阅读说明：本技术 一种松香基co2/n2响应型表面活性剂及其制备方法和应用 (Rosin-based CO2/N2Response type surfactant and preparation method and application thereof ) 是由 饶小平 闫鑫焱 宋湛谦 商士斌 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种松香基CO_2/N_2响应型表面活性剂,由马来海松酸与N,N-二甲基-1,3-丙二胺进行酰亚胺化反应引入可以对CO_2响应的叔胺基团,再与环氧丙醇进行酯化反应引入亲水基团,制备得到的MPANG具有较好的表面活性。MPANG溶于水后向水中通入CO_2,水溶液显弱酸性使得叔胺质子化形成叔胺盐而带正电荷变成阳离子表面活性剂MPANGH~+；通入N_2赶出CO_2后,带正电荷的叔胺盐去质子化恢复到最初的叔胺状态。本发明还公开该类表面活性剂的乳化性能,通入CO_2变成阳离子表面活性剂后乳化性能变好,所得乳液对CO_2/N_2同样具有很好的响应性。此外,不管是非离子表面活性剂还是阳离子表面活性剂所稳定的乳液,只要有带电粒子存在,都可以大大降低表面活性剂的用量。(The invention discloses rosin-based CO 2 /N 2 The response type surfactant is introduced by maleinization reaction of maleopimaric acid and N, N-dimethyl-1, 3-propane diamine to react with CO 2 The reacted tertiary amine group and epoxy propanol are subjected to esterification reaction to introduce a hydrophilic group, and the prepared MPANG has good surface activity. Dissolving MPANG in water, and introducing CO into water 2 The aqueous solution shows weak acidity, so that tertiary amine is protonated to form tertiary amine salt and has positive charge to become cationic surfactant MPANGH + (ii) a Introduction of N 2 Drive out CO 2 Thereafter, the positively charged tertiary amine salt is deprotonated back to the original tertiary amine state. The invention also discloses the emulsifying property of the surfactant, and CO is introduced 2 The emulsion becomes better after being changed into the cationic surfactant, and the obtained emulsion has better emulsifying property to CO 2 /N 2 also has good responsiveness. In addition, emulsions stabilized with either nonionic or cationic surfactants can be greatly reduced in surfactant usage, provided charged particles are present.)

1. Rosin-based CO₂/N₂The responsive surfactant, abbreviated as MPANG, has the following structural formula:

2. The rosin-based CO of claim 1₂/N₂A responsive surfactant characterized by: introducing CO into the aqueous solution of MPANG₂Thereafter, MPANG will protonate to cationic MPANG⁺(ii) a Redirected MPANGH⁺Introducing N into the aqueous solution of₂，MPANGH⁺Deprotonation back to MPANG; MPANG to CO₂/N₂The response process is as follows:

3. the rosin-based CO of claim 1₂/N₂The preparation method of the response type surfactant is characterized by comprising the following steps: the method comprises the following steps:

(1) Performing addition reaction on rosin and maleic anhydride to prepare maleopimaric acid;

(2) Maleopimaric acid and N, N-dimethyl-1, 3-propane diamine are subjected to imidization reaction to generate MPAN;

(3) MPAN and epoxypropanol are subjected to esterification reaction in an absolute ethyl alcohol solvent to obtain MPANG, namely rosin-based CO₂/N₂A responsive surfactant.

4. The production method according to claim 3, characterized in that: in the step (1), the mass ratio of rosin to maleic anhydride is 1 (1-1.5), acetic acid is used as a solvent, the reaction temperature is 120-140 ℃, the reaction time is 3-6 hours, the mixture is added into acetic acid after the reaction is finished and cooled, and the mixture is cooled, crystallized and filtered to obtain the maleopimaric acid.

5. The production method according to claim 3, characterized in that: in the step (2), the mass ratio of the maleopimaric acid to the N, N-dimethyl-1, 3-propane diamine is 1 (1-1.5), ethanol is used as a solvent, the reaction temperature is 60-80 ℃, and the reaction time is 4-6 h.

6. The production method according to claim 3, characterized in that: in the step (3), the mass ratio of MPAN to epoxypropanol is 1 (1-5), triethylamine is used as a catalyst, the mass of triethylamine is 0.5-2 wt% of the total mass of reactants, the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.

7. Rosin-based CO₂/N₂the application of the response type surfactant as an emulsifier in the preparation of response type emulsion.

Technical Field

The invention belongs to the technical field of green surfactants, and particularly relates to rosin-based CO₂/N₂A response type surfactant, a preparation method and application thereof.

Background

The traditional emulsion stabilized by amphiphilic compounds is a thermodynamically unstable system, and the cost is increased due to the fact that a large amount of amphiphilic compounds are required to be added to the emulsion to exist stably for a long time; the Pickering emulsion is an emulsion stabilized by solid particles, is a thermodynamic stable system and has better stability; there are generally two types of particles, including asymmetric surfaces, known as amphiphilic Janus particles, and symmetric surfaces, which are organic or inorganic particles with or without grafted functional groups. In addition, ionic surfactants can also be transferred to oppositely charged particles by electrostatic attraction to render the particles surface active to make Pickering emulsions.

With the development of intelligence, smart responsive surfactants capable of reversibly switching between having and not having surface activity under external stimuli have attracted a wide range of attention, and particles adsorbed by these responsive surfactants can respond to external stimuli such as pH, CO₂Light, heat, and magnetic fields, etc. CO 2₂Is widely welcomed as an environmental-friendly, nontoxic, cheap and easily removable stimulating factor.

However, in the existing reports, most of CO₂The responsive surfactants are also prepared from conventional petroleum-based and commercialized surfactants, which not only are harmful to the environment, but also greatly limit the types of surfactants. With the increasing awareness of environmental protection, the development of green and environmentally friendly CO is urgently needed₂The responsive surfactant replaces petrochemical resources with natural resources. The invention patent with the application number of ' 201810988241.X ' discloses ' rosin-based CO₂/N₂Responsive surfactant, its preparation method and application ", its product MPAGN prepared can not be dissolved in water, has no surface activity, only when CO is introduced₂Then changing it into tertiary amine salt ionic surface activeThe surface active agent can be dissolved in water. The invention is further improved on the basis of the prior art, the prepared product is a water-soluble surfactant with surface activity, and the application range of the rosin-based responsive surfactant can be further expanded.

Disclosure of Invention

the invention aims to provide rosin-based CO₂/N₂A responsive surfactant for preparing CO from rosin as raw material and its preparing process and application₂responsive surfactants, and their use in emulsions, study the mechanism by which ionic and nonionic surfactants stabilize emulsions in the presence of charged particles.

In order to achieve the purpose, the invention provides the following technical scheme:

Rosin-based CO₂/N₂The responsive surfactant, abbreviated as MPANG, has the following structural formula:

Introducing CO into the aqueous solution of MPANG₂Later, the nonionic surfactant MPANG will protonate to the cationic surfactant MPANGH⁺(ii) a Redirected MPANGH⁺Introducing N into the aqueous solution of₂deprotonation of the polymer to convert it back to the nonionic surfactant MPANG, which can be repeated several times; MPANG to CO₂/N₂The response process is as follows:

It is a second object of the present invention to provide the rosin-based CO mentioned above₂/N₂The preparation method of the response type surfactant comprises the following steps:

(1) performing addition reaction on rosin and maleic anhydride to prepare maleopimaric acid; wherein the mass ratio of the rosin to the maleic anhydride is 1 (1-1.5), for example, the ratio can be 1:1,1:1.1,1:1.2,1:1.3,1:1.4,1: 1.5; acetic acid is used as a solvent, and the reaction temperature is 120-140 ℃, such as 120 ℃, 130 ℃ and 140 ℃; the reaction time is 3-6 h, such as 3h, 4h, 5h and 6h, and the maleopimaric acid is obtained.

(2) maleopimaric acid and N, N-dimethyl-1, 3-propane diamine are subjected to imidization reaction to generate MPAN, and the chemical formula of the MPAN is shown as the following formula; wherein the mass ratio of the maleopimaric acid to the N, N-dimethyl-1, 3-propane diamine is 1 (1-1.5), for example, the ratio can be 1:1,1:1.1,1:1.2,1:1.3,1:1.4,1: 1.5; ethanol is used as a solvent, and the reaction temperature is 60-80 ℃, such as 60 ℃,70 ℃ and 80 ℃; the reaction time is 4-6 h, such as 4h, 5h, 6 h:

(3) MPAN and epoxy propanol are subjected to esterification reaction in an absolute ethyl alcohol solvent, triethylamine is used as a catalyst, and MPANG, namely rosin-based CO is obtained₂/N₂A responsive surfactant; wherein the mass ratio of MPAN to epoxypropanol is 1 (1-1.2), for example, the ratio is 1:1,1:1.1,1: 1.2; the amount of triethylamine catalyst is 0.5-2 wt% of the total mass of reactants, such as 0.5%, 1%, 1.5%, 2%; ethanol is used as a solvent, and the reaction temperature is 60-80 ℃, such as 60 ℃,70 ℃ and 80 ℃; the reaction time is 8-12 h, such as 8h,10h and 12 h.

It is a third object of the present invention to provide the rosin-based CO mentioned above₂/N₂The application of the response type surfactant as an emulsifier in the preparation of response type emulsion. And the mechanism of stabilizing the emulsion by ionic and nonionic surfactants is researched under the condition of the existence of charged particles.

MPANG with CO addition₂/N₂the conductivity of the solution can be cyclically changed to prove that the surfactant is applied to CO₂/N₂Has good responsiveness.

Dissolution of MPANG into CO₂The emulsion has good emulsifying property after the aqueous solution is changed into the cationic bicarbonate compared with nonionic, has good stability, and is filled with N at 40-60 ℃, such as 40 ℃, 50 ℃ and 60 DEG₂Stable emulsion willDemulsification occurs immediately, and CO is introduced again after demulsification₂The stable emulsion can be formed again after shearing, and the particle size is basically consistent with that of the previous time. In addition, the water phase after demulsification can be used for emulsifying a new oil phase after being collected, and the particle size is basically consistent with that of the first emulsification, so that the response type surfactant can be recycled.

0.1-1 wt% such as 0.1 wt%, 0.5 wt%, 1 wt% etc. of charged nanoparticles dispersed in MPANG and MPANGH with different concentrations⁺in the aqueous solution, the equal volume of the aqueous phase and the oil phase is subjected to high shearing at 8000-15000 rpm, such as 8000rpm,11000rpm,15000rpm, and the like for 3-10 min, such as 3min,5min,8min,10min, and the like to prepare the emulsion. MPANGH capable of reacting with cation when nanoparticle is negatively charged, such as silica, hectorite, etc⁺The Pickering emulsion is obtained by electrostatic attraction, and the dosage of the surfactant required for stabilizing the emulsion can be greatly reduced compared with the common emulsion (without charged particles); when the nanoparticles are positively charged, such as alumina, calcium carbonate, etc., they can be used in combination with cationic MPANGH⁺A novel emulsion is obtained through electrostatic repulsion, after a cationic surfactant forms a common emulsion, charged particles are dispersed among emulsion drops, the emulsion is stabilized through electrostatic repulsion, the dosage of the surfactant required by the emulsion can be greatly reduced compared with the common emulsion, and the rule is also suitable for other positively charged particles, the cationic surfactant, other negatively charged particles and anionic surfactant, for example, aluminum oxide is dispersed into cetyl trimethyl ammonium bromide solution, and silicon dioxide is dispersed into lauryl sodium sulfate solution. However, when an emulsion is prepared by dispersing charged particles (whether positive or negative) in a nonionic surfactant MPANG, the charged particles are dispersed between emulsion droplets after the nonionic surfactant forms an emulsion, and the emulsion is stabilized by electrostatic repulsion between the charged particles, the amount of the surfactant required for stabilizing the emulsion by the charged particles can be greatly reduced, and other nonionic surfactants are also suitable, such as silica dispersed in Tween 80 solution.

The raw material of the surfactant prepared by the invention is natural rosin, which accords with the concept of green sustainable development, and the ternary phenanthrene skeleton structure of the rosin, CO, is introduced₂/N₂responsive tertiary amines, surfactants of this kind in CO₂/N₂Under stimulation, the catalyst can be reversibly converted between a nonionic surfactant and a cationic surfactant, and CO is introduced₂The emulsion prepared by the cationic surfactant has better emulsifying property to CO₂/N₂Has good responsiveness and the surfactant can be recycled.

The amount of surfactant required to stabilize the emulsion can be greatly reduced when either nonionic or cationic surfactants are added to the charged nanoparticles.

Compared with the prior art, the invention has the beneficial effects that:

(1) The invention combines the structural characteristics of rosin, and synthesizes a rosin-based CO through methods such as imidization, esterification and the like₂/N₂A responsive surfactant MPANG; dissolving MPANG in water, introducing CO into water₂Form H₂CO₃Protonating MPAGN to form cationic tertiary amine carbonate MPANGH⁺Introduction of N₂Post CO₂is discharged, MPANGH⁺Returning to the original tertiary amine state MPANG, this process may be repeated.

(2) Introducing CO into MPAGN aqueous solution₂MPANGH converted to cationic form⁺Then, due to the effect of electrostatic repulsion, MPANGH⁺The emulsifying property of the emulsion is far better than that of MPANG, and the obtained emulsion is also CO-resistant₂/N₂Has good responsiveness and can be used for leading MPANGH to be converted at 40-60 DEG C⁺Introducing N into the stabilized emulsion₂The emulsion is immediately broken after the emulsion is broken, and CO is introduced again after the emulsion is broken₂The stable emulsion can be formed again after shearing, and the particle size is basically consistent with that of the previous time. In addition, the water phase after demulsification can be used for emulsifying a new oil phase after being collected, and the particle size is basically consistent with that of the first emulsification, so that the response type surfactant can be recycled.

(3) Cation MPANGH⁺Can be combined with nano silicon dioxide with negative electricity in water through electrostatic action to prepare Pickering emulsion under the condition of high shearing, and can also be combined with nano silicon dioxide with positive electricity in waterThe nano-alumina stabilizes the emulsion through electrostatic repulsion between the surfactant and the charged particles, when the charged particles exist, the amount of the nonionic surfactant required for stabilizing the emulsion can be greatly reduced, after the nonionic surfactant forms the traditional emulsion, the charged particles are dispersed among emulsion drops, and the emulsion is stabilized through the electrostatic repulsion between the charged particles, so that the dosage of the surfactant required for preparing the emulsion can be greatly reduced no matter what type of surfactant exists as long as the charged particles exist.

Drawings

FIG. 1 shows MPANG¹H NMR spectrum;

FIG. 2MPANG with CO₂/N₂Cyclic variation of post conductivity with alternating passes (pure water for comparison);

FIG. 3 is an appearance diagram of the emulsion obtained in example 4;

FIG. 4 is an appearance diagram of the emulsion obtained in example 5.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.