CN108640853A - A kind of fluorine-containing azo surfactant and preparation method thereof - Google Patents
A kind of fluorine-containing azo surfactant and preparation method thereof Download PDFInfo
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- CN108640853A CN108640853A CN201810609093.6A CN201810609093A CN108640853A CN 108640853 A CN108640853 A CN 108640853A CN 201810609093 A CN201810609093 A CN 201810609093A CN 108640853 A CN108640853 A CN 108640853A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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Abstract
The invention discloses a kind of fluorine-containing azo surfactants and preparation method thereof, belong to technical field of organic synthesis.The structural formula of above-mentioned fluorine-containing azo surfactant is as follows：Wherein, X is halogen, n=1,2,3 or 4.The present invention is prepared for a kind of novel fluorine-containing azo optical Response surfactant, has been widened the research field of fluorine-containing surfactant based on the excellent performance of fluorine-containing surfactant.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of fluorine-containing azo surfactant and its preparation side
Method.
Background technology
Fluorine-containing surfactant have preferable hydrophobic performance, thermal stability, chemical-resistance and weather resistance etc.,
The performance for depending on fluorine atom in application process is widely used in coating, ink, floor wax, pesticide, electronics cleaning, plating
In the products such as inorganic agent, but its purposes is relatively single.Simultaneously as the expensive application for making this kind of surfactant is limited
System.
Further to widen the application field of fluorine-containing surfactant, during studying novel fluorine surfactant,
We have found that azobenzene has photo absorption property, cis-trans isomerism can occur under different illumination conditions, generate different performances,
The fluorine-containing surfactant that the two combination can be prepared to optical Response, currently without report.
Invention content
For the above-mentioned prior art, the object of the present invention is to provide a kind of fluorine-containing azo surfactant and its preparation sides
Method.The preparation method of the present invention is simple, solves fluorine-containing surfactant and although has excellent performance, application range is wider, but contains
The single problem of fluorinated surfactant purposes.
In order to solve the above technical problems, present invention offer technical solution is as follows：
On the one hand, the present invention provides a kind of fluorine-containing azo surfactant, and structural formula is as follows：
Wherein, X is halogen, n=1,2,3 or 4.
Further, the halogen is chlorine, bromine or iodine
Further, the structural characterization of the fluorine-containing azo surfactant is1H NMR(400MHz,CDCl3)δ7.92
(t, J=9.2Hz, 2H), 7.32 (d, J=8.2Hz, 2H), 7.01 (t, J=7.5Hz, 4H), 4.33 (m, 2H), 3.82 (m,
2H), 3.19 (m, 9H).
The present invention also provides a kind of preparation methods of above-mentioned fluorine-containing azo surfactant, include the following steps：
(1) preparation of fluorine-containing azophenol；
(2) preparation of the halogenated alkoxy-to trifluoromethoxy azobenzene；
(3) preparation of fluorine-containing azo surfactant.
Further, the step (1) specifically comprises the following steps：
(11) it takes 21ml water in beaker, then the same volume concentrated sulfuric acid is added in beaker dropwise, is stirred while adding, so
After weigh 4- trifluoro-methoxyanilines 75mmol and instill in sulfuric acid solution dropwise, stir evenly, keep -10-10 DEG C of temperature；
(12) sodium nitrite 101.5mmol and 40ml water wiring solution-formings are weighed, is instilled in the solution of step (11) dropwise, is mixed
It closes uniform；
(13) sodium carbonate 443.4mmol, sodium hydroxide 75mmol, phenol 79.7mmol and water 270ml are weighed, mixing is equal
It is even；
(14) solution that step (12) obtains is instilled dropwise in the solution of step (13) preparation, obtains the solid production of yellow
It is raw, it is filtered after dripping, obtains yellow solid, dissolved with ethyl alcohol, filtered to get filtrate, dried, recrystallized with n-hexane.
Further, the step (2) specifically comprises the following steps：
(21) in three-necked flask, be added 40mmol the step of (1) synthesis trifluoromethoxy azophenol, 100ml's
Absolute ethyl alcohol, the sodium hydroxide of 200mmol, the halogenated hydrocarbons of 400mmol are heated to reflux stirring 16h；
(22) after reaction, it is cooled to room temperature, red solution, filtrate decompression distillation, product n-hexane is obtained by filtration
Recrystallization.
Further, the step (3) specifically comprises the following steps：
(31) it weighs the product that 20mmol steps (2) obtain to be dissolved in methyl phenyl ethers anisole, by 35wt% trimethylamine solutions 80mmol
It instills dropwise wherein, is warming up to 65 DEG C, flow back 48h；
(32) after reaction, it is cooled to room temperature, filters to obtain yellow solid product, with ethyl acetate and alcohol mixed solution
Recrystallization vacuum drying.
Further, in the step (21), halogenated hydrocarbons 1,2- Bromofumes, 1,2- dichloroethanes, 1,2- diiodo- second
Alkane, 1,4- dibromobutanes or 1,4- dichloroetane etc..
Further, in the step (32), the volume ratio of ethyl acetate and ethyl alcohol is 9:1.
The reactional equation of step (1) is as follows：
The reactional equation of step (2)-(3) is as follows：
Wherein, X is halogen, such as chlorine, bromine, iodine, n=1,2,3 or 4.
Fluorine-containing functional group has excellent hydrophobic performance, and surfactant is better in one end hydrophobicity of aqueous solution, surface
The water solubility of activating agent is better, and surface property also can be better.In addition to this, azo group is a kind of function of optical Response
Group, under the irradiation of visible light, will present trans- (trans-) structure, can enhance in the absorption intensity of 350nm, meeting at 430nm
Weaken, forms a similar light functional switch.
The invention has the advantages that：
The present invention is prepared for a kind of novel fluorine-containing azo photoresponse based on the excellent performance of fluorine-containing surfactant
Property surfactant, has widened the research field of fluorine-containing surfactant, reference is provided for later development.
Description of the drawings
Fig. 1 is the suction in different visible light irradiation time that the embodiment of the present invention 1 prepares fluorine-containing azo surfactant
Receive spectrum.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
Agents useful for same is commercial product unless otherwise specified in following embodiment.
A kind of fluorine-containing azo surfactant of present invention offer and preparation method thereof, is described as follows.
Embodiment 1
A kind of preparation method of fluorine-containing azo surfactant, includes the following steps：
(1) preparation of fluorine-containing azophenol
(11) it takes 21ml water in beaker, then the same volume concentrated sulfuric acid is added in beaker dropwise, is stirred while adding, so
After weigh 4- trifluoro-methoxyanilines 75mmol and instill in sulfuric acid solution dropwise, stir evenly, keep -10-10 DEG C of temperature；
(12) sodium nitrite 101.5mmol and 40ml water wiring solution-formings are weighed, is instilled in the solution of step (11) dropwise, is mixed
It closes uniform；
(13) sodium carbonate 443.4mmol, sodium hydroxide 75mmol, phenol 79.7mmol and water 270ml are weighed, mixing is equal
It is even；
(14) solution that step (12) obtains is instilled in (13) dropwise, the solid for obtaining yellow generates, mistake after dripping
Filter, obtains yellow solid, is dissolved with ethyl alcohol, filtered to get filtrate, and dries, is recrystallized with n-hexane；
(2) preparation of the halogenated alkoxy-to trifluoromethoxy azobenzene
(21) in three-necked flask, be added 40mmol the step of (1) synthesis trifluoromethoxy azophenol, 100ml's
Absolute ethyl alcohol, the sodium hydroxide of 200mmol, 1, the 2- Bromofumes of 400mmol are heated to reflux stirring 16h；
(22) after reaction, it is cooled to room temperature, red solution, filtrate decompression distillation, product n-hexane is obtained by filtration
Recrystallization；
(3) preparation of fluorine-containing azo surfactant
(31) it weighs the product that 20mmol steps (2) obtain to be dissolved in methyl phenyl ethers anisole, by 35wt% trimethylamine solutions 80mmol
It instills dropwise wherein, is warming up to 65 DEG C, flow back 48h；
(32) after reaction, it is cooled to room temperature, filters to obtain yellow solid product, with ethyl acetate and alcohol mixed solution
Recrystallization vacuum drying.
The product prepared to above-mentioned each step carries out structure detection, and data are as follows.
The trifluoromethoxy azophenol structure of step (1) synthesis：
1H NMR(400MHz,CDCl3) δ 7.94 (t, J=9.2Hz, 2H), 7.36 (d, J=8.2Hz, 2H), 7.00 (t, J
=7.5Hz, 4H)19F NMR(400MHz,CDCl3) δ -58.52 (d, J=6.4Hz)
The structural characterization of the bromo oxygroup -4- trifluoromethoxies azobenzene of step (2) synthesis；
1H NMR(400MHz,CDCl3) δ 7.94 (t, J=9.2Hz, 2H), 7.36 (d, J=8.2Hz, 2H), 7.00 (t, J
=7.5Hz, 4H), 4.36 (m, 2H), 3.87 (m, 2H)
Trifluoromethoxy -4 4- of step (3) synthesis, the structural characterization of-[(trimethylamine) oxygroup] azobenzene；
1H NMR(400MHz,CDCl3) δ 7.92 (t, J=9.2Hz, 2H), 7.32 (d, J=8.2Hz, 2H), 7.01 (t, J
=7.5Hz, 4H), 4.33 (m, 2H), 3.82 (m, 2H), 3.19 (m, 9H).
It proves successfully to prepare fluorine-containing azo surfactant.Then using visible light as respective sources, to the fluorine-containing idol of preparation
The optical Response of nitrogen surfactant is characterized, the result is shown in Figure 1.As shown in Figure 1, under no radiation of visible light, surface is lived
Property agent does not absorb at 350nm, there is faint absorption at 430nm.When surfactant is in radiation of visible light 1s,
Absorbance can increase sharply at 350nm, and the absorbance at 430nm reduces, and transconfiguration is formd, with prolonging for irradiation time
Long, transconfiguration is stablized.
Embodiment 2
1,2- Bromofumes in embodiment 1 are replaced with to 1, the 2- dichloroethanes of equimolar amounts, remaining condition and implementation
Example 1 is identical.
Embodiment 3
1,2- Bromofumes in embodiment 1 are replaced with to 1, the 2- ethylidene periodides of equimolar amounts, remaining condition and implementation
Example 1 is identical.
Embodiment 4
1,2- Bromofumes in embodiment 1 are replaced with to Isosorbide-5-Nitrae-dibromobutane of equimolar amounts, remaining condition and implementation
Example 1 is identical.
Above-described embodiment 2-4 also successfully prepares fluorine-containing azo surfactant and no longer goes to live in the household of one's in-laws on getting married one by one herein because length is limited
It states.
To sum up, the present invention is prepared for a kind of novel fluorine-containing azo based on the excellent performance of fluorine-containing surfactant
Optical Response surfactant has widened the research field of fluorine-containing surfactant.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of fluorine-containing azo surfactant, which is characterized in that structural formula is as follows：
Wherein, X is halogen, n=1,2,3 or 4.
2. fluorine-containing azo surfactant according to claim 1, which is characterized in that the halogen is chlorine, bromine or iodine.
3. fluorine-containing azo surfactant according to claim 1, which is characterized in that the fluorine-containing azo surfactant
Structural characterization be1H NMR(400MHz,CDCl3) δ 7.92 (t, J=9.2Hz, 2H), 7.32 (d, J=8.2Hz, 2H), 7.01
(t, J=7.5Hz, 4H), 4.33 (m, 2H), 3.82 (m, 2H), 3.19 (m, 9H).
4. the preparation method of fluorine-containing azo surfactant as claimed in claim 1 or 2, which is characterized in that include the following steps：
(1) preparation of fluorine-containing azophenol；
(2) preparation of the halogenated alkoxy-to trifluoromethoxy azobenzene；
(3) preparation of fluorine-containing azo surfactant.
5. the preparation method of fluorine-containing azo surfactant according to claim 4, which is characterized in that the step (1)
Specifically comprise the following steps：
(11) it takes 21ml water in beaker, then the same volume concentrated sulfuric acid is added in beaker dropwise, is stirred while adding, is then claimed
It takes 4- trifluoro-methoxyanilines 75mmol to instill in sulfuric acid solution dropwise, stirs evenly, keep -10-10 DEG C of temperature；
(12) sodium nitrite 101.5mmol and 40ml water wiring solution-formings are weighed, is instilled in the solution of step (11) dropwise, mixing is equal
It is even；
(13) sodium carbonate 443.4mmol, sodium hydroxide 75mmol, phenol 79.7mmol and water 270ml are weighed, is uniformly mixed；
(14) solution that step (12) obtains being instilled dropwise in the solution of step (13) preparation, the solid for obtaining yellow generates,
It is filtered after dripping, obtains yellow solid, dissolved with ethyl alcohol, filtered to get filtrate, dried, recrystallized with n-hexane.
6. the preparation method of fluorine-containing azo surfactant according to claim 4, which is characterized in that the step (2)
Specifically comprise the following steps：
(21) in three-necked flask, be added 40mmol the step of (1) synthesis trifluoromethoxy azophenol, 100ml's is anhydrous
Ethyl alcohol, the sodium hydroxide of 200mmol, the halogenated hydrocarbons of 400mmol are heated to reflux stirring 16h；
(22) after reaction, it is cooled to room temperature, red solution, filtrate decompression distillation is obtained by filtration, product is tied again with n-hexane
It is brilliant.
7. the preparation method of fluorine-containing azo surfactant according to claim 4, which is characterized in that the step (3)
Specifically comprise the following steps：
(31) it weighs the product that 20mmol steps (2) obtain to be dissolved in methyl phenyl ethers anisole, dropwise by 35wt% trimethylamine solutions 80mmol
It instills wherein, is warming up to 65 DEG C, flow back 48h；
(32) after reaction, it is cooled to room temperature, filters to obtain yellow solid product, tied again with ethyl acetate and alcohol mixed solution
Crystalline substance vacuum drying.
8. the preparation method of fluorine-containing azo surfactant according to claim 6, which is characterized in that the step (21)
In, halogenated hydrocarbons 1,2- Bromofumes, 1,2- dichloroethanes, 1,2- ethylidene periodides, Isosorbide-5-Nitrae-dibromobutane or Isosorbide-5-Nitrae-dichloroetane.
9. the preparation method of fluorine-containing azo surfactant according to claim 7, which is characterized in that the step (32)
In, the volume ratio of ethyl acetate and ethyl alcohol is 9:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110407723A (en) * | 2019-07-12 | 2019-11-05 | 江南大学 | A kind of preparation method and application of sulfate type photoresponse foam controller |
| CN111777535A (en) * | 2020-07-13 | 2020-10-16 | 济南大学 | Fluorine-containing azo surfactant prepared by clicking mercapto-alkene and method |
| CN115536545A (en) * | 2022-09-29 | 2022-12-30 | 惠科股份有限公司 | Surfactant, preparation method thereof, photoresist and photoetching method |
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| JP2013082651A (en) * | 2011-10-07 | 2013-05-09 | Tokyo Univ Of Science | Gemini surfactant and method of demulsifying emulsion |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407723A (en) * | 2019-07-12 | 2019-11-05 | 江南大学 | A kind of preparation method and application of sulfate type photoresponse foam controller |
| CN111777535A (en) * | 2020-07-13 | 2020-10-16 | 济南大学 | Fluorine-containing azo surfactant prepared by clicking mercapto-alkene and method |
| CN111777535B (en) * | 2020-07-13 | 2022-06-24 | 济南大学 | Fluorine-containing azo surfactant prepared by clicking mercapto-alkene and method |
| CN115536545A (en) * | 2022-09-29 | 2022-12-30 | 惠科股份有限公司 | Surfactant, preparation method thereof, photoresist and photoetching method |
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