CN111363315B - Epoxy resin insulating material and preparation method and application thereof - Google Patents
Epoxy resin insulating material and preparation method and application thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 158
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 158
- 239000011810 insulating material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 74
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 66
- 239000010703 silicon Substances 0.000 claims abstract description 66
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 103
- 239000002245 particle Substances 0.000 claims description 95
- 238000002156 mixing Methods 0.000 claims description 55
- 125000002723 alicyclic group Chemical group 0.000 claims description 34
- 239000012745 toughening agent Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 28
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000012774 insulation material Substances 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 23
- 150000008064 anhydrides Chemical class 0.000 claims description 22
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 claims description 21
- 229910021487 silica fume Inorganic materials 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000806 elastomer Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KPOXQAKDFUYNFA-UHFFFAOYSA-N 3-methyl-7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(O)=O)C(C)CC2OC21 KPOXQAKDFUYNFA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 18
- 238000013508 migration Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 230000003068 static effect Effects 0.000 description 21
- 239000000843 powder Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 13
- 238000001879 gelation Methods 0.000 description 13
- 150000002978 peroxides Chemical class 0.000 description 13
- 238000011417 postcuring Methods 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 238000009422 external insulation Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012212 insulator Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000011863 silicon-based powder Substances 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- 230000006750 UV protection Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- 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
-
- 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 belongs to the technical field of electric insulating material preparation, and particularly relates to an epoxy resin insulating material, and a preparation method and application thereof. The raw materials of the epoxy resin insulating material comprise 92-107 parts of epoxy resin, 20-50 parts of organic silicon modified resin and 130-190 parts of filler, wherein Si-CH in the organic silicon modified resin3The molar content of (A) is 23.33% -47.17%. The insulating material contains a large amount of Si-CH3The organic silicon modified resin modifies the epoxy resin, so that the epoxy resin has better hydrophobicity and hydrophobic migration, and meanwhile, the organic silicon modified resin and the epoxy resin can form a network cross-linking structure, so that the mechanical strength and the impact strength of the epoxy resin insulating material are improved; by adding the filler into the epoxy resin, the hydrophobic property, low-temperature brittleness and impact strength of the epoxy resin can be further improved by combining a physical filling modification technology.
Description
Technical Field
The invention belongs to the technical field of electric insulating material preparation, and particularly relates to an epoxy resin insulating material, and a preparation method and application thereof.
Background
The external insulation is the field with the most accidents of the power system, the level of the external insulation obviously affects the safe operation of the power system, and the improvement and promotion of the external insulation performance are always one of the key points of the research of the power system. Various line insulators need to meet the technical requirements of electrical performance, mechanical performance, aging resistance and the like in a long-term complex and severe operating environment, and an external insulation material is one of the key contents of external insulation research of an electric power system naturally. In terms of the overall application of the existing external insulation material, the electric porcelain and the glass which are used as the earliest materials of the outdoor insulator have good insulation performance, excellent ultraviolet resistance and chemical stability, but the surface of the electric porcelain and the glass does not have hydrophobic performance, so that pollution flashover is easy to occur in areas with serious pollution, the cleaning and maintenance cost is high, and the large-umbrella-diameter product is difficult to sinter, has the technical problems of running spontaneous explosion, zero value detection and the like. The silicone rubber composite insulator well solves the problems, particularly, the excellent hydrophobic property and the good ultraviolet resistance of the silicone rubber composite insulator are suitable for being applied to dirty areas, but the silicone rubber external insulation material has low mechanical strength and low surface hardness, a silicone rubber umbrella skirt is easily damaged by external force such as trampling and touch during line patrol, and is easily damaged by bird pecking in a bird damage area to cause related accidents in actual use, and the large umbrella diameter has the phenomena of strong wind swing damage and umbrella skirt support property insufficiency. Glass, porcelain and silicon rubber all have the technical problem that the umbrella diameter design is limited as outer insulation umbrella skirt materials, and effective promotion is difficult to realize in the aspect of anti-icing flashover.
At present, the mechanical, hydrophobic, tracking resistance and ultraviolet resistance of the epoxy insulating material in external insulation application are difficult to realize synergy, and the technical requirements of external insulation of high-voltage lines under complex working conditions are difficult to meet. Therefore, the development of the epoxy external insulation material which simultaneously has excellent mechanical property, electrical insulation property, good hydrophobic property, excellent tracking resistance and excellent ultraviolet resistance has important significance for solving the technical problems existing in the operation of the traditional external insulation material under the complex working condition.
Chinese patent document CN104177780A discloses an outdoor electrical insulation modified epoxy resin composition, which comprises epoxy resin, a curing agent, an inorganic filler and a curing accelerator, but the epoxy resin composition has poor hydrophobic effect and poor low-temperature impact toughness, which results in insufficient anti-pollution flashover performance in outdoor applications and a risk of local cracking in the environment of strong wind in the north in winter.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the technical defects of relatively insufficient hydrophobic property and obviously poor low temperature toughness of the epoxy resin material in practical application in the prior art, and thereby provide an epoxy resin insulating material, a preparation method and an application thereof.
Therefore, the invention provides the following technical scheme.
The invention provides an epoxy resin insulating material, which comprises the following raw materials, by weight, 92-107 parts of epoxy resin, 20-50 parts of organic silicon modified resin and 130-190 parts of filler;
Si-CH in the organosilicon modified resin3The molar content of (A) is 23.33% -47.17%.
The organic silicon modified resin comprises four organic silicon modified resins with different structures, and the molecular structural formulas are respectively as follows:
the organic silicon modified resin comprises four organic silicon modified resins with different structures, which can ensure that the organic silicon modified resin contains a large amount of Si-CH3And the organosilicon modified resin and the epoxy resin can form a network crosslinking structure.
The epoxy resin is alicyclic epoxy resin;
the epoxy resin is at least one of 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, 3, 4-epoxy group-6-methyl cyclohexane carboxylic acid-3 ', 4' -epoxy group-6-methyl cyclohexane methyl ester, bis ((3, 4-epoxy cyclohexyl) methyl) adipate and tetrahydroindene diepoxide.
The filler is active silica fume;
the active silica fume comprises the following components in percentage by mass (5.5-8.5): 3 and a second particle fraction;
the median diameter of the first particle fraction is from 25 to 35 μm; the median diameter of the second particle fraction is 10-15 μm.
The epoxy resin insulating material also comprises 90-130 parts of a curing agent, 0.3-1 part of an accelerator, 15-35 parts of a toughening agent and 2-4 parts of a silane coupling agent;
the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and polyazelaic anhydride;
the accelerator is dimethylbenzylamine;
the toughening agent is elastomer solid particles, and the average particle size is 30-70 μm, preferably 35-50 μm;
the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane (KH560) and/or gamma-aminopropyltriethoxysilane (KH 550).
The invention also provides a method for preparing the epoxy resin insulating material, which comprises the following steps,
(1) stirring and mixing the epoxy resin and the organic silicon modified resin in vacuum to obtain a premixed modified alicyclic epoxy resin;
(2) pretreating the filler to obtain premixed anhydride;
(3) and (3) adopting an APG process, and forming and curing the premixed modified alicyclic epoxy resin and the premixed anhydride to obtain the epoxy resin insulating material.
The modification method of the organic silicon modified resin comprises the following steps,
dripping 4-vinyl epoxy-cyclohexane into tetramethylcyclotetrasiloxane for 0.8-1.5h, and stirring and mixing uniformly; adding chloroplatinic acid/isopropanol catalyst, and stirring uniformly; then heating to 70-95 ℃, stirring and reacting for 4-6h under the protection of nitrogen, and carrying out reduced pressure distillation to obtain the organic silicon modified resin.
In the step (1), a step of adding a silane coupling agent and a toughening agent is also included before vacuum stirring and mixing;
the vacuum degree of the vacuum stirring is 200-300Pa, the temperature of the vacuum stirring is 70-80 ℃, and the time is 2-4 h.
The step of pretreatment in the step (2) comprises stirring the curing agent, the accelerator and the filler for 2-4h under the conditions of the vacuum degree of 400-600Pa and the temperature of 60-80 ℃ to obtain the premixed acid anhydride.
In the step (3), the molding temperature is 130-150 ℃, the pressure is 0.2-0.4MPa, and the time is 25-40 min;
the curing temperature is 130-150 ℃, and the curing time is 8-15 h.
In addition, the invention also provides an application of the epoxy resin insulating material or the epoxy resin insulating material prepared by the preparation method in a high-voltage line.
The technical scheme of the invention has the following advantages:
1. the invention provides an epoxy resin insulating materialThe raw materials of the epoxy resin insulating material comprise 92-107 parts of epoxy resin, 20-50 parts of organic silicon modified resin and 130-190 parts of filler, wherein Si-CH in the organic silicon modified resin3The molar content of (A) is 23.33% -47.17%. The insulating material contains a large amount of Si-CH3The organic silicon modified resin modifies the epoxy resin, so that the epoxy resin has better hydrophobicity and hydrophobic migration, and meanwhile, the organic silicon modified resin and the epoxy resin can form a network cross-linking structure, so that the mechanical strength and the impact strength of the epoxy resin insulating material are improved; by adding the filler into the epoxy resin, the hydrophobic property, low-temperature brittleness and impact strength of the epoxy resin can be further improved by combining a physical filling modification technology (namely a method for adding the filler). Through the synergistic effect of the organic silicon modified resin, the epoxy resin and the filler, the epoxy resin insulating material also has excellent electrical insulating property, ultraviolet resistance and weather resistance, and meanwhile, the mechanical strength, toughness and temperature resistance are also improved.
The epoxy resin insulating material has a technical foundation applied in high-voltage insulation, is particularly suitable for the technical field of outdoor high-voltage insulation, does not need paint film protection of external insulation, and is an ideal novel hard external insulating material.
2. According to the epoxy resin insulating material provided by the invention, the active silica fume is compounded by adopting the first particle fraction and the second particle fraction, so that the problem of filler settlement in an epoxy system can be effectively solved, the dispersibility of the filler in the epoxy resin insulating material is more uniform, the product uniformity is better, and the operable cycle of the epoxy resin insulating material is prolonged.
The alicyclic epoxy resin has excellent tracking resistance, can realize IA 4.5-grade excellent tracking resistance under the synergistic action of the alicyclic epoxy resin and the active silica fume, and avoids the problems of poor electrical property, weak hydrophobicity, reduced mechanical property and the like of a material caused by adding hydroxide in a traditional formula.
When the epoxy resin insulating material is applied to an insulator, the epoxy resin insulating material and an insulating core rod belong to an epoxy system, the interface combination and the linear expansion coefficient are more excellent, the mechanical property of the epoxy resin insulating material can overcome the problem that the umbrella diameter of silicon rubber, porcelain and glass umbrella skirts is limited in design, the unique design of large umbrella diameter and large space can be realized, and the ice flashover prevention effect is greatly improved.
Si-CH3The organic silicon modified resin with high content is matched with the elastomer solid particle flexibilizer, so that the hydrophobic property of the epoxy resin can be further improved.
3. According to the preparation method of the epoxy resin insulating material, the epoxy resin insulating material prepared by the method has good hydrophobicity and hydrophobicity migration;
in the preparation method of the organic silicon modified resin, four organic silicon modified resins with different molecular structures can be obtained by controlling the dripping time and the reaction temperature of the 4-vinyl epoxy-cyclohexane, and Si-CH in the organic silicon modified resins3The content of the epoxy resin is high, and the hydrophobicity and the hydrophobic migration of the epoxy resin insulating material are favorably improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides an epoxy resin insulation material, including 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 108g of methyltetrahydrophthalic anhydride, 0.6g of dimethylbenzylamine, 20g of silicone modified resin, 20g of particulate toughening agent (rubber elastomer particles having an average particle size of 40 μm), 130g of fine active silica powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 2
This example provides an epoxy resin insulation material, including 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 125g of methyltetrahydrophthalic anhydride, 0.7g of dimethylbenzylamine, 40g of silicone modified resin, 20g of a particulate toughening agent (rubber elastomer particles having an average particle size of 40 μm), 150g of fine active silica powder, 2g of KH 560; the active micro silicon powder comprises a first particle fraction and a second particle fraction in a mass ratio of 7:3, wherein the median diameter of the first particle fraction is 32 mu m; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 3
This example provides an epoxy resin insulation material comprising 100g of bis ((3, 4-epoxycyclohexyl) methyl) adipate, 101g of methyltetrahydrophthalic anhydride, 0.7g of dimethylbenzylamine, 40g of silicone modified resin, 20g of particulate toughening agent (rubber elastomer particles having an average particle size of 40 μm), 137g of fine active silica powder, 2g of KH 560; the active micro silicon powder comprises a first particle fraction and a second particle fraction in a mass ratio of 7:3, wherein the median diameter of the first particle fraction is 32 mu m; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing bis ((3, 4-epoxycyclohexyl) methyl) adipate, organosilicon modified resin, KH560 and particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare the premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 4
This example provides an epoxy resin insulation material comprising 50g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 50g of bis ((3, 4-epoxycyclohexyl) methyl) adipate, 112g of methyltetrahydrophthalic anhydride, 0.7g of dimethylbenzylamine, 40g of an organosilicon-modified resin, 20g of a particulate toughening agent (rubber elastomer particles having an average particle diameter of 40 μm), 142g of fine active silicon powder, 2g of KH 560; the active micro silicon powder comprises a first particle fraction and a second particle fraction in a mass ratio of 7:3, wherein the median diameter of the first particle fraction is 32 mu m; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane formic acid-3 ', 4' -epoxy cyclohexane methyl ester, bis ((3, 4-epoxy cyclohexyl) methyl) adipate, organic silicon modified resin, KH560 and particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare the premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 5
This example provides an epoxy resin insulation material, including 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 125g of methyltetrahydrophthalic anhydride, 0.7g of dimethylbenzylamine, 40g of silicone modified resin, 20g of a particulate toughening agent (rubber elastomer particles having an average particle size of 40 μm), 160g of fine active silica powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, and slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxaneIn a siloxane system, the dripping time is 1h, stirring is continued for 4h after the dripping is finished, and the toluene solvent of the system is removed by reduced pressure distillation to prepare the siloxane system containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 6
The embodiment provides an epoxy resin insulating material, which comprises 100g of 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ', 4' -epoxy-6-methylcyclohexanemethyl ester, 116g of methyltetrahydrophthalic anhydride, 0.7g of dimethylbenzylamine, 40g of organic silicon modified resin, 20g of particle toughening agent (rubber elastomer particles with the average particle size of 40 mu m), 150g of active silicon micropowder and 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy-6-methyl cyclohexanecarboxylic acid-3 ', 4' -epoxy-6-methyl cyclohexanemethyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2h under the condition that the vacuum degree is 200Pa to prepare the premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
120g of tetramethylcyclotetrasiloxane and 20g of toluene are stirred and mixed10min, heating to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dropwise adding 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dropwise adding is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 7
This example provides an epoxy resin insulation material, including 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 110g of methyltetrahydrophthalic anhydride, 15g of polyazelaic anhydride, 0.7g of dimethylbenzylamine, 40g of an organosilicon-modified resin, 20g of a particulate toughening agent (rubber elastomer particles, average particle size 40 μm), 150g of fine active silica powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, polyazelaic anhydride, dimethylbenzylamine and active silica micropowder in another stirring tank, heating to 75 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 400Pa to prepare premixed anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 145 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 8
This example provides an epoxy resin insulation material, including 92g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 130g of methyltetrahydrophthalic anhydride, 1.0g of dimethylbenzylamine, 50g of an organosilicon-modified resin, 35g of a particulate toughening agent (rubber elastomer particles having an average particle size of 35 μm), 130g of fine active silica powder, 4g of KH 550; wherein the active silica fume comprises the following components in a mass ratio of 6: 3, the median diameter of the first particle fraction being 25 μm; the median diameter of the second particle fraction is 15 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH550 and a particle toughening agent in a stirring tank, heating to 70 ℃, and stirring in vacuum for 4 hours under the condition that the vacuum degree is 300Pa to prepare the premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 80 ℃, and stirring in vacuum for 4 hours under the condition that the vacuum degree is 600Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 40min at the temperature of 130 ℃ and under the pressure of 0.4 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 150 ℃ for 8 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 9
This example provides an epoxy resin insulation material, including 107g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 90g of methyltetrahydrophthalic anhydride, 0.4g of dimethylbenzylamine, 30g of an organosilicon-modified resin, 15g of a particulate toughening agent (rubber elastomer particles having an average particle size of 50 μm), 190g of fine active silicon powder, 3g of a silane coupling agent; wherein the active silica fume comprises the following components in a mass ratio of 8: 3, the median diameter of the first particle fraction being 35 μm; the median diameter of the second particle fraction is 10 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, silane coupling agent and particle toughening agent in a stirring tank, heating to 70 ℃, and stirring in vacuum for 4 hours under the condition that the vacuum degree is 300Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 80 ℃, and stirring in vacuum for 4 hours under the condition that the vacuum degree is 600Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 40min at the temperature of 130 ℃ and under the pressure of 0.4 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 150 ℃ for 8 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 10
The embodiment provides an epoxy resin insulating material, which comprises 100g of 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, 108g of methyl tetrahydrophthalic anhydride, 0.6g of dimethylbenzylamine, 20g of organic silicon modified resin, 20g of particle toughening agent (organic silicon epoxy toughening agent purchased from Sanhua electronic insulating materials, Inc. in Huizhou city), 130g of active silicon micropowder and 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Example 11
This example provides an epoxy resin insulation material, including 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 108g of methyltetrahydrophthalic anhydride, 0.6g of dimethylbenzylamine, 20g of silicone modified resin, 20g of particulate toughening agent (rubber elastomer particles having an average particle size of 40 μm), 130g of fine active silica powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, the median diameter of the first particle fraction being 40 μm; the median diameter of the second particle fraction is 20 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Comparative example 1
This comparative example provides an epoxy resin insulation material comprising 100g of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 108g of methyltetrahydrophthalic anhydride, 0.6g of dimethylbenzylamine, 20g of an organosilicon-modified resin (available from mitani electronics insulation material ltd, huizhou), 20g of a particulate toughening agent, 130g of fine active silicon powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ', 4' -epoxy cyclohexane methyl ester, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
and then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain the epoxy resin insulating material.
Comparative example 2
The comparative example provides an epoxy resin insulation material comprising 100g of bisphenol A type epoxy resin, 108g of methyltetrahydrophthalic anhydride, 0.6g of dimethylbenzylamine, 20g of silicone modified resin, 20g of a particulate toughening agent, 130g of fine active silica powder, 2g of KH 560; wherein the active silica fume comprises the following components in a mass ratio of 7:3, a first particle fraction and a second particle fraction, the first particle fraction having a median diameter of 32 μm; the median diameter of the second particle fraction is 12 μm;
the preparation method of the epoxy resin insulating material comprises the following steps,
mixing bisphenol A type epoxy resin, organic silicon modified resin, KH560 and a particle toughening agent in a stirring tank, heating to 80 ℃, and stirring in vacuum for 2 hours under the condition that the vacuum degree is 200Pa to prepare premixed modified alicyclic epoxy resin;
mixing methyl tetrahydrophthalic anhydride, dimethylbenzylamine and active silicon micro powder in another stirring tank, heating to 60 ℃, and stirring for 2 hours in vacuum under the condition that the vacuum degree is 400Pa to prepare premixed acid anhydride;
injecting the premixed modified alicyclic epoxy resin and the premixed anhydride into a preheated steel mould through a static mixer by adopting an APG (alkaline peroxide mechanical gelation) process, and molding for 30min at the temperature of 140 ℃ and under the pressure of 0.2 MPa;
then, putting the molded product into a blast oven for post-curing at the curing temperature of 130 ℃ for 10 hours to obtain an epoxy resin insulating material;
wherein the preparation method of the organic silicon modified resin comprises the following steps,
stirring and mixing 120g of tetramethylcyclotetrasiloxane and 20g of toluene for 10min, raising the temperature to 85 ℃, adding 0.0003g of speier catalyst into the system, introducing nitrogen, stirring and mixing for 20min, slowly dripping 4-vinyl epoxy-cyclohexane into the tetramethylcyclotetrasiloxane system for 1h, continuously stirring for 4h after dripping is finished, and removing the toluene solvent of the system through reduced pressure distillation to prepare the catalyst containing a large amount of Si-CH3Bonded silicone-modified resin in which Si-CH is present3The molar content of (a) is 35.2%.
Test examples
The test example provides performance tests of the epoxy resin insulation materials prepared in examples 1-11 and comparative examples 1-2, the test method is as follows, and the test results are shown in table 1;
the method for testing the static contact angle of the epoxy resin insulating material comprises the following steps: the test was carried out according to bar b) of 10.3.6.3 in GB/T19519-2014, the static contact angle being represented by θ 1;
the method for testing the static contact angle of the epoxy resin insulating material under the condition of hydrophobic property loss comprises the following steps: the test was carried out according to bar c) of 10.3.6.3 in GB/T19519-2014, representing the static contact angle with loss of hydrophobicity by θ 2;
the method for testing the static contact angle of the epoxy resin insulating material under the hydrophobic recovery comprises the following steps: the test was carried out according to bar d) of 10.3.6.3 in GB/T19519-2014, the static contact angle at hydrophobic recovery is indicated by θ 3;
the method for testing the static contact angle of the epoxy resin insulating material under hydrophobic migration comprises the following steps: the test was carried out according to bar e) of 10.3.6.3 in GB/T19519-2014, the static contact angle under hydrophobic migration is indicated by θ 4;
the method for testing the notch impact strength of the simply supported beam made of the epoxy resin insulating material comprises the following steps: referring to 5.4 in GB/T2567-2008, the notch impact strength of the simply supported beam is represented by a;
the volume resistivity test method of the epoxy resin insulating material comprises the following steps: with reference to GB/T1410-2006, using pvRepresents the volume resistivity;
the method for testing the breakdown strength of the epoxy resin insulating material comprises the following steps: reference GB/T1408.1-2006;
the testing method of the tracking resistance grade of the epoxy resin insulating material comprises the following steps: reference GB/T6553-2014;
the test method of the tensile strength of the epoxy resin insulating material comprises the following steps: with reference to 5.1 in GB/T2567-mRepresents tensile strength;
the glass transition temperature test method of the epoxy resin insulating material comprises the following steps: with reference to GB/T19466.2-2004, Tg is used to denote the glass transition temperature;
TABLE 1 Performance test results for epoxy resin insulation materials
As can be seen from the results of the above experimental examples, the epoxy resin insulating materials provided in examples 1 to 11 all have excellent hydrophobic property, electrical property and impact strength, and simultaneously meet the tracking resistance requirement of 1A4.5, and meet the requirements of GB/T19519-.
The hydrophobicity of the epoxy resin insulating material provided by the comparative example 1 is slightly poor, the tracking resistance of the epoxy resin insulating material provided by the comparative example 2 is slightly poor, and the tracking resistance performance requirement of the outdoor high-voltage insulator umbrella cover material cannot be met.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (11)
1. An epoxy resin insulating material is characterized in that the raw materials comprise, by weight, 92-107 parts of epoxy resin, 20-50 parts of organic silicon modified resin and 130-190 parts of filler;
Si-CH in the organosilicon modified resin3The molar content of (A) is 23.33% -47.17%;
the epoxy resin is alicyclic epoxy resin.
2. The epoxy resin insulation material according to claim 1, wherein the epoxy resin is at least one of 3, 4-epoxycyclohexanecarboxylic acid-3 ', 4' -epoxycyclohexanemethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ', 4' -epoxy-6-methylcyclohexanemethyl ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, and tetrahydroindene diepoxide.
3. The epoxy resin insulation material according to claim 1 or 2, wherein the filler is an active silica fume;
the active silica fume comprises the following components in percentage by mass (5.5-8.5): 3 and a second particle fraction;
the median diameter of the first particle fraction is from 25 to 35 μm; the median diameter of the second particle fraction is 10-15 μm.
4. The epoxy resin insulating material according to claim 1 or 2, further comprising 90-130 parts of a curing agent, 0.3-1 part of an accelerator, 15-35 parts of a toughening agent, and 2-4 parts of a silane coupling agent;
the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and polyazelaic anhydride;
the accelerator is dimethylbenzylamine;
the toughening agent is elastomer solid particles, and the average particle size is 30-70 μm.
5. The epoxy resin insulation material of claim 4, wherein the toughening agent has an average particle size of 35-50 μm.
6. A method of preparing the epoxy resin insulation material according to any one of claims 1 to 5, comprising the steps of,
(1) stirring and mixing the epoxy resin and the organic silicon modified resin in vacuum to obtain a premixed modified alicyclic epoxy resin;
(2) pretreating the filler to obtain premixed anhydride;
(3) and (3) adopting an APG process, and forming and curing the premixed modified alicyclic epoxy resin and the premixed anhydride to obtain the epoxy resin insulating material.
7. The method of producing an epoxy resin insulating material according to claim 6, wherein the method of modifying the silicone-modified resin comprises,
dripping 4-vinyl epoxy-cyclohexane into tetramethylcyclotetrasiloxane for 0.8-1.5h, and stirring and mixing uniformly; adding chloroplatinic acid/isopropanol catalyst, and stirring uniformly; then heating to 70-95 ℃, stirring and reacting for 4-6h under the protection of nitrogen, and carrying out reduced pressure distillation to obtain the organic silicon modified resin.
8. The method for preparing the epoxy resin insulating material according to claim 6 or 7, wherein the step (1) further comprises the steps of adding a silane coupling agent and a toughening agent before vacuum stirring and mixing;
the vacuum degree of the vacuum stirring is 200-300Pa, the temperature of the vacuum stirring is 70-80 ℃, and the time is 2-4 h.
9. The method for preparing an epoxy resin insulating material according to claim 6 or 7, wherein the step of pretreating in the step (2) comprises stirring the curing agent, the accelerator and the filler under the conditions of a vacuum degree of 400-600Pa and a temperature of 60-80 ℃ for 2-4h to obtain the premixed acid anhydride.
10. The method for preparing the epoxy resin insulating material as claimed in claim 6 or 7, wherein in the step (3), the molding temperature is 130-150 ℃, the pressure is 0.2-0.4MPa, and the time is 25-40 min;
the curing temperature is 130-150 ℃, and the curing time is 8-15 h.
11. Use of the epoxy resin insulation material according to any one of claims 1 to 5 or the epoxy resin insulation material prepared by the preparation method according to any one of claims 6 to 10 in high voltage lines.
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| CN114702787B (en) * | 2022-04-25 | 2022-09-23 | 叶金蕊 | Super-high voltage resistant insulating resin suitable for vacuum suction injection molding and preparation method thereof |
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| CN104177780A (en) * | 2014-08-20 | 2014-12-03 | 国家电网公司 | Outdoor electric-insulation modified epoxy resin composition |
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