Self-stabilizing oil-in-oil emulsion by utilizing grafting modified heterocyclic aramid fiber and preparation method of self-stabilizing oil-in-oil emulsion

Abstract

The invention relates to the technical field of colloid interfaces, in particular to a self-stabilizing oil-in-oil emulsion using graft-modified heterocyclic aramid and a preparation method thereof.The method comprises the steps that after low-temperature polymerization is completed on heterocyclic aramid fibers, the heterocyclic aramid fibers are directly subjected to graft modification, and the obtained graft-modified heterocyclic aramid is an amphiphilic polymer; the oil-in-oil emulsion is stabilized by utilizing the characteristics that the hydrophilic and nonpolar end of the main chain of the amphiphilic polymer is in external affinity with the emulsion and the hydrophilic and polar end of the branch chain is in internal affinity with the emulsion, so that the oil-in-oil emulsion prepared by utilizing the amphiphilic polymer has a self-stabilizing function so as to achieve a self-stabilizing state independent of a surfactant, and the method is simple, low in cost and suitable for industrial production. And the method has better economical efficiency. The problems that in the prior art, stability of an oil-in-oil emulsion is high in dependence degree on a surfactant, and the stability effect of the emulsion is poor are solved.

Description

Technical Field

[0001] The invention relates to the technical field of colloid interface, in particular to a self-stabilizing oil-in-oil emulsion utilizing grafted modified heterocyclic aramid fibers and a preparation method thereof. Background Art

[0002] Emulsions are an important part of commercial products and have a wide range of applications in cosmetics, pharmaceuticals, foods, and other chemical products. Composed of two or more immiscible phases, usually stabilized by molecular surfactants, polymers, proteins, and / or solid particles, emulsions are part of our daily lives. Emulsions can be divided into conventional emulsions such as water-in-oil emulsions (W / O) and oil-in-water emulsions (O / W), unconventional emulsions such as multiple emulsions (W / O / W, O / W / O, W / W / W, or O / O / O), water-in-water emulsions (W / W), and oil-in-oil emulsions (O / O). Among them, O / O emulsions are emulsions formed by two oil phases with a lower dielectric constant, or an emulsion formed by an oil phase replaced by an anhydrous phase (higher dielectric constant) (polar non-aqueous phase). The stability of oil-in-oil emulsions depends largely on surfactants. The preparation of emulsions generally requires a large amount of surfactants and co-surfactants, especially when there are more oil substances as the oil phase such as oil-in-oil emulsions. The use of a large amount of surfactants and co-surfactants not only increases the cost of emulsion preparation and reduces its economic efficiency, but also surfactants and co-surfactants have adverse effects on water, soil and air during production, use and disposal. Therefore, finding ways to reduce the amount of auxiliary materials is currently a more urgent development requirement. Summary of the invention

[0003] In view of the problems in the prior art that the stability of oil-in-oil emulsions is highly dependent on surfactants and the emulsion stabilization effect is poor, the present invention provides a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid and a preparation method thereof.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fibers, comprising: Using N,N-dimethylacetamide and lithium chloride, a dissolving system is prepared; Adding 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-phenylenediamine and terephthaloyl chloride into the dissolving system to react and obtain a heterocyclic aramid solution; Under water bath conditions, adding alkaline substances and brominated long-chain alkanes into the heterocyclic aramid solution to react and obtain a graft-modified heterocyclic aramid solution; Self-stabilizing oil-in-oil emulsion was prepared using grafted heterocyclic aramid solution.

[0005] Optionally, the solid content of lithium chloride in the dissolution system is 3wt% to 3.5wt%, and the mass ratio of N,N-dimethylacetamide to lithium chloride is (350 to 700): (12 to 24).

[0006] Optionally, the molar ratio of the 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-phenylenediamine and terephthaloyl chloride is (9-4):(1-6):10.

[0007] Optionally, the sum of the molar amounts of the 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4-phenylenediamine is equal to the molar amount of terephthaloyl chloride.

[0008] Optionally, the temperature of the water bath is 80°C to 90°C.

[0009] Optionally, the amount of the alkaline substance used is 1% to 3% of the total system mass of the heterocyclic aramid solution.

[0010] Optionally, the brominated long-chain alkane includes one or more of brominated hexadecane, brominated octadecane, brominated eicosane, brominated docosane and brominated tetracosane.

[0011] Optionally, the molar ratio of the brominated long-chain alkane to 2-(4-aminophenyl)-5-aminobenzimidazole is 1:1.

[0012] Optionally, the mass ratio of the amount of N,N-dimethylacetamide and lithium chloride to the heterocyclic aramid is (350-700):(12-24):7.

[0013] The present invention also provides a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fibers, which is prepared using the above method.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid and a preparation method thereof. According to the method, after low-temperature polymerization of heterocyclic aramid fibers is completed, the heterocyclic aramid fibers are directly grafted and modified to obtain a grafted modified heterocyclic aramid as an amphiphilic polymer; the non-polar end of the main chain of the amphiphilic polymer is compatible with the external phase of the emulsion, and the polar end of the branched chain is compatible with the internal phase of the emulsion to achieve stability of the oil-in-oil emulsion, so that the oil-in-oil emulsion prepared by the amphiphilic polymer has a self-stabilizing function to achieve a self-stabilizing state that does not rely on surfactants. In addition, for the oil-in-oil emulsion with a phase change function, the amphiphilic polymer can also be used as an encapsulation shell of a phase change material and a solid-solid phase change material. When used as an encapsulation shell of a phase change material, the heterocyclic aramid has high mechanical properties and a rapid encapsulation means, and can achieve stable encapsulation of the phase change material; when used as a solid-solid phase change material, heat can be stored and released to enhance subsequent phase change performance, and performance support can be provided for subsequent processing. The preparation method is simple, the reaction conditions and temperature are moderate, and certain economic benefits are achieved.

[0015] The present invention also provides an oil-in-oil emulsion prepared by the method. The emulsion has self-stability, does not need to rely on surfactants or resident surfactants to achieve stability, has good stabilization effect, and has low preparation cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a schematic diagram of a method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fibers according to the present invention.

[0017] Figure 2 The process flow chart of the self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid in the embodiment of the present invention.

[0018] Figure 3 Schematic diagram of the grafting process of the amphiphilic polymer in an embodiment of the present invention.

[0019] Figure 4 Schematic diagram of the stable state of the oil-in-oil emulsion prepared in an embodiment of the present invention.

[0020] Figure 5 Comparison of microscopic images of the stable state of the oil-in-oil emulsion prepared in an embodiment of the present invention and stabilized by surfactant F127, wherein the left image is an oil-in-oil state image stabilized by surfactant F127, and the right image is a self-stabilizing oil-in-oil state image prepared by an embodiment of the present application. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0023] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0024] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0025] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0026] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0027] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0028] The present invention is further described in detail below in conjunction with specific embodiments, which are intended to explain the present invention rather than to limit it.

[0029] The present invention discloses a method for preparing a self-stabilizing oil-in-oil emulsion by using grafted modified heterocyclic aramid fibers. Figure 1 ,include: S1: Prepare a dissolving system using N,N-dimethylacetamide (DMAC) and lithium chloride, specifically: Lithium chloride is dissolved in N,N-dimethylacetamide to obtain a dissolution system, wherein the solid content of lithium chloride is 3wt% to 3.5wt%, and the mass ratio of N,N-dimethylacetamide to lithium chloride is (350 to 700): (12 to 24).

[0030] S2: Add 2-(4-aminophenyl)-5-aminobenzimidazole (APBZ), 1,4-phenylenediamine (PPD) and terephthaloyl chloride (TPC) to the dissolving system to react and obtain a heterocyclic aramid solution, specifically: Add 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4-phenylenediamine to the dissolving system, stir and dissolve under 0°C to 5°C water bath conditions, add terephthaloyl chloride, remove the ice water bath, and react for more than 1 hour to obtain a heterocyclic aramid solution; the sum of the molar amounts of the 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4-phenylenediamine is equal to the molar amount of terephthaloyl chloride, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4- The molar ratio of phenylenediamine to terephthaloyl chloride is (9-4): (1-6): 10; the solid content of heterocyclic aramid (HA) in the heterocyclic aramid solution is 1wt%-2wt%, and the mass ratio of N,N-dimethylacetamide, lithium chloride and heterocyclic aramid is (350-700): (12-24): 7; the sum of the molar amounts of 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4-phenylenediamine is equal to the molar amount of terephthaloyl chloride.

[0031] S3: Under water bath conditions, add alkaline substances and brominated long-chain alkanes to the heterocyclic aramid solution to react and obtain a grafted modified heterocyclic aramid solution, specifically: Add 1% to 3% of the total mass of the system to the heterocyclic aramid solution to provide an alkaline environment, heat and stir, and after the alkaline substance is dissolved, add a brominated long-chain alkane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole in S1, and stir for 2 hours in a water bath at 80° C. to 90° C. to obtain a grafted modified heterocyclic aramid solution; wherein the alkaline substance includes one of sodium hydroxide, potassium carbonate and potassium tert-butoxide; and the brominated long-chain alkane includes one or more of brominated hexadecane, brominated octadecane, brominated eicosane, brominated docosane and brominated tetracosane.

[0032] S4: using the graft-modified heterocyclic aramid solution to prepare a self-stabilizing oil-in-oil emulsion; preferably, directly adding a phase change material to the graft-modified heterocyclic aramid solution, heating and homogenizing and emulsifying, to obtain a self-stabilizing oil-in-oil emulsion, specifically: Add long-chain alkane, i.e. phase change material, to the grafted modified heterocyclic aramid solution, at 30°C to 60°C, pay attention to the heating temperature being higher than the phase change temperature of the phase change material, homogenize and emulsify to obtain a self-stabilized oil-in-oil emulsion of modified heterocyclic aramid; wherein the phase change material is one or more of phase change paraffin, octadecane, hexadecane and docosane; and the mass ratio of the added amount of the phase change material to the heterocyclic aramid is 1:(1-9).

[0033] The method directly grafts and modifies heterocyclic aramid fibers after low-temperature polymerization, and obtains grafted modified heterocyclic aramid fibers as amphiphilic polymers; the non-polar end of the main chain of the amphiphilic polymer is compatible with the external phase of the emulsion, and the polar end of the branch chain is compatible with the internal phase of the emulsion, so as to stabilize the oil-in-oil emulsion, so that the oil-in-oil emulsion prepared by the amphiphilic polymer has a self-stabilizing function to achieve a self-stabilizing state that does not rely on surfactants. In addition, for the oil-in-oil emulsion with phase change function, the amphiphilic polymer can also be used as an encapsulation shell of the phase change material and a solid-solid phase change material. When used as an encapsulation shell of the phase change material, the heterocyclic aramid has high mechanical properties and a rapid encapsulation method, and can achieve stable encapsulation of the phase change material; when used as a solid-solid phase change material, it can also store and release heat to enhance the subsequent phase change performance, and can provide performance support for subsequent processing. The preparation method is simple, the reaction conditions are moderate, and it has certain economic benefits.

[0034] Example 1 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0035] Example 2 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 8:2:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0036] Example 3 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 7:3:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0037] Example 4 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 6:4:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0038] Example 5 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 5:5:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0039] Example 6 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 4:6:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 700:24:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.0wt%; sodium hydroxide (1% by weight of the total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, hexadecane bromide (with a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, phase change paraffin was added, heated at 60℃, homogenized and emulsified, to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0040] Example 7 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0041] Example 8 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 8:2:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass ratio of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0042] Example 9 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 7:3:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0043] Example 10 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 6:4:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0044] Embodiment 11 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 5:5:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass ratio of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0045] Example 12 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 4:6:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 580:20:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.2wt%; potassium carbonate was added to the heterocyclic aramid solution at a total mass ratio of 2% of the system to provide an alkaline environment, and heated and stirred. After the potassium carbonate was dissolved, octadecane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:2, hexadecane was added, heated at 30℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0046] Example 13 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass of 3% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0047] Embodiment 14 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 8:2:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 3% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0048] Embodiment 15 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 7:3:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; Potassium tert-butoxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane (1:1 in molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0049] Example 16 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 6:4:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; Potassium tert-butoxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane (1:1 in molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0050] Embodiment 17 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 5:5:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; 3% potassium tert-butoxide of the total mass of the system was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0051] Embodiment 18 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 4:6:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 466:16.3:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.5wt%; 3% potassium tert-butoxide of the total mass of the system was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, bromoeicosane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:4, octadecane was added, heated at 45℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0052] Embodiment 19 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodocosane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added, and heated at 80°C to obtain a solution of 1.75wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0053] Embodiment 20 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 8:2:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodioxane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0054] Embodiment 21 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 7:3:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodocosane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added, and heated at 80°C to obtain a solution of 1.75wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0055] Embodiment 22 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 6:4:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodocosane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0056] Embodiment 23 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 5:5:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodocosane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0057] Embodiment 24 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 4:6:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 400:14:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 1.75wt%; sodium hydroxide (3% by total mass of the system) was added to the heterocyclic aramid solution to provide an alkaline environment, and heated and stirred. After the sodium hydroxide was dissolved, bromodocosane (1:1 molar ratio with 2-(4-aminophenyl)-5-aminobenzimidazole) was added, and heated at 80°C to obtain a solution of 1.75wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:7, eicosane was added, heated at 50℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0058] Embodiment 25 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:1, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0059] Embodiment 26 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 8:2:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and stirred at 80°C. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:9, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0060] Embodiment 27 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 7:3:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:9, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0061] Embodiment 28 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 6:4:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:9, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0062] Embodiment 29 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 5:5:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:9, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0063] Embodiment 30 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 4:6:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; 1% potassium tert-butoxide of the total mass of the system was added to the heterocyclic aramid solution to provide an alkaline environment, and the solution was heated and stirred. After the potassium tert-butoxide was dissolved, bromotetracosane in a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole was added at 80 ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to phase change paraffin in the heterocyclic aramid solution of 1:9, docosane was added, heated at 60℃, homogenized and emulsified to obtain a modified heterocyclic aramid self-stabilized oil-in-oil emulsion.

[0064] Embodiment 31 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, and stirred for 2 hours to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to docosane, n-octadecane and phase change paraffin in the heterocyclic aramid solution of 1:3:3:3, a mixed phase change material was added, heated at 60℃, and homogenized and emulsified to obtain a self-stabilized oil-in-oil emulsion of modified heterocyclic aramid.

[0065] Embodiment 32 Lithium chloride was dissolved in N,N-dimethylacetamide to obtain a dissolving system, wherein the solid content of lithium chloride was 3.3wt%; APBZ and PPD were added to the dissolving system, and then mechanically stirred in an ice-water bath at 0°C to dissolve them, and then TPC was added, and the ice-water bath was removed. After reacting for 1 hour, a heterocyclic aramid solution was obtained, wherein the molar ratio of APBZ, PPD and TPC was 9:1:10, and the mass ratio of DMAC, LiCl and heterocyclic aramid was 350:12:7. The solid content of heterocyclic aramid in the obtained heterocyclic aramid solution was 2.0wt%; Potassium tert-butoxide was added to the heterocyclic aramid solution at a total mass ratio of 1% of the system to provide an alkaline environment, and heated and stirred. After the potassium tert-butoxide was dissolved, tetracosane bromide was added at a molar ratio of 1:1 to 2-(4-aminophenyl)-5-aminobenzimidazole, and heated at 80°C to obtain a solution of 2.0wt% of the heterocyclic aramid solution. ℃ water bath, stirring for 2h to obtain a grafted modified heterocyclic aramid solution; according to the mass ratio of heterocyclic aramid to hexadecane, n-octadecane, docosane and phase change paraffin in the heterocyclic aramid solution of 1:1:1:1:1, adding the mixed phase change material, heating at 60℃, homogenizing and emulsifying, to obtain a self-stabilized oil-in-oil emulsion of modified heterocyclic aramid.

[0066] Take Example 7-12 as an example, see Figure 3 After the heterocyclic aramid fiber is polymerized at low temperature, octadecane bromide is combined with the active sites on the imidazole of the heterocyclic aramid fiber to graft-modify the heterocyclic aramid fiber to obtain the graft-modified heterocyclic aramid fiber, i.e., the amphiphilic polymer; the amphiphilic polymer is used as an emulsion stabilizer, see Figure 4 By utilizing the characteristics of the non-polar end of the main chain of the amphiphilic polymer being compatible with the external phase of the emulsion and the polar end of the side chain being compatible with the internal phase of the emulsion, the oil-in-oil emulsion can be stabilized to achieve a self-stabilizing state independent of surfactants. Figure 5 By comparing the micrographs of the heterocyclic aramid oil-in-oil emulsion stabilized by the conventional surfactant F127 and the amphiphilic polymer of the present invention, it is shown that the amphiphilic polymer has better stabilizing ability than the conventional method.

[0067] In summary, the present invention provides a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid and a preparation method thereof. According to the method, after low-temperature polymerization of heterocyclic aramid fibers is completed, the heterocyclic aramid fibers are directly grafted and modified to obtain a grafted modified heterocyclic aramid as an amphiphilic polymer; the non-polar end of the main chain of the amphiphilic polymer is used to be compatible with the external phase of the emulsion, and the polar end of the branched chain is used to be compatible with the internal phase of the emulsion to achieve stabilization of the oil-in-oil emulsion, so that the oil-in-oil emulsion prepared by the method has a self-stabilizing function to achieve a self-stabilizing state that is independent of a surfactant. The method is simple and low in cost, and has better economy.

[0068] The above description is only a preferred embodiment of the present invention and is not intended to impose any limitation on the technical solution of the present invention. Those skilled in the art should understand that, without departing from the spirit and principles of the present invention, the technical solution can also be subjected to several simple modifications and substitutions, and these modifications and substitutions are also within the scope of protection covered by the claims.

Claims

1. A method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid, characterized in that: include: Using N,N-dimethylacetamide and lithium chloride, a dissolving system is prepared; Adding 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-phenylenediamine and terephthaloyl chloride into the dissolving system to react and obtain a heterocyclic aramid solution; Under water bath conditions, adding alkaline substances and brominated long-chain alkanes into the heterocyclic aramid solution to react and obtain a graft-modified heterocyclic aramid solution; Self-stabilizing oil-in-oil emulsion was prepared using grafted heterocyclic aramid solution.

2. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The solid content of lithium chloride in the dissolution system is 3wt% to 3.5wt%, and the mass ratio of N,N-dimethylacetamide to lithium chloride is (350 to 700): (12 to 24).

3. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid according to claim 1, characterized in that: The molar ratio of the 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-phenylenediamine and terephthaloyl chloride is (9-4):(1-6):

10.

4. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid according to claim 3, characterized in that: The sum of the molar amounts of the 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4-phenylenediamine is equal to the molar amount of terephthaloyl chloride.

5. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The temperature of the water bath is 80°C to 90°C.

6. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The amount of the alkaline substance used is 1% to 3% of the total system mass of the heterocyclic aramid solution.

7. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The brominated long-chain alkane includes one or more of brominated hexadecane, brominated octadecane, brominated eicosane, brominated docosane and brominated tetracosane.

8. The method for preparing a self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The molar ratio of the brominated long-chain alkane to 2-(4-aminophenyl)-5-aminobenzimidazole is 1:

1.

9. The method for preparing a self-stabilized oil-in-oil emulsion using grafted modified heterocyclic aramid fiber according to claim 1, characterized in that: The mass ratio of the amount of N,N-dimethylacetamide and lithium chloride to the heterocyclic aramid is (350-700):(12-24):

7.

10. A self-stabilizing oil-in-oil emulsion using grafted modified heterocyclic aramid, characterized in that: Prepared by the method according to any one of claims 1 to 9.

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