CN113773794A - High-barrier PBT-polysiloxane copolymer-based composite material for packaging lightning arrester - Google Patents
High-barrier PBT-polysiloxane copolymer-based composite material for packaging lightning arrester Download PDFInfo
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 12
- -1 polysiloxane Polymers 0.000 claims abstract description 36
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000005538 encapsulation Methods 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000011147 inorganic material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004945 silicone rubber Substances 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/125—Adhesives in organic diluents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C1/00—Details
- H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/12—Overvoltage protection resistors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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- Microelectronics & Electronic Packaging (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-barrier PBT-polysiloxane copolymer-based composite material for packaging a lightning arrester, and preparation and use methods thereof, wherein a) hydroxyl-terminated PBT prepolymer and isocyanate-terminated polysiloxane prepolymer are selected as reaction raw materials; b) adding a tetrachloroethane solution into a reaction kettle, adding the PBT prepolymer, the polysiloxane prepolymer and the butyltin catalyst into the reaction kettle, reacting at the temperature of 60-120 ℃ for 1-2 hours, removing 90% of tetrachloroethane solvent, adding phenol, and reacting for 2 hours to obtain a copolymer; c) and (3) blending the montmorillonite modified by the high molecular weight polysiloxane and the copolymer, and stirring uniformly to finish the preparation of the high-barrier PBT-polysiloxane copolymer-based composite material. The composite material has the performances of high barrier, high temperature resistance and better adhesive force.
Description
Technical Field
The invention belongs to the technical field of materials for packaging arresters, and particularly relates to a high-barrier PBT-polysiloxane copolymer-based composite material for a packaging arrester, and preparation and use methods thereof.
Background
At present, a silane coupling agent is a main material for improving the bonding performance between the two, but the bonding performance with PBT is not ideal enough, and the molecular weight is low, so that the strength and the high-temperature resistance of the bonding layer are poor.
The method for improving the blocking performance of the lightning arrester mainly comprises three methods, wherein the method is used for improving the blocking performance of PBT, and the modification principle is mainly to add high-blocking materials, such as graphene, montmorillonite and other two-dimensional inorganic materials, into the PBT. However, because the volume of the PBT in the lightning arrester is large, in order to obviously improve the barrier property of the PBT layer, the addition amount of the two-dimensional inorganic material is high, and the effective orientation of the two-dimensional inorganic material is difficult to realize in the extrusion and injection molding processes, so that the process difficulty is high, and the cost is high. And secondly, the barrier property of the silicone rubber is improved, but the silicone rubber is similar to PBT and also has the problem of higher volume fraction, and the process difficulty and the cost are increased when a higher content of two-dimensional inorganic material is added. Thirdly, the barrier property of the PBT and silicon rubber interface bonding layer is enhanced, which is a simple and easy method with obviously improved performance, but the method still has the following problems: the adhesive layer is small molecules (usually used is silane coupling agent KH 550), the adhesive thickness is small, the interaction with a two-dimensional inorganic material is weak, surface desorption is easy to occur, and the strength and the barrier property of the adhesive are not ideal. Therefore, the development of high molecular weight and high adhesion strength with PBT and silicone rubber is the basis for solving the existing problems in the third method. In addition, special surface modification of the two-dimensional inorganic material is required in order to ensure that the two-dimensional inorganic material used has an optimum interaction with the binder to prevent surface desorption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-barrier PBT-polysiloxane copolymer-based composite material for a packaged lightning arrester, which has high barrier property, high temperature resistance and better bonding force, and a preparation method and a use method thereof.
A high-barrier PBT-polysiloxane copolymer-based composite material for packaging a lightning arrester has a molecular formula as follows:
the molecular formula of the isocyanate-terminated polysiloxane prepolymer is:
the molecular formula of the hydroxyl-terminated PBT prepolymer is:
a preparation method of a high-barrier PBT-polysiloxane copolymer-based composite material for encapsulating a lightning arrester comprises the following steps:
a) selecting hydroxyl-terminated PBT prepolymer and isocyanate-terminated polysiloxane prepolymer as reaction raw materials;
b) adding a tetrachloroethane solution into a reaction kettle, adding the PBT prepolymer, the polysiloxane prepolymer and the butyltin catalyst into the reaction kettle, reacting for 1-2 hours at the temperature of between room temperature and 120 ℃, then removing 90% of tetrachloroethane solvent, adding phenol, and reacting for 2 hours to obtain a copolymer;
c) and (3) blending the montmorillonite modified by the high molecular weight polysiloxane and the copolymer, and stirring uniformly to finish the preparation of the high-barrier PBT-polysiloxane copolymer-based composite material.
A use method of a high-barrier PBT-polysiloxane copolymer-based composite material for packaging a lightning arrester comprises the following steps: uniformly coating the adhesive on the surface of the PBT by using the prepared high-barrier PBT-polysiloxane copolymer-based composite material solution through a blade coating method;
and (3) placing the silicon rubber on the surface of the coated PBT, and performing hot press molding at 160 ℃ to complete the bonding between the PBT and the silicon rubber, namely completing the complete packaging of the lightning arrester.
The molecular weight of the hydroxyl-terminated PBT prepolymer is 500-1000, and the molecular weight of the isocyanate-terminated polysiloxane prepolymer is 300-1000.
The molar ratio of isocyanate terminated polysiloxane prepolymer to hydroxyl terminated PBT prepolymer is 1: 1.05.
the mass content of the catalyst butyl tin is 0.5-1% of the total mass of the PBT prepolymer and the polysiloxane prepolymer.
The solid content of the PBT prepolymer, the polysiloxane prepolymer and the butyl tin catalyst in a tetrachloroethane solvent is less than or equal to 30 wt%.
The particle size of the montmorillonite is 12500 meshes, and the addition amount of the montmorillonite in the composite material is 5-10 wt%.
The molecular weight of the polysiloxane used for montmorillonite surface modification is 500-1000, and the molecular weight is matched with the chain segment degree of the polysiloxane in the copolymer, so that the effect is optimal.
The thickness of the composite coating is between 50 and 200 microns.
According to the invention, the block copolymer of PBT and polysiloxane is prepared by a copolymerization method, so that the interaction between PBT and silicone rubber is fundamentally improved, the high temperature resistance of the block copolymer is improved by utilizing the macromolecular characteristic of the block copolymer, and the desorption phenomenon at high temperature is avoided. The preparation difficulty of the PBT-polysiloxane copolymer is that the compatibility of PBT and polysiloxane is very poor, the contact efficiency of functional end groups is low, and the synthesis of high molecular weight copolymer is difficult. The invention firstly adopts a solution polymerization method to ensure that two prepolymers quickly react to generate polymers, and the solubility of the copolymer in a solvent is reduced along with the reaction. At this time, vacuum degassing treatment was carried out while retaining a part of the solvent in the reaction system and a certain amount of phenol was added. The main purpose of vacuum degassing is to reduce the distance between the reactive end groups of the polymer by volatilization of the solvent; the purpose of retaining part of the solvent and adding a certain amount of phenol is to retain the solubility of the low molecular weight PBT, wet the surfaces of two phases and enhance the reactivity of functional end groups, and researches show that the PBT prepolymer and the polysiloxane prepolymer can only have a dispersible or phase-separated size capable of reacting when the molecular weights of the PBT prepolymer and the polysiloxane prepolymer are 500-1000 and 300-1000 so as to ensure the smooth progress of the reaction. And then filling high molecular weight polysiloxane modified montmorillonite into the PBT-polysiloxane copolymer, coating the filled composite material solution on the surface of the PBT by a blade coating method, drying, and thermally pressing silicon rubber on the coating to form a final finished product of the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester. Different from other inventions, the montmorillonite in the invention is modified by polysiloxane with higher molecular weight, and the effect is best when the molecular chain and chain length of the surface polysiloxane are equal to the chain segment length in the copolymer. In addition, the best bonding and packaging effects can be realized by adopting a high-temperature coating mode. When a surface modifier is selected that has a chain length comparable to the polysiloxane block chain length of the adhesive, the interaction between the two is strongest. Meanwhile, because the critical stress between the two phases is more similar, the two phases are easier to orient in the processes of adhesive blade coating and silicon rubber hot pressing, so that the barrier property is optimal, and the mechanical strength is enhanced.
Detailed Description
Example 1: mixing the components in a molar ratio of 1.05: 1, putting a commercially available hydroxyl-terminated PBT prepolymer (molecular weight 500) and an isocyanate-terminated polysiloxane prepolymer (molecular weight 300) into a reaction kettle, adding a solvent accounting for 70 percent of the total mass and a butyltin catalyst accounting for 0.5 percent of the solid content of the prepolymer, reacting at the temperature of 60 ℃ for 2 hours, removing 90 percent of tetrachloroethane solvent, adding phenol, wherein the adding amount of the phenol is equivalent to that of the residual tetrachloroethane solvent, and reacting for 4 hours to obtain the copolymer. 5wt% of high molecular weight polysiloxane modified montmorillonite (the modified montmorillonite accounts for 5wt% of the composite material) and 95wt% of copolymer (the copolymer accounts for 95wt% of the composite material) are mixed, coated on the surface of PBT, the thickness is about 50 micrometers, and silicon rubber is hot-pressed on the surface to form the complete lightning arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 6.9MPa, the direct current 1mA reference voltage of the lightning arrester before boiling in boiling water is 68kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, after boiling in water (the lightning arrester is soaked in boiling salt water bath for 42 hours, and the same is carried out below), the direct current 1mA reference voltage of the lightning arrester is 67.9kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, and the resistance current change rate under the continuous operation voltage is within 4%, so that the stability requirement can be met.
Comparative example 1: mixing the components in a molar ratio of 1.05: 1 (molecular weight 500) and isocyanate terminated polysiloxane prepolymer (molecular weight 300), adding a solvent accounting for 70% of the total mass and a butyl tin catalyst accounting for 0.5% of the solid content, and reacting for 4 hours to obtain the copolymer. The copolymer was coated on the surface of PBT to a thickness of about 50 micrometers, and silicone rubber was hot-pressed onto the surface to form a complete arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 7.3MPa, the direct current 1mA reference voltage of the lightning arrester before boiling in boiling water is 68.5kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, after boiling in water (the lightning arrester is soaked in boiling salt water bath for 42 hours, and the same is carried out below), the direct current 1mA reference voltage of the lightning arrester is 68.1kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 11 muA, and the resistance current change rate under the continuous operation voltage is within 7%, so that the stability requirement can be met.
Comparative example 2: and coating the silane coupling agent on the surface of the PBT, controlling the thickness to be 50 microns, and hot-pressing silicon rubber on the surface to form the complete lightning arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 4.5MPa, the direct current 1mA reference voltage of the lightning arrester before boiling water is 68.1kV, the leakage current under 0.75 times of the direct current 1mA reference voltage is 5.5 mu A, the direct current 1mA reference voltage of the lightning arrester after boiling water is 66.7kV, the leakage current under 0.75 times of the direct current 1mA reference voltage is 25 mu A, the resistive current change rate under continuous operation voltage is about 94%, and the requirements on stability and durability are difficult to meet.
Comparative example 3: and directly hot-pressing the silicon rubber on the surface of the PBT to form the complete lightning arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 1.7MPa, the direct current 1mA reference voltage of the lightning arrester before boiling in water is 68.9kV, the leakage current under 0.75 times of the direct current 1mA reference voltage is 5 mu A, after boiling in water, the direct current 1mA reference voltage of the lightning arrester is 67kV, the leakage current under 0.75 times of the direct current 1mA reference voltage is 76 mu A, the change rate of the resistive current under the continuous operation voltage is up to 353%, and the requirements on stability and durability cannot be met.
Example 2: mixing the components in a molar ratio of 1.05: 1, putting a commercially available hydroxyl-terminated PBT prepolymer (molecular weight 1000) and an isocyanate-terminated polysiloxane prepolymer (molecular weight 1000) into a reaction kettle, adding a solvent accounting for 70 percent of the total mass and a butyltin catalyst accounting for 1 percent of the solid content of the prepolymer, reacting at the temperature of 80 ℃ for 1.5 hours, removing 90 percent of tetrachloroethane solvent, adding phenol, wherein the adding amount of the phenol is equivalent to that of the residual tetrachloroethane solvent, and reacting for 4 hours to obtain the copolymer. Mixing 10wt% of high molecular weight polysiloxane modified montmorillonite (the modified montmorillonite accounts for 10wt% of the composite material) and a copolymer (the copolymer accounts for 90 wt% of the composite material), coating the mixture on the surface of PBT, wherein the thickness of the mixture is about 50 micrometers, and hot-pressing silicon rubber on the surface to form the complete lightning arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 7.9MPa, the direct current 1mA reference voltage of the lightning arrester before boiling in boiling water is 68kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, after boiling in water (the lightning arrester is soaked in boiling salt water bath for 42 hours, and the same is carried out below), the direct current 1mA reference voltage of the lightning arrester is 67.9kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, and the resistance current change rate under the continuous operation voltage is within 5%, so that the stability requirement can be met.
Example 3: mixing the components in a molar ratio of 1.05: 1, putting a commercially available hydroxyl-terminated PBT prepolymer (molecular weight 800) and an isocyanate-terminated polysiloxane prepolymer (molecular weight 700) into a reaction kettle, adding a solvent accounting for 70 percent of the total mass and a butyltin catalyst accounting for 0.8 percent of the solid content of the prepolymer, reacting at the temperature of 120 ℃ for 1 hour, removing 90 percent of tetrachloroethane solvent, adding phenol, wherein the adding amount of the phenol is equivalent to that of the residual tetrachloroethane solvent, and reacting for 2 hours to obtain the copolymer. 8wt% of high molecular weight polysiloxane modified montmorillonite (the modified montmorillonite accounts for 8wt% of the composite material) and a copolymer (the modified montmorillonite accounts for 92 wt% of the composite material) are mixed, coated on the surface of PBT, the thickness of the mixture is about 50 micrometers, and silicon rubber is hot-pressed on the surface to form the complete lightning arrester.
Through tests, the bonding strength of the silicon rubber and the PBT is 7.6MPa, the direct current 1mA reference voltage of the lightning arrester before boiling in boiling water is 68.4 kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, after boiling in water (the lightning arrester is soaked in boiling salt water bath for 42 hours, and the lower part is the same), the direct current 1mA reference voltage of the lightning arrester is 67.9kV, the leakage current under the direct current 1mA reference voltage of 0.75 time is 5 muA, and the resistance current change rate under the continuous operation voltage is within 5%, so that the stability requirement can be met.
Claims (10)
1. A preparation method of a high-barrier PBT-polysiloxane copolymer-based composite material for encapsulating a lightning arrester comprises the following steps:
a) selecting hydroxyl-terminated PBT prepolymer and isocyanate-terminated polysiloxane prepolymer as reaction raw materials;
b) adding a tetrachloroethane solution into a reaction kettle, adding the PBT prepolymer, the polysiloxane prepolymer and the butyltin catalyst into the reaction kettle, reacting at the temperature of 60-120 ℃ for 1-2 hours, removing 90% of tetrachloroethane solvent, adding phenol, and reacting for 2 hours to obtain a copolymer;
c) and (3) blending the montmorillonite modified by the high molecular weight polysiloxane and the copolymer, and stirring uniformly to finish the preparation of the high-barrier PBT-polysiloxane copolymer-based composite material.
2. A use method of a high-barrier PBT-polysiloxane copolymer-based composite material for packaging a lightning arrester is characterized by comprising the following steps: the method comprises the following steps: uniformly coating the prepared high-barrier PBT-polysiloxane copolymer-based composite material solution on the surface of PBT by a blade coating method;
and (3) placing the silicon rubber on the surface of the coated PBT, and performing hot press molding at 160 ℃ to complete the bonding between the PBT and the silicon rubber, namely completing the complete packaging of the lightning arrester.
3. The method for preparing the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester according to claim 2, wherein: the molecular weight of the hydroxyl-terminated PBT prepolymer is 500-1000, and the molecular weight of the isocyanate-terminated polysiloxane prepolymer is 300-1000.
4. The method for preparing the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester according to claim 2, wherein: the molar ratio of isocyanate terminated polysiloxane prepolymer to hydroxyl terminated PBT prepolymer is 1: 1.05.
5. the method for preparing the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester according to claim 2, wherein the method comprises the following steps: the mass content of the catalyst butyl tin is 0.5-1% of the total mass of the PBT prepolymer and the polysiloxane prepolymer.
6. The method for preparing the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester according to claim 2, wherein: the solid content of the PBT prepolymer, the polysiloxane prepolymer and the butyl tin catalyst in a tetrachloroethane solvent is less than or equal to 30 wt%.
7. The method for preparing the high-barrier PBT-polysiloxane copolymer-based composite material for the encapsulated lightning arrester according to claim 2, wherein: the particle size of the montmorillonite is 12500 meshes, and the addition amount of the montmorillonite in the composite material is 5-10 wt%.
8. The method for using the high-barrier PBT-polysiloxane copolymer-based composite material for encapsulating the lightning arrester according to claim 3, wherein: the molecular weight of the polysiloxane for montmorillonite surface modification is 500-1000, and the coating thickness of the composite material is 50-200 microns.
9. The use of a high barrier PBT-polysiloxane copolymer based composite material for encapsulating lightning arresters according to claim 1 for the encapsulation of zinc oxide lightning arresters.
10. A high-barrier PBT-polysiloxane copolymer-based composite material for packaging a lightning arrester is characterized in that: the molecular formula of the copolymer is as follows:
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