CN108409591B - Star-shaped carboxylic acid group zwitterionic compound and preparation method and application thereof - Google Patents
Star-shaped carboxylic acid group zwitterionic compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of dispersant preparation, and discloses a star carboxylic acid group zwitterionic compound, a preparation method and application thereof, which can be applied to a graphene dispersion technology. The dispersant is prepared by the following steps: dropwise adding a quantitative trimethylolpropane-tri (3-aziridinyl propionate) reaction solution into a reaction bottle filled with methylamine (or ethylamine) aqueous solution and an acid catalyst to perform a first step aziridine ring-opening reaction; then adding a certain amount of sodium chloroacetate reaction solution into the reaction solution to carry out a second step of carboxyl substitution and quaternization reaction, and obtaining a product which is a star amphoteric dispersant containing polycarboxylic acid groups. According to the star-shaped amphoteric dispersant prepared by the invention, carboxylate ions are introduced into a molecular chain of the star-shaped amphoteric dispersant, so that a combination of dispersant molecules and graphene can be fully dispersed in water, the repulsion between graphene particles is enhanced, and the dispersion effect is improved. Meanwhile, quaternary ammonium salt cations are introduced into the molecular chain of the dispersing agent, so that the hydration capability and the thermal stability of the dispersing agent are improved.
Description
Technical Field
The invention relates to the technical field of preparation of multi-quaternary ammonium salt cationic compounds, in particular to a star-shaped carboxylic acid group zwitterionic compound and a preparation method and application thereof.
Background
The aziridine crosslinking agent has larger tension and higher activity, can react with amino, carboxyl and hydroxyl to form a compound with a star structure or a net structure, and has the functions of emulsification, dispersion, flocculation, wetting, foaming, spreading, permeation, lubrication, antistatic, sterilization and the like in order to introduce two quaternary ammonium salt cationic groups and two sulfonic anionic groups into the compound.
The graphene is represented by sp2The hybridized carbon atoms are mutually connected to form the carbon material with a monoatomic layer thickness two-dimensional honeycomb-shaped lattice structure. The graphene has excellent electrical, mechanical, thermal and mechanical properties, and is expected to be widely applied to the fields of transparent conductive films, composite materials, energy sources, sensors, biotechnology, catalytic materials and the like. Graphene sheets have strong van der waals force between layers, aggregation is easy to occur, and the graphene sheets are difficult to dissolve in water and common organic solvents, so that the performance of graphene in practical application is greatly influenced. Therefore, in order to fully exert its excellent properties, the preparation of uniform, highly stable graphene dispersions is an important condition for its research and application in many fields.
The solution ultrasonic exfoliation method is the most common method for preparing graphene, and is a method for exfoliating graphene from graphite by ultrasound and dispersing the graphene in a solution with the aid of a dispersing agent. The method has the advantages of low raw material price, low defect content of the obtained graphene and capability of large-scale preparation. However, graphene itself is insoluble in water and lacks an effective dispersant to improve the dispersibility of graphene in water, so that graphene obtained by ultrasonic exfoliation is easy to re-aggregate. This seriously hinders the application of the solution ultrasonic exfoliation method in the macro preparation of graphene. Therefore, the development of a dispersing agent capable of greatly improving the dispersion performance of graphene in an aqueous solution is a problem to be solved in the mass preparation of graphene.
Disclosure of Invention
The invention uses aziridine cross-linking agent with high activity to react with active amine group to form independent star structure, and then carries out sulfonic acid substitution reaction to obtain star carboxylic acid group zwitterionic compound with novel structure. The invention aims to provide a star amphoteric dispersant containing polycarboxylic acid groups, which has a novel structure. The second purpose of the invention is to provide a preparation method of the dispersant. The third purpose of the invention is to apply the amphoteric dispersant to graphene dispersion technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a star-shaped carboxylic acid group zwitterionic compound has a structural formula as follows:
wherein R1-is-CH3or-CH2CH3。
A preparation method of a star-shaped carboxylic acid group zwitterionic compound comprises the following steps:
adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into methylamine or ethylamine water solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 40-70 ℃ for 5-7 h;
under the alkalescent condition, adding sodium chloroacetate aqueous solution into the reactants to carry out carboxyl substitution and quaternization reaction, and reacting for 8-14 h at 70-90 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
In the aziridine ring opening reaction, trimethylolpropane-tris (3-aziridinylpropionate) and methylamine or ethylamine were in a molar ratio of 1: 3.
In the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
In carboxyl substitution and quaternization, the pH value is 9-10 under the alkalescent condition, and the reaction solution is adjusted to be alkalescent by NaOH.
In the carboxy substitution and quaternization reactions, the amount of sodium chloroacetate species was 6 times greater than trimethylolpropane-tris (3-aziridinylpropionate).
An application of a star-shaped carboxylic acid group zwitterionic compound as a graphene dispersing agent.
The mass ratio of the graphene dispersing agent to the graphene powder is as follows: (2-5): 25.
compared with the prior art, the invention has the following advantages:
the invention uses aziridine cross-linking agent with high activity to react with active amine group to form independent star structure, and then carries out sulfonic acid substitution reaction to obtain star carboxylic acid group zwitterionic compound with novel structure. According to the invention, a star-shaped surfactant carrying active secondary amine is formed by reacting a high-activity aziridine crosslinking agent with an active amine group, and a quaternary ammonium salt reagent carrying quaternary ammonium salt is introduced for reaction to obtain a star-shaped carboxylic acid group zwitterionic compound.
According to the amphoteric star-shaped dispersant prepared by the invention, sulfonate ions are introduced into a molecular chain of the amphoteric star-shaped dispersant, so that a combination of dispersant molecules and graphene can be fully dispersed in water, the repulsion between graphene particles is enhanced, and the dispersion effect of the amphoteric star-shaped dispersant is improved. Meanwhile, quaternary ammonium salt cations are introduced into the molecular chain of the dispersing agent, so that the hydration capability and the thermal stability of the dispersing agent are improved. The main advantages are:
(1) according to the invention, a large amount of carboxylate ions are introduced into a molecular chain of the dispersing agent, and the carboxylate groups have good water solubility, so that a combination of molecules and graphene can be fully dispersed in water.
(2) According to the invention, quaternary ammonium salt cations are introduced into the molecular chain of the dispersant, so that the hydration capability and the thermal stability of the star-shaped amphoteric dispersant are improved.
(3) The molecular structure of the dispersant is a star-shaped structure, and the space blocking effect among graphene particles is increased. Therefore, the star amphoteric dispersant has more efficient dispersion effect and good dispersion stability.
Drawings
FIG. 1 is a chemical structural formula of the present invention;
FIG. 2 is a scheme of the synthesis of the reaction of the present invention.
Detailed Description
As shown in figures 1 and 2 of the drawings,
the invention adopts the following technical scheme:
a multi-carboxylic-group-containing star amphoteric dispersant has a structural formula as follows:
wherein R is1is-CH3or-CH2CH3。
The preparation method of the polycarboxylic acid group-containing star amphoteric dispersant comprises the following steps:
dropwise adding trimethylolpropane-tri (3-aziridinyl propionate) reaction liquid into a reaction bottle filled with methylamine (or ethylamine) water solution and an acid catalyst to perform a first-step aziridine ring-opening reaction, wherein the molar ratio of the trimethylolpropane-tri (3-aziridinyl propionate) to methylamine (or ethylamine) is 1:3, and reacting for 5-7 h at 40-70 ℃; and adjusting the reaction solution to be alkalescent (pH is 9-10) by NaOH, dropwise adding a sodium chloroacetate aqueous solution to perform a second step of carboxyl substitution and quaternization reaction, wherein the amount of the sodium chloroacetate is 6 times of that of trimethylolpropane-tris (3-aziridinyl propionate), and reacting for 8-14 h at 70-90 ℃. Removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product. The synthesis equation is as follows:
wherein R is1is-CH3or-CH2CH3。
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 reactor containing 20% by mass of methylamine water solution (23.25g, containing 4.65g, 0.15mol of methylamine) and acidic catalyst (85% H)3PO40.30g), heated to 40 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition, the temperature is raised to 70 ℃ for reaction for 5 hours.
(2) Adjusting the reaction solution to be alkalescent (pH is 9-10) by using NaOH, dropwise adding 80% sodium chloroacetate aqueous solution (43.68g, wherein 34.94g of sodium chloroacetate is contained, 0.30mol) in mass fraction, and reacting at 70 ℃ for 14 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum to constant weight to obtain the product.
The structural formula of the product obtained in example 1 is:
1H NMR(300MHz，DMSO)：δ4.35(s，24H)，3.94(s，6H)，3.63～3.68(m，18H)，3.30(s，9H)，2.69(t，6H)，1.69(m，2H)，0.83(t，3H)ppm。
13C NMR(300MHz，DMSO)：δ175.4，173.1，68.6，66.1，56.2，52.9，48.9，35.7，26.7，23.0，7.0ppm。
and (3) testing the dispersion performance:
commercially available graphene (Qingdao Jinpeng graphite, Inc.) was ground into graphene powder. Selecting a clean reagent bottle, respectively weighing 5mg of the dispersing agent prepared in example 1 and 25mg of graphene powder, adding 10mL of water, uniformly mixing by oscillation, sealing, and putting into an ultrasonic instrument for ultrasonic treatment. Carrying out ultrasonic treatment for 12 hours under the power of 100W, and keeping the water temperature at 40-50 ℃ in the ultrasonic treatment process. And after the ultrasonic treatment is finished, carrying out centrifugal separation, centrifuging for 30min at a centrifugal rotating speed of 1000r/min, and obtaining a supernatant liquid by separation, namely the graphene dispersion liquid. And a blank test is performed. The concentration of graphene in the dispersion with the dispersant added was 0.82mg/mL, while the concentration of graphene in the dispersion of the blank sample was 0.06 mg/mL.
The graphene dispersion prepared in example 1 was allowed to stand at 25 ℃ for 10 hours, and the stability was observed. The results showed no sedimentation in the dispersion. Whereas the dispersion of the blank test, the graphene was almost completely settled.
Example 2
(1) In a 70% ethylamine water solution (9.54g, containing 6.75g of ethylamine and 0.15mol) and an acid catalyst (85% H)3PO40.30g), heated to 50 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition, the temperature is raised to 70 ℃ for reaction for 7 hours.
(2) Adjusting the reaction solution to be alkalescent (pH is 9-10) by using NaOH, dropwise adding 80% sodium chloroacetate aqueous solution (43.68g, wherein 34.94g of sodium chloroacetate is contained, 0.30mol) in mass fraction, and reacting at 90 ℃ for 8 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The structural formula of the product obtained in example 2 is:
1H NMR(300MHz，DMSO)：δ4.35(s，24H)，3.94(s，6H)，3.63～3.68(m，18H)，3.28(s，6H)，2.69(t，6H)，1.69(m，2H)，1.25(t，9H)，0.84(t，3H)ppm。
13C NMR(300MHz，DMSO)：δ175.4，173.1，66.1，56.2，54.4，53.2，35.7，26.7，22.9，7.0～7.7ppm。
and (3) testing the dispersion performance:
commercially available graphene (Qingdao Jinpeng graphite, Inc.) was ground into graphene powder. Selecting a clean reagent bottle, respectively weighing 2mg of the dispersing agent prepared in example 2 and 25mg of graphene powder, adding 10mL of water, uniformly mixing by oscillation, sealing, and putting into an ultrasonic instrument for ultrasonic treatment. Carrying out ultrasonic treatment for 12 hours under the power of 100W, and keeping the water temperature at 40-50 ℃ in the ultrasonic treatment process. And after the ultrasonic treatment is finished, carrying out centrifugal separation for 30min at a centrifugal rotating speed of 1000r/min, wherein the separated supernatant is graphene dispersion liquid, and the concentration of graphene is 0.95 mg/mL.
The graphene dispersion prepared in example 2 was allowed to stand at 50 ℃ for 15 hours, and the stability was observed. The results showed no sedimentation in the dispersion.
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 (3)
1. A preparation method of a star-shaped carboxylic acid group zwitterionic compound is characterized in that the structural formula is as follows:
wherein R1-is-CH3or-CH2CH3；
The preparation method of the star carboxylic acid group zwitterionic compound comprises the following steps:
adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into methylamine or ethylamine water solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 40-70 ℃ for 5-7 h;
under the alkalescent condition, adding sodium chloroacetate aqueous solution into the reactants to carry out carboxyl substitution and quaternization reaction, and reacting for 8-14 h at 70-90 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating a product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product;
in the aziridine ring opening reaction, trimethylolpropane-tris (3-aziridinylpropionate) and methylamine or ethylamine were in a molar ratio of 1: 3.
2. The method for preparing the radial carboxylic acid group zwitterionic compound according to claim 1, characterized in that: in the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
3. The method for preparing the star-shaped carboxylic acid group zwitterionic compound as claimed in claim 1, wherein in the carboxyl substitution and quaternization reaction, the pH value is 9-10 under the weak alkaline condition, and the reaction solution is adjusted to be weak alkaline by NaOH.
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| WO2016172436A1 (en) * | 2015-04-23 | 2016-10-27 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles and polymers thereof as antimicrobial agents and methods using same |
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| WO2016172436A1 (en) * | 2015-04-23 | 2016-10-27 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles and polymers thereof as antimicrobial agents and methods using same |
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