PH-responsive rosin-based surfactant, preparation method thereof and pseudo-gemini surfactant constructed by same
阅读说明：本技术 一种pH响应型松香基表面活性剂、其制备方法及其构筑的伪双子表面活性剂 (PH-responsive rosin-based surfactant, preparation method thereof and pseudo-gemini surfactant constructed by same ) 是由 翟兆兰 叶圣丰 商士斌 宋湛谦 于 2021-09-13 设计创作，主要内容包括：本发明公开了一种pH响应型松香基表面活性剂、其制备方法及其构筑的伪双子表面活性剂。pH响应型松香基表面活性剂,其分子结构式如下：其中n＝10,12,14,16,18。pH响应型松香基伪双子表面活性剂,由pH响应型松香基表面活性剂和马来酸复配制得。pH响应型松香基表面活性剂和pH响应型松香基伪双子表面活性剂均具有非常优异的表面活性和pH响应性,可用于洗漱用品、废水处理、三级采油、药物和基因传递等领域中,为松香的高值化利用提供了新的方向。(The invention discloses a pH response type rosin-based surfactant, a preparation method thereof and a pseudo gemini surfactant constructed by the same. The pH response type rosin-based surfactant has the following molecular structural formula: where n is 10,12,14,16, 18. The pH response type rosin-based pseudo gemini surfactant is prepared by compounding a pH response type rosin-based surfactant and maleic acid. The pH response type rosin-based surfactant and the pH response type rosin-based pseudo-gemini surfactant have excellent surface activity and pH response, can be used in the fields of washing articles, wastewater treatment, tertiary oil recovery, medicines, gene transfer and the like, and provide a new direction for high-value utilization of rosin.)
1. A pH response type rosin-based surfactant is characterized in that: the molecular structural formula is as follows:
where n is 10,12,14,16, 18.
2. The method for producing a pH-responsive rosin-based surfactant according to claim 1, characterized in that: the method comprises the following steps:
s1, adding rosin and maleic anhydride into an acid solvent to carry out D-A addition reaction to prepare maleopimaric acid;
s2, adding maleopimaric acid and long-chain amine into an organic solvent to carry out imidization reaction to prepare an intermediate N-alkyl imide maleopimaric acid, wherein the long-chain amine can be at least one of N-decylamine, dodecylamine, tetradecylamine, hexadecylamine or octadecylamine;
s3, adding N-alkyl imide maleopimaric acid into an organic solvent, adding an acyl chlorination reagent for acyl chlorination reaction, and preparing N-alkyl imide maleopimaric acid chloride;
s4, dissolving N-alkyl imide maleopimaric acid chloride in an organic solvent, and dropwise adding the N-alkyl imide maleopimaric acid chloride into the organic solvent containing N, N-dimethyl ethylenediamine to perform amidation reaction to prepare the pH response type rosin-based surfactant.
3. The method of claim 2, wherein: in step S1, the mass ratio of rosin to maleic anhydride is 1 (1.10-1.20); the acidic solvent is glacial acetic acid; the temperature of the D-A addition reaction is 140-150 ℃, and the time is 4-5 h.
4. The production method according to claim 2 or 3, characterized in that: in step S2, the mass ratio of the maleopimaric acid to the long chain amine is 1 (1.05-1.15); the organic solvent is ethanol; the temperature of the imidization reaction is 70-80 ℃, and the time is 10-12 h.
5. The production method according to claim 2 or 3, characterized in that: in step S3, the organic solvent is dichloromethane; the acyl chlorination reagent is thionyl chloride; the mass ratio of the N-alkyl imide maleopimaric acid to the thionyl chloride is 1 (1.50-1.80); the temperature of the acyl chlorination reaction is 25-60 ℃, and the time is 2-5 h.
6. The production method according to claim 2 or 3, characterized in that: in step S4, the organic solvent is dichloromethane; the mass ratio of the N-alkyl imide maleopimaric acid chloride to the N, N-dimethyl ethylenediamine is 1: (1.10-1.20); the temperature of the acyl chlorination reaction is 0-5 ℃, and the time is 2-4 h.
7. A pH response type rosinyl pseudo gemini surfactant is characterized in that: prepared by compounding the pH-responsive rosin-based surfactant of claim 1 with maleic acid.
8. The pH-responsive rosin-based pseudo-gemini surfactant according to claim 7, characterized in that: adding maleic acid and pH response type rosin-based surfactant into ultrapure water, performing ultrasonic treatment, and heating to 70 +/-5 ℃ to completely dissolve the maleic acid and the pH response type rosin-based surfactant to obtain a semitransparent uniform solution; adjusting the pH value within 1.00-5.35, and keeping the temperature at 20-40 ℃ for 24 +/-2 hours to form different aggregates.
9. The pH-responsive rosin-based pseudo-gemini surfactant according to claim 8, characterized in that: the concentration of the pH response type rosin-based surfactant is 60-100 mmol-1(ii) a The concentration of the maleic acid is 30-50 mmol-1。
10. The pH-responsive rosin-based pseudo-gemini surfactant according to claim 8 or 9, characterized in that: when the pH is 5.35 and the temperature is kept at 20-40 ℃ for 24 +/-2 hours, the formed micelle is a unilamellar vesicle; when the pH is 5.00-5.35 and the temperature is kept at 20-40 ℃ for 24 +/-2 hours, the formed micelle is a multi-layer vesicle; when the pH value is 2.00-5.00 and the temperature is kept at 20-40 ℃ for 24 +/-2 hours, the formed micelle is a worm micelle; when the pH value is 1.00-2.00, the formed micelle is a large lamellar structure.
Technical Field
The invention relates to a pH response type rosin-based surfactant, a preparation method thereof and a pseudo gemini surfactant constructed by the same, belonging to the technical field of surfactants.
Background
The surfactant can form aggregates such as worm micelles, vesicles, lamellar structures, nanofibers and the like in aqueous solution, and the formation of the aggregates provides a basis for the application of the surfactant in the fields of cosmetics, industrial washing, petroleum extraction, medicines, gene delivery and the like. Pseudo-gemini surfactants are formed by non-covalent interactions of conventional surfactants and hydrotropes and, due to their specific structure, generally form relatively novel aggregates in aqueous solutions. In addition, the non-covalent bonds of the pseudo-gemini surfactants are stimulated at the outside (e.g., pH, CO)2/N2Light, redox, etc.), the macroscopic physicochemical properties and the microscopic aggregate morphology of the system can be reversibly transformed. Based on these characteristics, pseudo-gemini surfactants have recently shown great advantages in the fields of nanomaterials, biomedicines, tertiary oil recovery, and the like. However, most of the pseudo gemini surfactants reported at present are prepared from petroleum products, which obviously does not conform to the concept of developing green chemistry in the modern times, and the application range of the pseudo gemini surfactants is limited.
Rosin is a renewable resource with abundant yield and low price, and has been widely applied to the fields of adhesives, coatings, printing ink, rubber, papermaking, food, metal processing and the like, but no report is found for constructing a pseudo gemini surfactant by taking rosin as a raw material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pH response type rosin-based surfactant, a preparation method thereof and a pseudo gemini surfactant constructed by the pH response type rosin-based surfactant.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a pH response type rosin-based surfactant has a molecular structural formula as follows:
where n is 10,12,14,16, 18.
The pH response type rosin-based surfactant has extremely strong surface activity under an acidic condition due to the introduction of a tertiary amine group, becomes a completely hydrophobic compound under an alkaline condition, and loses the surface activity. Based on the response characteristic, the pH response type rosin-based surfactant has great advantages in preparing a single-component pH response type surfactant or a pH response type compound system, and can be used as an emulsifier, an oil displacement agent, a drug delivery slow release carrier and the like.
The synthetic route of the pH response type rosin-based surfactant is as follows:
where n is 10,12,14,16, 18.
The preparation method of the pH response type rosin-based surfactant comprises the following steps:
s1, adding rosin and maleic anhydride into an acid solvent to carry out D-A addition reaction to prepare maleopimaric acid;
s2, adding maleopimaric acid and long-chain amine into an organic solvent to carry out imidization reaction to prepare an intermediate N-alkyl imide maleopimaric acid, wherein the long-chain amine can be at least one of N-decylamine, dodecylamine, tetradecylamine, hexadecylamine or octadecylamine;
s3, adding N-alkyl imide maleopimaric acid into an organic solvent, adding an acyl chlorination reagent for acyl chlorination reaction, and preparing N-alkyl imide maleopimaric acid chloride;
s4, dissolving N-alkyl imide maleopimaric acid chloride in an organic solvent, and dropwise adding the N-alkyl imide maleopimaric acid chloride into the organic solvent containing N, N-dimethyl ethylenediamine for amidation reaction to obtain a pH response type rosin-based surfactant CnMPAN。
In the step S1, the ratio of the amounts of the rosin and the maleic anhydride is 1 (1.10-1.20); the acidic solvent is glacial acetic acid; the temperature of the D-A addition reaction is 140-150 ℃, and the time is 4-5 h.
In the step S2, the ratio of the amounts of the maleopimaric acid and the long chain amine is 1 (1.05-1.15); the organic solvent is ethanol; the temperature of the imidization reaction is 70-80 ℃, and the time is 10-12 h.
In order to improve the product yield and reduce side reactions, in step S3, the organic solvent is dichloromethane; the acyl chlorination reagent is thionyl chloride; the mass ratio of the N-alkyl imide maleopimaric acid to the thionyl chloride is 1 (1.50-1.80); the temperature of the acyl chlorination reaction is 25-60 ℃, and the time is 2-5 h.
In order to improve the product yield and reduce side reactions, in step S4, the organic solvent is dichloromethane; the mass ratio of the N-alkyl imide maleopimaric acid chloride to the N, N-dimethyl ethylenediamine is 1: (1.10-1.20); the temperature of the acyl chlorination reaction is 0-5 ℃, and the time is 2-4 h.
A pH-responsive rosin-based pseudo gemini surfactant prepared by compounding the pH-responsive rosin-based surfactant according to claim 1 and maleic acid.
The tertiary amine group and the carboxyl group in the surfactant system have certain responsiveness to HCl, different aggregates can be formed under different pH values, and a foundation is provided for the application of the surfactant system in the fields of industrial washing, drug delivery, tertiary oil recovery and the like.
The preparation of the pH response type rosinyl pseudo-gemini surfactant comprises the following steps: adding maleic acid and pH response type rosin-based surfactant into ultrapure water, performing ultrasonic treatment, and heating to 70 +/-5 ℃ to completely dissolve the maleic acid and the pH response type rosin-based surfactant to obtain a semitransparent uniform solution (pH response type rosin-based pseudo-gemini surfactant); adjusting the pH value within 1.00-5.35, carrying out different transformation on micelles in the solution, and keeping the temperature at 20-40 ℃ for 24 +/-2 hours to form different aggregates.
When the pH value of the semitransparent uniform solution is adjusted to 5.35, and the solution is kept at the constant temperature of 20-40 ℃ for 24 +/-2 hours, the formed micelle is a unilamellar vesicle which is in a slight blue opaque gel state; when the pH value is 5.00-5.35, and the temperature is kept at 20-40 ℃ for 24 +/-2 hours, the formed micelle is a multi-layer vesicle which is a slight blue opaque gel; when the pH value is 2.00-5.00 and the temperature is kept at 20-40 ℃ for 24 +/-2 hours, the formed micelle is a worm micelle and is a clear and transparent viscoelastic solution; when the pH value is 1.00-2.00, the formed micelle is a large lamellar structure and is milky opaque gel. When the pH value of the regulating system is gradually increased from 5.35 to 1.00, the micelles in the solution realize the conversion process from the unilamellar vesicles to the multilamellar vesicles, worm micelles and lamellar micelles. The above conversion can be realized only by adding hydrochloric acid, so that the system can be used for slow release and delivery of medicines, tertiary oil recovery engineering, pipeline oil displacement agents, fertilizer slow release and the like.
In order to improve the response sensitivity, the concentration of the pH response type rosin-based surfactant is 60-100 mmol-1(ii) a The concentration of the maleic acid is 30-50 mmol-1。
The prior art is referred to in the art for techniques not mentioned in the present invention.
The invention obtains the following technical effects:
1. the invention utilizes the super-strong hydrophobicity of the tricyclic diterpene rigid structure of the rosin, takes the rosin as an initial raw material, synthesizes the maleopimaric acid through D-A addition, introduces a long carbon chain into the anhydride part of the maleopimaric acid through imidization reaction, introduces a tertiary amine group with responsiveness through acylchlorination and amidation reaction to prepare the rosin-based pH responsive surfactant, and compared with the sodium alkyl maleimide carboxylate, the surface activity of the surfactant is obviously enhanced; the surfactant and maleic acid are compounded to obtain a novel rosin-based gemini surfactant system C10MPAN/MA, the system has better response to pH and can form abundant aggregates in water; meanwhile, the invention provides a new direction for the development and utilization of the rosin-based surfactant, and widens the application of rosin in the aspects of industrial washing, drug delivery, tertiary oil recovery and the like.
2. The novel gemini surfactant system C is obtained by compounding pH response type rosin-based surfactant and maleic acid10The MPAN/MA system can form gel or viscoelastic solution constructed by different aggregates under different pH values, provides theoretical basis for the construction of rosin-based quasi-gemini surfactant and gel, and simultaneously shows the advantages of rosin rigid groups in the aspect of self-assembly to form novel aggregates.
3. C obtained by the invention10The MPAN/MA can form different aggregates under different pH values, when the pH value of the solution is gradually reduced, the surfactant system can form an aggregation structure such as a unilamellar vesicle, a multilamellar vesicle, a worm micelle and a lamellar micelle in water at one time, can be used for toiletries, drug delivery, genetic engineering, tertiary oil recovery, drug and gene delivery, and simultaneously provides a foundation for high-value utilization of rosin.
Drawings
FIG. 1 is a graph showing a pH-responsive rosin-based surfactant prepared in example 11A HNMR map;
FIG. 2 is a surface tension graph of pH responsive rosin-based surfactants prepared in example 1 at different pH's.
FIG. 3 is a surface tension graph of pH-responsive rosin-based pseudo-gemini surfactants prepared in example 3 at different pH's.
FIG. 4 is a graph of the appearance of pH responsive rosin-based pseudo-gemini surfactants prepared in example 3 at different pH values;
fig. 5 is a steady state rheology plot of a viscoelastic solution formed at pH 3.00 and pH 4.00 for pH-responsive rosin-based pseudo-gemini surfactants prepared in example 3;
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The preparation method of the pH response type rosin-based surfactant comprises the following steps:
(1) synthesis of maleopimaric acid: ordinary rosin (400.00g, 1.32mol), maleic anhydride (142.4g, 1.45mol) and 160g of acetic acid were weighed out accurately into a four-necked flask equipped with mechanical stirring and charged into a condensing reflux apparatus. The temperature was raised to 140 ℃ and the reaction was terminated after 5 h. Cooling the reaction liquid to room temperature, adding 400g of acetic acid for crystallization, performing suction filtration to obtain a crude product of the maleopimaric acid, and recrystallizing for 3 times to obtain a white solid, namely the maleopimaric acid, wherein the purity is 97%.
(2) Synthesis of N-alkyl imide maleopimaric acid: malathionine (30g, 0.075mol) was accurately weighed out together with 1-decylamine (13.05g, 0.083mol) and 200mL of absolute ethanol in a round-bottomed flask, and a magnetic stirrer was added with a reflux condenser to conduct reflux reaction at 80 ℃ for 12 hours. After the reaction is finished, the product becomes light yellow liquid, the solvent is removed by rotary evaporation, and then 150mL of dichloromethane is added for dissolution, and the mixture is dried by anhydrous sodium sulfate. Column chromatography on silica gel with spin-dried dichloromethane afforded a colourless solid after silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1), i.e. the N-alkylimide maleopimaric acid (24.51g), yield: 60.53 percent.
(3) Synthesis of N-alkyl imide maleopimaric acid chloride: n-alkylimide maleopimaric acid (11.09g, 0.021mol) and 50mL of dichloromethane are accurately weighed in a three-neck flask, a magnetic stirrer is added, and SOCl is dropwise added at room temperature2(3.75g, 0.0315 mol). After the dropwise adding, the temperature is raised to 60 ℃ for reaction for 5 hours, and after the reaction is finished, excessive dichloromethane and SOCl are removed by rotary evaporation2To give a pale yellow solid, N-alkylimide maleopimaric acid chloride (11.72g, 0.021 mol).
(4) Synthesizing N-dimethylethylenediamine N-alkyl imide maleopimaric amide: dissolving the N-alkyl imide maleopimaric acid chloride (11.52g) prepared in the step (3) into 30mL of anhydrous dichloromethane, slowly dripping the solution into 50mL of dichloromethane solution containing N, N-dimethylethylenediamine (1.94g, 0.022mol) and triethylamine (6.1g, 0.06mol) in an ice bath, and continuing to react for 4 hours after finishing dripping. After the reaction is finished, the solution is light yellow, and a large amount of crystals are separated out from the upper layer. Washing the reaction solution with ultrapure water and saturated sodium bicarbonate solution for three times respectively, drying the reaction solution with anhydrous sodium sulfate, and performing silica gel column chromatography (dichloromethane: methanol: 8:1) to obtain a light yellow solid, namely N-dimethyl ethylenediamine N-alkyl acylImine maleopimaric amide C10MPAN (8.1g, 0.013mol), yield: the content of the active carbon is 61.9%,1HNMR is shown in FIG. 1 and has a structure ofn＝10。
Example 2
The critical micelle concentration (cmc) and the surface tension (gamma) at the critical micelle concentration of the sample solution at different pH values were measured by a surface tension methodcmc) The method comprises the following steps:
the critical micelle concentration and surface tension of the surfactant were measured by a Sigma 701 type surface tensiometer hanging Wilhelmy plate method at 25 deg.C with a Wilhelmy plate width of 19.44mm, a thickness of 0.1mm and a height of 65 mm. Each point was repeatedly measured 3 times, and the measurement error of each point was set to 0.05mN · m-1. The surface tension of the surfactant was plotted as a function of concentration, as shown in fig. 2. C10The cmc of MPAN at pH 5.00,4.00,3.00,2.00,1.00 is 0.012,0.021,0.032,0.015,0.0097mM, respectively, corresponding to gammacmcRespectively are 31.16,32.16,31.05,33.35,30.25 and 29.68mN · m-1. As can be seen, C10MPAN has extremely strong surface activity under an acidic condition; becomes a completely hydrophobic compound under alkaline conditions and loses surface activity. Based on the response characteristic, the surfactant is used for preparing emulsion under an acidic condition to recover waste organic matters in the sewage, then the pH is adjusted to be alkaline, demulsification is carried out, release of pollutants is realized, the aim of wastewater treatment is fulfilled, and the surfactant can be recycled.
Example 3
preparing a pH response type rosinyl pseudo gemini surfactant:
the pH-responsive rosin-based surfactant C prepared in example 1 was accurately weighed10MPAN(0.1647g,90mmol-1) Maleic acid MA (0.0157g,45 mmol)-1) And ultrapure water (3g) in a vial in six-fold format, heated and sonicated to dissolve completely to give C10MPAN/MA; adjusting the pH of the solution to 5.35,5.00,4.00,3.00,2.00,1.00 with hydrochloric acid, respectively, and adjusting the pH to C at different pH values10The surface activity of MPAN/MA was tested and the results are shown in FIG. 3, from FIG. 3, C10The cmc of MPAN/MA at pH 5.35,5.00,4.00,3.00,2.00,1.00 is 0.0251,0.0297,0.033,0.0219,0.0083,0.0088mM, respectively, corresponding to γcmcAre respectively 31.04,32.14,31.14,33.27,30.37 and 29.74mN/m, namely C10MPAN/MA has extremely strong surface activity under an acidic condition; then C of different pH10The MPAN/MA is put into a thermostat and is balanced for 24h at 25 ℃, the corresponding macroscopic view of the aggregate is shown in figure 4, and as can be seen from figure 4, when the pH is adjusted to 5.35, the formed micelle is a unilamellar vesicle which is a slight blue opaque gel; when the pH is 5.00, the formed micelle is a multi-layer vesicle which is in a slight blue opaque gel state; when the pH is 3 and 4, the formed micelle is a worm micelle, and is a clear and transparent viscoelastic solution; at a pH of 1.00, the micelles formed were large lamellar structures and were milky opaque gels. Namely when the pH value of the regulating system is gradually changed from 5.35 to 1.00, the micelle in the solution realizes the conversion process from the unilamellar vesicle to the multilamellar vesicle, the worm micelle and the lamellar micelle, the vesicle is used for wrapping the medicament, and then the pH is regulated to change the form of the micelle, so that the medicament is released and is used for the slow release and delivery of the medicament.
Example 4
The viscoelastic solutions prepared above with pH 3 and pH 4 were subjected to rheological tests as follows:
the samples at pH 3 and pH 4 were subjected to steady state rheology using a rotary rheometer, and the results are shown in fig. 5. In the low shear rate region, the viscosity of the sample is not substantially changed along with the increase of the shear rate; when the shear rate exceeds a critical value, the sample solution undergoes shear thinning, which is a typical steady-state rheological characteristic of worm micelles. I.e. when pH 3 and pH 4, C10MPAN/MA exists in water mainly as worm micelles. Based on the characteristics, the pseudo gemini surfactant can form a viscoelastic fluid with higher viscosity at the pH value of 3 and the pH value of 4, and can be added into crude oil to serve as a drag reducer, and on one hand, the added drag reducer does not react with an oil product and does not influence the quality of the oil; on the other hand, the addition of the drag reducer can reduce the flow of the crude oil under the turbulent flow conversion stateDynamic resistance, increased pipeline transportation and reduced energy consumption.