CN113185448A - Rosin-based zwitterionic surfactant and preparation method and application thereof - Google Patents
Rosin-based zwitterionic surfactant and preparation method and application thereof Download PDFInfo
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- CN113185448A CN113185448A CN202110460219.XA CN202110460219A CN113185448A CN 113185448 A CN113185448 A CN 113185448A CN 202110460219 A CN202110460219 A CN 202110460219A CN 113185448 A CN113185448 A CN 113185448A
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Abstract
The invention discloses a rosin-based zwitterionic surfactant, and a preparation method and application thereof. The main component abietic acid of rosin and bismaleimide are subjected to addition reaction to generate abietic acid bismaleimide, and the abietic acid bismaleimide is reacted with choline to obtain the rosin-based zwitterionic surfactant. CO can be prepared by using the rosin-based zwitterionic surfactant2/N2A responsive foam. Introducing CO into the prepared surfactant aqueous solution2/N2The structure of the surfactant is changed, so that the foam stability of the surfactant is changed, and when the pH value is 10.4,the foam volume is 7mL, the foam is completely broken within 2h, and at pH 7.4, the foam volume is slightly reduced to 6.2mL, but the half-life period is 336 h. The surfactant is natural and renewable in raw materials, accords with the green development strategy, and is expected to be widely applied in the fields of cosmetics, fire fighting and the like due to the excellent foamability, foam stabilizing performance and defoaming performance.
Description
Technical Field
The invention belongs to the field of preparation and application of green surfactants, and particularly relates to a rosin-based zwitterionic surfactant and stable foam formed by the rosin-based zwitterionic surfactant.
Background
Foams are dispersion systems of insoluble gases dispersed in liquids or molten solids, have small diameters, high surface areas and excellent flow characteristics, and are useful in a wide variety of applications such as oil recovery, cosmetics and wastewater treatment. It is well known that foams are thermally unstable systems that break down over time to form gaseous and aqueous phases. To effectively stabilize the foam, stabilizers such as macromolecules, surfactants, and nanoparticles are commonly used, which produce a stable foam by reducing the coalescence, coarsening, and drainage processes of the foam. In food, cosmetics and fire fighting applications, stable foam is required, but in oil recovery, wastewater treatment and mineral flotation, foam only needs to be temporarily stable, and defoaming needs to be carried out in time after use to avoid pollution in the process. At present, defoaming agents are commonly used for eliminating foams, however, the addition of the defoaming agent changes the composition of a system and is difficult to separate from the system. For effective stabilization of the foam and avoidance of the adverse effects of antifoams, by changing the external stimulus, e.g. pH, CO2/N2Temperature and light, responsive foams that can switch between stable and unstable states are of great interest.
Meanwhile, the surfactant is a common foam-stabilizing substance, most of the production raw materials of the surfactant at present are petrochemical resources, which obviously is not beneficial to green sustainable development, and the natural product serving as the raw material replaces the traditional petroleum resource to synthesize the green surfactant, so that the industry development trend is reached.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rosin-based zwitterionic surfactant, and a preparation method and application thereof. Abietic acid is used as a raw material, and the abietic acid is subjected to addition and neutralization reaction to prepare the amphoteric ion-containing rosin-based response typeA surfactant, and a stable foam is prepared with the surfactant. By introducing CO into an aqueous solution of the above surfactant2/N2Adjusting the pH of the solution to alter the structure of the surfactant to obtain CO that can be switched between stable and unstable states2/N2A responsive foam system.
In order to achieve the purpose, one of the technical schemes adopted by the invention is as follows:
the molecular structure of the rosin-based zwitterionic surfactant contains an abietic acid bismaleimide rigid skeleton, and the structural formula of the rosin-based zwitterionic surfactant is shown as the following formula:
the second technical scheme adopted by the invention is as follows:
the preparation method of the rosin-based zwitterionic surfactant comprises the following steps:
1) the abietic acid and the bismaleimide are subjected to addition reaction to generate the abietic acid bismaleimide, wherein the mass ratio of the abietic acid to the bismaleimide is (1.9-2.8): 1, using acetic acid as a reaction solvent, wherein the reaction temperature is 120-140 ℃, and the reaction time is 12-15 h; cooling the reacted solution to room temperature, carrying out solid-liquid separation (such as suction filtration), washing the solid part with water to obtain yellow powder, carrying out reflux recrystallization with acetone, filtering and drying to obtain the abietic acid bismaleimide;
2) neutralizing the abietic acid bismaleimide obtained in the step 1) with choline to prepare a rosinyl dicarboxylates surfactant; wherein the mass ratio of the abietic acid bismaleimide to the choline is 1: (2.2-2.8), the reaction solvent is water, the reaction temperature is preferably 75-90 ℃, and the reaction time is preferably 1-2 h; and (3) reacting to obtain a yellow solution, extracting with an organic solvent for three times, and drying the water phase to obtain a target product abietic acid bismaleimide choline salt, namely the rosin-based zwitterionic surfactant.
Further, because abietic acid is subjected to isomerization reaction under the action of heat or acid, levopimaric acid is most stable and easy to react, in order to further improve the controllability of the reaction, in the step 1), the addition reaction is carried out in the presence of an acid catalyst, the acid catalyst can be selected from at least one of aliphatic sulfonic acid or aromatic sulfonic acid, preferably at least one of p-toluenesulfonic acid, o-toluenesulfonic acid or methanesulfonic acid, and the mass of the acid catalyst is 1-5% of that of the abietic acid.
Further, in order to further increase the reaction rate of the abietic acid bismaleimide, in the step 1), the addition reaction is performed under a high temperature condition, preferably at a temperature of 120 to 140 ℃.
Further, in order to further ensure the formation of the rosin-based zwitterionic surfactant, in the step 2), the ratio of the amount of the substance of abietic acid bismaleimide to choline in the amount of 1: (2.2-2.8).
Further, in order to further purify the obtained rosin-based zwitterionic surfactant, in the step 2), the solution after the reaction is extracted with an organic solvent, preferably petroleum ether.
Further, in the step 1), the drying mode is vacuum drying, the drying temperature is 60-70 ℃, and the drying time is 10-12 hours; in the step 2), the drying mode is freeze drying.
The third technical scheme adopted by the invention is as follows:
the rosin-based zwitterionic surfactant is applied to preparation of responsive foam.
Further, the response type foam is prepared by foaming an aqueous solution of the rosin-based zwitterionic surfactant, and the concentration of the rosin-based zwitterionic surfactant in the aqueous solution is not lower than 2 mmol-L-1. The foaming is for example by vigorous shaking. For example: dissolving rosinyl zwitterionic surfactant in water to prepare the solution with the concentration of 2 mmol.L-1The surfactant aqueous solution of (1) was added to 4mL of the above aqueous solution in a 10mL measuring cylinder, and vigorously shaken for 30 seconds to prepare a stable and abundant foam.
Further, the responsive foam is CO2/N2Responsive foam. Introducing CO into the aqueous solution of the rosin-based zwitterionic surfactant2/N2The structure of the surfactant is changed by adjusting the pH value of the solution, so that the foam system is switched between a stable state and an unstable state. Specifically, the response type foam obtained by the invention is introduced with CO2Then relatively stable, introducing N2And then relatively unstable.
For example: introducing CO into aqueous solution of rosin-based zwitterionic surfactant2Then, partial carboxyl of the surfactant reacts with carbonate ions, the pH of the surfactant aqueous solution is reduced to 10.4, the volume of the formed foam is 7mL, the stabilization time is 2h, and CO is continuously introduced2The pH value of the surfactant aqueous solution is reduced to 7.4, the volume of the formed foam is 6.2mL, and the half-life period of the foam is 336 h; the process has responsiveness, and N is introduced into the surfactant aqueous solution with the pH of 7.4 at the temperature of 65 DEG C2The pH of the solution was again raised to 10.4, at which time the foam volume was restored to 7mL and the stabilization time was 2h, and the process responded at least three times.
To further improve the foam response profile, CO2The gas is introduced at the temperature of 20-40 ℃ for 20-40 min; n is a radical of2The gas is introduced at the temperature of 60-70 ℃, preferably at the temperature of 64-66 ℃ (for example, 65 ℃) for 1-2 h.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
In the invention, the room temperature, namely the normal environment temperature, can be 10-30 ℃.
The invention has the following beneficial effects:
1) rosin is a forest resource with rich yield in China, is one of main raw materials for preparing a green surfactant, and has a unique tricyclic diterpene rigid skeleton structure which can be more regularly arranged on a gas/liquid interface, so that the strength of an interface film is increased, and more stable foam is formed. The rosin-based zwitterionic surfactant is prepared by taking the green renewable forest resource rosin as a raw material, can replace part of petrochemical resources, and accords with the development trend of the current industry.
2) The rosin-based zwitterionic surfactant is obtained by combining the structural characteristics of rosin and adopting the methods of addition and acid-base neutralization, and the critical micelle concentration of the rosin-based zwitterionic surfactant is 0.62 mmol.L-1Has better aggregation capability; contains a larger abietic acid bismaleimide rigid structure, has better foam stability, and the half-life period of the formed stable foam is as long as 336 h.
3) The surfactant of the invention has responsiveness and is introduced with CO2Adjusting the pH value of the surfactant aqueous solution to 10.4, wherein the volume of the formed foam is 7mL, and the stabilization time is 2 h; continuously introducing CO2Adjusting the pH of the solution to 7.4, wherein the formed foam has the volume of 6.2mL and the half-life period of 336h, and introducing N into the solution with the pH of 7.42The pH of the solution can be raised to 10.4, and the foaming property and the foam stability can be recovered.
Drawings
FIG. 1 is a Fourier infrared spectrum of a rosin-based zwitterionic surfactant according to an embodiment of the present invention.
FIG. 2 is a plot of surface tension as a function of concentration (25 ℃ C.) for a rosin-based zwitterionic surfactant according to an example of the present invention.
FIG. 3 is a graph of foam volume versus time (room temperature) for a rosin-based zwitterionic surfactant of an example of the invention at pH 7.4.
FIG. 4 is a graph of foam volume versus time (room temperature) for a rosin-based zwitterionic surfactant according to an example of the invention at pH 10.4.
FIG. 5 is a macroscopic view of the foam at pH 7.4 and pH 10.4 in response to three times for aqueous rosin-based zwitterionic surfactant solutions of examples of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1:
preparation of rosin-based zwitterionic surfactant: accurately weighing 10g of abietic acid (CAS No.: 514-10-3, purity > 70%), 4.3g N, N '- (4,4' -methylenediphenyl) bismaleimide (CAS No.: 13676-54-5) and 0.46g of p-toluenesulfonic acid, measuring 30mL of acetic acid in a four-neck flask, connecting a reflux and stirring device, refluxing for 15h at 120 ℃, cooling to room temperature, performing suction filtration to obtain yellow powder, recrystallizing with acetone, drying, and drying in a vacuum drying oven at 70 ℃ for 12h to obtain the abietic acid bismaleimide.
9.6327g of the obtained abietic acid bismaleimide is weighed, 5.65mL of choline hydroxide with the content of 44 wt% and 40mL of deionized water are weighed and put in a three-neck flask, a reflux and stirring device is connected, the reaction is carried out for 1h under the condition that the temperature is 75 ℃, the reaction liquid is extracted with petroleum ether for three times, and freeze drying is carried out for 12h, so that abietic acid bismaleimide choline salt is obtained, namely the rosinyl zwitterionic surfactant.
Example 2:
the structural formula of the rosin-based zwitterionic surfactant obtained in example 1 is shown as follows:
the structure was characterized by FT-IR, the FT-IR spectrum is shown in FIG. 1, 3416.50cm-1The absorption peak of (a) is a stretching vibration peak of a hydroxyl group (-OH), 2930.03cm-1And 2866.53cm-1The absorption peak of (a) is a stretching vibration peak of methyl and methylene (CH3-, -CH2-), 1560.07cm-1Has an absorption peak of carboxylate ions (-COO)-) The FT-IR result shows that the synthesized product is the target compound.
Example 3:
measurement of surface tension: preparing a series of aqueous solutions of abietic acid bismaleimide choline salt prepared in example 1 with different concentrations, measuring the critical micelle concentration of the surfactant aqueous solution by adopting a BZY-3B type surface tensiometer hanging ring method, repeating each point for 3 times, and taking the average value; plotting the surface tension of the surfactant as a function of concentration, CO2/N2Responsive rosinyl zwitterionThe critical micelle concentration of the surfactant was 0.62 mmol.L-1。
Example 4:
preparation of the foam: the rosin-based zwitterionic surfactant prepared in example 1 was formulated to have a concentration of 2 mmol. multidot.L-1Two 20mL portions of the above aqueous solution of the surfactant (2) were introduced with CO at 25 deg.C2The pH of the solution was adjusted to 7.4 and 10.4, respectively, and 4mL of aqueous surfactant solution at pH 7.4 and 10.4 were added to a 10mL stoppered cylinder, and shaken vigorously for 30s, and the change in lather volume of the surfactant over time was recorded. N was added to an aqueous solution of a surfactant having a pH of 7.4 at 65 deg.C2The pH of the aqueous surfactant solution may be raised to 10.4. The foam half-life of the surfactant at pH 7.4 is as long as 336h, and the foam of the surfactant at pH 10.4 disappears completely within 2 h.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A rosin-based zwitterionic surfactant is characterized in that: the structural formula is shown as the following formula:
2. a method for preparing a rosin-based zwitterionic surfactant according to claim 1, characterized in that: the method comprises the following steps:
1) reacting abietic acid with bismaleimide to generate abietic acid bismaleimide, wherein the mass ratio of the abietic acid to the bismaleimide is 1.9-2.8: 1, using acetic acid as a reaction solvent, cooling the solution after reaction to room temperature, carrying out solid-liquid separation, washing a solid part, recrystallizing and drying to obtain the abietic acid bismaleimide, wherein the reaction temperature is 120-140 ℃, and the reaction time is 12-15 hours;
2) reacting the abietic acid bismaleimide obtained in the step 1) with choline to prepare the rosinyl zwitterionic surfactant, wherein the mass ratio of the abietic acid bismaleimide to the choline is 1: 2.2-2.8, taking water as a reaction solvent, taking the reaction temperature of 75-90 ℃, taking the reaction time of 1-2 hours, extracting the solution after the reaction by using an organic solvent, and drying the water phase to obtain the abietic acid bismaleimide choline salt, namely the rosin-based zwitterionic surfactant.
3. The method of claim 2, wherein: in the step 1), the reaction is carried out in the presence of an acid catalyst, wherein the acid catalyst comprises at least one of aliphatic sulfonic acid or aromatic sulfonic acid, and the mass of the acid catalyst is 1-5% of that of abietic acid.
4. The production method according to claim 3, characterized in that: the acid catalyst includes at least one of p-toluenesulfonic acid, o-toluenesulfonic acid, or methanesulfonic acid.
5. Use of a rosin-based zwitterionic surfactant of claim 1 in the preparation of a responsive foam.
6. Use according to claim 5, characterized in that: the response type foam is prepared by foaming the aqueous solution of the rosin-based zwitterionic surfactant, and the concentration of the rosin-based zwitterionic surfactant in the aqueous solution is not lower than 2 mmol-L-1。
7. Use according to claim 5, characterized in that: the responsive foam is CO2/N2A responsive foam.
8. Use according to claim 7, characterized in that: CO 22Introducing the aqueous solution of the rosin-based zwitterionic surfactant at the temperature of 20-40 DEG CThe introducing time is 20-40 min.
9. Use according to claim 7, characterized in that: n is a radical of2And introducing the rosin-based zwitterionic surfactant into the aqueous solution at the temperature of 60-70 ℃ for 1-2 h.
10. Use according to claim 9, characterized in that: n is a radical of2And introducing the rosin-based zwitterionic surfactant into an aqueous solution of the rosin-based zwitterionic surfactant at the temperature of 64-66 ℃.
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