CN108042488A - A kind of method for reducing micro emulsion dosage of surfactant - Google Patents

Abstract

The present invention provides a kind of method for reducing dosage of surfactant in micro emulsion.Using the common oily and another grease class material mixing for preparing micro emulsion as oil phase, under the action of surfactant, stir, micro emulsion can be formed by being titrated dropwise with water.When mixing such as olive oil with Vitamin E succinate as oil phase, the micro emulsion region of olive oil increased dramatically, and can form the ratio between oil and surfactant of micro emulsion region（O/S）More than 5/5 can be increased to by the 1/9 of simple olive oil, significantly reduce the dosage of surfactant and without the participation of cosurfactant short chain alcohol.The invention can be such that micro emulsion is more widely applied in terms of industrial or agricultural and medicine as carrier, more can provide foundation for the theoretical in-depth of micro emulsion solubilising and supplement.

Description

A method for reducing the amount of microemulsion surfactant

technical field

The invention relates to a preparation method of microemulsion, in particular to a preparation method of microemulsion without co-surfactant and greatly reducing the amount of surfactant.

Background technique

Microemulsions are usually composed of four components: surfactant (S), co-surfactant (C), oil (O) and water. Commonly used oils are isopropyl myristate, glyceryl stearate, ethyl acetate, oleic acid, peppermint oil, and various vegetable oils such as soybean oil, olive oil, and corn oil. When using these oils to prepare microemulsions, the amount of S and C is very large. Only when the mass ratio of oil to surfactant (O/SC) is lower than 2/8, is it possible to form microemulsions, and the microemulsion area of vegetable oils is Smaller, O/SC lower than 0.5/9.5. The large amount of S and C limits the application of microemulsion, especially as the application of drug and cosmetic carrier.

Contents of the invention

In order to reduce the amount of surfactant used in the microemulsion and make it more safely and effectively used as a carrier for medicines and cosmetics, the present invention provides a method for reducing the amount of surfactant used in the microemulsion.

A method for reducing the amount of surfactant in the microemulsion. The oil in the microemulsion is mixed with another oily ester as the oil phase. Under the action of the surfactant, it is stirred and titrated with water drop by drop.

The present invention avoids the use of a large amount of co-surfactant short-chain alcohols in conventional microemulsion preparation, that is, the formation of microemulsion does not require the participation of co-surfactant.

The method for reducing the amount of surfactant in the microemulsion according to the present invention, correspondingly, that is to say, the method for improving the load of the oil phase substance in the microemulsion is to add another kind of oily ester substance, both of the two kinds of oily substances Mutual solubilization, there are no special restrictions on its properties and the ratio of the two, that is, there are no special restrictions on the properties and compounding ratio of oily substances.

In the present invention, the choice of surfactant is only related to the HLB value (hydrophilic-lipophilic balance value of the surfactant) and has nothing to do with the type; safety considerations are preferably non-ionic surfactants, which can be one or more complex match.

The advantages of the present invention are:

(1) The preparation of the invention is simple, no dispersing equipment and conditions are required, and it can be formed spontaneously only by stirring.

(2) The invention greatly improves the microemulsion area, that is, in the case of low surfactant content and high oil phase loading, the water content can be adjusted in a wide range, thereby preparing water-in-oil and oil-in-water Various types of microemulsions of type or bicontinuous type.

(3) This invention can greatly improve the solubilization of microemulsions, regardless of macromolecules, small molecules, oil-soluble substances or fat-soluble substances can be solubilized in different parts of microemulsions according to their solubility characteristics, such as oil phase, aqueous phase or the surface of microemulsion particles.

Description of drawings

Fig. 1 Ternary phase diagram described in Example 1; olive oil/vitamin E succinate=6:1 RH40:Span80=3:1.

The ternary phase diagram described in Fig. 2 embodiment 2; olive oil/vitamin E succinate=5:1 RH40:Span80=5:1.

Fig. 3 The ternary phase diagram described in Example 3; olive oil/vitamin E succinate=4:1 RH40:Span80=3:1.

The ternary phase diagram described in Fig. 4 Example 4; olive oil/vitamin E succinate=3:1 RH40:Span80=4:1.

The ternary phase diagram described in Fig. 5 Example 5; olive oil/vitamin E succinate=2:1 RH40:Span80=4:1.

The ternary phase diagram described in Fig. 6 Example 6; olive oil/tetraethyl silicate=5:1 Tween80:Span80=3:1.

The ternary phase diagram described in Fig. 7 embodiment 7; Olive oil/ethyl acetate=6:1 Tween80:Span80=4:1

The ternary phase diagram described in Fig. 8 Example 8; isopropyl myristate/vitamin E succinate=4:1 RH40:Span80=4:1.

Figure 9 is the ternary phase diagram described in Example 9; the mass ratio of isopropyl myristate/tetraethyl silicate is 4:1, and the mass ratio of Tween80 and Span80 is 3:1.

Fig. 10 represents the particle size distribution diagram of sample 1 in the examples.

Fig. 11 represents the particle size distribution diagram of sample 2 in the examples.

Fig. 12 represents a particle size distribution diagram of sample 3 in Examples.

Fig. 13 The microscopic morphology of sample 1 observed under a TEM-100XII transmission electron microscope; the picture on the left shows a 50-fold dilution with a magnification of 15K; the picture on the right shows a 50-fold dilution with a magnification of 60K.

The electron micrograph of Fig. 14 water-based facial mask.

Detailed ways

Example 1

Mix olive oil and vitamin E succinate in a mass ratio of 6:1 to obtain an oil phase stock solution. Mix polyoxyethylene hydrogenated castor oil (RH40) and Span80 at a mass ratio of 3:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 1 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 2

Mix olive oil and vitamin E succinate in a mass ratio of 5:1 to obtain an oil phase stock solution. Mix RH40 and Span80 at a mass ratio of 5:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 2 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 3

Mix olive oil and vitamin E succinate in a mass ratio of 4:1 to obtain an oil phase stock solution. Mix RH40 and Span80 at a mass ratio of 3:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 3 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 4

Mix olive oil and vitamin E succinate in a mass ratio of 3:1 to obtain an oil phase stock solution. Mix RH40 and Span80 at a mass ratio of 4:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 4 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 5

Mix olive oil and vitamin E succinate in a mass ratio of 2:1 to obtain an oil phase stock solution. Mix RH40 and Span80 at a mass ratio of 4:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 5 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 6

Mix olive oil and tetraethyl silicate at a mass ratio of 5:1 to obtain an oil phase stock solution. Mix Tween80 and Span80 at a mass ratio of 3:1 to obtain a surfactant stock solution. Mix the oil phase and surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 6 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 7

Mix olive oil and ethyl acetate in a mass ratio of 6:1 to obtain an oil phase stock solution. Mix Tween80 and Span80 at a mass ratio of 4:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 7 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 8

Mix isopropyl myristate and vitamin E succinate in a mass ratio of 4:1 to obtain an oil phase stock solution. Mix RH40 and Span80 at a mass ratio of 4:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 8 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

Example 9

Mix isopropyl myristate and tetraethyl silicate at a mass ratio of 4:1 to obtain an oil phase stock solution. Mix Tween80 and Span80 at a mass ratio of 3:1 to obtain a surfactant stock solution. Mix the oil phase and the surfactant in proportion to form a 10g mixture, stir evenly, and the O/S are 0.5/9.5, 1/9, 1.5/8.5, 2/8, ..., 9/1, 9.5/0.5 . Titrate the mixed solution of each O/S ratio with distilled water, and record the consumption of distilled water when changing from clear to turbid or from turbid to clear to obtain the boundary point of the microemulsion area. With the percentage of oil, surfactant, and distilled water as variables, the ternary phase diagram is drawn, and the translucent area that is transparent or slightly blue halo is the microemulsion area. Figure 9 is the phase diagram under the condition of this ratio, and the black area is the microemulsion area.

The present inventor uses olive oil microemulsion as a carrier to develop cosmetics. Through single factor investigation, it is found that the component that improves the olive oil microemulsion area is vitamin E succinate, and other components in the microemulsion such as cosurfactant short chain The osmotic agents have no effect on the formation of microemulsions, and the choice of S is only related to HLB and has nothing to do with the type of S. On this basis, the inventor selected several other oils and fats to compound in pairs, and further verified that after the two oils and fats are compounded, both sides can solubilize each other, which can greatly improve the objective fact of the microemulsion area.

There are many mechanisms for the formation of microemulsions, the mixed film theory and the instantaneous negative interfacial tension theory are generally accepted, and the solubilization theory is the least generally accepted. The invention provides good experimental support for the acceptance and deepening of the solubilization theory, and also provides a material basis for the wide application of the microemulsion carrier.

Representation example:

Three microemulsion formulations were selected, and their average particle size and poly index PDI were measured respectively. The results are shown in Table 1 and Figures 10, 11, and 12. The compositions of the three microemulsions are: sample 1, mass ratio of olive oil to vitamin E succinate 6:1, mass ratio of RH40 to Span80 3:1, O/S 4.5 / 5.5; sample 2, mass ratio of RH40 to Span80 Ratio 4:1, O/S is 4.6 / 5.4; sample 3, mass ratio of RH40 and Span80 is 5:1, O/S is 4.8 / 5.2; three samples are prepared in 20g, and their water content is 80%.

It can be seen that the particle sizes of the three samples are all in the range of microemulsions less than 100nm, the particle size distribution is uniform, and the poly index is all less than 0.2.

The sample was prepared by negative staining method, and the microscopic morphology of sample 1 was observed under a TEM-100XII transmission electron microscope. The results are shown in Figure 13. The left picture shows a 50-fold dilution with a magnification of 15K; the right picture shows a 50-fold dilution with a magnification 60k. It can be seen that the particle size of the microemulsion is in the nanometer range, the particles are spherically distributed, and the shape is round.

Applications:

A blank microemulsion was first prepared according to the ratio of olive oil 2.46%, vitamin E succinate 0.41%, RH40 2.80%, Span80 0.56%, and the rest deionized water. Then add hyaluronic acid 0.3%, sodium alginate 0.1%, allantoin 0.1%, collagen 0.5%, propylene glycol 3%, arbutin 1%, glycerin 5%, sodium methylparaben 0.025%, paraben Sodium auryl propylate 0.25%, a few drops of lavender essential oil, to be prepared into a water-based facial mask.

Its particle size was determined to be 59.5nm, its PDI index was 0.27, and its viscosity was 140.95±0.35mPa·s. The microscopic morphology is shown in Figure 14. It can be seen that regardless of macromolecules or small molecules, water-soluble or fat-soluble substances can be loaded into microemulsions, and the characteristics of microemulsions are still met after loading a large amount of substances.

Claims (4)

1. A method for reducing the amount of surfactant in the microemulsion is characterized in that the common oil used to prepare the microemulsion is mixed with another oily ester substance as the oil phase, under the effect of the surfactant, stirring, and water gradually Droplets are titrated to form. 2. a kind of method reducing surfactant consumption in microemulsion according to claim 1 is characterized in that: the formation of microemulsion does not need the participation of cosurfactant i.e. short-chain alcohol. 3. a kind of method for reducing surfactant consumption in microemulsion according to claim 1, is characterized in that: reduce the method for surfactant consumption in microemulsion, correspondingly, that is to say improves oil phase substance in microemulsion The medium loading method is to add another oil and ester substance, and the two oil and fat substances solubilize each other, and there is no special limitation on their properties and the ratio of the two. 4. a kind of method reducing surfactant consumption in microemulsion according to claim 1 is characterized in that: surfactant is mainly relevant to its HLB value to the influence of microemulsion area, and has nothing to do with kind; Ionic surfactants can be one or more compounds.