KR102095115B1 - Self-healing silicon insulator and manufacturing method for thereof - Google Patents

Abstract

The present invention relates to a self-healing silicone insulator and a method for manufacturing the same, which is dispersed in the insulating resin and the insulating resin, and when voids and cracks occur in the insulating resin, it is destroyed by an electric tree that is generated and propagates. And microcapsules to release the core material to restore the voids and cracks.
Since the present invention has a self-healing property when damage to the insulator occurs, it is applied to power cables, insulators inside the junction box, etc., and thus has the advantage of being easily self-healing when damage to the insulator occurs due to various external environmental changes.

Description

Self-healing silicone insulator and its manufacturing method {SELF-HEALING SILICON INSULATOR AND MANUFACTURING METHOD FOR THEREOF}

The present invention relates to a self-healing silicone insulator and a method for manufacturing the same, and more particularly, to a self-healing silicone insulator having a self-healing property using a microcapsule and a manufacturing method thereof.

The intermediate junction box, which serves to electrically and mechanically connect the ultra-high voltage underground cables of the underground line, is a combination of epoxy insulation and rubber stress cones to maintain mechanical and electrical performance. Epoxy insulation is a TMJ (tape molded joint) that crosslinks in the field using uncrosslinked polyethylene, a prefabricated joint (PJ) that has a composite insulation structure of epoxy and EPDM rubber, and PMJ (premolded) that uses EPDM or silicone rubber alone. Joint) is mainly used.

However, in recent years, the occurrence of failures in underground transmission facilities (eg, underground cables) has increased, and among them, the middle junction box has a high share of 58% of all failures.

The major failure of the intermediate junction box is interpreted as various causes, but it is known that it is caused by the advancement of the electric tree from cracks, voids, foreign substances and silicon semiconducting / insulating parts, and semiconducting protrusions. Therefore, a solution to this is urgently required.

An object of the present invention is to provide a self-healing silicone insulator having a self-healing property using a microcapsule so as to have self-healing properties when damage to the insulator occurs without deteriorating the performance of the insulator and a method of manufacturing the same.

According to the features of the present invention for achieving the above object, the present invention is dispersed in the insulating resin and the insulating resin, and when the voids and cracks occur in the insulating resin, electricity generated and propagates And microcapsules that are destroyed by the tree and release the core material to restore the voids and cracks.

The microcapsule comprises a self-healing core material and a cell surrounding the core material, and releases the core material by destruction of the cell.

The microcapsule includes capsule A and capsule B having different core materials, and the core material of the capsule A and the core material of the capsule B are crosslinked to restore the voids and cracks.

The capsule A is an epoxy capsule in which the core material is epoxy, the capsule is an amine-based capsule in which the core material is an amine, and the epoxy capsule and the amine-based capsule have a weight ratio of 2: 1 in the core material.

The core material is one selected from a hydrocarbon-based amine core material and a hydrocarbon-based epoxide core material, and the cell (the outer wall of the capsule) is a MUF capsule, a UF capsule, an epoxy capsule, a polyurethane capsule, a silica coated MUF capsule It is one selected from.

The hydrocarbon-based amine core material is synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine.

The hydrocarbon-based epoxide core material is a core material including a terminal hydroxyl group using bisphenol A diglycidyl ether and PEG, a core material including a hydroxyl group at the end using Terephthaloyl chloride and diethyleneglycol, Terephthaloyl chloride (DEG) And epichlorohydrin is one selected from core materials containing epoxide groups at the ends.

The microcapsule has a weight ratio of the cell to the core material in a range of 1: 2 to 1: 5.

The microcapsule has a size of 140 to 280 µm.

A step of preparing a microcapsule having an epoxy core material and an amine-based microcapsule, and mixing the microcapsule having an epoxy core material and a microcapsule having an amine-based core material in an insulating resin, stirring and uniformly mixing it, extruding it into an insulator. And manufacturing.

The microcapsule, wherein the core material is epoxy, adds urea, outer wall strengthening agent, ammonium, and EMA to distilled water and adjusts the pH to form a cell, and further adds and stirs the core material to the distilled water, and agitates the distilled water after stirring. And adding formaldehyde to the mixture, followed by stirring, and obtaining a capsule submerged in the distilled water.

The stirring is performed at 600-800 rpm.

The capsule is silica coated by further adding a silica coating precursor.

The core material of the amine-based microcapsule is a step of manufacturing a hollow capsule having a hollow inside (hollow capsule) and dipping the hole capsule in a water tank containing an amine solution and applying vacuum to fill the hole capsule with an amine solution. And obtaining a capsule that has sunk to the bottom of the water tank.

The present invention has a self-healing property using a microcapsule so as to have self-healing properties when damage to the insulation occurs without deteriorating the performance of the insulation.

Therefore, the present invention is used as an internal insulator such as a silicone insulator inside an intermediate junction box connecting a high-voltage cable, a stress cone, a coating of an ultra-high-voltage cable, and a cable system of a transmission system, which causes damage due to various external environmental changes. Even in this case, there is an effect that can be easily self-healing.

In addition, according to the present invention, when the (ultra) high voltage cable is connected, damage to the internal / external scratches generated in the field, cracks or voids in / out the insulator can be used to mitigate or suppress the progress of the electric tree based on the void. It can effectively respond to social and economic losses caused by the destruction of insulation.

1 is a conceptual diagram of a self-healing silicone insulator according to the present invention.
2 is an NMR spectra graph of p-Toluenesulfonyl chloride.
3 is an NMR spectra graph of 4,7,10-trioxa-1,13-diamine.
Figure 4 is a product NMR spectra graph after the reaction progress for 5 hours.
5 is a TGA analysis graph of 4,7,10-trioxa-1,13-diamine and product.
6 is a NMR spectra graph of a product after 2 hours of reaction.
7 is a product NMR spectra graph after the reaction proceeds for 4 hours.
8 is a product NMR spectra graph after reaction progress.
Figure 9 is a product TGA graph synthesized terephthaloyl chloride (DEG) and epichlorohydrin at the end.
10 is a schematic diagram of the synthesis of UF capsules.
11 is a synthetic reaction formula of the final obtained UF capsule.
12 is a graph of the capsule size according to the content ratio of the shell monomer and the core material of the UF capsule.
13 is a capsule size control graph according to the stirring speed of the UF capsule.
14 is a graph of the capsule size control according to the viscosity of the core material.
15 is a graph of thermal stability analysis of UF capsules and OM pictures.
Figure 16 is a SEM photograph showing the surface condition of the UF capsules by core content
Figure 17 is a SEM photograph showing the thickness of the capsule with the most core content
Figure 18 is a photograph confirming the self-healing characteristics of the place where there are a lot of capsules of two types and less

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

As shown in Fig. 1, the self-healing silicone insulator of the present invention includes dispersing a microcapsule having self-healing properties in an insulating resin. When the voids and cracks occur in the insulating resin, the microcapsules are destroyed by the generated and advancing electric tree and release the core material to restore the voids and cracks.

The electric tree means that when voids or cracks occur in the insulator, the electric field is concentrated in the voids or cracks and the insulator is destroyed in a tree shape. Therefore, when the microcapsule is destroyed by external force, electric force, temperature, etc. due to an electric field advancing in a tree shape, the core material inside the microcapsule can be released.

The insulating resin may be one or more selected from silicone, rubber, and elastomer.

The microcapsule consists of a self-healing core material and a cell surrounding the core material, and releases the core material by destruction of the cell. The cell corresponds to the outer wall of the capsule, and if there is destruction of the cell, the core material inside the cell is released.

The microcapsule contains capsule A and capsule B having different core materials, and the core material of capsule A and the core material of capsule B are crosslinked to restore voids and cracks.

The core material includes amine and epoxy. Epoxy functions as an insulator to restore voids, and the amine-based crosslinks with the epoxy to cure the epoxy. The epoxy is cured by the crosslinking structure generated by the reaction of the active hydrogen and the epoxy functional group present in the amine system, and the structure becomes dense due to the crosslinking reaction, so the performance of the cured product is excellent.

When voids and cracks occur in the insulating resin, in order for the voids and cracks to self-restore (self-healing), an amine-based and epoxy core material is manufactured in a capsule structure surrounding the cell, and the cell is destroyed by an electric tree. It is important to be able to release the amine-based core material and the epoxy core material, respectively.

The microcapsule is produced by synthesizing a core material and a cell.

The core material is one selected from amine core materials based on hydrocarbons and epoxide core materials based on hydrocarbons, and the cell (outer wall of the capsule) is selected from MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, and silica coated MUF capsules. It is one.

Hydrocarbon-based amine core materials and MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, silica coated MUF capsules can be synthesized to synthesize a selected one of the amine-based core material to produce a microcapsule.

A microcapsule having an epoxy core material can be produced by synthesizing a hydrocarbon-based epoxide core material and one selected from MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, and silica coated MUF capsules.

A microcapsule having an amine-based core material may be referred to as capsule A, and a microcapsule having an epoxy core material may be referred to as capsule B. The capsule A and the capsule B are uniformly dispersed in the insulating resin, and when destroyed by an electric tree, the core material of the capsule A and the core material of the capsule B can perform a crosslinking reaction.

Hydrocarbon-based amine core material may be a core material synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine. The core material synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine has excellent thermal stability and good flowability.

Hydrocarbon-based epoxide core materials include bisphenol A diglycidyl ether and PEG, a core material containing a terminal hydroxyl group, terephthaloyl chloride and diethyleneglycol, a core material containing a hydroxyl group at the end, and Terephthaloyl chloride (DEG) and It may be one selected from core materials containing an epoxide group at the terminal by using epichlorohydrin.

The above hydrocarbon-based epoxide core material has good thermal stability, maintains ring shape, and is easy to synthesize with cells.

The microcapsule has a cell-to-core weight ratio (Shell: Core) of 1: 2 to 1: 5, preferably 1: 2.5. If the weight ratio of the cell to the core material is less than 1: 2 or greater than 1: 5, the capsule shape is not maintained. The stability of the capsule can be improved and the stable content of the core material can be maintained even after water washing.

 MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, and silica coated MUF capsules have excellent thermal stability and maintain a stable shape to stably contain a core material therein. MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, silica-coated MUF capsules are destroyed at 200 ° C. or higher, so that the microcapsule is not destroyed due to the extrusion temperature during insulator production. The shape of the capsule in the insulator is maintained stably and destroyed by the electric tree to perform self-healing function.

Silica coated MUF capsules maintain a stable shape compared to other silica uncoated capsules.

The size of the microcapsules ranges from 140 to 280 μm. In the capsule size range, the core material is stably contained inside the cell.

On the other hand, the silicone insulator manufacturing method is to prepare a microcapsule having a core material as an epoxy and a microcapsule having an amine-based core material, and mixing a microcapsule having an epoxy core material and a microcapsule having an amine-based core material in an insulating resin, followed by uniform mixing. Extruded to prepare an insulator.

When the microcapsule whose core material is epoxy is added to urea, outer wall strengthening agent, ammonium, and EMA in distilled water to form a cell by adjusting the pH, the core material is further added to and stirred in distilled water, and then formaldehyde is added again and stirred. As the core material is filled in the cell, the capsule is manufactured. After that, it is enough to obtain a capsule that has been sunk in distilled water.

Stirring is performed at 600-800 rpm. The stirring speed is related to the capsule size, but the stirring speed is too high, the capsule size is too small to contain the core material, and if the stirring speed is too low, the amount of the core material is increased and the capsule shape is not maintained.

A silica coating precursor may be further added to the prepared capsule to coat the silica with the capsule. The silica coating keeps the capsule shape stable.

A microcapsule having an amine-based core material is prepared by preparing a hollow capsule with an empty inside, dipping the hole capsule in a water bath containing an amine solution, and applying vacuum to fill the hole capsule with an amine solution. The prepared capsules sink to the bottom of the water tank, so a capsule at the bottom of the water tank can be obtained.

Hereinafter, the present invention will be described through synthetic experiments.

1. Core material synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine

The structure and synthesis scheme of the hydrocarbon-based capsule core material using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine are as follows.

<Amine-based core material structure and synthetic reaction formula>

a. Response design

For the synthesis of a hydrocarbon-based capsule core material containing a terminal amine group, easy tosylation is used, and 4,7,10-trioxa-1,13-diamine is used to increase the flowability of the product. The reaction proceeded.

b. Synthesis progress

4,7,10-trioxa-1,13-diamine, CuO, and EA as a reaction solvent were added to a round bottom flask, p-toluenesulfonyl chloride and EA were added to the drop funnel, and the reaction was continued for 5 hours after slowly dropwise. After the product produced for the purification process was dissolved in MC, D.I water and extraction were performed.

c. Synthesis results analysis

FIG. 2 is an NMR spectra graph of p-Toluenesulfonyl chloride, FIG. 3 is an NMR spectra graph of 4,7,10-trioxa-1,13-diamine, and FIG. 4 is a product NMR spectra graph after reaction for 5 hours.

2 to 5, 7.5-ppm and 7.1-ppm peaks of p-toluenesulfonyl chloride were shifted in the product NMR spectra, and peaks of 2.6ppm and 1.6ppm of 4,7,10-trioxa-1,13-diamine were It was confirmed that the composition was synthesized according to the designed synthetic structure.

 In addition, since the flowability of the product is good, it is confirmed that it is suitable as a capsule core material.

d. TGA analysis

5 is a TGA analysis graph of 4,7,10-trioxa-1,13-diamine and product.

In FIG. 5, it was confirmed that the thermal stability was increased compared to the starting material by seeing that the decomposition temperature of the product was higher than that of the starting material 4,7,10-trioxa-1,13-diamine.

Therefore, since the product has thermal stability than the starting material, it is suitable for application as a capsule core material.

As a result of the experiment, it can be confirmed that the core material synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine is suitable as an amine-based core material.

2. Core material containing terminal hydroxyl groups using bisphenol A diglycidyl ether and PEG

The structure and synthetic reaction scheme of the core material including the terminal hydroxy group using bisphenol A diglycidyl ether and PEG are as follows.

<Epoxy core material structure and synthetic reaction formula>

a. Response design

For the synthesis of a hydrocarbon-based capsule core material containing an epoxide group at the terminal, a monomer containing a hydroxyl group at the terminal was first synthesized.

b. Synthesis progress

After adding bisphenol A diglycidyl ether, PEG and KOH to the round bottom flask, the reaction was performed for 2 hours under reflux. After the reaction proceeded, extraction was performed using D.I water and EA.

c. Synthesis results analysis

6 is a NMR spectra graph of a product after 2 hours of reaction.

As a result of NMR analysis of FIG. 6, it can be confirmed that PEG was synthesized at the terminal through the open of the epoxy ring of bisphenol A diglycidyl ether.

In addition, when comparing the integral values, it can be confirmed that PEG was synthesized at both ends.

As a result of the experiment, it can be confirmed that a core material containing a terminal hydroxy group is suitable as an epoxy core material using bisphenol A diglycidyl ether and PEG.

3. Core material containing hydroxy groups at the ends using terephthaloyl chloride and diethyleneglycol

Terephthaloyl chloride and diethyleneglycol are used for the structure of the core material containing hydroxy groups at the ends and the synthetic reaction scheme is as follows.

<Epoxy core material structure and synthetic reaction formula>

a. Response design

In order to synthesize a capsule core material containing an epoxide group at the terminal, a substance containing a hydroxyl group at the terminal was first synthesized. In addition, synthesis was performed using diethyleneglycol to increase the flowability of the product.

b. Synthesis progress

After diethyleneglycol and TEA were added to the round bottom flask, stir. After adding terephthaloyl chloride and reaction solvent to the drop funnel, drop wise into a round bottom flask. The reaction was conducted for 4 hours after drop wise. After the reaction was completed, TEA salt was removed through filteration. After removal of the solvent, extraction was performed using EA and D.I water.

c. Synthesis results analysis

7 is a product NMR spectra graph after the reaction proceeds for 4 hours.

According to FIG. 7, after reacting for 4 hours, it was confirmed that diethyleneglycol was synthesized at both ends of terephthaloyl chloride.

As a result of the experiment, it can be confirmed that a core material containing a hydroxyl group at the terminal is suitable as an epoxy core material using Terephthaloyl chloride and diethyleneglycol.

4. Core material containing epoxide groups at the ends using terephthaloyl chloride (DEG) and epichlorohydrin

Terephthaloyl chloride (DEG) and the structure of the core material containing epoxide groups at the ends using epichlorohydrin and the synthetic reaction scheme are as follows.

<Epoxy core material structure and synthetic reaction formula>

a. Response design

A capsule core material containing epoxide was synthesized using epichlorohydrin containing a hydroxy group at the terephthaloyl chloride (DEG) terminal and a halogen group having high reactivity.

b. Synthesis progress

After adding NaOH, TBAB and deionized water to the round bottom flask, stir. After dissolving terephthaloyl chloride (DEG) in a small amount of acetone, it was added to a round bottom flask. After stir for 1 hour in a 40 ℃ oil bath, epichlorohydrin was added and the reaction was carried out for 1 hour.

c. Synthesis results analysis

8 is a product NMR spectra graph after reaction progress.

As shown in FIG. 8, after the reaction proceeded, it was confirmed that the epoxy ring was synthesized without being opened by seeing that a peak corresponding to the epoxy ring was present. In addition, it was confirmed that epichlorohydrin was synthesized at both ends of terephthaloyl chloride (DEG) through an integral ratio comparison.

d.TGA analysis

9 is a product TGA graph of the synthesis of terephthaloyl chloride (DEG) and epichlorohydrin at the end.

When analyzing the thermal stability of the product through the TGA analysis of FIG. 9, it is determined that the thermal stability is weaker than terephthaloyl chloride (DEG), but is suitable for application as a capsule core material.

As a result of the experiment, it can be confirmed that a core material containing an epoxide group at the terminal is suitable as an epoxy core material using Terephthaloyl chloride (DEG) and epichlorohydrin.

5. UF capsules containing core material (epoxy)

10 is a schematic diagram of the synthesis of UF capsules.

Capsules are made with an oil in water system using in-situ polymerization.

Urea, a precursor that forms the outer wall of the UF capsule, the outer wall strengthening agent (resorcinol), which helps to strengthen the outer wall of the capsule, and ammonium chloride, which acts as a buffer for pH changes, and finally the emulsion of the core ( Emulsion stabilizes ethylene maleic anhydride (EMA) in 20 ml of distilled water, and then adjusts the pH to 3.5 using sodium hydroxide and hydrochloric acid. The core material was added to the prepared solution, and stirring was performed at a fixed rpm of 10 to 15 minutes to stably form an emulsion.

Subsequently, formaldehyde was added, followed by stirring at 60 ° C. for 4 hours to prepare a capsule. Thereafter, the residue was removed by distillation using distilled water, and after filtering, dried for 24 hours to obtain a final capsule. Figure 11 shows the synthetic reaction formula of the final obtained UF capsule.

12 shows the capsule size graph according to the content ratio of the shell monomer and core material of the UF capsule.

Capsules were synthesized by adjusting the content ratio of shell monomer and core material in the UF capsule. As the content of the core material increases, the RPM of the mechanical stirer is fixed to check the effect of the capsule synthesis, and the size of the capsule becomes smaller as the core material content ratio increases from 3 to 5 times the core weight compared to the shell weight. It was confirmed to lose.

It is confirmed that if the core material is added to the reaction solution over a certain amount, the effect of the capsule size due to the increase in the shear stress of the reaction solution increases.

13 is a graph showing the capsule size control according to the stirring speed of the UF capsule.

As shown in FIG. 13, when the capsule is synthesized, the synthesis is performed under mechanical agitation, which means that the capsule size can be adjusted by adjusting the RPM of the stirrer during capsule production.

As a result of observing the change in capsule size while increasing the RPM from 500 RPM to 1500 RPM, capsules with a diameter of about 280 μm were synthesized at low RPM, and capsules with a size of about 140 μm were synthesized at 1500 RPM.

The viscosity of the epoxy (EPON826) used as the core material has 65-95 Poise, which is inconvenient to handle in the process and needs to lower the viscosity of the core material. In this experiment, B.G.E (Butyl Glycidyl ehter) was used, and the viscosity was adjusted by adding a content ratio of 10 to 30 wt%.

The higher the content of B.G.E, the lower the viscosity of the core material, and the experiment was carried out by fixing the viscosity of the core at 700 RPM to confirm the effect on the capsule size.

14, the capsule size control according to the viscosity of the core material is illustrated in a graph.

As shown in FIG. 14, as the BGE content increased, a small capsule could be obtained even at the same RPM, and the content of the BGE, which had the highest yield, increased the RPM of the agitator to 3000 RPM under the condition of 20 wt%, and the size was less than 50 μm. Could synthesize a capsule with.

The thermal stability of the UF capsules was analyzed.

15 is a thermal stability analysis graph and OM picture of the UF capsule.

In order to analyze the thermal stability of the UF capsules, it was analyzed using TGA equipment and OM equipment that can be observed in real time. It is necessary to secure the thermal stability of the capsule in order to withstand the curing temperatures of 120 ° C and 170 ° C when manufacturing an insulator.

As shown in Fig. 15, as a result of analyzing the TGA of the capsule, a -5 wt% weight loss point did not come up to around 250 ° C. However, as a result of checking through the OM equipment observed in real time, it can be confirmed that a part of the capsule was destroyed from 200 ° C and thermal stability was secured.

In order for the synthesized UF capsule to be destroyed in the electric tree, it is important to control the thickness of the capsule. The capsule was synthesized while increasing the content ratio of the core material for thickness control, and SEM, TGA, DSC, etc. were used to confirm the thickness.

First, as a result of observing the surface state of the capsule through SEM, as the content ratio of the core material increased, a capsule with a relatively smooth surface as shown in FIG. 16 could be obtained. In addition, as shown in FIG. 17, the capsule thickness of the capsule (CAP6.C20.R700), which had the largest core content, was obtained to be considered to be approximately 8.4 μm.

It was also confirmed through a thermogravimetric analyzer (TGA) that the capsule exhibited a change in thickness. The higher the core material content of the capsule, the faster the pyrolysis temperature appeared.

It was confirmed from the differential scanning calorimeter (DSC) that the endothermic peak was advanced.

6. UF capsule containing core material (amine)

An amine capsule can be prepared through vacuum infiltration. First, an empty hollow capsule is first manufactured, then a hollow capsule is immersed in a bath containing an amine solution, and then vacuum is applied to fill the empty hollow capsule with the amine solution. Lose.

Through this method, the capsule filled with the amine solution sinks to the bottom, and when the capsule sinks to the bottom, an amine capsule can be obtained.

7. The self-healing properties of the synthesized epoxy capsules (Capsule 1) and amine-based capsules (Capsule 2) were confirmed.

It was confirmed through real-time optical microscopy (O.M) equipment that curing occurs when voids are formed in the parts where the capsules are substantially dispersed through the synthesized epoxy capsules and amine-based capsules. First, the synthesized epoxy capsule and the amine-based capsule were prepared in a weight ratio of 2: 1.

Since the composition ratio of the curing conditions of the epoxy and the amine is approximately 2: 1, the weight ratio of the epoxy capsule and the amine capsule is also 2: 1, and the self-healing properties are confirmed by dispersing in the commonly used epoxy as a matrix material. Did.

First, the place where the capsule was dispersed a lot was wound, and second, the portion where the capsule was dispersed a little was wounded to see if it was self-healing. As shown in FIG. 18, it was confirmed that the voids were restored by raising both parts to a temperature at which the epoxy and the amine could be cured.

As a result of the experiment, the epoxy capsule (Capsule 1) and the amine-based capsule (Capsule 2) did not affect the epoxy, and only voids were restored. Through this, it can be confirmed that the microcapsule has self-healing properties when damage to the insulator occurs without deteriorating the performance of the insulator.

Through the above experiment results, the present invention is used as an internal additive such as a silicone insulator inside an intermediate junction box connecting a high voltage cable, a stress cone, a coating of a high voltage cable, and a cable system of a transmission system. It can be seen that even if damage occurs, it can be easily self-healing.

In addition, the present invention relates to the restoration of internal / external scratches that occur in the field when (high) high voltage cables are connected (combined), cracks or voids in or out of insulators, or to mitigate or advance the progress of electric trees based on voids. It can be seen that suppression, etc. can effectively counter social and economic losses caused by the destruction of insulation.

The present invention has been described with the best embodiments in the drawings and specifications. Here, although specific terms are used, they are used for the purpose of describing the present invention only, and are not used to limit the scope of the present invention described in the meaning limitation or the claims. Therefore, the present invention will be understood by those of ordinary skill in the art that various modifications and other equivalent embodiments are possible. Therefore, the true technical scope of the present invention should be defined by the technical spirit of the appended claims.

Claims (14)

Insulating resin; And
A microcapsule which is dispersed in the insulating resin, and when voids and cracks occur in the insulating resin, the generated and advancing electric tree is destroyed by the electric tree and releases the core material to restore the voids and cracks;
Including,
The microcapsule is composed of a self-healing core material and a cell surrounding the core material, and releases the core material by destruction of the cell,
The microcapsules include capsule A and capsule B having different core materials,
The core material of the capsule A and the core material of the capsule B are cross-linked to restore the voids and cracks,
The capsule A is an epoxy capsule in which the core material is a hydrocarbon-based epoxide core material,
The capsule B is an amine-based capsule in which the core material is a hydrocarbon-based amine core material,
The hydrocarbon-based amine core material
It was synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine,
The hydrocarbon-based epoxide core material is
A core material containing a terminal hydroxy group using bisphenol A diglycidyl ether and PEG, a core material containing a terminal hydroxyl group using Terephthaloyl chloride and diethyleneglycol, and a terminal epoxide using Terephthaloyl chloride (DEG) and epichlorohydrin Self-healing silicone insulator, characterized in that it is one selected from the core material comprising a group. delete delete The method according to claim 1,
The epoxy capsule and the amine-based capsule is a self-healing silicone insulator, characterized in that the core material has a weight ratio of 2: 1. The method according to claim 1,
The cell (capsule outer wall) is a self-healing silicone insulator, characterized in that one selected from MUF capsules, UF capsules, epoxy capsules, polyurethane capsules, silica coated MUF capsules. delete delete The method according to claim 1,
The microcapsules
Self-healing silicone insulator, characterized in that the weight ratio of the cell to the core material ranges from 1: 2 to 1: 5. The method according to claim 1,
The microcapsule is a self-healing silicone insulator, characterized in that the size ranges from 140 to 280 µm. Preparing a microcapsule in which the core material is epoxy and a microcapsule in which the core material is amine; And
Mixing the microcapsule having the core material as an epoxy and the microcapsule having the core material as an amine in an insulating resin, stirring and uniformly mixing, and then extruding to prepare an insulator;
It includes,
In the microcapsule in which the core material is epoxy, the core material is a hydrocarbon-based epoxide core material,
The core material is an amine-based microcapsule, the core material is a hydrocarbon-based amine core material,
The hydrocarbon-based amine core material
It is an amine solution synthesized using p-Toluenesulfonyl chloride and 4,7,10-trioxa-1,13-diamine,
The hydrocarbon-based epoxide core material is
A core material containing a terminal hydroxy group using bisphenol A diglycidyl ether and PEG, a core material containing a terminal hydroxyl group using Terephthaloyl chloride and diethyleneglycol, and a terminal epoxide using Terephthaloyl chloride (DEG) and epichlorohydrin A method of manufacturing a self-healing silicone insulator, characterized in that it is one selected from core materials comprising a group. The method according to claim 10,
The microcapsules wherein the core material is epoxy
Adding urea, outer wall strengthening agent, ammonium, and EMA to distilled water and adjusting the pH to form a cell;
Adding and stirring the core material to the distilled water;
After stirring, adding formaldehyde to the distilled water and stirring; And
Obtaining a capsule submerged in the distilled water;
Self-healing silicone insulator manufacturing method comprising a. The method according to claim 11,
The stirring is a self-healing silicone insulator manufacturing method, characterized in that performed at 600 ~ 800rpm. The method according to claim 11,
A method of manufacturing a self-healing silicone insulator, characterized in that the capsule is silica coated by further adding a silica coating precursor. The method according to claim 10,
The core material is an amine-based microcapsule
Manufacturing an empty hollow capsule;
Dipping the hole capsule in a water tank containing the amine solution and applying a vacuum to fill the hole capsule with an amine solution; And
Obtaining a capsule that has sunk to the bottom of the water tank;
Self-healing silicone insulator manufacturing method comprising a.

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