Insulator material hydrophobically modified by alicyclic epoxy resin as well as preparation method and application of insulator material

Abstract

The invention relates to the technical field of electric insulating materials, and discloses an alicyclic epoxy resin hydrophobically modified insulator material and a preparation method and application thereof, the insulator material comprises an alicyclic epoxy resin matrix material and a surface modification material coated on the surface of the alicyclic epoxy resin matrix material; the alicyclic epoxy resin matrix material is prepared from the following raw materials: alicyclic epoxy resin, a curing agent A and an accelerant, raw materials for preparing the surface modification material comprise matrix resin, a curing agent B and a catalyst, and the matrix resin is dihydroxy polydimethylsiloxane and / or diphenyl (siloxane and polysiloxane). The novel insulator material based on alicyclic epoxy resin hydrophobic modification prepared by the invention not only has high mechanical strength, high pressure resistance and high weather resistance of an alicyclic epoxy resin insulating material, but also has excellent hydrophobic performance of a silicone rubber composite insulating material, avoids respective disadvantages of the alicyclic epoxy resin insulating material and the silicone rubber composite insulating material, and has a wide market prospect.

Description

Technical Field

[0001] The invention relates to the technical field of electric power insulation materials, and in particular to an insulator material hydrophobically modified by an alicyclic epoxy resin, a preparation method and an application thereof. Background Art

[0002] In recent years, in order to solve the problems and challenges faced by existing ceramic, glass and silicone rubber insulators during network operation, high-voltage insulation materials represented by alicyclic epoxy resins have gradually become a research hotspot. Compared with traditional outdoor insulation materials, alicyclic epoxy resins have the advantages of high temperature resistance, high voltage resistance, good weather resistance, and high mechanical strength, so that when used in outdoor high-voltage scenarios, they can not only effectively withstand the effects of multiple physical fields such as heat, electricity, and force, but also have excellent core rod-sheath interface bonding performance and a long service life. However, the hydrophobicity of alicyclic epoxy resin-based insulation materials is still insufficient, and it is difficult to meet the needs of the rapidly developing high-voltage power industry, especially when used in outdoor high-voltage transmission lines. It not only has to withstand extremely high voltages, but also faces harsh climatic environments. Under such complex conditions, insulation equipment often flashes over or even fails. Summary of the invention

[0003] The purpose of the present invention is to overcome the poor hydrophobicity of existing cycloaliphatic epoxy resin-based insulating materials, and to provide an insulator material, a preparation method and an application of hydrophobically modified alicyclic epoxy resin. The solution uses a modified material to hydrophobically modify the surface of the alicyclic epoxy resin material so that its hydrophobicity reaches the standard for use in the insulating material industry. The method can greatly improve the hydrophobicity of the surface of the insulating material.

[0004] In order to achieve the above-mentioned object, the present invention provides, on one hand, an alicyclic epoxy resin hydrophobically modified insulator material, the insulator material comprising an alicyclic epoxy resin base material and a surface modification material coated on the surface of the alicyclic epoxy resin base material;

[0005] The raw materials for preparing the alicyclic epoxy resin matrix material contain alicyclic epoxy resin, curing agent A and accelerator;

[0006] The raw materials for preparing the surface modified material contain base resin, curing agent B and catalyst;

[0007] The base resin is dihydroxy polydimethylsiloxane and / or diphenyl (siloxane and polysiloxane).

[0008] The present invention adopts a polar functional group-terminated organosilicon material, which enhances the interaction between the surface modified material and the surface of the alicyclic epoxy resin material through hydrogen bonds and van der Waals forces between organic groups, improves the interfacial compatibility between heterogeneous materials, and can obtain a stable and firm bonding interface.

[0009] Preferably, the weight ratio of the alicyclic epoxy resin, the curing agent A and the accelerator is 100:110 to 130:1.

[0010] In a preferred embodiment, the alicyclic epoxy resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or diglycidyl phthalate.

[0011] Furthermore, the curing agent A is methylhexahydrophthalic anhydride and / or ethylenediamine; and the accelerator is benzyldimethylamine.

[0012] In a preferred embodiment, the weight ratio of the base resin, the curing agent B and the catalyst is 50:3 to 4:1.

[0013] Preferably, the curing agent B is selected from one or more of methyltriacetoxysilane, γ-aminopropyltriethoxysilane and methyltributylidene oxime silane;

[0014] Preferably, the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate and dibutyltin isodicetoate.

[0015] In the present invention, in order to maintain appropriate viscosity and fluidity and facilitate operation, the weight ratio of each substance is controlled within the above range.

[0016] A second aspect of the present invention provides a method for preparing the above-mentioned alicyclic epoxy resin hydrophobically modified insulator material, the preparation method comprising the following steps:

[0017] The alicyclic epoxy resin is mixed with a curing agent A and an accelerator and then heated and cured to obtain an alicyclic epoxy resin matrix material;

[0018] The base resin is mixed with the curing agent B and the catalyst and then vacuum dried to obtain a mixture;

[0019] The mixture is coated on the surface of the alicyclic epoxy resin matrix material, and then cured to obtain an alicyclic epoxy resin hydrophobically modified insulator material.

[0020] In the present invention, the specific operation of the heating curing includes: heating at 90-100° C. for 2-2.5 hours, then heating at 110-130° C. for 1-1.5 hours, and finally heating at 140-160° C. for 3-3.5 hours.

[0021] The purpose of vacuum drying is to remove the bubbles inside the material (if the bubbles are not removed, the mechanical properties of the final material will be affected). Therefore, the vacuum drying conditions only need to be able to remove the bubbles inside the material.

[0022] Furthermore, the curing conditions include: a temperature of 20 to 30° C. and a time of 72 to 96 hours.

[0023] In a preferred case, the coating method is selected from one or more of brushing, spraying, dipping and pouring; wherein the coating thickness of the mixture is 0.5 to 2 mm, that is, during coating, the thickness of the mixture coated on the surface of the alicyclic epoxy resin matrix material is controlled to be 0.5 to 2 mm.

[0024] In the present invention, the mixture coated on the alicyclic epoxy resin matrix material is cured to obtain a surface modified material.

[0025] A third aspect of the present invention provides a use of the above-mentioned alicyclic epoxy resin hydrophobically modified insulator material in the preparation of an insulator.

[0026] The beneficial effects of the present invention are as follows:

[0027] (1) The present invention coats the surface of the alicyclic epoxy resin with an organic silicon material, thereby completing the hydrophobic modification of the surface of the alicyclic epoxy resin material, and overcoming the problem that the alicyclic epoxy resin itself has poor hydrophobic properties as an insulating material.

[0028] (2) The present invention uses a polar functional group-terminated silicone material to enhance the interaction between the surface modified material and the surface of the alicyclic epoxy resin material through hydrogen bonds between organic groups (the hydroxyl groups on the base resin will form hydrogen bonds with the oxygen atoms on the alicyclic epoxy resin) and van der Waals forces, thereby improving the interfacial compatibility between heterogeneous materials and obtaining a stable and firm bonding interface.

[0029] (3) The novel insulator material based on hydrophobic modification of alicyclic epoxy resin prepared by the present invention has both the high mechanical strength, high voltage resistance and high weather resistance of alicyclic epoxy resin insulating materials and the excellent hydrophobic properties of silicone rubber composite insulating materials, thus avoiding the disadvantages of both and having broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a graph showing the hydrophobicity classification test results of the hydrophobically modified insulator material of the alicyclic epoxy resin prepared in Example 1;

[0031] Figure 2 This is a graph showing the cross-hatch adhesion test result of the surface of the insulator material modified with hydrophobic alicyclic epoxy resin prepared in Example 1;

[0032] Figure 3 This is a graph showing the hydrophobicity classification test results of the hydrophobically modified insulator material of the alicyclic epoxy resin prepared in Example 2;

[0033] Figure 4This is a graph showing the cross-hatch adhesion test result of the surface of the insulator material modified with hydrophobic alicyclic epoxy resin prepared in Example 2;

[0034] Figure 5 This is a graph showing the hydrophobicity classification test results of the alicyclic epoxy resin matrix material prepared in Comparative Example 1;

[0035] Figure 6 This is a graph showing the cross-hatch adhesion test results of the surface of the insulator material modified with hydrophobic alicyclic epoxy resin prepared in Comparative Example 2. DETAILED DESCRIPTION

[0036] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings and examples. It should be understood that the specific implementation described herein is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0037] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0038] Example 1

[0039] (1) 100 g of alicyclic epoxy resin (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate) was uniformly mixed with 130 g of curing agent A (methyl hexahydrophthalic anhydride) and 1 g of accelerator (benzyldimethylamine) and then heated and cured. The specific operation of the heating and curing included: heating at 90° C. for 2 h, then heating at 120° C. for 1 h, and finally heating at 150° C. for 3 h to obtain an alicyclic epoxy resin matrix material;

[0040] (2) 100 g of base resin (dihydroxy polydimethylsiloxane) was mixed with 8 g of curing agent B (methyltriacetoxysilane) and 2 g of catalyst (dibutyltin dilaurate) and then placed in a vacuum drying oven for vacuum drying to remove bubbles inside the material to obtain a mixture;

[0041] (3) coating the mixture obtained in step (2) on the surface of the alicyclic epoxy resin matrix material obtained in step (1) (the coating method is pouring coating), the coating thickness of the mixture is 0.5 mm, and then curing is performed. The curing conditions include: temperature of 25° C. and time of 72 hours, to obtain an alicyclic epoxy resin hydrophobically modified insulator material, the insulator material includes an alicyclic epoxy resin matrix material and a surface modification material coated on the surface of the alicyclic epoxy resin matrix material; after the alicyclic epoxy resin hydrophobically modified insulator material is cut vertically, the two materials do not debond, indicating that the curing is complete.

[0042] Example 2

[0043] (1) 100 g of alicyclic epoxy resin (diglycidyl phthalate) was uniformly mixed with 110 g of curing agent A (ethylenediamine) and 1 g of accelerator (benzyldimethylamine) and then heated and cured. The specific operation of the heating and curing included: heating at 90° C. for 2 h, then heating at 120° C. for 1 h, and finally heating at 150° C. for 3 h to obtain an alicyclic epoxy resin matrix material;

[0044] (2) 100 g of base resin (dihydroxy polydimethylsiloxane) was mixed with 8 g of curing agent B (methyl tributylidene oxime silane) and 2 g of catalyst (stannous octoate), and then placed in a vacuum drying oven for vacuum drying to remove bubbles inside the material to obtain a mixture;

[0045] (3) coating the mixture obtained in step (2) on the surface of the alicyclic epoxy resin matrix material obtained in step (1) (by brushing), the coating thickness of the mixture being 1 mm, and then curing the mixture. The curing conditions include: a temperature of 25° C. and a time of 72 h, to obtain an alicyclic epoxy resin hydrophobically modified insulator material, the insulator material including an alicyclic epoxy resin matrix material and a surface modified material coated on the surface of the alicyclic epoxy resin matrix material; after the alicyclic epoxy resin hydrophobically modified insulator material is cut vertically, the two materials do not debond, indicating that the curing is complete.

[0046] Comparative Example 1

[0047] 100g of alicyclic epoxy resin (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate) is evenly mixed with 120g of curing agent A (methylhexahydrophthalic anhydride) and 1g of accelerator (benzyldimethylamine) and then heat-cured. The specific operation of heat-curing includes: heating at 90°C for 2h, then heating at 120°C for 1h, and finally heating at 150°C for 3h to obtain an alicyclic epoxy resin matrix material.

[0048] Comparative Example 2

[0049] (1) 100 g of alicyclic epoxy resin (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate) was uniformly mixed with 120 g of curing agent A (methylhexahydrophthalic anhydride) and 1 g of accelerator (benzyldimethylamine) and then heated and cured. The specific operation of the heating and curing included: heating at 90° C. for 2 h, then heating at 120° C. for 1 h, and finally heating at 150° C. for 3 h to obtain an alicyclic epoxy resin matrix material;

[0050] (2) 100 g of a conventional commercially available coating material (brand name: HBD-01) was mixed evenly with 8 g of curing agent B (methyltriacetoxysilane) and 2 g of a catalyst (dibutyltin dilaurate), and the mixture was placed in a vacuum drying oven for vacuum drying to remove bubbles inside the material, thereby obtaining a mixture;

[0051] (3) coating the mixture obtained in step (2) on the surface of the alicyclic epoxy resin matrix material obtained in step (1) (by spraying), the coating thickness of the mixture being 1.5 mm, and then curing, the curing conditions comprising: a temperature of 25° C. and a time of 72 h, to obtain an alicyclic epoxy resin hydrophobically modified insulator material, the insulator material comprising an alicyclic epoxy resin matrix material and a surface modified material coated on the surface of the alicyclic epoxy resin matrix material; after the alicyclic epoxy resin hydrophobically modified insulator material is cut vertically, the two materials do not debond, indicating that the curing is complete.

[0052] Test Case

[0053] The hydrophobicity classification and adhesion grade of the hydrophobically modified insulator material of the cycloaliphatic epoxy resin obtained in Examples 1-2 and Comparative Example 2 and the hydrophobicity classification and adhesion grade of the cycloaliphatic epoxy resin matrix material obtained in Comparative Example 1 were respectively detected;

[0054] The hydrophobicity classification was tested according to the industry standard DL / T 376-2010, and the adhesion grade was tested according to GB / T9286-1998. The results are shown in Table 1. The hydrophobicity classification test results of the materials obtained in Examples 1-2 and Comparative Example 1 are shown in Table 1. Figure 1 , 3 5 (the hydrophobic classification test result diagram of comparative example 2 is similar to that of the embodiment), the surface cross-hatch adhesion test result diagrams of the materials obtained in embodiments 1-2 and comparative example 2 are respectively as shown in Figure 2 , 4 and 6 (Comparative Example 1 has only one material and there is no adhesion).

[0055] Table 1

[0056]

[0057] It can be seen from the above results that the hydrophobically modified insulator material of the alicyclic epoxy resin obtained in the present invention has good hydrophobicity and good adhesion between the materials; it can be seen that the present invention completes the hydrophobic modification of the surface of the alicyclic epoxy resin material by coating the organosilicon material terminated with polar functional groups on the surface of the alicyclic epoxy resin, overcoming the problem that the alicyclic epoxy resin itself has poor hydrophobicity as an insulating material. At the same time, the hydrogen bonds and van der Waals forces between the polar functional groups enhance the interaction between the surface modified material and the surface of the alicyclic epoxy resin material, improve the interface compatibility between heterogeneous materials, and obtain a stable and firm bonding interface.

[0058] It should be understood that parts not elaborated in detail in this specification belong to the prior art.

[0059] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An insulator material hydrophobically modified by alicyclic epoxy resin, characterized in that: The insulator material comprises an alicyclic epoxy resin matrix material and a surface modification material coated on the surface of the alicyclic epoxy resin matrix material; The raw materials for preparing the alicyclic epoxy resin matrix material contain alicyclic epoxy resin, curing agent A and accelerator; The raw materials for preparing the surface modified material contain base resin, curing agent B and catalyst; The base resin is dihydroxy polydimethylsiloxane and / or diphenyl (siloxane and polysiloxane).

2. The hydrophobically modified insulator material of alicyclic epoxy resin according to claim 1, characterized in that: The weight ratio of the alicyclic epoxy resin, the curing agent A and the accelerator is 100:110 to 130:

1.

3. The hydrophobically modified insulator material of alicyclic epoxy resin according to claim 1 or 2, characterized in that: The alicyclic epoxy resin is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or diglycidyl phthalate.

4. The hydrophobically modified insulator material of alicyclic epoxy resin according to claim 1 or 2, characterized in that: The curing agent A is methyl hexahydrophthalic anhydride and / or ethylenediamine; The accelerator is benzyl dimethylamine.

5. The hydrophobically modified insulator material of alicyclic epoxy resin according to claim 1, characterized in that: The weight ratio of the base resin, curing agent B and catalyst is 50:3 to 4:1; The curing agent B is selected from one or more of methyltriacetoxysilane, γ-aminopropyltriethoxysilane and methyltributylidene oxime silane; The catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diisooctoate.

6. The method for preparing the hydrophobically modified insulator material of alicyclic epoxy resin according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The alicyclic epoxy resin is mixed with a curing agent A and an accelerator and then heated and cured to obtain an alicyclic epoxy resin matrix material; The base resin is mixed with the curing agent B and the catalyst and then vacuum dried to obtain a mixture; The mixture is coated on the surface of the alicyclic epoxy resin matrix material, and then cured to obtain an alicyclic epoxy resin hydrophobically modified insulator material.

7. The preparation method according to claim 6, characterized in that: The specific operation of the heating curing includes: heating at 90-100° C. for 2-2.5 hours, then heating at 110-130° C. for 1-1.5 hours, and finally heating at 140-160° C. for 3-3.5 hours.

8. The preparation method according to claim 6, characterized in that: The curing conditions include: a temperature of 20 to 30° C. and a time of 72 to 96 hours.

9. The preparation method according to claim 6, characterized in that: The coating method is selected from one or more of brush coating, spray coating, dip coating and pour coating; The coating thickness of the mixed material is 0.5-2 mm.

10. Use of the hydrophobically modified insulator material of alicyclic epoxy resin according to any one of claims 1 to 5 in the preparation of insulators.

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