CN110105716B - High-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable - Google Patents
High-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable Download PDFInfo
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- CN110105716B CN110105716B CN201910466231.4A CN201910466231A CN110105716B CN 110105716 B CN110105716 B CN 110105716B CN 201910466231 A CN201910466231 A CN 201910466231A CN 110105716 B CN110105716 B CN 110105716B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable. The castable comprises the following components: 100-200 parts of alicyclic epoxy resin, 50-200 parts of curing agent, 0.1-50 parts of accelerator, 1-50 parts of flame retardant and 50-500 parts of filler, wherein the flame retardant is at least one of 2, 4, 6-tribromoaniline and antimony trioxide. According to the invention, by optimizing the type of the flame retardant and the using amount and the proportion of each component, the prepared insulator castable has good outdoor weather resistance, heat resistance, insulating property, mechanical property and flame retardant property.
Description
Technical Field
The invention relates to the technical field of outdoor high-voltage insulating materials, in particular to a high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Background
The insulator is an insulating device which is used in a large number in a transmission and distribution network, and has low cost and simple structure, but plays an indispensable role in stable and safe operation of the whole power system. When any insulator fails, safety accidents of the whole power system can be caused.
At present, insulators widely used in power systems mainly include porcelain insulators, glass insulators, and silicone rubber composite insulators. The porcelain glass insulator has excellent mechanical property and strong aging resistance, but has poor related electrical property and large weight. The silicone rubber composite insulator has excellent electrical performance, but poor mechanical performance and poor aging resistance. Therefore, the ideal insulator which has the good mechanical property of the porcelain glass insulator, the excellent electrical property of the silicon rubber composite insulator, light weight and stable structure can be produced.
The alicyclic epoxy resin material is an ideal insulator material for preparing the composite insulator with excellent performances of glass, porcelain insulators and silicon rubber. The alicyclic epoxy resin is a high molecular Oligomer (Oligomer) having two or more epoxy groups, having an alicyclic organic compound as a skeleton, and being capable of forming a useful thermosetting by reaction of the epoxy groups, and is called an alicyclic epoxy compound when the polymerization degree thereof is zero. Although these low molecular weight resins do not completely satisfy the strict definition, they are collectively called alicyclic epoxy resins, which are not distinguished in terms of their names because they have the basic properties of epoxy resins, and their structures are represented by the formula (I):
the alicyclic epoxy resin has good ultraviolet resistance and weather resistance because the alicyclic epoxy resin does not contain benzene rings. The product of the cured alicyclic epoxy resin has high crosslinking density and high heat resistance. Because the alicyclic epoxy resin curing system does not contain Na+、Cl-And ions, so that the alloy has excellent arc resistance and tracking resistance. Compared with a porcelain glass insulator, the alicyclic epoxy resin insulator is higher in toughness, light in weight and strong in thermal shock resistance; compared with a silicon rubber composite insulator, the alicyclic epoxy resin insulator has excellent mechanical property, aging resistance and tracking resistance and low cost, and is an ideal material for preparing a new-generation insulator. However, cycloaliphatic epoxy resins have a Low Oxygen Index (LOI) and are flammable materials, thereby limiting their use in high voltage insulation applications.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable which has good heat resistance, insulating property and flame retardant property.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components:
wherein, the flame retardant is at least one of 2, 4, 6-tribromoaniline and antimony trioxide in parts by weight.
The insulator castable material prepared by compounding the alicyclic epoxy resin, the curing agent, the accelerator, the flame retardant and the filler, preferably selecting the type of the flame retardant and optimizing the dosage ratio of the components has good outdoor weather resistance, excellent heat resistance, insulating property and mechanical property, and the flame retardant property of the insulator castable material is also obviously improved.
Preferably, the alicyclic epoxy resin is an alicyclic glycidyl type epoxy resin.
Preferably, the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
Preferably, the accelerator is an amine accelerator.
Preferably, the flame retardant is a mixture of 2, 4, 6-tribromoaniline and antimony trioxide, and the weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1.
the invention adopts 2, 4, 6-Tribromoaniline (TBA) to cooperate with antimony trioxide (Sb)2O3) As a flame retardant of the alicyclic epoxy resin, the flame retardance of the castable is obviously improved. The weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1, compared with other compounding ratios, the prepared castable has better flame retardance and optimal heat resistance.
Preferably, the filler is at least one of silicon micropowder, aluminum hydroxide and magnesium hydroxide.
Preferably, the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components:
wherein all parts are by weight.
Preferably, the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components:
wherein all parts are by weight.
The invention adopts 2, 4, 6-tribromoaniline in cooperation with antimony trioxide as the flame retardant of the alicyclic epoxy resin, and further optimizes the proportion of each component, thereby obviously improving the oxygen index (LOI) of the castable, improving the flame retardance and having better application effect.
Preferably, the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable further comprises color paste, wherein the color paste is 0.1-5 parts by weight.
The invention also provides a preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable, which comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and after the alicyclic epoxy resin and the curing agent are uniformly stirred, adding the flame retardant, the filler and the color paste, uniformly stirring, adding the accelerant, and continuously stirring to obtain the efficient flame-retardant alicyclic epoxy resin outdoor insulation.
Compared with the prior art, the invention has the beneficial effects that:
the insulator castable material prepared by compounding the alicyclic epoxy resin, the curing agent, the accelerator, the flame retardant and the filler, optimizing the type of the flame retardant and optimizing the dosage and proportion of the components has good outdoor weather resistance, excellent heat resistance, insulating property and mechanical property, and the flame retardant property is also obviously improved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 2
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the filler and the color paste, uniformly stirring, adding the amine accelerant, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 3
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1.
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 4
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1.
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 5
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1.
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 6
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the weight ratio of the 2, 4, 6-tribromoaniline to the red phosphorus is 2.2: 1.
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 7
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the weight ratio of red phosphorus to antimony trioxide is 2.2: 1.
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the flame retardant, the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerator, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
Example 8
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the curing agent is 60 parts by weight in this embodiment.
Example 9
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the curing agent is 70 parts by weight in this embodiment.
Example 10
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the curing agent is 130 parts by weight in this embodiment.
Example 11
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the curing agent is 150 parts by weight in this embodiment.
Example 12
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the curing agent is 200 parts by weight in this embodiment.
Example 13
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the amine-based accelerator is 0.1 part by weight in this embodiment.
Example 14
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the amine-based accelerator is 10 parts by weight in this embodiment.
Example 15
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the amine-based accelerator is 50 parts by weight in this embodiment.
Example 16
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this example are substantially the same as those in example 4, except that the filler is 50 parts by weight in this example.
Example 17
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in the embodiment are basically the same as those in the embodiment 4, except that the weight part of the filler in the embodiment is 150 parts.
Example 18
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in the embodiment are basically the same as those in the embodiment 4, except that the filler is 250 parts by weight in the embodiment.
Example 19
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in the embodiment are basically the same as those in the embodiment 4, except that the filler is 400 parts by weight in the embodiment.
Example 20
The components and the preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable in this embodiment are substantially the same as those in example 4, except that the filler is 500 parts by weight in this embodiment.
Comparative example 1
The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable comprises the following components in parts by weight:
the preparation method of the castable provided by the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and (2) uniformly stirring the alicyclic glycidyl epoxy resin and the methyl tetrahydrophthalic anhydride, adding the aluminum hydroxide and the color paste, uniformly stirring, adding the amine accelerant, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
The castable materials of examples 1 to 20 and comparative example 1 were subjected to performance tests according to relevant standards, and the results are shown in table 1.
TABLE 1
From the results of examples 1 to 7 and comparative example 1, it can be seen that the flame retardant performance of the castable can be effectively improved by using 2, 4, 6-tribromoaniline in cooperation with antimony trioxide as the flame retardant of the alicyclic epoxy resin compared with other flame retardants. From the results of examples 8 to 12, it is understood that as the content of the curing agent increases, the flame retardancy of the castable decreases, the breakdown voltage tends to increase first and then decrease, and the heat resistance decreases. From the results of examples 13 to 15, it is understood that the accelerator in an amount of 0.1 to 10 parts has a high oxygen index, breakdown voltage and heat resistance. From the results of examples 16-20, it can be seen that the amount of the filler also affects the flame retardancy, breakdown voltage and heat resistance of the castable, and the effect is better when the amount is 400 portions of 250-20.
According to the invention, the curing agent is at least one selected from methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride; the filler is at least one selected from silicon micropowder, aluminum hydroxide and magnesium hydroxide.
The weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide can be adjusted correspondingly, but the weight ratio of the two is 2.2: 1, the prepared castable has better flame retardance and better heat resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable is characterized by comprising the following components:
wherein, all the parts by weight are as follows, the flame retardant is a mixture of 2, 4, 6-tribromoaniline and antimony trioxide, and the weight ratio of the 2, 4, 6-tribromoaniline to the antimony trioxide is 2.2: 1,
the filler is aluminum hydroxide.
2. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to claim 1, wherein the alicyclic epoxy resin is alicyclic glycidyl type epoxy resin.
3. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to claim 1, wherein the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
4. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to claim 1, wherein the accelerator is an amine accelerator.
5. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to claim 1, comprising the following components:
wherein all parts are by weight.
6. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to claim 5, characterized by comprising the following components:
wherein all parts are by weight.
7. The efficient flame-retardant alicyclic epoxy resin outdoor insulator castable material according to any one of claims 1 to 6, further comprising color paste, wherein the color paste is 0.1 to 5 parts by weight.
8. The preparation method of the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable material according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) and after the alicyclic epoxy resin and the curing agent are uniformly stirred, adding the flame retardant, the filler and the color paste, uniformly stirring, adding the accelerant, and continuously stirring to obtain the high-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable.
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| CN112194879A (en) * | 2020-08-31 | 2021-01-08 | 南方电网科学研究院有限责任公司 | Flame-retardant alicyclic epoxy resin castable for outdoor insulators |
| CN112143172A (en) * | 2020-08-31 | 2020-12-29 | 南方电网科学研究院有限责任公司 | Insulator sheath material with low water absorption rate and preparation method thereof |
| CN112852102B (en) * | 2021-01-11 | 2023-01-17 | 江苏泰特尔新材料科技股份有限公司 | Preparation method of flexible epoxy composition for outdoor composite insulator |
| CN112980148A (en) * | 2021-03-29 | 2021-06-18 | 浙江紫电新材料有限公司 | Composite insulator low-temperature-resistant hard sheath alicyclic epoxy resin injection material and preparation method thereof |
| CN112898735A (en) * | 2021-03-29 | 2021-06-04 | 浙江紫电新材料有限公司 | Anti-brittle-cracking parachute alicyclic epoxy resin injection material for hard composite insulator and preparation method thereof |
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| CN103709608A (en) * | 2013-12-30 | 2014-04-09 | 江西腾德实业有限公司 | Electric-insulation epoxy resin castable for outdoor mutual inductor |
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