CN113583386A - Epoxy resin for closed combined electrical appliance and preparation method thereof - Google Patents
Epoxy resin for closed combined electrical appliance and preparation method thereof Download PDFInfo
- Publication number
- CN113583386A CN113583386A CN202110958579.2A CN202110958579A CN113583386A CN 113583386 A CN113583386 A CN 113583386A CN 202110958579 A CN202110958579 A CN 202110958579A CN 113583386 A CN113583386 A CN 113583386A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- closed
- mixture
- combined electrical
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- 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
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention provides an epoxy resin for a closed combined electrical appliance and a preparation method thereof, belonging to the technical field of preparation of high polymer materials. The product produced by the modified epoxy resin obtained by hydrogenating the benzene ring of the solid bisphenol A epoxy resin with larger molecular weight is more excellent in oxidation resistance, small in shrinkage rate of a cured product, stable in size and high in precision; the mixture of the modified hexahydrophthalic anhydride and the hexahydrophthalic anhydride is used as the curing agent, so that the shrinkage rate of a cured product is effectively reduced, and the product is stable in size and high in precision; the antioxidant capable of being subjected to addition reaction with the epoxy resin is used as an anti-yellowing agent, the influence on mechanical strength and the like is small, and the original necessary performance of the product is not influenced while the anti-yellowing effect is achieved.
Description
Technical Field
The invention belongs to the technical field of polymer material preparation, and particularly relates to epoxy resin for a closed type combined electrical apparatus and a preparation method thereof.
Background
Most of the existing high-voltage epoxy resin products are prepared by curing and molding epoxy resin composite materials cured at medium and high temperatures, particularly are applied to insulating parts in GIS combined electrical appliances, and are mostly prepared by mixing and reacting epoxy resin with large molecular weight, an anhydride curing agent and an alumina powder filler, and the color of the product just prepared is white due to the influence of alumina in the components; however, because the organic polymerization reaction is incomplete, free molecular groups exist in the epoxy polymer, and the polymer also has an active molecular structure, and the epoxy polymer and the polymer are easy to undergo oxidation reaction and turn yellow in an oxygen-rich environment and under a photo-thermal condition, so that the product performance is influenced.
Chinese patent application 201010171884.9 discloses an epoxy resin composition for high voltage power insulation, which comprises A, B two components, wherein a component is an epoxy resin, and B component comprises an acid anhydride curing agent, a modified acid anhydride polymer and a catalyst. The epoxy resin composition of the present invention may further contain a filler. The cured product of the epoxy resin composition has excellent heat resistance, mechanical strength, high and low temperature impact resistance, cracking resistance, electric insulation and other properties; the epoxy resin can be widely applied to high-voltage power insulation such as insulation devices of insulation switches, power transmission devices, circuit breakers, disc insulators, supporting insulators, power insulation pull rods and the like, and has good market prospect, but the application does not research the yellowing resistance and the aging resistance of the obtained epoxy resin.
Chinese patent application 201410412657.9 discloses an outdoor type electrical insulation modified epoxy resin composition, which comprises an epoxy resin, a curing agent, a curing accelerator and an inorganic filler; the epoxy resin is a mixed epoxy resin containing 50-80% of modified epoxy resin by mass and the balance of unmodified epoxy resin or 100% of modified epoxy resin; the modified epoxy resin is modified by an organic silicon modifier, and the curing agent is a dianhydride curing agent which comprises one or a mixture of several selected from methyl tetrahydrophthalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride; the inorganic filler is one or a mixture of more selected from silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide and the like; the outdoor electrical insulation modified epoxy resin composition has excellent performances of high weather resistance, better hydrophobicity, high volume resistivity, high tracking resistance, high electric arc resistance, low thermal expansion and the like, can be used for manufacturing sheds of outdoor insulation parts such as suspension insulators and cross arms for alternating current transmission lines, can prevent bird pecking, line patrol and treading and avoid transportation damage and the like compared with silicon rubber sheds, and does not research the yellowing resistance and aging resistance of the obtained epoxy resin.
Therefore, it is necessary to develop an epoxy resin with good yellowing resistance and aging resistance, which is more suitable for closed combined electrical appliances.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an epoxy resin for a closed combined electrical appliance and a preparation method thereof. The invention adopts the modified hydrogenated bisphenol A epoxy resin and the modified hexahydrophthalic anhydride as raw materials, so that the obtained epoxy resin has better yellowing resistance and mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
the epoxy resin for the closed combined electrical appliance comprises the following raw materials in parts by weight:
preferably, the epoxy resin for the closed-type combined electrical apparatus comprises the following raw materials in parts by weight:
still preferably, the epoxy resin for the closed-type combined electrical apparatus comprises the following raw materials in parts by weight:
the synthetic route of the modified hydrogenated bisphenol A epoxy resin is as follows:
the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 220-250eq/100 g; preferably 230-240eq/100 g.
The viscosity of the hydrogenated bisphenol A epoxy resin at 25 ℃ is 2800-; preferably 3000-3200 mPas.
The curing agent is a mixture of modified hexahydrophthalic anhydride and hexahydrophthalic anhydride, and the mass ratio of the modified hexahydrophthalic anhydride to the hexahydrophthalic anhydride is 1: 2.5.
The synthetic route of the modified hexahydrophthalic anhydride is as follows:
wherein, the modified hydrogenated bisphenol A epoxy resin is 100 percent of modified epoxy resin; the modified hexahydrophthalic anhydride is 100 percent of modified hexahydrophthalic anhydride.
The antioxidant is an antioxidant 703.
The filler is electrical alumina filler.
The invention also provides a preparation method of the epoxy resin for the closed combined electrical appliance, which comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding a small amount of melted modified hydrogenated bisphenol A epoxy resin into the antioxidant 703 with the formula dosage, and uniformly dispersing to obtain a mixture 1; adding the mixture 1 into the rest of the modified hydrogenated bisphenol A epoxy resin, and uniformly dispersing to obtain a mixture 2;
(2) adding the electrical alumina filler with the formula dosage into the mixture 2 in three batches, adding the curing agent after uniformly stirring, and stirring under a vacuum condition to obtain a mixture 3;
(3) and pouring the obtained mixture 3 into a mold, and curing and demolding to obtain the epoxy resin for the closed combined electrical appliance.
The amount of the modified hydrogenated bisphenol A epoxy resin added for the first time in the step (1) is 100 times of the amount of the antioxidant 703.
The electrical aluminum oxide filler and the curing agent are pre-dried at the temperature of 120 +/-5 ℃;
the casting described in step (3) is performed under vacuum conditions.
The invention also provides application of the epoxy resin for the closed combined electrical appliance in preparation of the closed combined electrical appliance.
Compared with the prior art, the invention has the beneficial effects that:
1. the product produced by the modified epoxy resin obtained by hydrogenating the benzene ring of the solid bisphenol A epoxy resin with larger molecular weight is adopted, the modified epoxy resin has no unstable benzene ring bond, and the oxidation resistance is more excellent, and the product has stable size and high precision due to the larger molecular weight and the small shrinkage of a cured product;
2. the modified hexahydrophthalic anhydride is used as a curing agent, the hexahydrophthalic anhydride has light color compared with tetrahydrophthalic anhydride, no C-C double bond and better oxidation resistance than the tetrahydrophthalic anhydride, so that a product produced by the curing agent has light color and less probability of yellowing; the modified hexahydrophthalic anhydride has lower viscosity than that of hexahydrophthalic anhydride, the process operability is more excellent, and the use amount of the filler is increased, the mixture of the modified hexahydrophthalic anhydride and the hexahydrophthalic anhydride is not used as a curing agent, so that the shrinkage rate of a cured product is effectively reduced, and the product has stable size and high precision;
3. the antioxidant capable of performing addition reaction with the epoxy resin is used as the anti-yellowing agent, so that the influence on the mechanical strength of the product is small, and the original necessary performance of the product is not influenced while the anti-yellowing effect is achieved.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples. The following examples are merely illustrative of the invention and are not to be construed as limiting thereof.
Unless otherwise specified, the experimental procedures in the following examples are conventional procedures well known to those skilled in the art; the reagents and test materials are commercially available.
The modified hydrogenated bisphenol A epoxy resin is solid epoxy resin.
Embodiment 1 an epoxy resin for a closed composite apparatus, comprising the following raw materials in parts by weight:
wherein the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 221eq/100 g; the viscosity at 25 ℃ was 2845 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding 100 times of modified hydrogenated bisphenol A epoxy resin of the antioxidant 703 into the antioxidant 703 in the formula amount, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the rest modified hydrogenated bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 120 +/-5 ℃ in the formula amount into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 120 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) placing the mold pre-dried at 120 +/-5 ℃ into a vacuum casting tank at 120 +/-5 ℃, and casting the mixture 3 in a vacuum state; and (3) placing the poured mould in an oven at 120 +/-5 ℃ for curing for 10 hours to obtain the epoxy resin for the closed combined electrical apparatus.
Embodiment 2 an epoxy resin for a closed composite apparatus, comprising the following raw materials in parts by weight:
wherein the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 247eq/100 g; the viscosity at 25 ℃ was 3458 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding 100 times of modified hydrogenated bisphenol A epoxy resin of the antioxidant 703 into the antioxidant 703 in the formula amount, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the rest modified hydrogenated bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 120 +/-5 ℃ in the formula amount into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 120 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) placing the mold pre-dried at 120 +/-5 ℃ into a vacuum casting tank at 120 +/-5 ℃, and casting the mixture 3 in a vacuum state; and (3) placing the poured mould in an oven at 120 +/-5 ℃ for curing for 16 hours to obtain the epoxy resin for the closed combined electrical apparatus.
Embodiment 3 an epoxy resin for a closed composite apparatus, comprising the following raw materials in parts by weight:
wherein the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 236eq/100 g; the viscosity at 25 ℃ was 3246 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding 100 times of modified hydrogenated bisphenol A epoxy resin of the antioxidant 703 into the antioxidant 703 in the formula amount, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the rest modified hydrogenated bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 120 +/-5 ℃ in the formula amount into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 120 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) placing the mold pre-dried at 120 +/-5 ℃ into a vacuum casting tank at 120 +/-5 ℃, and casting the mixture 3 in a vacuum state; and (3) placing the poured mould in an oven at 120 +/-5 ℃ for curing for 12 hours to obtain the epoxy resin for the closed combined electrical apparatus.
Embodiment 4 an epoxy resin for a closed composite apparatus, comprising the following raw materials in parts by weight:
wherein the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 232eq/100 g; the viscosity at 25 ℃ was 3152 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding 100 times of modified hydrogenated bisphenol A epoxy resin of the antioxidant 703 into the antioxidant 703 in the formula amount, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the rest modified hydrogenated bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 120 +/-5 ℃ in the formula amount into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 120 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) placing the mold pre-dried at 120 +/-5 ℃ into a vacuum casting tank at 120 +/-5 ℃, and casting the mixture 3 in a vacuum state; and (3) placing the poured mould in an oven at 120 +/-5 ℃ for curing for 15 hours to obtain the epoxy resin for the closed combined electrical apparatus.
Comparative example 1
The difference from example 4 is that: the starting material was hydrogenated bisphenol A epoxy resin replaced with solid bisphenol A epoxy resin, and the other operations and steps were the same as in example 4.
Comparative example 2
The difference from example 4 is that: the curing agent used was hexahydrophthalic anhydride alone, and the other operations and steps were the same as in example 4.
Comparative example 3
The difference from example 4 is that: the curing agent used was only modified hexahydrophthalic anhydride and the other operations and steps were the same as in example 4.
Comparative example 4
The difference from example 4 is that: antioxidant 1076 was used as the antioxidant, and the other operations and steps were the same as in example 4.
Comparative example 5
The difference from example 4 is that: the curing agents were modified hexahydrophthalic anhydride and hexahydrophthalic anhydride at a mass ratio of 2.5:1, and the other operations and steps were the same as in example 4.
Comparative example 6
The difference from example 4 is that: the raw material was an organosilicon-modified bisphenol A epoxy resin in place of the modified hydrogenated bisphenol A epoxy resin, and the other operations and steps were the same as in example 4.
Performance testing
1. Yellowing resistance test
The test method comprises the following steps:
high temperature yellowing resistance: two groups of the epoxy resin compositions prepared in examples 1-4 and comparative examples 1-6 are respectively sprayed on clean aluminum sheets with clean surfaces, wherein the aluminum sheets sprayed with the epoxy resin compositions of one group of examples 1-4 are taken out as standard plates after being baked for 10 minutes at 280 ℃, the rest aluminum sheets are taken out after being continuously baked for 1 hour at 280 ℃, and the change situation of the surface pattern layers of the test plates is tested
Light-irradiation yellowing resistance: two groups of the epoxy resin compositions prepared in the examples 1-4 and the comparative examples 1-6 are respectively sprayed on clean aluminum sheets with cleaned surfaces, light sources with power of 300w and voltage of 220V are selected, ultraviolet light waves of the light sources are 280-400mm, and part of visible light exists, the temperature in a test box is controlled at 50 ℃, wherein the aluminum sheets sprayed with the epoxy resin compositions in the examples 1-4 are taken out as a standard plate after being irradiated in the test box for 10 minutes, the rest of the aluminum sheets are taken out after being continuously irradiated in the test box for 24 hours, and the change condition of the surface pattern layer of the sample plate is tested.
In specific comparison, the experimental plate of example 1 is compared with the standard plate of example 1, and the experimental plate of example 2 is compared with the standard plate of example 2; example 3 experimental plates were compared to example 3 standard plates; the experimental panels of example 4 and comparative examples 1-6 were compared to the standard panels of example 4, respectively.
Yellowing resistance was evaluated using Δ E values:
the Delta E is 0.25-0.5, which shows that the yellowing degree is small and the anti-yellowing performance is strong;
the Delta E is 0.6-2.0, which indicates that the yellowing degree is medium and the anti-yellowing performance is certain;
the Delta E is 2.1-4.0, which indicates that the yellowing degree is large and the anti-yellowing performance is general;
a Delta E of more than 4.0 indicates a large degree of yellowing and poor yellowing resistance.
The specific test results are shown in Table 1 below
TABLE 1
| High temperature yellowing resistance/. DELTA.E | Yellowing resistance under illumination/. DELTA.E | |
| Example 1 | 2.2 | 1.9 |
| Example 2 | 2.1 | 1.9 |
| Example 3 | 2.3 | 2.1 |
| Example 4 | 1.9 | 1.6 |
| Comparative example 1 | 2.5 | 2.3 |
| Comparative example 2 | 2.4 | 2.3 |
| Comparative example 3 | 2.5 | 2.2 |
| Comparative example 4 | 3.6 | 3.3 |
| Comparative example 5 | 2.4 | 2.0 |
| Comparative example 6 | 2.5 | 2.1 |
According to the test data in the above table 1, it can be seen that the epoxy resins prepared in examples 1-4 of the present invention have certain yellowing resistance, especially the yellowing resistance of the epoxy resin prepared in example 4 is the best, while the epoxy resins prepared in comparative examples 1-6 have a certain effect on the yellowing resistance of the epoxy resin by changing the types of the components, and the epoxy resins have a significant effect on the yellowing resistance by changing the types of the antioxidants in comparative example 4, so that the components in the present invention interact with each other to improve the yellowing resistance of the epoxy resin, and even if the antioxidants are the same, the epoxy resins have a significant effect on the yellowing resistance by changing the types of the antioxidants.
2. Shrinkage detection
The shrinkage rate is the volume shrinkage rate of the epoxy resin composition in the molding process, the density of the epoxy resin composition before and after photocuring at room temperature is measured according to the GB12007.5-89 standard, the volume shrinkage rate is calculated according to the density, and the absolute value of the detection result is obtained.
The specific test results are shown in Table 2 below
TABLE 2
According to the detection data in the table 2, it can be seen that the volume shrinkage rate of the epoxy resin provided by the invention in the molding process is very small, especially the shrinkage rate of the epoxy resin provided by the embodiment 4 is the minimum, which is only 0.12%, and the product has stable size and high precision; comparative examples 1 and 6 change the kind of hydrogenated bisphenol a epoxy resin in the raw material on the basis of example 4, which affects the shrinkage of the epoxy resin composition to a certain extent, and obviously reduces the precision of the product; comparative examples 2 to 3, which change the kind of curing agent, have an effect on the shrinkage of the epoxy resin composition to a degree significantly greater than that of comparative example 1, comparative example 5, which change the mass ratio of the specific components of the curing agent, also has an effect on the shrinkage of the epoxy resin composition, but comparative example 6, which change the kind of antioxidant to a degree significantly less than that of comparative examples 2 to 3, has little effect on the shrinkage of the resulting epoxy resin composition.
3. Mechanical property detection
The test method comprises the following steps: tensile strength was tested according to the specifications of GB/T1040-2006; impact performance was tested according to the regulations of GB/T1843-2008.
The specific test results are shown in Table 3 below
TABLE 3
According to the detection data in the above table 3, it can be seen that the epoxy resin provided by the present invention has good mechanical properties, especially the epoxy resin provided in the embodiment 4 has the best mechanical properties, the tensile strength can reach 82.7MPa, and the impact strength can reach 17.8KJ/m2(ii) a Comparative examples 1 and 6 change the situation that the hydrogenated bisphenol A epoxy resin in the raw materials can influence the mechanical properties of the epoxy resin composition to a certain extent; comparative examples 2 to 3, which change the kind of the curing agent, had an effect on the mechanical properties of the epoxy resin, but the degree of the effect was significantly greater than that of comparative examples 1 and 6, and comparative example 5, which change the mass ratio of the curing agent components, also had an effect on the mechanical properties of the epoxy resin, but the degree of the effect was significantly less than that of comparative examples 2 to 3, and comparative example 6, which change the kind of the antioxidant, had little effect on the mechanical properties of the resulting epoxy resin composition, consistent with the shrinkage test results.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An epoxy resin for a closed combined electrical apparatus, which is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the epoxy resin for a closed type combined electrical appliance according to claim 1, characterized in that: the feed comprises the following raw materials in parts by weight:
3. the epoxy resin for a closed-type combined electrical apparatus according to claim 2, characterized in that: the feed comprises the following raw materials in parts by weight:
4. the epoxy resin for a closed type combined electrical appliance according to claim 3, wherein: the hydrogenated bisphenol A epoxy resin is 100% modified epoxy resin.
5. The epoxy resin for a closed type combined electrical appliance according to claim 3, wherein: the epoxy equivalent of the hydrogenated bisphenol A epoxy resin was 220-250eq/100 g.
6. The epoxy resin for a closed-type combined electrical apparatus according to claim 5, characterized in that: the viscosity of the hydrogenated bisphenol A epoxy resin at 25 ℃ is 2800-.
7. The epoxy resin for a closed type combined electrical appliance according to claim 3, wherein: the curing agent is a mixture of modified hexahydrophthalic anhydride and hexahydrophthalic anhydride.
8. The epoxy resin for a closed-type combined electrical apparatus according to claim 7, wherein: the mass ratio of the modified hexahydrophthalic anhydride to the hexahydrophthalic anhydride is 1: 2.5.
9. The method for preparing the epoxy resin for a closed type composite apparatus according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
(1) firstly, melting modified hydrogenated bisphenol A epoxy resin at 120 +/-5 ℃ for later use; adding a small amount of melted modified hydrogenated bisphenol A epoxy resin into the antioxidant 703 with the formula dosage, and uniformly dispersing to obtain a mixture 1; adding the mixture 1 into the rest of the modified hydrogenated bisphenol A epoxy resin, and uniformly dispersing to obtain a mixture 2;
(2) adding the electrical alumina filler with the formula dosage into the mixture 2 in three batches, adding the curing agent after uniformly stirring, and stirring under a vacuum condition to obtain a mixture 3;
(3) pouring the obtained mixture 3 into a mold, and curing and demolding to obtain the epoxy resin for the closed combined electrical appliance;
the amount of the modified hydrogenated bisphenol A epoxy resin added for the first time in the step (1) is 100 times of the amount of the antioxidant 703.
10. Use of the epoxy resin for a closed electrical combiner according to any one of claims 1 to 8 for the preparation of a closed electrical combiner component.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110958579.2A CN113583386A (en) | 2021-08-20 | 2021-08-20 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
| CN202210586729.6A CN114773789B (en) | 2021-08-20 | 2022-05-26 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110958579.2A CN113583386A (en) | 2021-08-20 | 2021-08-20 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113583386A true CN113583386A (en) | 2021-11-02 |
Family
ID=78238730
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110958579.2A Withdrawn CN113583386A (en) | 2021-08-20 | 2021-08-20 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
| CN202210586729.6A Active CN114773789B (en) | 2021-08-20 | 2022-05-26 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210586729.6A Active CN114773789B (en) | 2021-08-20 | 2022-05-26 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113583386A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508825A (en) * | 2009-03-30 | 2009-08-19 | 汕头市骏码凯撒有限公司 | Epoxy resin embedding glue and method for producing the same |
| CN102241868A (en) * | 2010-05-11 | 2011-11-16 | 上海赛沃化工材料有限公司 | Epoxy resin composition for high-voltage power insulation |
| CN104558527A (en) * | 2013-10-16 | 2015-04-29 | 台湾太阳油墨股份有限公司 | White thermosetting resin composition, cured product thereof and display member using the same |
| CN110016205A (en) * | 2019-03-07 | 2019-07-16 | 全球能源互联网研究院有限公司 | A kind of epoxy resin heat-conducting insulation material and preparation method thereof |
| CN110218414A (en) * | 2019-05-09 | 2019-09-10 | 全球能源互联网研究院有限公司 | A kind of composition epoxy resin and its preparation method and application |
| CN111909486A (en) * | 2019-05-07 | 2020-11-10 | 长春人造树脂厂股份有限公司 | Resin composition and use thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4079125B2 (en) * | 2004-06-25 | 2008-04-23 | 松下電工株式会社 | Epoxy resin composition, semiconductor device and manufacturing method thereof |
| JP5210494B2 (en) * | 2006-02-13 | 2013-06-12 | アイカ工業株式会社 | Construction method |
| EP2275489B1 (en) * | 2008-01-28 | 2019-11-13 | Kaneka Corporation | Rubbery polymer-containing resin composition, cured product thereof, and production method thereof |
| CN104403277B (en) * | 2014-12-25 | 2018-06-08 | 无锡嘉联电子材料有限公司 | A kind of preparation method of LED encapsulation high-performance epoxy resin composition |
| CN105255428A (en) * | 2015-10-09 | 2016-01-20 | 烟台德邦先进硅材料有限公司 | Packaging epoxy resin mixture and preparation method thereof |
| CN107057623A (en) * | 2017-05-22 | 2017-08-18 | 重庆江川化工（集团）有限公司 | A kind of filling special epoxy pouring sealant of transformer large volume and preparation method and application |
| CN110511536B (en) * | 2018-05-22 | 2022-12-06 | 广东众森实业发展有限公司 | Epoxy resin composition and preparation method thereof |
| CN113201206A (en) * | 2021-06-21 | 2021-08-03 | 大连北方互感器集团有限公司 | Epoxy resin formula material suitable for vacuum pouring process and preparation method thereof |
-
2021
- 2021-08-20 CN CN202110958579.2A patent/CN113583386A/en not_active Withdrawn
-
2022
- 2022-05-26 CN CN202210586729.6A patent/CN114773789B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508825A (en) * | 2009-03-30 | 2009-08-19 | 汕头市骏码凯撒有限公司 | Epoxy resin embedding glue and method for producing the same |
| CN102241868A (en) * | 2010-05-11 | 2011-11-16 | 上海赛沃化工材料有限公司 | Epoxy resin composition for high-voltage power insulation |
| CN104558527A (en) * | 2013-10-16 | 2015-04-29 | 台湾太阳油墨股份有限公司 | White thermosetting resin composition, cured product thereof and display member using the same |
| CN110016205A (en) * | 2019-03-07 | 2019-07-16 | 全球能源互联网研究院有限公司 | A kind of epoxy resin heat-conducting insulation material and preparation method thereof |
| CN111909486A (en) * | 2019-05-07 | 2020-11-10 | 长春人造树脂厂股份有限公司 | Resin composition and use thereof |
| CN110218414A (en) * | 2019-05-09 | 2019-09-10 | 全球能源互联网研究院有限公司 | A kind of composition epoxy resin and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773789A (en) | 2022-07-22 |
| CN114773789B (en) | 2022-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1176171B1 (en) | Electric insulating material and method of manufacture thereof | |
| CN110105716B (en) | High-efficiency flame-retardant alicyclic epoxy resin outdoor insulator castable | |
| EP2230267A1 (en) | Curable Epoxy Resin Composition | |
| TW201307421A (en) | Insulation formulations | |
| JP6686071B2 (en) | Epoxy resin composition and transformer containing the same | |
| CN111533486A (en) | Graphene modified resin packaging material and preparation method thereof | |
| WO2008037545A1 (en) | Electrical insulation system based on polybenzoxazine | |
| CN112372910A (en) | Epoxy resin insulating material and pouring method thereof | |
| CN109825231B (en) | Flame-retardant ultraviolet-resistant epoxy encapsulating adhesive and preparation method thereof | |
| CN113583386A (en) | Epoxy resin for closed combined electrical appliance and preparation method thereof | |
| CN113637291A (en) | Low-shrinkage epoxy resin and preparation method and application thereof | |
| CN111234181B (en) | High-toughness insulating epoxy resin condensate and preparation method and application thereof | |
| CN110628183B (en) | Epoxy glass fiber nanocomposite for high-voltage switch insulating pull rod and preparation method thereof | |
| CN115011074B (en) | Epoxy resin composition, preparation method and application thereof | |
| CN112852102A (en) | Preparation method of flexible epoxy composition for outdoor composite insulator | |
| KR102224020B1 (en) | Exoxy resin composition having low shrinkage and low viscosity for heavy electricals and its making method | |
| CN110885543B (en) | Organic silicon modified unsaturated resin insulation impregnating resin and preparation method thereof | |
| CN106433023B (en) | The method for preparing Cast Resin Dry-Type Transformer elastic epoxy resin | |
| JP2847936B2 (en) | Epoxy resin composition | |
| KR20230071643A (en) | Higher Arc resistance bio-based Epoxy resin material composition for heavy electric and method of manufacturing the same | |
| JPH0887914A (en) | Outdoor use insulating polymeric material composition | |
| JPH06139856A (en) | Insulating polymer material composition for outdoor use | |
| JPH06131933A (en) | Outdoor insulating high polymer material composition | |
| JPH06139854A (en) | Insulating polymer material composition for outdoor use | |
| JPH06139855A (en) | Insulating polymer material composition for outdoor use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211102 |