CN112138604A - Double-carboxyl surfactant with anion-cation reversal capability and preparation method thereof - Google Patents
Double-carboxyl surfactant with anion-cation reversal capability and preparation method thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
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- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 21
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 16
- 150000003949 imides Chemical class 0.000 claims abstract description 15
- 239000012467 final product Substances 0.000 claims abstract description 11
- 229910010084 LiAlH4 Inorganic materials 0.000 claims abstract description 10
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 238000003379 elimination reaction Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 7
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 6
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- HAUDLKKUHAFHRO-UHFFFAOYSA-N 2-oxaspiro[3.3]hept-6-ene-1,3-dione Chemical compound O=C1OC(=O)C11C=CC1 HAUDLKKUHAFHRO-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910010082 LiAlH Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007865 diluting Methods 0.000 abstract description 2
- ZJFOZWUVVZAYGJ-UHFFFAOYSA-N C(=O)OC=O.C1CC=C1 Chemical compound C(=O)OC=O.C1CC=C1 ZJFOZWUVVZAYGJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a bi-carboxyl surfactant with anion-cation reversal capability and a preparation method thereof, wherein the preparation method comprises the following steps: 1) adding dodecylamine and cyclobut-3-ene diformic anhydride into a three-neck flask, introducing nitrogen, and performing nucleophilic addition-elimination reaction to generate imide; followed by LiAlH4Reducing the carbonyl group as a reducing agent. 2) Diluting the product, slowly adding potassium permanganate, heating to perform oxidation reaction to generate carboxyl, adding sodium sulfite to remove excessive potassium permanganate after the reaction is finished, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to 2-4 to separate out the product, and filtering and drying to constant weight to obtain the final product. The surfactant has excellent anion-cation reversal characteristics, and the type of the surfactant can be changed according to the external environment. The surfactant is anionic surfactant under the condition that the external environment is alkaline, and is cationic surfactant under the condition that the external environment is acidicA surfactant.
Description
Technical Field
The invention belongs to the field of functional surfactants, and particularly relates to a dicarboxyl surfactant with anion-cation reversal capability and a preparation method thereof.
Background
The surfactant is an amphiphilic compound containing a nonpolar oleophilic group and a polar hydrophilic group in a molecular structure, can form directional arrangement on a gas-liquid interface and a solid-liquid interface, can remarkably reduce the surface tension of the solution by adding a small amount of the surfactant into the solution, and effectively changes the physical and chemical properties of the interface. Therefore, the method is widely applied to the fields of daily life, industry and agriculture, high and new technology and the like, and becomes one of important industries of chemical processes. The surfactant industry has the defects of single variety, simple structure, lagged process and the like due to the long-standing weak foundation, and particularly, the high-end surfactant product and technology have great gap with foreign countries.
Disclosure of Invention
In order to enrich the types of surfactants and endow the surfactants with functionalization, the invention designs and prepares a double-carboxyl surfactant with cation and anion reversal capability and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bi-carboxyl surfactant with anion-cation reversal capability, the structural formula of the compound is as follows:
as a further improvement of the invention, the surfactant reverses the properties of cations and anions according to the change of the pH value of the external environment.
As a further improvement of the invention, the bi-carboxyl surfactant is an anionic surfactant under the condition that the external environment is alkaline, and is a cationic surfactant under the condition that the external environment is acidic. The surfactant has excellent anion-cation reversal characteristics, and the type of the surfactant can be changed according to the external environment. The anionic surfactant is used under the condition that the external environment is alkaline, and the cationic surfactant is used under the condition that the external environment is acidic.
A method for preparing a dicarboxyl surfactant with cation and anion reversal capability comprises the following steps:
mixing dodecylamine and cyclobut-3-ene dicarboxylic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide;
adding reducing agent LiAlH into imide4Reducing carbonyl at 0-35 ℃;
and adding an oxidant potassium permanganate, heating to 90-100 ℃ for oxidation reaction to generate carboxyl, and performing post-treatment to obtain a final product.
As a further improvement of the present invention, the nucleophilic addition-elimination reaction is carried out in a molar ratio of dodecylamine to cyclobut-3-enedicarboxylic anhydride of 1: 2.
As a further improvement of the invention, in the reduced carbonyl group, LiAlH4The mol ratio of the dodecylamine to the dodecylamine is 1-1.2: 1;
as a further improvement of the invention, the amount of the potassium permanganate substance is 1-2 times of the amount of the dodecylamine substance.
As a further improvement of the invention, in the oxidation reaction, after the product after carbonyl reduction is diluted, potassium permanganate is slowly added at 0 ℃, and then the temperature is raised for reaction.
As a further development of the invention, the post-treatment comprises:
and after the reaction is finished, adding sodium sulfite to remove excessive potassium permanganate, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to be 2-4 to separate out a product, and filtering and drying to constant weight to obtain a final product.
The invention has the following advantages:
the preparation method generates imide through the nucleophilic addition-elimination reaction of dodecylamine and cyclobut-3-ene dicarboxylic anhydride, and uses LiAlH4Reducing the imide to a reducing agent; and then a final product is obtained by a reducing agent potassium permanganate. The whole preparation method is simple and convenient, and the dicarboxyl surfactant with the anion-cation reversal capability is prepared.
The prepared double-carboxyl surfactant with negative and positive ion reversal capability can be applied to the fields of oil exploitation, crude oil recovery, soil remediation and the like. The surfactant has excellent anion-cation reversal characteristics, and the type of the surfactant can be changed according to the external environment. The anionic surfactant is used under the condition that the external environment is alkaline, and the cationic surfactant is used under the condition that the external environment is acidic.
Drawings
FIG. 1 is a synthesis scheme of the dicarboxyl surfactant with cation-anion reversal ability obtained in example 4.
FIG. 2 is a graph showing the change of surface tension with pH of the dicarboxyl surfactant having cation-anion reversing ability obtained in example 4.
Detailed Description
The invention relates to a bi-carboxyl surfactant with anion-cation reversal capability, the reaction equation of the preparation process is as follows:
according to the reaction mechanism, the invention adopts the following technical scheme:
a bi-carboxyl surfactant with anion-cation reversal capability has a structural formula as follows:
the method for preparing the double-carboxyl surfactant with the anion-cation reversal capability comprises the following steps:
1) dripping dodecylamine and cyclobut-3-ene dicarboxylic anhydride into a three-neck flask provided with a reflux condenser tube in sequence, introducing nitrogen, reacting for 2-5 h at 150-200 ℃, and performing a first nucleophilic addition-elimination reaction to generate imide, wherein the molar ratio of the dodecylamine to the cyclobut-3-ene dicarboxylic anhydride is 1: 2; followed by LiAlH4Reduction of imide for reducing agent, in which LiAlH4The mol ratio of the catalyst to the dodecylamine is 1-1.2: 1, the reduction temperature is 0-35 ℃, and the optimization is 20 DEG CThe reduction time is 4-6 h at the temperature of-35 ℃.
2) Diluting the product, slowly adding potassium permanganate at 0 ℃, and heating to react for 10-12 h, wherein the amount of potassium permanganate is 1-2 times of that of dodecylamine; and reducing excessive potassium permanganate by using sodium sulfite, dropwise adding dilute hydrochloric acid until the pH of the reaction solution is 2-4, separating out the product, and filtering and drying to constant weight to obtain the final product.
The surfactant can realize reversal of anion and cation properties according to the change of external environment pH.
The inversion principle of the bi-carboxyl surfactant with the anion-cation inversion capability is realized by the following reactions:
the bi-carboxyl surfactant with the anion-cation reversal capability is an anionic surfactant under the condition that the external environment is alkaline, and is a cationic surfactant under the condition that the external environment is acidic.
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) In a 250mL three-necked flask equipped with a reflux condenser, dodecylamine (18.5g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (24.8g, 0.2mol) were added dropwise in this order, and nitrogen was introduced 3 times, followed by heating to 180 ℃ for 3 hours, and TLC (Thin Layer Chromatography) was used to monitor completion of the reaction. After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 80mL of tetrahydrofuran dried over sodium metal were added to 250mL of trisIn a flask, the mixture was cooled to 0 ℃ using a cold salt bath, and 3.8g of LiAlH was slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 25 ℃ after the addition is finished to react for 4 h. The completion of the reaction was monitored by TLC (thinLayerChromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 3.8mLH into the mixture under ice salt bath2O, 3.8mL 15% aqueous NaOH and 11.4mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using 20ml of ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain the product.
(3) Adding the product and 40mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(20g, the adding time is 40min), and after the adding is finished, slowly raising the temperature to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The product obtained in example 1 was obtained in 58% yield.
Example 2
(1) In a 250mL three-necked flask equipped with a reflux condenser, dodecylamine (18.5g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (24.8g, 0.2mol) were added dropwise in this order, and nitrogen was introduced 3 times, followed by heating to 150 ℃ for 2 hours, and completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 90mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 4.18g of LiAlH were slowly added in portions4Stirring for 3min, dissolving in tetrahydrofuranThe imide in the pyran is slowly dripped into a three-neck flask, and after the addition is finished, the temperature is raised to 30 ℃ for reaction for 5 hours. The completion of the reaction was monitored by TLC (thinLayerChromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 4.2mLH under ice salt bath2O, 4.2mL 15% aqueous NaOH solution and 12.6mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using 20ml of ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain the product.
(3) Adding the product and 40mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(15.8g, the adding time is 40min), after the adding is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 3 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The yield of the product obtained in example 2 was 51%.
Example 3
(1) In a 250mL three-necked flask equipped with a reflux condenser, dodecylamine (18.5g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (24.8g, 0.2mol) were added dropwise in this order, and nitrogen was introduced 3 times, followed by heating to 200 ℃ for 5 hours, and completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 100mL of tetrahydrofuran dried with sodium metal was charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 3.99g of LiAlH was slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 35 ℃ after the addition for reacting for 6 h. TLC (thinLayerChromatograpy, thin layer)Chromatography) to monitor the reaction for completion. Cooling to 0 deg.C after reaction, adding 4mLH in sequence under ice salt bath2O, 4mL of 15% aqueous NaOH solution and 12mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using 20ml of ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain the product.
(3) Adding the product and 40mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(25g, the addition time is 40min), and after the addition is finished, the temperature is slowly raised to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 4 by using dilute hydrochloric acid to precipitate solids, and filtering and drying to obtain a pure final product.
The product obtained in example 3 was obtained in 53% yield.
Example 4
(1) In a 250mL three-necked flask equipped with a reflux condenser, dodecylamine (18.5g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (24.8g, 0.2mol) were added dropwise in this order, and nitrogen was introduced 3 times, followed by heating to 190 ℃ for 5 hours, and completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 80mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 4.56g of LiAlH were slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 20 ℃ after the addition is finished to react for 6 h. The completion of the reaction was monitored by TLC (thinLayerChromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 4.6mLH under ice salt bath2O, 4.6mL 15% NaOH in waterLiquid and 13.8mLH2O quenching excess LiAlH4Filtering, fully washing a filter cake by using 20ml of ethyl acetate, drying the filtrate by using anhydrous magnesium sulfate, concentrating under reduced pressure to obtain a crude product, and finally separating by using a column to obtain the product.
(3) Adding the product and 40mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(31.6g, the addition time is 40min), and after the addition is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The product obtained in example 4 was obtained in 60% yield.
In order to characterize the structural characteristics of a dicarboxyl surfactant with cation and anion reversal capability, the dicarboxyl surfactant with cation and anion reversal capability synthesized in example 4 was subjected to nuclear magnetic hydrogen spectroscopy, and the results are shown as follows:
1H NMR(300MHz,DMSO):12.13(s,2H),2.78-2.43(m,8H),1.36-1.26(m,20H),0.88(t,J＝7.4Hz,3H)ppm。
in order to characterize the surface tension of a dicarboxyl surfactant with the ability to reverse the cations and anions. The surfactant solution of example 4 was tested for surface tension using a JK99C full automatic surface tensiometer. First, a surfactant solution having a concentration of 0.01mol/L was prepared, and the surface tension thereof was measured at 25 ℃. Continuously reading 5 data with rise and fall in the testing process, wherein the difference of the 5 data is less than 1, taking the average value of the data as the final surface tension value of the solution, and the testing method is a platinum ring method. The surface tension of the surfactant solution as a function of pH is shown in figure 2. As can be seen, as the pH of the surfactant solution increases, its surface tension increases first and then decreases. When the pH is 6, the surface tension reaches a maximum of 65.2mN/m, indicating that the surfactant has a strong surface activity under acidic or alkaline conditions.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A bi-carboxyl surfactant with anion-cation reversal capability is characterized in that the structural formula of the compound is as follows:
2. the dicarboxyl surfactant of claim 1, wherein the cationic and anionic properties of the surfactant are reversed according to the change of pH of the external environment.
3. The dicarboxyl surfactant of claim 2, wherein the dicarboxyl surfactant is an anionic surfactant under alkaline conditions in an external environment and a cationic surfactant under acidic conditions in an external environment.
4. A preparation method of a dicarboxyl surfactant with cation and anion reversal capability is characterized by comprising the following steps:
mixing dodecylamine and cyclobut-3-ene dicarboxylic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide;
adding reducing agent LiAlH into imide4Reducing carbonyl at 0-35 ℃;
and adding an oxidant potassium permanganate, heating to 90-100 ℃ for oxidation reaction to generate carboxyl, and performing post-treatment to obtain a final product.
5. The method according to claim 4, wherein the nucleophilic addition-elimination reaction is performed in a molar ratio of dodecylamine to cyclobut-3-enedicarboxylic anhydride of 1: 2.
6. The method according to claim 4, wherein in the reduced carbonyl group, LiAlH4The mol ratio of the dodecylamine to the dodecylamine is 1-1.2: 1.
7. The method according to claim 4, wherein the amount of the potassium permanganate is 1 to 2 times the amount of the dodecylamine.
8. The preparation method according to claim 4, wherein in the oxidation reaction, after the product after carbonyl reduction is diluted, potassium permanganate is slowly added at 0 ℃, and then the temperature is raised for reaction.
9. The method of manufacturing according to claim 4, wherein the post-treatment comprises:
and after the reaction is finished, adding sodium sulfite to remove excessive potassium permanganate, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to be 2-4 to separate out a product, and filtering and drying to constant weight to obtain a final product.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238236A (en) * | 1963-04-29 | 1966-03-01 | Pennsalt Chemicals Corp | N-(monochloro-perfluoro-higher alkanoyl)amino-lower carboxylic acids |
| US3985722A (en) * | 1973-12-12 | 1976-10-12 | Ajinomoto Co., Inc. | Process for preparing N-higher aliphatic acyl derivatives of amino acids, peptides or proteins |
| JP2000219654A (en) * | 1999-01-29 | 2000-08-08 | Chukyo Yushi Kk | Multiple chain dipolar group compound and its production |
| JP2004161940A (en) * | 2002-11-14 | 2004-06-10 | Teepol Diversey Kk | Liquid fungicidal detergent composition |
| CN101037570A (en) * | 2007-03-23 | 2007-09-19 | 广西民族大学 | Preparation method of multi-carboxyl colophony oxidation product |
| CN101683601A (en) * | 2008-09-28 | 2010-03-31 | 郑州轻工业学院 | Alkyl-iminodisuccinate chelating surfactant and method for synthesizing same |
| CN102101837A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | Preparation method of cis-hexahydroisoindoline |
| CN103242216A (en) * | 2013-05-07 | 2013-08-14 | 兰州梦唐精细化工有限公司 | Synthesis method of N-Boc-hexahydro-5-oxo-cyclopenta (C) pyrrole |
| CN103772333A (en) * | 2014-02-19 | 2014-05-07 | 吉林众鑫化工集团有限公司 | Method for synthesizing cis-4-cyclohexene-1, 2-dimethylbenzene anhydride |
| CN104311821A (en) * | 2014-10-15 | 2015-01-28 | 江南大学 | Preparation of polymer medicine-carrying nano micelle with dual responsiveness |
| CN106473948A (en) * | 2015-09-02 | 2017-03-08 | 花王株式会社 | Cleanser compositions |
| CN111229121A (en) * | 2020-02-26 | 2020-06-05 | 江南大学 | pH-responsive amphiphilic-strong-polarity intelligently-switched emulsion and preparation method thereof |
| CN112125830A (en) * | 2020-09-22 | 2020-12-25 | 陕西科技大学 | Polyamide compound and preparation method thereof |
| CN112142640A (en) * | 2020-09-22 | 2020-12-29 | 陕西科技大学 | Bola type surfactant with anion-cation reversal capability and preparation method thereof |
-
2020
- 2020-09-22 CN CN202011003307.9A patent/CN112138604B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238236A (en) * | 1963-04-29 | 1966-03-01 | Pennsalt Chemicals Corp | N-(monochloro-perfluoro-higher alkanoyl)amino-lower carboxylic acids |
| US3985722A (en) * | 1973-12-12 | 1976-10-12 | Ajinomoto Co., Inc. | Process for preparing N-higher aliphatic acyl derivatives of amino acids, peptides or proteins |
| JP2000219654A (en) * | 1999-01-29 | 2000-08-08 | Chukyo Yushi Kk | Multiple chain dipolar group compound and its production |
| JP2004161940A (en) * | 2002-11-14 | 2004-06-10 | Teepol Diversey Kk | Liquid fungicidal detergent composition |
| CN101037570A (en) * | 2007-03-23 | 2007-09-19 | 广西民族大学 | Preparation method of multi-carboxyl colophony oxidation product |
| CN101683601A (en) * | 2008-09-28 | 2010-03-31 | 郑州轻工业学院 | Alkyl-iminodisuccinate chelating surfactant and method for synthesizing same |
| CN102101837A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | Preparation method of cis-hexahydroisoindoline |
| CN103242216A (en) * | 2013-05-07 | 2013-08-14 | 兰州梦唐精细化工有限公司 | Synthesis method of N-Boc-hexahydro-5-oxo-cyclopenta (C) pyrrole |
| CN103772333A (en) * | 2014-02-19 | 2014-05-07 | 吉林众鑫化工集团有限公司 | Method for synthesizing cis-4-cyclohexene-1, 2-dimethylbenzene anhydride |
| CN104311821A (en) * | 2014-10-15 | 2015-01-28 | 江南大学 | Preparation of polymer medicine-carrying nano micelle with dual responsiveness |
| CN106473948A (en) * | 2015-09-02 | 2017-03-08 | 花王株式会社 | Cleanser compositions |
| CN111229121A (en) * | 2020-02-26 | 2020-06-05 | 江南大学 | pH-responsive amphiphilic-strong-polarity intelligently-switched emulsion and preparation method thereof |
| CN112125830A (en) * | 2020-09-22 | 2020-12-25 | 陕西科技大学 | Polyamide compound and preparation method thereof |
| CN112142640A (en) * | 2020-09-22 | 2020-12-29 | 陕西科技大学 | Bola type surfactant with anion-cation reversal capability and preparation method thereof |
Non-Patent Citations (14)
| Title |
|---|
| R.A. SCHMIDT等: "3a,4,7,7a-Tetrahydroisoindoline and n-substituted derivatives", 《ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS》 * |
| R.A. SCHMIDT等: "3a,4,7,7a-Tetrahydroisoindoline and n-substituted derivatives", 《ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS》, vol. 83, no. 1, 31 July 1959 (1959-07-31), pages 1, XP024815805, DOI: 10.1016/0003-9861(59)90028-1 * |
| TOKUZO KAWASE等: "Synthesis and Properties of 1,2,3,4-Butanetetracarboxylic Acid Type Gemini Surfactants with Semifluoroalkyl Chain as Hydrophobic Group", 《TENSIDE SURFACTANTS DETERGENTS: JOURNAL FOR THEORY, TECHNOLOGY AND APPLICATION OF SURFACTANTS》 * |
| TOKUZO KAWASE等: "Synthesis and Properties of 1,2,3,4-Butanetetracarboxylic Acid Type Gemini Surfactants with Semifluoroalkyl Chain as Hydrophobic Group", 《TENSIDE SURFACTANTS DETERGENTS: JOURNAL FOR THEORY, TECHNOLOGY AND APPLICATION OF SURFACTANTS》, vol. 52, no. 5, 28 February 2015 (2015-02-28), pages 2 * |
| 何志荣等: "多羧基表面活性剂的合成及应用进展", 《中国洗涤用品工业》 * |
| 何志荣等: "多羧基表面活性剂的合成及应用进展", 《中国洗涤用品工业》, no. 02, 15 February 2018 (2018-02-15) * |
| 刘祥: "乙二胺四乙酸合成双子型阳离子表面活性剂", 《上海化工》 * |
| 刘祥: "乙二胺四乙酸合成双子型阳离子表面活性剂", 《上海化工》, no. 01, 15 January 2009 (2009-01-15) * |
| 张付利等: "《有机化学 第2版》", 31 December 2017, 开封：河南大学出版社 * |
| 钱建华等: "《精细化学品化学》", 31 December 2010, 沈阳：东北大学出版社 * |
| 陈燕妮等: "N-酰基氨基酸系列表面活性剂的合成和应用", 《化学研究与应用》 * |
| 陈燕妮等: "N-酰基氨基酸系列表面活性剂的合成和应用", 《化学研究与应用》, no. 02, 28 April 2001 (2001-04-28) * |
| 马喜平等: "阴离子型双子表面活性剂GMAS-14的合成与性能", 《油田化学》, no. 03 * |
| 魏文德等: "《有机化工原料大全 第2卷》", 31 May 1989, 北京：化学工业出版社 * |
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