阅读说明：本技术 苦皮藤素水乳剂的制备方法 (Preparation method of celastrus angulatus aqueous emulsion ) 是由 孙正杰 韦永宏 于 2019-09-30 设计创作，主要内容包括：本发明提供一种苦皮藤素水乳剂的制备方法,其包括以下步骤：1)构建反应容器,所述反应容器为圆筒状结构,所述反应容器的上下两端均设置有密封板以将反应容器围成密闭空间,所述反应容器的上、下端分别设置有连续相出口和连续相进口,所述反应容器中设置有单层线圈状的分散相挤出管,相邻两层分散相挤出管间首尾连通；2)将去离子水与乳化剂混合均匀,然后从连续相进口输入,并使其从连续相出口输出；3)将苦皮藤素与溶剂混合均匀,然后恒压通入所述分散相挤出管的始端以使分散相从挤出孔中挤出与连续相结合,所述连续相出口输出所述苦皮藤素水乳剂。本发明方法具有制备效率高、制备的水乳剂的粒径大小较均匀等特点。(The invention provides a preparation method of celastrus angulatus aqueous emulsion, which comprises the following steps: 1) constructing a reaction vessel, wherein the reaction vessel is of a cylindrical structure, sealing plates are arranged at the upper end and the lower end of the reaction vessel to enclose the reaction vessel into a closed space, a continuous phase outlet and a continuous phase inlet are respectively arranged at the upper end and the lower end of the reaction vessel, a single-layer coiled dispersed phase extrusion pipe is arranged in the reaction vessel, and the adjacent two layers of dispersed phase extrusion pipes are communicated end to end; 2) uniformly mixing deionized water and an emulsifier, inputting the mixture from a continuous phase inlet, and outputting the mixture from a continuous phase outlet; 3) mixing the celastrus angulatus and the solvent uniformly, then introducing the mixture into the initial end of the dispersed phase extrusion pipe at constant pressure to ensure that the dispersed phase is extruded from the extrusion hole and combined with continuous extrusion, and outputting the celastrus angulatus aqueous emulsion from the continuous phase outlet. The method has the characteristics of high preparation efficiency, uniform particle size of the prepared emulsion in water and the like.)

1. A preparation method of celastrus angulatus aqueous emulsion is characterized by comprising the following steps:

1) constructing a reaction vessel, wherein the reaction vessel is of a cylindrical structure, sealing plates are arranged at the upper end and the lower end of the reaction vessel to enclose the reaction vessel into a closed space, the sealing plates are of a funnel-shaped structure, a continuous phase inlet is arranged at the lower end of the reaction vessel, a continuous phase outlet is arranged at the upper end of the reaction vessel, a single-layer coiled disperse phase extrusion pipe is arranged in the reaction vessel, the interturn distance between the disperse phase extrusion pipes is 0.5cm, the disperse phase extrusion pipe is provided with a plurality of layers, the distance between two adjacent layers of disperse phase extrusion pipes is 0.5cm, the two adjacent layers of disperse phase extrusion pipes are communicated end to end, the side wall of the disperse phase extrusion pipe is provided with an extrusion hole, a microporous membrane is arranged on the disperse phase extrusion pipe, and the tail end of the disperse phase;

2) preparing a continuous phase, uniformly mixing deionized water and an emulsifier, inputting the mixture from a continuous phase inlet, and outputting the mixture from a continuous phase outlet;

3) and (3) preparing a dispersed phase, uniformly mixing the celastrus angulatus and a solvent, and then introducing the mixture into the initial end of the dispersed phase extrusion pipe at constant pressure to ensure that the dispersed phase is extruded from the extrusion hole and is combined with continuous extrusion, wherein the celastrus angulatus aqueous emulsion is output from the continuous phase outlet.

2. The method for preparing celastrus angulatus aqueous emulsion of claim 1, wherein the method for preparing the dispersed phase extruded tube comprises the following steps:

a. dissolving 25g of polyvinylidene fluoride powder in 250mL of N-methyl pyrrolidone, fully stirring to completely dissolve the polyvinylidene fluoride powder, then hanging a film on clean glass, immediately placing the film in a deionized water gel bath after the film is exposed in the air for 30s, taking out the film after the film is automatically peeled off from the glass, and soaking the film in deionized water for 3h to obtain a first film body;

b. immersing the first membrane body into a potassium hydroxide/potassium permanganate solution, carrying out water bath reaction at 65 ℃ for 2h, taking out and immersing in deionized water for 2h, then immersing in a sulfuric acid solution containing sodium bisulfate, taking out the membrane and immersing in deionized water for 2h when the membrane turns from black to white, and taking out to obtain a second membrane body;

c. immersing the second membrane body in an itaconic acid solution, adding hydrogen peroxide as an initiator, introducing nitrogen, reacting for 4 hours at 65 ℃, taking out, repeatedly soaking and washing for 3 times by using deionized water, and drying at low temperature to obtain a third membrane body;

d. and dissolving the third membrane body in N-methyl pyrrolidone, adding polyvinyl pyrrolidone, heating and stirring to completely dissolve and uniformly disperse the third membrane body, standing for 2 hours to obtain a membrane casting solution, placing a porous glass tube on the membrane casting solution to form a membrane, immediately placing the porous glass tube into a supersaturated sodium chloride solution solidification solution for 1 hour after the porous glass tube is exposed in the air for 60 seconds, taking out the membrane, repeatedly soaking the membrane for 3 times in deionized water, and drying to obtain the dispersed phase extruded tube.

3. The method for preparing celastrus angulatus aqueous emulsion of claim 2, wherein the aperture of the porous glass tube is 0.5-1 mm.

4. The method for preparing celastrus angulatus aqueous emulsion of claim 2, wherein in step d), after placing the porous glass tube in the casting solution, vacuum defoaming is carried out, the vacuum defoaming condition is 0.08MPa, the vacuum defoaming is carried out for 3h at 50 ℃, and after the defoaming is finished, the casting solution is formed into a film on the porous glass tube.

5. The preparation method of the celastrus angulatus aqueous emulsion of claim 1, characterized in that the emulsifier is block copolymer of alkylaryl polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, ethylene oxide propylene oxide with mass ratio of 10:4: 1.

6. The method for preparing celastrus angulatus aqueous emulsion of claim 1, characterized in that the solvent is cyclohexanone.

7. The preparation method of celastrus angulatus aqueous emulsion of claim 1, characterized in that, the preparation method of celastrus angulatus is: the preparation method of the celastrus angulatus comprises the following steps: crushing celastrus angulatus root and bark, placing the crushed celastrus angulatus root and bark into a phosphate buffer solution, then placing the phosphate buffer solution into a microwave extractor for primary extraction, filtering the solution to obtain filter residue, repeatedly washing the filter residue 3 times by using distilled water, placing the washed filter residue into ethanol, soaking the filter residue for 12 hours, then soaking the soaked substance into the microwave extractor for extraction, filtering the solution, collecting filtrate, performing reduced pressure distillation on the filtrate to recover the ethanol, purifying the obtained concentrated solution by using macroporous resin, and obtaining the purified substance, namely celastrus angulatus.

8. The method for preparing celastrus angulatus aqueous emulsion of claim 1, characterized in that, between two adjacent layers of dispersed phase extruded tubes, the tube body of one layer of dispersed phase extruded tube corresponds to the turn-to-turn position of the other layer of dispersed phase extruded tube.

Technical Field

The invention belongs to the field of plant source pesticides. More specifically, the invention relates to a preparation method of celastrus angulatus aqueous emulsion

Background

Celastrus angulatus (academic name: Celastrus angustifolia Maxim.) is a plant of Celastraceae Celastrus, is a perennial woody vine, and is one of insecticidal plants with development potential in China. The bioactive components contained in the root bark of Celastrus angulatus are mainly beta-dihydroagarofuran polyol ester compounds and alkaloids thereof. The beta-dihydroagarofuran polyol ester compound, namely the celastrol, has the effects of poisoning, antifeedant, anaesthetizing and the like on pests, so the celastrol is developed into an emulsifiable solution form to be supplied to the market. However, the emulsifiable concentrate has the advantages of large usage amount of organic solvent, environmental toxicity and the like, so that the development of the celastrus angulatus aqueous emulsion for reducing the usage of the organic solvent has important significance.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.

The invention also aims to provide a preparation method of the celastrus angulatus aqueous emulsion, which can reduce the usage amount of organic solvent and avoid the harm to the environment caused by the residual organic solvent.

To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a celastrus angulatus aqueous emulsion, comprising the steps of:

1) constructing a reaction vessel, wherein the reaction vessel is of a cylindrical structure, sealing plates are arranged at the upper end and the lower end of the reaction vessel to enclose the reaction vessel into a closed space, the sealing plates are of a funnel-shaped structure, a continuous phase inlet is arranged at the lower end of the reaction vessel, a continuous phase outlet is arranged at the upper end of the reaction vessel, a single-layer coiled disperse phase extrusion pipe is arranged in the reaction vessel, the interturn distance between the disperse phase extrusion pipes is 0.5cm, the disperse phase extrusion pipe is provided with a plurality of layers, the distance between two adjacent layers of disperse phase extrusion pipes is 0.5cm, the two adjacent layers of disperse phase extrusion pipes are communicated end to end, the side wall of the disperse phase extrusion pipe is provided with an extrusion hole, a microporous membrane is arranged on the disperse phase extrusion pipe, and the tail end of the disperse phase;

2) preparing a continuous phase, uniformly mixing deionized water and an emulsifier, inputting the mixture from a continuous phase inlet, and outputting the mixture from a continuous phase outlet;

3) and preparing a dispersed phase, uniformly mixing the celastrus angulatus and a solvent, and then introducing the mixture into the initial end of the dispersed phase extrusion pipe at constant pressure to ensure that the dispersed phase is extruded from an extrusion hole and is combined with continuous extrusion, wherein the liquid output from the continuous phase outlet is celastrus angulatus aqueous emulsion.

Preferably, the method for preparing the dispersed phase extruded tube comprises the following steps:

a. dissolving 25g of polyvinylidene fluoride powder in 250mL of N-methyl pyrrolidone, fully stirring to completely dissolve the polyvinylidene fluoride powder, then hanging a film on clean glass, immediately placing the film in a deionized water gel bath after the film is exposed in the air for 30s, taking out the film after the film is automatically peeled off from the glass, and soaking the film in deionized water for 3h to obtain a first film body;

b. immersing the first membrane body into a potassium hydroxide/potassium permanganate solution, carrying out water bath reaction at 65 ℃ for 2h, taking out and immersing in deionized water for 2h, then immersing in a sulfuric acid solution containing sodium bisulfate, taking out the membrane and immersing in deionized water for 2h when the membrane turns from black to white, and taking out to obtain a second membrane body;

c. immersing the second membrane body in an itaconic acid solution, adding hydrogen peroxide as an initiator, introducing nitrogen, reacting for 4 hours at 65 ℃, taking out, repeatedly soaking and washing for 3 times by using deionized water, and drying at low temperature to obtain a third membrane body;

d. and dissolving the third membrane body in N-methyl pyrrolidone, adding polyvinyl pyrrolidone, heating and stirring to completely dissolve and uniformly disperse the third membrane body, standing for 2 hours to obtain a membrane casting solution, placing a porous glass tube on the membrane casting solution to form a membrane, immediately placing the porous glass tube into a supersaturated sodium chloride solution solidification solution for 1 hour after the porous glass tube is exposed in the air for 60 seconds, taking out the membrane, repeatedly soaking the membrane for 3 times in deionized water, and drying to obtain the dispersed phase extruded tube.

Preferably, the pore size of the porous glass tube is 0.5 to 1 mm.

Preferably, in the step d), after the porous glass tube is placed in the casting solution, vacuum defoaming is performed for 3 hours under the conditions of pressure of 0.08MPa and temperature of 50 ℃, and after the defoaming is finished, the casting solution is formed into a film on the porous glass tube.

Preferably, the emulsifier is alkyl aryl polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether and ethylene oxide propylene oxide block copolymer with the mass ratio of 10:4: 1. By regulating and controlling the proportion of the alkyl aryl polyoxyethylene polyoxypropylene ether, the castor oil polyoxyethylene ether and the ethylene oxide propylene oxide segmented copolymer, the aqueous emulsion can still keep a good stable state in a higher hard water environment, and the problems of flocculation and delamination are not easy to occur.

Preferably, the solvent is cyclohexanone.

Preferably, the preparation method of the celastrus angulatus comprises the following steps: crushing celastrus angulatus root and bark, placing the crushed celastrus angulatus root and bark into a phosphate buffer solution, then placing the phosphate buffer solution into a microwave extractor for primary extraction, filtering the solution to obtain filter residue, repeatedly washing the filter residue 3 times by using distilled water, placing the washed filter residue into ethanol, soaking the filter residue for 12 hours, then soaking the soaked substance into the microwave extractor for extraction, filtering the solution, collecting filtrate, performing reduced pressure distillation on the filtrate to recover the ethanol, purifying the obtained concentrated solution by using macroporous resin, and obtaining the purified substance, namely celastrus angulatus. The method comprises the following steps of performing primary extraction on the Celastrus angulatus root bark by using a phosphate buffer to remove water-soluble substances such as dulcitol and triterpenes, and reducing the difficulty of later-stage purification.

Preferably, between two adjacent dispersed phase extruded pipes, the pipe body of one dispersed phase extruded pipe corresponds to the turn-to-turn position of the other dispersed phase extruded pipe, so that the continuous phase is blocked by the pipe body of the next adjacent dispersed phase extruded pipe to flow towards two sides of the pipe body when the continuous phase is reserved at the turn-to-turn position of the dispersed phase extruded pipe, so that the emulsifier in the continuous phase is mixed more uniformly, and the emulsifier is combined with the dispersed phase more uniformly.

The invention at least comprises the following beneficial effects: by winding the dispersed phase extrusion pipes in a single-layer coil shape and arranging the dispersed phase extrusion pipes in a laminated manner, the length of the dispersed phase extrusion pipes is effectively increased, so that the dispersed phase extrusion pipes have more extrusion holes, and the preparation efficiency of the emulsifier is improved; coating a film body on the porous glass tube to ensure that the dispersed phase extrusion tube has hydrophilic and oleophobic properties; the third film body is dissolved in N-methyl pyrrolidone, and the polyvinylpyrrolidone is added, so that the dissolution state of the third film body is changed, when the third film body in the film casting solution encounters a coagulating bath sodium chloride aqueous solution, the third film body is separated into films instantly due to insolubility in water, and simultaneously, the polyvinylpyrrolidone quickly diffuses into the aqueous solution due to high solubility in water, so that holes are formed in the space occupied by the polyvinylpyrrolidone, and the formed holes are uniform in size and density due to the fact that the polyvinylpyrrolidone is uniformly mixed in the N-methyl pyrrolidone solution of the third film body. The method has the characteristics of high preparation efficiency, uniform particle size of the prepared emulsion in water and the like.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Drawings

FIG. 1 is a schematic sectional view of a reaction vessel according to the present invention.

1. A reaction vessel; 2. a sealing plate; 3. a continuous phase inlet; 4. a continuous phase outlet; 5. the dispersed phase is extruded out of the tube.

Detailed Description

The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.