CN107442038B - Ultraviolet response amino acid surfactant and preparation method thereof - Google Patents
Ultraviolet response amino acid surfactant and preparation method thereof Download PDFInfo
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- CN107442038B CN107442038B CN201710670774.9A CN201710670774A CN107442038B CN 107442038 B CN107442038 B CN 107442038B CN 201710670774 A CN201710670774 A CN 201710670774A CN 107442038 B CN107442038 B CN 107442038B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The present invention relates to a kind of ultraviolet response amino acid surfactant and preparation method thereof with such as following formula I structure.
Description
Technical field
The present invention relates to compound and chemosynthesis technical fields, living more particularly to a kind of ultraviolet response amino acid surface
Property agent and preparation method thereof.
Background technique
In recent years, in field of daily chemicals, consumer increasingly pay close attention to the safety of all kinds of daily chemical products, mildness with
And environment friendly；More and more high quality, multi-functional environmentally-friendly surfactant are developed, and are increasingly becoming
The main direction of development of Surfactant Industry.Amino acid surfactant belongs to the surface-active based on biological substance
Agent not only has good water solubility, foaming characteristic, soil release performance, emulsibility and thickening property etc. compared with conventional surfactant；And
And it is excellent to have low irritant, nontoxicity, high quality, multi-functional, slow corrosivity, good biodegradability properties and environment friendly etc.
Point.
For nontraditional amino acid surfactant based on fatty acyl amino-acid salt, self assembly behavior is simpler, is difficult to realize
Accurate, the reversible regulation of aggregate structure, property and function.It is being pierced to largely limit amino acid surfactant
Swash the application in response type nano self-assembled material side field.Pay close attention at present most stimuli responsive sources be concentrated mainly on electrochemistry,
Temperature, pH, magnetic field, redox, gas and light stimulation etc..Wherein light (ultraviolet light, visible light) is used as a kind of nothing
It pollutes, clean controllable environmental stimuli factor, have without external additive, easy to operate, experiment process is controllable and applies
The advantages that range is wide.
Based on this, a kind of ultraviolet response type amino acid surfactant is developed, is allowed to have nontraditional amino acid surface-active
It is had both intelligent speciality (ultraviolet response) while agent excellent application performance, it is significant.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of ultraviolet response amino acid surfactants.
Specific technical solution is as follows:
A kind of ultraviolet response amino acid surfactant has such as following formula I structure:
Wherein, M is selected from Na or K.
It is a further object of the present invention to provide the preparation methods of above-mentioned ultraviolet response amino acid surfactant.
Specific technical solution is as follows:
The preparation method of the ultraviolet response amino acid surfactant of Formulas I structure, includes the following steps:
(1) 4- [[4- (decyloxy) phenyl] azo] is prepared by raw material of 4- [[4- (decyloxy) phenyl] azo] benzoic acid
Chlorobenzoyl chloride；
(2) 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride and sodium glutamate carry out being condensed in reaction dissolvent anti-
It answers, generates 4- [[4- (decyloxy) phenyl] azo] benzoyl sodium glutamate；
(3) the reaction solution tune pH for obtaining step (2) is settled out crude product to acidity, be filtered, washed, dry after obtain
4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid；
(4) 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid is neutralized to get 4- [[4- (decyloxy) phenyl]
Azo] benzoyl glutamate.
In wherein some embodiments, in step (1), the tool of 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride is prepared
Body technology are as follows: weigh 4- [[4- (decyloxy) phenyl] azo] benzoic acid, be added excessive thionyl chloride, after back flow reaction 10-14h
Excessive thionyl chloride is distilled off to get 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride.
In wherein some embodiments, in step (2), 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride and glutamic acid
The molar feed ratio of sodium is 1:2.0-5.0；Reaction temperature is 15-25 DEG C；Reaction pH maintains 11.0-13.0；Reaction time is
12-24h。
In wherein some embodiments, the reaction dissolvent is water in the mixed solvent of hydrophilic organic solvent, wherein water with
The volume ratio of hydrophilic organic solvent is 1:0.4-1.0.
In wherein some embodiments, the hydrophilic organic solvent is selected from ethyl alcohol, isopropanol, the tert-butyl alcohol, acetone or dioxy
Six rings.
In wherein some embodiments, in step (3), the reaction solution pH that step (2) obtains is adjusted to 1.0-2.0, is made thick
Product is sufficiently precipitated, and filtering with organic solvent washing filter cake, then washes, 4- [[4- (decyloxy) benzene is obtained after vacuum drying
Base] azo] benzoyl glutamic acid.
In wherein some embodiments, the organic solvent is the ethyl acetate and n-hexane of volume ratio 1:8-10.
In wherein some embodiments, the reaction solution uses hydrochloric acid or sulphur acid for adjusting pH value.
In wherein some embodiments, in step (4), first by 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid
PH value of solution in deionized water, 60-70 DEG C of temperature control, is adjusted to 9.0-10.0 with alkali by dispersion, is obtained brown-red solution, is after dry
Obtain 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamate.
In wherein some embodiments, the alkali is selected from sodium hydroxide or potassium hydroxide.
Beneficial effects of the present invention:
Above-mentioned ultraviolet response amino acid surfactant has the following structure:
Wherein, M is selected from Na or K.
The functional characteristics of this kind of amino acid surfactant is:
1, under 365nm ultraviolet radioactive, the transformation that trans- (trans) arrives cis- (cis) can occur rapidly, conversion ratio is reachable
95%, specific as follows:
2, under visible optical radiation, can take advantage of a situation rapidly (cis) arrive the transformation of trans- (trans), conversion ratio is reachable
95%, specific as follows:
3,4- [[4- (decyloxy) phenyl] azo] benzoyl glutamate solution (0.1-0.5mg/mL) is ultraviolet in 365nm
Under radiation, gelation can occur rapidly；This gel is placed under visible light, then can revert to solution；The transformation of this solution-gel is existing
As completely reversibility.
The advantages of preparation method, is:
1, in the preparation process of 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride, thionyl chloride undertakes chloride simultaneously
The effect of reagent and solvent；
2,4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride activity it is higher, can rapidly with sodium glutamate monohydrate
In amino reaction；
3, Yi Shui/hydrophilic organic solvent is reaction dissolvent, it is suppressed that 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride
Hydrolysis, improve conversion ratio；
4, solid product is obtained, convenient for storage, transport and is used.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Embodiment 1:
A kind of preparation method of ultraviolet response amino acid surfactant of the present embodiment, includes the following steps:
(1) 10.0g 4- [[4- (decyloxy) phenyl] azo] benzoic acid is weighed, 100.0g thionyl chloride is added, flowed back
Excessive thionyl chloride is distilled off after night, 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride can be obtained, can directly be used
It is reacted in next step.
4- [[4- (decyloxy) phenyl] azo] benzoic acid can be prepared in the following ways:
4- [[4- (hydroxyl) phenyl] azo] benzoic acid, weighs 4.0g, is dissolved in the anhydrous n,N-Dimethylformamide of 100mL
(DMF) in, 30.0g potassium carbonate and 43.0g iodine decane is added, reaction was completed by reflux 16h at 160 DEG C of temperature control.Vacuum distillation removes
DMF obtains 4- [[4- (decyloxy) phenyl] azo], yield 64% by column chromatography for separation.
(2) it weighs 16.7g sodium glutamate monohydrate to be dissolved in 100g deionized water, is adjusted to pH with 32% sodium hydroxide
12.1,60mL ethyl alcohol is added；15-25 DEG C of temperature control, 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride that step obtains before being added,
Terminate after being stirred to react 16h (maintaining pH 11.5-12.5), generates 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid
Sodium.
(3) reaction solution pH is adjusted to 1.52 with 31% hydrochloric acid, obtains a large amount of brown color precipitatings, acetic acid second is successively used in filtering
Ester/n-hexane (volume ratio 1:9), deionized water repeatedly wash filter cake, obtain 12.2g 4- [[4- (decyloxy) phenyl] after dry
Azo] benzoyl glutamic acid.
(4) 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid that preceding step obtains is dispersed in 250g deionization
In, 65 DEG C of temperature control, it is neutralized to pH 9.81 with 31% sodium hydroxide, 13.2g 4- is obtained after dry, and [[4- (decyloxy) phenyl] is even
Nitrogen] benzoyl sodium glutamate, yield 82.0%.
4- [[4- (decyloxy) phenyl] azo] benzoyl sodium glutamate is dissolved in deionized water (0.1mg/mL), is placed in
It is irradiated under 365nm ultraviolet lamp (100w), solution is just changed into gel in 1min；If this gel is placed under visible light,
Solution can be completely transformed into 10min.
Embodiment 2:
A kind of preparation method of ultraviolet response amino acid surfactant of the present embodiment, includes the following steps:
(1) 4- [[4- (decyloxy) phenyl] azo] benzoic acid weighs 10.0g, and 100.0g thionyl chloride is added, returns overnight
Excessive thionyl chloride is distilled off after stream, 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride can be obtained, can directly be used
It is reacted in next step.
4- [[4- (decyloxy) phenyl] azo] benzoic acid can be prepared in the following ways:
4- [[4- (hydroxyl) phenyl] azo] benzoic acid, weighs 4.0g, is dissolved in the anhydrous n,N-Dimethylformamide of 100mL
(DMF) in, 30.0g potassium carbonate and 43.0g iodine decane is added, reaction was completed by reflux 16h at 160 DEG C of temperature control.Vacuum distillation removes
DMF obtains 4- [[4- (decyloxy) phenyl] azo], yield 64% by column chromatography for separation.
(2) it weighs 16.7g sodium glutamate monohydrate to be dissolved in 100g deionized water, is adjusted to pH with 32% sodium hydroxide
11.7,75mL acetone is added；15-25 DEG C of temperature control, 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride that step obtains before being added,
Terminate after being stirred to react 16h (maintaining pH 11.5-12.5), generates 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid
Sodium.
(3) reaction solution pH is adjusted to 1.75 with 31% hydrochloric acid, obtains a large amount of brown color precipitatings, acetic acid second is successively used in filtering
Ester/n-hexane (volume ratio 1:9), deionized water repeatedly wash filter cake, obtain 12.0g 4- [[4- (decyloxy) phenyl] after dry
Azo] benzoyl glutamic acid.
(4) 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid that preceding step obtains is dispersed in 250g deionization
In, 65 DEG C of temperature control, it is neutralized to pH 9.62 with 48% potassium hydroxide, 13.8g 4- is obtained after dry, and [[4- (decyloxy) phenyl] is even
Nitrogen] benzoyl potassium glutamate, yield 85.5%.
4- [[4- (decyloxy) phenyl] azo] benzoyl potassium glutamate is dissolved in deionized water (0.2mg/mL), is placed in
It is irradiated under 365nm ultraviolet lamp (100w), solution is just changed into gel in 1min；If this gel is placed under visible light,
Solution can be completely transformed into 10min.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of ultraviolet response amino acid surfactant, which is characterized in that have such as following formula I structure:
Wherein, M is selected from Na or K.
2. the preparation method of ultraviolet response amino acid surfactant described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) 4- [[4- (decyloxy) phenyl] azo] benzene first is prepared by raw material of 4- [[4- (decyloxy) phenyl] azo] benzoic acid
Acyl chlorides；
(2) 4- [[4- (decyloxy) phenyl] azo] chlorobenzoyl chloride and sodium glutamate carry out condensation reaction in reaction dissolvent, raw
At 4- [[4- (decyloxy) phenyl] azo] benzoyl sodium glutamate；
(3) the reaction solution tune pH for obtaining step (2) is settled out crude product to acidity, be filtered, washed, dry after obtain 4-
[[4- (decyloxy) phenyl] azo] benzoyl glutamic acid；
(4) by the neutralization of 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamic acid, to get 4-, [[4- (decyloxy) phenyl] is even
Nitrogen] benzoyl glutamate.
3. preparation method according to claim 2, which is characterized in that in step (1), prepare 4- [[4- (decyloxy) benzene
Base] azo] chlorobenzoyl chloride specifically comprises the processes of: 4- [[4- (decyloxy) phenyl] azo] benzoic acid is weighed, excessive dichloro is added
Sulfoxide excessive thionyl chloride is distilled off to get 4- [[4- (decyloxy) phenyl] azo] benzene first after back flow reaction 10-14h
Acyl chlorides.
4. preparation method according to claim 2, which is characterized in that in step (2), [[4- (decyloxy) phenyl] is even by 4-
Nitrogen] molar feed ratio of chlorobenzoyl chloride and sodium glutamate is 1:2.0-5.0；Reaction temperature is 15-25 DEG C；Reaction pH is maintained
11.0-13.0；Reaction time is 12-24h.
5. the preparation method according to claim 4, which is characterized in that the reaction dissolvent is water and hydrophilic organic solvent
Mixed solvent, wherein the volume ratio of water and hydrophilic organic solvent is 1:0.4-1.0.
6. preparation method according to claim 5, which is characterized in that the hydrophilic organic solvent be selected from ethyl alcohol, isopropanol,
The tert-butyl alcohol, acetone or dioxane.
7. preparation method according to claim 2, which is characterized in that in step (3), reaction solution that step (2) is obtained
PH is adjusted to 1.0-2.0, and crude product is precipitated sufficiently, and filtering with organic solvent washing filter cake, is then washed, dry, obtains 4-
[[4- (decyloxy) phenyl] azo] benzoyl glutamic acid.
8. preparation method according to claim 7, which is characterized in that the organic solvent is the acetic acid of volume ratio 1:8-10
Ethyl ester and n-hexane；The reaction solution uses hydrochloric acid or sulphur acid for adjusting pH value.
9. preparation method according to claim 2, which is characterized in that in step (4), first by 4- [[4- (decyloxy) benzene
Base] azo] benzoyl glutamic acid dispersion in deionized water, 60-70 DEG C of temperature control, solution is neutralized to pH 9.0-10.0 with alkali,
Brown-red solution is obtained, up to 4- [[4- (decyloxy) phenyl] azo] benzoyl glutamate after drying.
10. preparation method according to claim 9, which is characterized in that the alkali is selected from sodium hydroxide or potassium hydroxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376655B1 (en) * | 1995-06-02 | 2002-04-23 | Riso National Laboratory | Physically functional materials |
| CN104496844A (en) * | 2014-11-25 | 2015-04-08 | 江南大学 | Preparation method of alkyloxy azobenzene photosensitive foam control agent |
| CN104826544A (en) * | 2015-04-02 | 2015-08-12 | 中国石油大学(华东) | Lipopeptide molecule surfactant containing azobenzene photosensitive group, and synthetic method thereof |
-
2017
- 2017-08-08 CN CN201710670774.9A patent/CN107442038B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376655B1 (en) * | 1995-06-02 | 2002-04-23 | Riso National Laboratory | Physically functional materials |
| CN104496844A (en) * | 2014-11-25 | 2015-04-08 | 江南大学 | Preparation method of alkyloxy azobenzene photosensitive foam control agent |
| CN104826544A (en) * | 2015-04-02 | 2015-08-12 | 中国石油大学(华东) | Lipopeptide molecule surfactant containing azobenzene photosensitive group, and synthetic method thereof |
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