CN114854431B - A kind of intelligent Pickering emulsion based on dynamic covalent bond and preparation method thereof - Google Patents

A kind of intelligent Pickering emulsion based on dynamic covalent bond and preparation method thereof Download PDF

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CN114854431B
CN114854431B CN202210573951.2A CN202210573951A CN114854431B CN 114854431 B CN114854431 B CN 114854431B CN 202210573951 A CN202210573951 A CN 202210573951A CN 114854431 B CN114854431 B CN 114854431B
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崔正刚
刘佩
裴晓梅
吴俊辉
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Abstract

The invention discloses an intelligent Pickering emulsion based on dynamic covalent bonds and a preparation method thereof, belonging to the field of colloid and interface chemistry. The invention utilizes a surfactant system (H) + AA and FA) and oppositely charged SiO 2 The particles act to form surface active particles with pH as a trigger mechanism, and the Pickering emulsion is synergistically stabilized; bola compounds which are "strongly polar" under alkaline conditions, which compounds do not possess surface activity and cannot synergistically act on SiO 2 The granules stabilize Pickering emulsions; the intelligent conversion of the compound from 'amphiphilicity', 'strong polarity' and the conversion of the emulsion from 'milk formation' to 'non-milk formation' are realized, and the circulation times are six times; meanwhile, the surfactant does not remain in the oil phase, so that the recovery and the reutilization of the surfactant are realized, and the surfactant has important roles in the fields of oil transportation, emulsion polymerization, nano material synthesis, heterogeneous catalysis, oil exploitation, cosmetics, food science and the like.

Description

一种基于动态共价键的智能Pickering乳状液及其制备方法Intelligent Pickering emulsion based on dynamic covalent bond and preparation method thereof

技术领域Technical Field

本发明属于胶体与界面化学领域,具体涉及一种基于动态共价键的智能Pickering乳状液及其制备方法。The invention belongs to the field of colloid and interface chemistry, and specifically relates to an intelligent Pickering emulsion based on dynamic covalent bonds and a preparation method thereof.

背景技术Background Art

近年来,随着纳米技术的快速发展,由胶体颗粒或者表面活性颗粒稳定的Pickering乳状液引起了人们的广泛关注。胶体颗粒可以在油水界面处紧密的排列,因此使得Pickering乳状液具有超强的稳定性。然而,当将其应用于油品运输、乳液聚合、纳米材料合成以及非均相催化等领域时,这种超强的稳定性又为其破乳带来了巨大的挑战,为此催生了一种具有刺激响应性能的Pickering乳状液。In recent years, with the rapid development of nanotechnology, Pickering emulsions stabilized by colloidal particles or surfactant particles have attracted widespread attention. Colloidal particles can be tightly arranged at the oil-water interface, making Pickering emulsions extremely stable. However, when it is applied to oil transportation, emulsion polymerization, nanomaterial synthesis, and heterogeneous catalysis, this super stability brings great challenges to its demulsification, which has spawned a Pickering emulsion with stimulus-responsive properties.

刺激-响应性Pickering乳状液的形成往往依靠具有刺激-响应性的表面活性剂。目前报道的刺激方式包括pH、氧化还原、CO2/N2、温度、离子对、磁和光等,主要的调控方式是将极性基团转变为非极性基团或者弱极性基团。然而在乳液体系中,这种类型的调控方式会使得表面活性剂在失活后转移到油相中,这不仅会污染油相,而且不利于表面活性剂的回收和再利用。已经报道的,可以在“双亲性”和“强极性”之间智能转换的表面活性剂,其主要的调控方式是将弱极性基团转变为极性基团,从而使表面活性剂亲水性过强,在失去表面活性后溶于水中,实现了表面活性剂的回收和再利用。然而,该类表面活性剂的合成过程又比较复杂,不仅转化率极低(约15.16%)而且涉及诸多有机溶剂的使用,合成过程不够“绿色”,极大地限制了其在石油开采、化妆品以及食品科学等领域的应用。The formation of stimulus-responsive Pickering emulsions often relies on surfactants with stimulus-responsiveness. The stimulus methods reported so far include pH, redox, CO 2 /N 2 , temperature, ion pairs, magnetism and light, and the main control method is to convert polar groups into non-polar groups or weak polar groups. However, in the emulsion system, this type of control method will cause the surfactant to transfer to the oil phase after inactivation, which will not only pollute the oil phase, but also be unfavorable for the recovery and reuse of the surfactant. Surfactants that can be intelligently converted between "amphiphilic" and "strong polarity" have been reported. The main control method is to convert weak polar groups into polar groups, so that the surfactant is too hydrophilic and dissolves in water after losing its surface activity, thus realizing the recovery and reuse of the surfactant. However, the synthesis process of this type of surfactant is relatively complicated. Not only is the conversion rate extremely low (about 15.16%), but it also involves the use of many organic solvents. The synthesis process is not "green" enough, which greatly limits its application in fields such as oil extraction, cosmetics and food science.

因此,开发出一种“环境友好”的“可循环使用”的乳化剂工艺至关重要。Therefore, it is very important to develop an "environmentally friendly" and "recyclable" emulsifier process.

发明内容Summary of the invention

技术问题Technical issues

一般的刺激响应性表面活性剂通过调控其极性基团使其在“有表面活性”和“无表面活性”之间转换,但这种调控方式往往使得表面活性剂在失活后溶于油相,不仅影响油相的品质,而且不利于表面活性剂的回收和再利用。现有的可以实现回收和再利用的表面活性剂,又存在合成过程复杂,合成成本高,转化率低,合成过程“不绿色”,应用领域受限等问题。除此之外,由常规表面活性剂稳定的乳状液,还存在稳定性较差,使用浓度过高等缺点。Generally, stimulus-responsive surfactants switch between "surfactant" and "non-surfactant" by regulating their polar groups. However, this regulation method often causes the surfactant to dissolve in the oil phase after deactivation, which not only affects the quality of the oil phase, but also is not conducive to the recovery and reuse of the surfactant. Existing surfactants that can be recycled and reused have problems such as complex synthesis process, high synthesis cost, low conversion rate, "ungreen" synthesis process, and limited application fields. In addition, emulsions stabilized by conventional surfactants have disadvantages such as poor stability and excessively high concentrations.

因此,本发明试图提供一种基于动态共价键的智能Pickering乳状液,解决上述问题。该Pickering乳状液由阳离子表面活性剂H+AA(可以在“双亲性”和“强极性”之间转换)和带相反电荷的SiO2颗粒协同稳定,将合成简单,合成成本低,合成过程绿色,乳液稳定性好,使用浓度低,可循环使用等诸多优势融为一体。其中,动态共价键的引入使表面活性剂可以在“双亲性”和“强极性”之间智能转换。酸性条件下,表面活性剂(H+AA)保留双亲性,具有表面活性;碱性条件下,表面活性剂和另一种物质形成Bola化合物(FA-AA),表现出“强极性”,失去表面活性,溶于水中。整个过程可以进行多次循环,实现“双亲性”和“强极性”的智能转换,且表面活性剂始终处在水溶液中,方便回收和再利用。Therefore, the present invention attempts to provide a smart Pickering emulsion based on dynamic covalent bonds to solve the above problems. The Pickering emulsion is synergistically stabilized by a cationic surfactant H + AA (which can be converted between "amphiphilicity" and "strong polarity") and SiO2 particles with opposite charges, which integrates many advantages such as simple synthesis, low synthesis cost, green synthesis process, good emulsion stability, low concentration, and recyclable use. Among them, the introduction of dynamic covalent bonds enables the surfactant to be intelligently converted between "amphiphilicity" and "strong polarity". Under acidic conditions, the surfactant (H + AA) retains amphiphilicity and has surface activity; under alkaline conditions, the surfactant and another substance form a Bola compound (FA-AA), which exhibits "strong polarity", loses surface activity, and dissolves in water. The whole process can be cycled multiple times to achieve intelligent conversion of "amphiphilicity" and "strong polarity", and the surfactant is always in an aqueous solution, which is convenient for recycling and reuse.

技术方案Technical Solution

本发明利用一种基于动态共价键的表面活性体系(H+AA和FA),该表面活性体系具有“双亲性”,可与带相反电荷的SiO2颗粒作用形成以pH为触发机制的表面活性颗粒,选用正癸烷作为油相,在11000r/min转速下均质2min,便可以制备得到稳定的Pickering乳状液。再交替加入酸碱,转换溶液中表面活性剂的结构,形成“强极性”Bola化合物FA-AA,该化合物因其较强的亲水性无法与SiO2颗粒一起稳定乳状液;则可使表面活性颗粒在“双亲性”和“强极性”,也即“有表面活性”和“无表面活性”之间转换。向体系中加入适量的酸,FA-AA中动态共价键则会发生断裂,生成“双亲性”阳离子型表面活性剂H+AA和FA,从而实现循环。值得注意的是,FA在此循环过程中起到了相当大的作用,不仅赋予了表面活性剂刺激响应性能,而且也是该体系得以循环的关键。同时,在乳状液破乳后,更换新鲜的油相,验证表面活性剂是否溶解在油相中,被破乳后的正癸烷带走。The present invention utilizes a surfactant system (H + AA and FA) based on dynamic covalent bonds. The surfactant system has "amphiphilicity" and can react with SiO2 particles with opposite charges to form surfactant particles with pH as the trigger mechanism. Select n-decane as the oil phase and homogenize at a speed of 11000r/min for 2min to prepare a stable Pickering emulsion. Then, acid and alkali are added alternately to convert the structure of the surfactant in the solution to form a "strong polarity" Bola compound FA-AA, which cannot stabilize the emulsion with SiO2 particles due to its strong hydrophilicity; the surfactant particles can be converted between "amphiphilicity" and "strong polarity", that is, "surface active" and "non-surface active". Add an appropriate amount of acid to the system, and the dynamic covalent bonds in FA-AA will break, generating "amphiphilic" cationic surfactants H + AA and FA, thereby realizing circulation. It is worth noting that FA plays a considerable role in this circulation process, not only giving the surfactant stimulus response performance, but also being the key to the circulation of the system. At the same time, after the emulsion is broken, the fresh oil phase is replaced to verify whether the surfactant is dissolved in the oil phase and taken away by the n-decane after the emulsion is broken.

本发明的第一个目的是提供一种基于动态共价键的智能Pickering乳状液,所述智能Pickering乳状液的制备方法是将水相、亲水性SiO2颗粒、表面活性体系与油相混合均质制得;The first object of the present invention is to provide a smart Pickering emulsion based on dynamic covalent bonds, wherein the preparation method of the smart Pickering emulsion is to mix and homogenize a water phase, hydrophilic SiO2 particles, a surfactant system and an oil phase;

所述表面活性体系由组分H+AA、FA组成:The surfactant system is composed of components H + AA, FA:

Figure BDA0003659968670000021
Figure BDA0003659968670000021

其中,n=7~9,X为Cl或Br。Wherein, n=7-9, and X is Cl or Br.

在本发明的一种实施方式中,两种组分的摩尔比为1:1。In one embodiment of the present invention, the molar ratio of the two components is 1:1.

在本发明的一种实施方式中,表面活性体系的制备方法,所述方法如下:In one embodiment of the present invention, a method for preparing a surfactant system is as follows:

Figure BDA0003659968670000022
Figure BDA0003659968670000022

利用氨基烷基酸AA与FA在碱性条件下,常温反应形成共价键,得到FA-AA;然后FA-AA在酸HX的作用下获得表面活性剂体系;表面活性体系又能在碱性作用下再次恢复得到FA-AA,从而实现表面活性体系的重复使用。Aminoalkyl acid AA and FA react under alkaline conditions at room temperature to form a covalent bond to obtain FA-AA; then FA-AA obtains a surfactant system under the action of acid HX; the surfactant system can be restored again under the action of alkalinity to obtain FA-AA, thereby realizing the reuse of the surfactant system.

在本发明的一种实施方式中,所述方法中的AA是一种含伯胺的,常温下可与醛基形成动态共价键并在碱性条件下带负电荷的化合物。In one embodiment of the present invention, the AA in the method is a compound containing a primary amine, which can form a dynamic covalent bond with an aldehyde group at room temperature and has a negative charge under alkaline conditions.

在本发明的一种实施方式中,所述方法中的FA是一种含苯环的,常温下可与伯胺形成动态共价键并在碱性条件下带负电荷的化合物。In one embodiment of the present invention, the FA in the method is a compound containing a benzene ring, which can form a dynamic covalent bond with a primary amine at room temperature and has a negative charge under alkaline conditions.

在本发明的一种实施方式中,所述方法中的碱性pH值为10~13,优选11~12。In one embodiment of the present invention, the alkaline pH value in the method is 10-13, preferably 11-12.

在本发明的一种实施方式中,所述方法中的反应温度为常温。In one embodiment of the present invention, the reaction temperature in the method is room temperature.

在本发明的一种实施方式中,所述方法中的反应时间为≥30min,以保证充分反应。In one embodiment of the present invention, the reaction time in the method is ≥30 min to ensure sufficient reaction.

在本发明的一种实施方式中,所述方法中的反应条件为搅拌。In one embodiment of the present invention, the reaction condition in the method is stirring.

在本发明的一种实施方式中,所述方法中的FA-AA具有较强的亲水性。In one embodiment of the present invention, the FA-AA in the method has strong hydrophilicity.

在本发明的一种实施方式中,所述方法中的酸性pH值为3~5。In one embodiment of the present invention, the acidic pH value in the method is 3-5.

在本发明的一种实施方式中,所述方法中的H+AA为表面活性剂。In one embodiment of the present invention, the H + AA in the method is a surfactant.

在本发明的一种实施方式中,表面活性体系通过以下过程实现智能响应:In one embodiment of the present invention, the surfactant system achieves intelligent response through the following process:

Figure BDA0003659968670000031
Figure BDA0003659968670000031

在本发明的一种实施方式中,碱的pH值为10~13,优选11~12;酸的pH值为3~5。In one embodiment of the present invention, the pH value of the base is 10-13, preferably 11-12; the pH value of the acid is 3-5.

在本发明的一种实施方式中,亲水性SiO2颗粒相对水相的质量浓度为0.001%~3%。In one embodiment of the present invention, the mass concentration of the hydrophilic SiO2 particles relative to the aqueous phase is 0.001% to 3%.

在本发明的一种实施方式中,表面活性体系,以FA计,相对水相的浓度为0.01~10mmol/L。In one embodiment of the present invention, the concentration of the surfactant system, calculated as FA, relative to the aqueous phase is 0.01 to 10 mmol/L.

在本发明的一种实施方式中,所述油相包括如下任意一种或多种:正癸烷、甲苯、三辛酸甘油酯。In one embodiment of the present invention, the oil phase comprises any one or more of the following: n-decane, toluene, and tricaprylin.

本发明另一个目的是将上述的基于动态共价键的智能Pickering乳状液应用于油品运输、乳液聚合、纳米材料合成、非均相催化、石油开采、化妆品以及食品科学等领域中。Another object of the present invention is to apply the above-mentioned intelligent Pickering emulsion based on dynamic covalent bonds to the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil extraction, cosmetics and food science.

有益效果Beneficial Effects

本发明利用表面活性体系(H+AA和FA),该表面活性体系具有“双亲性”,可与带相反电荷的SiO2颗粒作用形成以pH为触发机制的表面活性颗粒,协同SiO2颗粒稳定Pickering乳状液;在碱性条件下呈“强极性”的Bola化合物,该化合物不具备表面活性,无法协同SiO2颗粒稳定Pickering乳状液。实现了化合物从到“双亲性”“强极性”的智能转换和乳状液从“成乳”到“不成乳”的转换,而且这一转换可加以循环,循环次数可达六次。同时,通过对破乳后的油相进行紫外吸光度检测,证明表面活性剂没有残留在油相中,实现了表面活性剂的回收和再利用。这一特性在油品运输、乳液聚合、纳米材料合成、非均相催化、石油开采、化妆品以及食品科学等领域中具有重要的作用。The present invention utilizes a surfactant system (H + AA and FA), which has "amphiphilicity" and can react with SiO2 particles with opposite charges to form surfactant particles with pH as the trigger mechanism, and cooperate with SiO2 particles to stabilize Pickering emulsions; Bola compounds that are "strongly polar" under alkaline conditions do not have surface activity and cannot cooperate with SiO2 particles to stabilize Pickering emulsions. The intelligent conversion of compounds from "amphiphilicity" to "strong polarity" and the conversion of emulsions from "emulsification" to "non-emulsification" are realized, and this conversion can be recycled up to six times. At the same time, by detecting the ultraviolet absorbance of the oil phase after demulsification, it is proved that the surfactant does not remain in the oil phase, and the recovery and reuse of the surfactant is realized. This characteristic plays an important role in the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil extraction, cosmetics, and food science.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为Bola化合物FA-AA的ESI-MS谱图。Figure 1 is the ESI-MS spectrum of Bola compound FA-AA.

图2为Bola化合物FA-AA的1H NMR谱图(60mM,pH=12.00,D2O)。FIG2 is the 1 H NMR spectrum of Bola compound FA-AA (60 mM, pH=12.00, D 2 O).

图3为(A)FA-AA,(B)AA和(C)FA的1H NMR谱图对比(60mM,pH=12.00,D2O)。FIG3 is a comparison of 1 H NMR spectra of (A) FA-AA, (B) AA, and (C) FA (60 mM, pH=12.00, D 2 O).

图4为(A)FA-AA,(B)AA和(C)FA的FT-IR谱图对比(pH=12.00)。FIG4 is a comparison of FT-IR spectra of (A) FA-AA, (B) AA and (C) FA (pH = 12.00).

图5为表面活性剂H+AA的1HNMR谱图(60mM,pH=4.00,DMSO)。FIG5 is the 1 H NMR spectrum of the surfactant H + AA (60 mM, pH=4.00, DMSO).

图6为纳米SiO2颗粒的(a)SEM和(b)TEM以及(c)Zeta电位随pH值的变化图。FIG. 6 shows (a) SEM and (b) TEM of nano-SiO 2 particles and (c) Zeta potential as a function of pH value.

图7为单独纳米SiO2颗粒(0.1wt.%,相对于水相)稳定的正癸烷/水(3mL/3mL)乳状液的外观照片。FIG. 7 is a photograph showing the appearance of a n-decane/water (3 mL/3 mL) emulsion stabilized by nano-SiO 2 particles alone (0.1 wt.%, relative to the aqueous phase).

图8为0.1wt.%纳米SiO2颗粒和不同浓度H+AA稳定的正癸烷/水Pickering乳状液的(A和B)外观照片和(C)显微照片。其中,A为打乳后立即拍摄,(B和C)为乳液稳定24h后拍摄。Figure 8 shows (A and B) appearance photos and (C) microphotographs of n-decane/water Pickering emulsions stabilized with 0.1wt.% nano- SiO2 particles and different concentrations of H + AA, where A was taken immediately after emulsification, and (B and C) were taken after the emulsions were stabilized for 24 hours.

图9为0.1wt.%纳米SiO2颗粒和不同浓度H+AA稳定的正癸烷/水Pickering乳状液的(A)外观照片和(B)显微照片。其中,A和B均为稳定一个月后拍摄。Figure 9 shows (A) appearance photos and (B) microscopic photos of n-decane/water Pickering emulsions stabilized with 0.1 wt.% nano-SiO 2 particles and different concentrations of H + AA. Both A and B were taken after stabilization for one month.

图10为乳状液刺激响应流程。添加HCl和NaOH进行开关:(a)初始溶液,(b)添加正癸烷并均质2min,(c)分离上层析出油相并添加HCl进行酸化,(d)添加新鲜正癸烷并均质2min。Figure 10 shows the emulsion stimulus response process. Switching by adding HCl and NaOH: (a) initial solution, (b) adding n-decane and homogenizing for 2 min, (c) separating the upper oil phase and adding HCl for acidification, (d) adding fresh n-decane and homogenizing for 2 min.

图11为0.1wt.%纳米SiO2颗粒与0.6mM H+AA稳定的Pickering乳状液的(A)外观照片和(B)显微照片。通过添加HCl和NaOH进行开或关循环。Figure 11 shows (A) appearance photos and (B) micrographs of Pickering emulsions stabilized with 0.1 wt.% nano-SiO 2 particles and 0.6 mM H + AA. On or off cycles were performed by adding HCl and NaOH.

图12为纳米SiO2颗粒与表面活性剂H+AA稳定智能Pickering乳状液的机理图。Figure 12 is a mechanism diagram of nano- SiO2 particles and surfactant H + AA stabilizing smart Pickering emulsion.

图13为(a)不同浓度FA-AA水溶液的吸光度-波长扫描曲线(pH=12.00);(b)不同浓度FA-AA水溶液在波长为296nm处的吸光度-浓度标准曲线(pH=12.00)。Figure 13 is (a) the absorbance-wavelength scanning curve of FA-AA aqueous solution with different concentrations (pH = 12.00); (b) the absorbance-concentration standard curve of FA-AA aqueous solution with different concentrations at a wavelength of 296 nm (pH = 12.00).

具体实施方式DETAILED DESCRIPTION

乳状液外观照片使用数码相机或手机拍摄;乳状液显微照片使用基恩士(香港)有限公司的超景深三维显微镜拍摄,下光源,放大倍数为250~2500倍,测试的温度25℃。The emulsion appearance photos are taken with a digital camera or mobile phone; the emulsion micrographs are taken with a super-depth-of-field three-dimensional microscope of Keyence (Hong Kong) Co., Ltd., with a lower light source, a magnification of 250 to 2500 times, and a test temperature of 25°C.

实施例1:Embodiment 1:

Bola化合物FA-AA的合成路线如下:The synthetic route of Bola compound FA-AA is as follows:

Figure BDA0003659968670000051
Figure BDA0003659968670000051

将等摩尔量的FA和AA,以及2倍摩尔量的NaOH加入到100mL的容量瓶中,并使用超纯水定容。然后调节溶液pH至12.00,加入磁子,搅拌半个小时以确保反应完全。最后,得到由动态共价键构筑的FA-AA的水溶液。FA-AA的ESI-MS,1H NMR和FT-IR谱图,见图1-4。Equimolar amounts of FA and AA and 2 times the molar amount of NaOH were added to a 100 mL volumetric flask and fixed to volume with ultrapure water. The pH of the solution was then adjusted to 12.00, a magnetic particle was added, and stirred for half an hour to ensure that the reaction was complete. Finally, an aqueous solution of FA-AA constructed by dynamic covalent bonds was obtained. The ESI-MS, 1 H NMR and FT-IR spectra of FA-AA are shown in Figures 1-4.

同样的,将11-氨基十一酸分别替换为10-氨基癸酸和12-氨基十二酸,可获得相应的Bola化合物10-FA-AA和12-FA-AA。Similarly, by replacing 11-aminoundecanoic acid with 10-aminodecanoic acid and 12-aminododecanoic acid, the corresponding Bola compounds 10-FA-AA and 12-FA-AA can be obtained.

实施例2:表面活性体系的制备Example 2: Preparation of surfactant system

将10mmol 11-氨基十一酸加入到100mL的容量瓶中,并使用超纯水定容。然后使用浓度为2M的盐酸溶液调节体系pH至4.00,加入磁子,搅拌半个小时以确保质子化完全。最后,得到表面活性剂11-H+AA的水溶液。表面活性剂的1H NMR见图5。10 mmol of 11-aminoundecanoic acid was added to a 100 mL volumetric flask and made up to volume with ultrapure water. Then, a 2 M hydrochloric acid solution was used to adjust the system pH to 4.00, a magnetic particle was added, and stirred for half an hour to ensure complete protonation. Finally, an aqueous solution of surfactant 11-H + AA was obtained. The 1 H NMR of the surfactant is shown in Figure 5.

同样的,将11-氨基十一酸分别替换为10-氨基壬酸和12-氨基十二酸,可获得相应的表面活性剂10-H+AA和12-H+AA。Similarly, by replacing 11-aminoundecanoic acid with 10-aminononanoic acid and 12-aminododecanoic acid, the corresponding surfactants 10-H + AA and 12-H + AA can be obtained.

分别将10-H+AA、11-H+AA和12-H+AA与等摩尔的FA复合,得到表面活性体系。10-H + AA, 11-H + AA and 12-H + AA were respectively compounded with equimolar FA to obtain a surfactant system.

实施例3:纳米SiO2颗粒的表面活性检验Example 3: Surface activity test of nano- SiO2 particles

在一个10mL的玻璃瓶中,称取0.003g商品纳米SiO2颗粒(原生粒径约20nm,比表面积SBET约为200±20m2/g,SEM和TEM见图6),加入3mL的超纯水,然后用超声分散器将颗粒分散均匀(0.1wt.%)。再向玻璃瓶中加入3mL正癸烷,然后使用高剪切均质机在11000r/min转速下均质乳化2min,如图7所示,不能得到稳定的乳状液,表明所用的商用纳米SiO2颗粒不具有表面活性。In a 10mL glass bottle, 0.003g of commercial nano- SiO2 particles (primary particle size of about 20nm, specific surface area S BET of about 200± 20m2 /g, SEM and TEM see Figure 6) were weighed, 3mL of ultrapure water was added, and then the particles were evenly dispersed (0.1wt.%) using an ultrasonic disperser. 3mL of n-decane was added to the glass bottle, and then a high shear homogenizer was used for homogenization and emulsification at a speed of 11000r/min for 2min. As shown in Figure 7, no stable emulsion could be obtained, indicating that the commercial nano- SiO2 particles used were not surface active.

实施例4:Pickering乳状液的制备Example 4: Preparation of Pickering emulsion

称取0.003g的纳米SiO2颗粒超声分散于3mL不同浓度表面活性体系(以FA计,相对水相的浓度分别为0.01mM、0.03mM、0.06mM、0.1mM、0.3mM、0.6mM、1.0mM、3.0mM、6.0mM)中,加入3mL正癸烷,用高剪切均质机均质乳化2min后,得到稳定的O/W型Pickering乳状液,如图8所示。该乳状液放置一个月后,未发生乳析或破乳现象,表明所得Pickering乳状液具有非常好的稳定性,如图9所示。0.003 g of nano-SiO 2 particles were ultrasonically dispersed in 3 mL of surfactant systems with different concentrations (in terms of FA, the concentrations relative to the aqueous phase were 0.01 mM, 0.03 mM, 0.06 mM, 0.1 mM, 0.3 mM, 0.6 mM, 1.0 mM, 3.0 mM, and 6.0 mM, respectively), and 3 mL of n-decane was added. After homogenization and emulsification with a high shear homogenizer for 2 minutes, a stable O/W Pickering emulsion was obtained, as shown in Figure 8. After the emulsion was placed for one month, no emulsion or demulsification occurred, indicating that the obtained Pickering emulsion had very good stability, as shown in Figure 9.

实施例5:Pickering乳状液的pH刺激-响应性能Example 5: pH stimulus-response properties of Pickering emulsions

为了方便实验的进行,按照图10的流程进行测试。In order to facilitate the experiment, the test was performed according to the process in Figure 10.

以0.1wt.%纳米SiO2颗粒与0.6mM FA-AA为基准进行研究。称取0.003g的纳米SiO2颗粒超声分散于0.6mM FA-AA溶液中(pH=12.00),加入7mL正癸烷,用高剪切均质机均质2min,不能形成稳定的Pickering乳状液。将上层析出的油相分离出来,然后向下层的水相中加入50μL 20mM HCl溶液,再加入3mL新鲜的正癸烷,用高剪切均质机均质2min后,形成稳定的O/W型Pickering乳状液,将乳状液放置在25℃恒温箱中,静置24h考察其稳定性。交替加入NaOH和HCl,可以实现至少6次循环,如图11所示。机理图见图12。The study was conducted based on 0.1wt.% nano-SiO 2 particles and 0.6mM FA-AA. Weigh 0.003g of nano-SiO 2 particles and ultrasonically disperse them in 0.6mM FA-AA solution (pH=12.00), add 7mL of n-decane, and homogenize with a high shear homogenizer for 2min. No stable Pickering emulsion can be formed. The oil phase precipitated from the upper layer is separated, and then 50μL of 20mM HCl solution is added to the aqueous phase of the lower layer, and then 3mL of fresh n-decane is added. After homogenizing with a high shear homogenizer for 2min, a stable O/W type Pickering emulsion is formed. The emulsion is placed in a 25℃ thermostat and left to stand for 24h to investigate its stability. Alternating the addition of NaOH and HCl can achieve at least 6 cycles, as shown in Figure 11. The mechanism diagram is shown in Figure 12.

实施例6:不同表面活性剂的乳化性能Example 6: Emulsification properties of different surfactants

参照实施例3,称取0.003g的纳米SiO2颗粒超声分散于3mL 0.6mM表面活性体系中,加入3mL正癸烷,用高剪切均质机均质乳化2min后,得到稳定的O/W型Pickering乳状液。Referring to Example 3, 0.003 g of nano-SiO 2 particles were weighed and ultrasonically dispersed in 3 mL of 0.6 mM surfactant system, 3 mL of n-decane was added, and the mixture was homogenized and emulsified with a high shear homogenizer for 2 min to obtain a stable O/W Pickering emulsion.

仅替换表面活性剂为10-H+AA(n=7)和12-H+AA(n=9),其他条件不变,所得相应的Pickering乳状液。将所得的乳状液常温放置,测定其稳定性。Only the surfactants were replaced with 10-H + AA (n=7) and 12-H + AA (n=9), and other conditions remained unchanged, and the corresponding Pickering emulsions were obtained. The obtained emulsions were placed at room temperature to determine their stability.

参照实施例4,通过调节pH测试pH响应性能。所得乳状液的性能结果见表1。The pH response performance was tested by adjusting the pH with reference to Example 4. The performance results of the obtained emulsion are shown in Table 1.

表1不同表面活性剂的乳化性能结果Table 1 Emulsification performance results of different surfactants

Figure BDA0003659968670000061
Figure BDA0003659968670000061

实施例7:油相中残留表面活性剂的检测Example 7: Detection of residual surfactant in oil phase

使用紫外分光光度计进行检测,如图13所示,检测出不同浓度FA-AA的最大吸收波长和最大吸收波长处的吸光度。从图13(a)可以看出,FA-AA有两个最大吸收波长,考虑到E1带的吸收强度较大,不易将吸光度控制在1以内,因此选择E2吸收带下的最大吸收波长(λmax=296nm)作为实验依据。然后,根据不同浓度FA-AA在这一吸收波长下的吸光度绘制出吸光度-浓度标准曲线(图13(b))。拟合曲线的方程式为y=1.7333x,方差r2=0.9995。The UV spectrophotometer was used for detection. As shown in FIG13 , the maximum absorption wavelength and the absorbance at the maximum absorption wavelength of FA-AA of different concentrations were detected. As can be seen from FIG13 (a), FA-AA has two maximum absorption wavelengths. Considering that the absorption intensity of the E1 band is relatively large, it is not easy to control the absorbance within 1. Therefore, the maximum absorption wavelength under the E2 absorption band (λ max = 296nm) was selected as the experimental basis. Then, the absorbance-concentration standard curve was drawn according to the absorbance of FA-AA of different concentrations at this absorption wavelength ( FIG13 (b) ). The equation of the fitting curve is y = 1.7333x, and the variance r 2 = 0.9995.

收集每次循环分离出来的油相,检测其紫外吸光度,并测定其与超纯水之间的界面张力,测试结果如表2所示。The oil phase separated in each cycle was collected, its UV absorbance was detected, and the interfacial tension between it and ultrapure water was measured. The test results are shown in Table 2.

表2新鲜正癸烷和每次破乳后分离出正癸烷的紫外吸光度Table 2 UV absorbance of fresh n-decane and n-decane separated after each demulsification

Figure BDA0003659968670000062
Figure BDA0003659968670000062

Figure BDA0003659968670000071
Figure BDA0003659968670000071

分离出来的油相的总吸光度为0.098,这意味着六次循环有9.4%的FA被损失掉,这在一定程度上会影响H+AA的回收和再利用,可能这也是为什么只能循环六次的原因,当然除此之外,还会受到稀释作用和积累的NaCl的影响。The total absorbance of the separated oil phase was 0.098, which means that 9.4% of FA was lost after six cycles, which would affect the recovery and reuse of H + AA to a certain extent. This may be the reason why it can only be cycled six times. Of course, in addition to this, it will also be affected by the dilution effect and accumulated NaCl.

Claims (9)

1. A method for preparing intelligent Pickering emulsion based on dynamic covalent bonds is characterized in that aqueous phase and hydrophilic SiO 2 Mixing the particles, the surface active system and the oil phase, and homogenizing to obtain the product;
the saidThe surface active system is composed of a component H + AA. FA composition:
Figure FDA0004154822690000011
wherein n=7 to 9, and x is Cl or Br;
dynamic covalent bonding refers to:
Figure FDA0004154822690000012
intelligence refers to intelligent switching between amphiphilicity and strong polarity.
2. The method of claim 1, wherein the hydrophilic SiO 2 The mass concentration of the particles relative to the water phase is 0.001-3%.
3. The process according to claim 1, wherein the concentration of the surface-active system, calculated as FA, relative to the aqueous phase is from 0.01 to 10mmol/L.
4. The method of claim 1, wherein the oil phase comprises any one or more of: n-decane, toluene, glyceryl tricaprylate.
5. The method according to claim 1, wherein the molar ratio of the two components in the surface-active system is 1:1.
6. the method according to claim 1, characterized in that the method for preparing the surface-active system is as follows:
Figure FDA0004154822690000013
reacting amino alkyl acid AA and FA under alkaline condition at normal temperature to form covalent bond to obtain FA-AA; then FA-AA is subjected to the action of acid HX to obtain a surfactant system; the surface active system can be recovered again under the alkaline action to obtain FA-AA for repeated use.
7. An intelligent Pickering emulsion prepared by the method of any one of claims 1-6; wherein the surfactant system achieves intelligent response by:
Figure FDA0004154822690000021
8. the intelligent Pickering emulsion of claim 7, wherein the pH of the base is 10 to 13; the pH value of the acid is 3-5.
9. Use of the intelligent Pickering emulsion of claim 7 in the fields of oil transportation, emulsion polymerization, nanomaterial synthesis, heterogeneous catalysis, oil exploitation, cosmetics, food science, and the like.
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