CN112852103B - Flexible epoxy composition for outdoor composite insulator - Google Patents
Flexible epoxy composition for outdoor composite insulator Download PDFInfo
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- CN112852103B CN112852103B CN202110028040.7A CN202110028040A CN112852103B CN 112852103 B CN112852103 B CN 112852103B CN 202110028040 A CN202110028040 A CN 202110028040A CN 112852103 B CN112852103 B CN 112852103B
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- epoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a flexible epoxy composition for an outdoor composite insulator; the epoxy resin toughening agent is prepared by heating and mixing epoxy resin, a toughening agent, an epoxy diluent, a curing agent, inorganic filler and an accelerant and then thermally curing. The epoxy resin consists of alicyclic epoxy resin and aliphatic long-chain epoxy resin; the epoxy composition is suitable for replacing silicon rubber to prepare the composite insulator shed material, and has light weight, high mechanical strength and excellent electrical property compared with the traditional ceramic, glass and silicon rubber shed materials. The invention has excellent elasticity, especially has excellent low-temperature elongation at break. The invention discloses a modified epoxy resin with excellent high toughness and high elongation, an outdoor epoxy system without unsaturated bonds and a process for realizing the modified epoxy resin.
Description
Technical Field
The invention belongs to the composite material technology, and particularly relates to a flexible epoxy composition for an outdoor composite insulator.
Background
The insulator materials in the current power grid comprise a porcelain insulator, a glass insulator, a silicon rubber composite insulator and an epoxy composite insulator, wherein the porcelain and glass materials are large in mass and easy to damage, the silicon rubber materials are mainly poor in rigidity and have the problems of bird pecking and limiting the overhaul of personnel, the epoxy material composite insulator is an ideal material at present, and a polymer material with high and low temperature resistance, heat resistance, ultraviolet resistance, good electrical insulation and mechanical properties can be obtained by blending and modifying weather-resistant alicyclic epoxy resin or hydrogenated bisphenol A epoxy resin and organosilicon modified epoxy resin or a nano rubber toughening agent.
From the material perspective, the existing organosilicon modified epoxy resin has the problems of poor stability, low silicon content and high cost, the nanometer rubber type is resistant to the purple heterodyne, and an outdoor system can only select the epoxy resin without benzene rings and unsaturated bonds for modification; from the application perspective, in the area with large temperature difference between day and night, the composite insulator is easy to crack, so that the area is powered off, and the composite insulator is not suitable for the area with large temperature difference.
Disclosure of Invention
In view of the problems and disadvantages of the prior art, the present invention provides an epoxy composition for a medium voltage outdoor electrical insulation system, which has specific mechanical and electrical insulation properties by adding a functional filler to a modified epoxy resin obtained by introducing an epoxy compound having a long aliphatic chain and a polyol polymer having a trace amount of hydroxyl groups. The invention discloses a novel epoxy composition, which belongs to the field of outdoor insulation and electricity and is mainly used for medium-voltage composite insulators.
The invention adopts the following technical scheme:
the flexible epoxy composition for the outdoor composite insulator is prepared from the following raw materials in parts by mass:
preferably, the composition is prepared from the following raw materials in parts by mass:
further preferably, the composition is prepared from the following raw materials in parts by mass:
the preparation method of the flexible epoxy composition for the outdoor composite insulator comprises the following steps of heating and pre-polymerizing epoxy resin, a toughening agent, an epoxy diluent and a part of curing agent, and then heating and mixing the epoxy resin, the toughening agent, the epoxy diluent and the part of curing agent with the rest of curing agent, inorganic filler and accelerator to obtain the flexible epoxy premix for the outdoor composite insulator; the flexible epoxy premix for the outdoor composite insulator is subjected to thermosetting to obtain the flexible epoxy composition for the outdoor composite insulator.
In the invention, the prepolymerization temperature is 90-110 ℃, and the time is 4-6 h; the temperature of heating and mixing is 90-110 ℃, the time is 4-6 h, and the heating and mixing are preferably carried out under vacuum; heat curing at 130-150 deg.C for 20-35min; preferably, post-curing is carried out after thermal curing, and the post-curing is carried out for 8-10h at 120-150 ℃.
In the invention, the epoxy resin (A) consists of alicyclic epoxy resin and aliphatic long-chain epoxy resin; the aliphatic long-chain epoxy resin is C 12 -C 36 A monofunctional epoxy group or a bifunctional epoxy group.
In the invention, the flexibilizer (B) is a polyol polymer containing hydroxyl groups, so that the high and low temperature resistance, the flexibility and the elongation at break of the material are improved.
In the invention, the diluent (C) is active monofunctional epoxy or difunctional epoxy glycidyl ether, which can reduce the system viscosity and the cost of the epoxy resin, and has the functions of partially toughening the epoxy resin and not causing obvious change to the use performance of the composite material.
In the invention, the inorganic filler (D) is composed of flame-retardant, heat-resistant and low-expansibility fillers, for example, the inorganic filler is selected from one or more of aluminum hydroxide, silicon micropowder, red phosphorus and melamine cyanurate; the mesh number of the inorganic filler is 400-2000 meshes.
In the invention, the curing agent (E) is an anhydride curing agent without unsaturated bonds, so that the epoxy resin is cured and crosslinked into a three-dimensional reticular high molecular polymer at a certain temperature; methylhexahydrophthalic anhydride, polyazelaic anhydride, polysebacic anhydride and the like are preferred.
In the present invention, the accelerator (F) is a tertiary amine or an imidazole such as benzyldimethylamine, tris- (dimethylaminomethyl) phenol, 1-methylimidazole. Accelerators are materials that lower the epoxy curing temperature and accelerate the epoxy reaction rate.
THE ADVANTAGES OF THE PRESENT INVENTION
1. The epoxy composition is suitable for replacing silicon rubber to prepare the composite insulator shed material, and has light weight, high mechanical strength and excellent electrical property compared with the traditional ceramic, glass and silicon rubber shed materials. The problem of bird pecking, personnel's maintenance and composite insulator at the tensile problem that ftractures of low temperature can be solved, and composite insulator can also keep normal operating in the place that the difference in temperature is big round the clock promptly, and the full skirt does not ftracture.
2. Compared with the closest technology at present, the method has certain advantages in cost, and the preparation process is simpler and easier to operate.
Detailed Description
The flexible epoxy composition for the outdoor composite insulator is prepared from epoxy resin, a toughening agent, an epoxy diluent, an inorganic filler, a curing agent and an accelerant; heating and pre-polymerizing epoxy resin, a toughening agent, an epoxy diluent and a part of curing agent, and then heating and mixing with the rest curing agent, inorganic filler and an accelerant to obtain a flexible epoxy premix for the outdoor composite insulator; the flexible epoxy premix for the outdoor composite insulator is subjected to thermosetting to obtain the flexible epoxy composition for the outdoor composite insulator. The epoxy resin cured product obtained has excellent elongation at break, particularly excellent elongation at break at low temperature, without other components and steps.
The invention discloses a preparation method of a flexible epoxy composition for an outdoor composite insulator, which comprises the following steps:
(1) Putting an anhydride curing agent accounting for 35-45% of the total weight of the alicyclic epoxy resin, the aliphatic long-chain epoxy resin, the epoxy diluent (B), the toughening agent (C) and the curing agent (E) into a mixing and stirring kettle, heating to 90-110 ℃, and fully stirring at a constant speed of 600-800 r/min for 4-6 h; obtaining modified epoxy resin;
(2) Putting the modified epoxy resin in the step (1), the residual curing agent (E) and the accelerator (F) into a mixing and stirring kettle again, heating to 60-80 ℃, uniformly stirring, putting the filler (D) into the stirring kettle, controlling the temperature at 100 ℃, and dehydrating in vacuum for 4 hours with the vacuum degree of less than or equal to-0.09 to obtain a mixture; the mixing and stirring kettle keeps the rotating speed of 600-800 r/min;
(3) Adding the mixture obtained in the step (2) into a preheated mold according to a conventional method, and heating at 130-150 ℃ for 20-35min for molding; then demoulding, and placing the product in a blast drying oven for post-curing for 8-10h at 120-150 ℃.
The present invention is further illustrated in detail below with reference to examples, which are representative, but not limiting, examples of the invention. Specific examples are shown in Table 1.
Table 1 example formulations
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| (A) Epoxy resin | 100 | 100 | 120 | 100 | 120 | 120 |
| (B) Toughening agent | 15 | 15 | 15 | 20 | 20 | 20 |
| (C) Epoxy diluent | 10 | 10 | 10 | 10 | 10 | 20 |
| (D) Inorganic filler | 250 | 250 | 250 | 250 | 250 | 250 |
| (E) Curing agent | 100 | 90 | 75 | 100 | 75 | 75 |
| (F) Accelerator | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Wherein the epoxy resin consists of alicyclic epoxy resin (TTA 184) and long-chain epoxy resin (UDO chemical YD-171) in a weight ratio of 100: 20; the diluent is polypropylene glycol diglycidyl ether (CAS No. 26142-30-3); the toughening agent is purchased from VL-2 of Beijing Qingdaqishi; the inorganic filler is silicon micropowder (1000 meshes); the curing agent is methyl hexahydrophthalic anhydride; the accelerator is 1-methylimidazole.
The preparation method of the novel flexible epoxy composition for the outdoor composite insulator comprises the following steps:
(1) Putting alicyclic epoxy resin, aliphatic long-chain epoxy resin, epoxy diluent, toughening agent and anhydride curing agent accounting for 40 percent of the total weight of the curing agent into a mixing and stirring kettle, heating to 100 ℃, and fully stirring at a constant speed for 5 hours at a rotating speed of 700r/min; obtaining modified epoxy resin;
(2) Adding the modified epoxy resin, the rest curing agent and the accelerator in the step (1) into a mixing and stirring kettle, heating to 70 ℃, uniformly stirring, adding the filler into the stirring kettle, controlling the temperature at 100 ℃, performing vacuum dehydration for 4 hours, and keeping the vacuum degree at less than or equal to-0.09 MPa to obtain a mixture, namely a flexible epoxy premix; the material mixing and stirring kettle keeps the rotating speed at 800r/min;
(3) Adding the mixture obtained in the step (2) into a preheated (140 ℃) mould according to a conventional method, and heating at 140 ℃ for 30min for forming; then demoulding, placing the mixture in a forced air drying oven, and carrying out postcuring for 9 hours at the temperature of 140 ℃ to obtain the epoxy composition.
Performing performance test according to a conventional method, wherein the mechanical property is tested by using a universal tester, and the flame retardance is according to UL94 standard; the results are shown in Table 2.
Table 2 example test results
Comparative example
The epoxy resin in example 6 was used as a cycloaliphatic epoxy resin (TTA 184) in its entirety, and the remainder was unchanged, and the resulting epoxy composition was subjected to the same test, and had a tensile elongation at break at low temperature (-15 ℃ C.) of 0.5%.
The epoxy resin in example 6 was all long-chain epoxy resin (guodi chemical YD-171), and the rest were unchanged, and the obtained epoxy composition was subjected to the same test, and the tensile elongation at break at low temperature (-15 ℃) was 4.5%.
The preparation process of example 6 was adjusted to:
(1) Putting alicyclic epoxy resin, aliphatic long-chain epoxy resin, epoxy diluent, toughening agent, curing agent, accelerating agent and filler into a stirring kettle together, controlling the temperature at 100 ℃, performing vacuum dehydration for 4 hours, and keeping the vacuum degree at less than or equal to-0.09 MPa to obtain a mixture which is a flexible epoxy premix; the material mixing and stirring kettle keeps the rotating speed at 800r/min;
(2) Adding the mixture obtained in the step (1) into a preheated (140 ℃) mould according to a conventional method, and heating at 140 ℃ for 30min for forming; then, the epoxy resin composition was demolded, placed in a forced air drying oven, and post-cured at 140 ℃ for 9 hours to obtain an epoxy resin composition having a tensile elongation at break of 5.8% at a low temperature (-15 ℃) according to the same test.
In example 6, the tensile strength was 23MPa, the flexural strength was 25MPa, and the impact strength was 21KJ/m 2 It is demonstrated that the present invention has excellent elasticity, especially excellent low temperature elongation at break. The invention discloses a modified epoxy resin with excellent high toughness and high elongation, an outdoor epoxy system without unsaturated bonds and a process for realizing the modified epoxy resin.
Claims (6)
1. The flexible epoxy composition for the outdoor composite insulator is characterized by being prepared from the following raw materials in parts by mass:
120 parts of epoxy resin
20 portions of flexibilizer
10 to 20 portions of epoxy diluent
240 to 260 portions of inorganic filler
70 to 80 portions of curing agent
0.2 portion of accelerator
The epoxy resin consists of alicyclic epoxy resin and aliphatic long-chain epoxy resin in a weight ratio of 100: 20, wherein the alicyclic epoxy resin is TTA184 of Tyler, and the aliphatic long-chain epoxy resin is YD-171 of national institute of chemistry; the toughening agent is a polyol polymer containing hydroxyl groups; the epoxy diluent is active monofunctional epoxy or difunctional epoxy glycidyl ether; the inorganic filler is composed of flame-retardant, heat-resistant and low-expansibility fillers; the curing agent is an anhydride curing agent; the accelerator is tertiary amine or imidazole accelerator.
2. The flexible epoxy composition for outdoor composite insulators according to claim 1, wherein the inorganic filler is one or more selected from aluminum hydroxide, silica micropowder and red phosphorus.
3. Use of the flexible epoxy composition for outdoor composite insulators according to claim 1 for the preparation of outdoor composite insulators.
4. The preparation method of the flexible epoxy premix for the outdoor composite insulator is characterized by comprising the following steps of heating and pre-polymerizing epoxy resin, a toughening agent, an epoxy diluent and a part of curing agent, and then heating and mixing the epoxy resin, the toughening agent, the epoxy diluent and the part of curing agent with the rest of curing agent, inorganic filler and accelerator to obtain the flexible epoxy premix for the outdoor composite insulator; wherein, calculated by mass portion, the epoxy resin comprises 120 portions of epoxy resin, 20 portions of toughening agent, 10 to 20 portions of epoxy diluent, 240 to 260 portions of inorganic filler, 70 to 80 portions of curing agent and 0.2 portion of accelerant, the epoxy resin comprises alicyclic epoxy resin and aliphatic long-chain epoxy resin with the weight ratio of 100: 20, wherein the alicyclic epoxy resin is TTA184 of Tyter, and the aliphatic long-chain epoxy resin is YD-171 of national institute chemistry; the toughening agent is a polyol polymer containing hydroxyl groups; the epoxy diluent is active monofunctional epoxy or difunctional epoxy glycidyl ether; the inorganic filler is composed of flame-retardant, heat-resistant and low-expansibility filler; the curing agent is an anhydride curing agent; the accelerator is tertiary amine or imidazole accelerator.
5. The flexible epoxy premix for outdoor composite insulators according to claim 4, wherein the prepolymerization temperature is 90-110 ℃ and the time is 4-6 h; the temperature for heating and mixing is 90-110 ℃, and the time is 4-6 h.
6. Use of the flexible epoxy premix for outdoor composite insulators according to claim 4 for preparing the flexible epoxy composition for outdoor composite insulators according to claim 1.
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| CN202110028040.7A CN112852103B (en) | 2021-01-11 | 2021-01-11 | Flexible epoxy composition for outdoor composite insulator |
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| CN202110028040.7A CN112852103B (en) | 2021-01-11 | 2021-01-11 | Flexible epoxy composition for outdoor composite insulator |
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| CN112852103B true CN112852103B (en) | 2023-02-28 |
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| CN113817286A (en) * | 2021-08-24 | 2021-12-21 | 安徽众博新材料有限公司 | Salt spray resistant, high-pressure scratch resistant and pollution flashover resistant insulating part material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433533A (en) * | 2016-07-27 | 2017-02-22 | 苏州巨峰电气绝缘系统股份有限公司 | Outdoor high-low-temperature-resistant and thermally-conductive epoxy encapsulating resin and preparation method thereof |
| CN109628039A (en) * | 2018-12-28 | 2019-04-16 | 深圳德邦界面材料有限公司 | A kind of epoxy resin flexibility heat conduction adhesive and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433533A (en) * | 2016-07-27 | 2017-02-22 | 苏州巨峰电气绝缘系统股份有限公司 | Outdoor high-low-temperature-resistant and thermally-conductive epoxy encapsulating resin and preparation method thereof |
| CN109628039A (en) * | 2018-12-28 | 2019-04-16 | 深圳德邦界面材料有限公司 | A kind of epoxy resin flexibility heat conduction adhesive and preparation method thereof |
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