acid (0.02mol,3.35g), excessive thionyl chloride and 2 drops of DMF into a flask with a reflux device, continuously stirring in a water bath at 55 ℃ for 12 hours to react, wherein the reaction system is a yellow solution, then distilling the excessive thionyl chloride by the reflux device to obtain an intermediate I, dissolving dodecylamine (6.0g, 0.032mol) in 40g of anhydrous methanol, then dropwise adding methyl acrylate (3.874g, 0.045mol), keeping the constant temperature of 35 ℃ for reflux reaction for 8 hours, then changing the reflux into distillation to distill excessive methyl acrylate and methanol to obtain a white solid intermediate II, adding N-dodecyl- β -methyl aminopropionate (6.511g, 0.024mol) into the flask with the reflux device by taking chloroform as a solvent, adding a certain amount of 2, 6-pyridinedicarboxylic acid chloride (2.04g, 0.01mol) into the ice water bath with the reflux device, strongly stirring in 45 ℃ for 8 hours, washing the reaction system to obtain a light yellow solid solution, washing the white liquid-free solvent, washing the white liquid-free from NaOH, and saponifying the mixture to obtain a white solid solution.
Example 2
The preparation method of fourteen-carbon amide type Gemini surfactant juice comprises the following specific preparation steps:
adding a certain amount of 2, 6-pyridinedicarboxylic acid (0.02mol,3.35g), excessive thionyl chloride and 2 drops of DMF into a flask with a reflux device, continuously stirring in a water bath at 55 ℃ for 12 hours to react, then changing the reflux device into distillation to distill the excessive thionyl chloride to obtain an intermediate I, decatetramine (6.83g, 0.032mol) to be dissolved in 40g of anhydrous methanol, then dropwise adding methyl acrylate (3.874g, 0.045mol), keeping the constant temperature of 35 ℃ for reflux reaction for 8 hours, then changing the reflux into distillation to distill the excessive methyl acrylate and the methanol to obtain a white solid intermediate II, using chloroform as a solvent, adding N-tetradecyl- β -methyl aminopropionate (7.183g, 0.024mol) into the flask with the reflux device, 2 drops of triethylamine, then proportionally adding a certain amount of 2, 6-pyridinedicarboxylic chloride (2.04g, 0.01mol), strongly stirring in a water bath at 45 ℃ for 8 hours, washing the reaction system into a light yellow solid solution, washing the solution, and saponifying the white solid solution without water and separating and water.
Example 3
The preparation method of the sixteen-carbon amide type Gemini surfactant juice comprises the following specific preparation steps:
adding a certain amount of 2, 6-pyridinedicarboxylic acid (0.02mol,3.35g), excessive thionyl chloride and 2 drops of DMF into a flask with a reflux device, continuously stirring in a water bath at 55 ℃ for 12 hours to react, wherein the reaction system is a yellow solution, then distilling the excessive thionyl chloride by the reflux device to obtain an intermediate I, hexadecylamine (7.727g, 0.032mol) is dissolved in 40g of anhydrous methanol, then dropwise adding methyl acrylate (3.874g, 0.045mol), keeping the constant temperature of 35 ℃ for reflux reaction for 8 hours, then changing the reflux into distillation to distill excessive methyl acrylate and methanol to obtain a white solid intermediate II, adding N-hexadecyl- β -methyl aminopropionate (7.855g, 0.024mol) into the flask with the reflux device by using chloroform as a solvent, then adding a certain amount of 2, 6-pyridinedicarboxylic chloride (2.04g, 0.01mol) according to a certain ratio, strongly stirring in a water bath at 45 ℃ for 8 hours, reacting to obtain a light yellow waxy solid solution, washing the reaction system, washing the light yellow solution, washing, and saponifying the white solid solution without water and 16-liquid-free of NaOH.
Example 4
Determination of critical micelle concentration of amide type Gemini surfactant:
a series of different concentration gradients of the example 1, the example 2 and the example 3, as well as the traditional surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and Sodium Dodecyl Sulfate (SDS) aqueous solutions are prepared, the temperature is kept constant at 25 ℃ for a certain time, and the Critical Micelle Concentration (CMC) is measured by a hanging piece method, and the results are as follows:
TABLE 1 Critical micelle concentration of the product determined in example 4
Example 5
And (3) determining the emulsifying property of the amide type Gemini surfactant:
40mL of each of example 1, example 2 and example 3, an aqueous solution of conventional surfactant cetyltrimethylammonium bromide (CTAB), Sodium Dodecyl Sulfate (SDS) and 40mL of liquid paraffin or n-octane, with a mass fraction of 0.1%, were added to a 100mL stoppered cylinder. The stopper was closed, incubated at 25 ℃ for a period of time, then shaken vigorously for 30 seconds, placed on a table, and the time taken to separate 10mL of water phase from standing was recorded, and the measurements were repeated three times, averaged, and the results are shown in Table 2:
table 2 results of testing emulsification properties of the product obtained in example 5
Claims (9)
1. An amide type Gemini surfactant is characterized in that the structural general formula is as follows:
in the formula: r ═ C12H25、C14H29Or C16H33。
2. The method for preparing amide type Gemini surfactant according to claim 1, which is characterized by comprising the following steps:
1) synthesis of 2, 6-pyridinedicarboxylic acid dichloride: adding 2, 6-pyridinedicarboxylic acid into a polar solvent, then adding 2-3 drops of an acid-binding agent, and then adding thionyl chloride, wherein the mass ratio of the 2, 6-pyridinedicarboxylic acid to the thionyl chloride is 1: 5-1: 8; then violently stirring for 12-15 h, and carrying out reduced pressure distillation to obtain a wine red intermediate, namely 2, 6-pyridine diformyl chloride;
2) synthesizing N-alkyl- β -methyl aminopropionate, namely adding alkylamine into a polar solvent, then dropwise adding methyl acrylate, wherein the mass ratio of the alkylamine to the methyl acrylate is 1: 1.1-1: 1.5, stirring for reacting for 8-10 hours, and decompressing and steaming out excessive methyl acrylate to obtain a white waxy solid, namely N-alkyl- β -methyl aminopropionate;
3) dissolving 2, 6-pyridine diformyl chloride, N-alkyl- β -methyl aminopropionate and 2-3 drop acid-binding agents in a polar solvent, wherein the mass ratio of the 2, 6-pyridine diformyl chloride to the N-alkyl- β -methyl aminopropionate is 1: 2.1-1: 2.5, violently stirring and reacting for 8-12 h, washing with ice water, distilling under reduced pressure to remove the solvent, saponifying NaOH solution, and recrystallizing to obtain a white target product, namely the amide Gemini surfactant.
3. The method for preparing amide type Gemini surfactant according to claim 2, wherein the solvent in step 1) is dichloromethane; the solvent in the step 2) is absolute methanol; the solvent in the step 3) is chloroform.
4. The preparation method of the amide Gemini surfactant according to claim 2 or 3, wherein the reaction temperature in the step 1) is 55-60 ℃; the reaction temperature in the step 2) is 25-35 ℃, and the reaction temperature in the step 3) is 35-55 ℃.
5. The method for preparing amide type Gemini surfactant according to claim 2 or 3, wherein the acid-binding agent used in step 1) is N, N-dimethylformamide; the acid-binding agent used in the step 3) is triethylamine.
6. The method for preparing amide type Gemini surfactant according to claim 4, wherein the acid-binding agent used in step 1) is N, N-dimethylformamide; the acid-binding agent used in the step 3) is triethylamine.
7. The method of claim 2, 3 or 6, wherein the alkylamine is dodecylamine, tetradecylamine or hexadecylamine.
8. The method of claim 4, wherein the alkylamine is dodecylamine, tetradecylamine or hexadecylamine.
9. The method of claim 5, wherein the alkylamine is dodecylamine, tetradecylamine or hexadecylamine.
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| CN201911254490.7A CN111072557A (en) | 2019-12-10 | 2019-12-10 | Amide type Gemini surfactant and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010667A (en) * | 2022-08-03 | 2022-09-06 | 山东科兴化工有限责任公司 | Temperature-resistant and salt-resistant polymer surfactant for oil displacement and preparation method thereof |
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| CN108299288A (en) * | 2018-01-30 | 2018-07-20 | 阜阳师范学院 | A kind of copper ion fluorescent optical sensor molecule and preparation method and the application in detecting copper ion |
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| CN108299288A (en) * | 2018-01-30 | 2018-07-20 | 阜阳师范学院 | A kind of copper ion fluorescent optical sensor molecule and preparation method and the application in detecting copper ion |
| CN109705098A (en) * | 2019-01-31 | 2019-05-03 | 吉林师范大学 | A kind of fragrance helical fold body and its preparation method and application |
| CN110218166A (en) * | 2019-06-12 | 2019-09-10 | 西南石油大学 | A kind of synthetic method of the bissulfosalt double surface active agent of bisamide base connection |
Non-Patent Citations (2)
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| 王培义等: "酰胺型Gemini表面活性剂的合成与性能", 《精细化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010667A (en) * | 2022-08-03 | 2022-09-06 | 山东科兴化工有限责任公司 | Temperature-resistant and salt-resistant polymer surfactant for oil displacement and preparation method thereof |
| CN115010667B (en) * | 2022-08-03 | 2022-11-01 | 山东科兴化工有限责任公司 | Temperature-resistant and salt-resistant polymer surfactant for oil displacement and preparation method thereof |
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