CN111234751A - High-strength cracking-resistant liquid pouring sealant and preparation method thereof - Google Patents
High-strength cracking-resistant liquid pouring sealant and preparation method thereof Download PDFInfo
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- CN111234751A CN111234751A CN202010229339.4A CN202010229339A CN111234751A CN 111234751 A CN111234751 A CN 111234751A CN 202010229339 A CN202010229339 A CN 202010229339A CN 111234751 A CN111234751 A CN 111234751A
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a high-strength cracking-resistant liquid pouring sealant and a preparation method thereof, wherein the high-strength cracking-resistant liquid pouring sealant is formed by mixing 70-110 parts by weight of a component A and 10-30 parts by weight of a component B; the component A is formed by mixing toughened liquid epoxy resin, epoxy active diluent, a defoaming agent, aluminum hydroxide, spherical silicon micro powder and reinforcing chopped fibers; the component B is formed by mixing an anhydride curing agent and an accelerator; the preparation method comprises the steps of preparing the toughened liquid epoxy resin, adding other materials, uniformly dispersing to prepare the component A, and directly and uniformly mixing the component B. The pouring sealant has moderate viscosity and convenient use, has the characteristics of high bonding strength, low thermal expansion coefficient, low stress, high strength, excellent insulativity, excellent high and low temperature impact resistance and the like after being heated and cured, and is suitable for insulating and packaging of power electronic containers related to special metal materials such as large steel, copper and the like.
Description
Technical Field
The invention belongs to an organic polymer material and preparation thereof, and relates to a high-strength cracking-resistant liquid pouring sealant and a preparation method thereof. The high-strength cracking-resistant liquid pouring sealant disclosed by the invention is an epoxy pouring sealant with high strength, low thermal expansion coefficient and excellent high-low temperature impact resistance, can be widely applied to the fields of electronics, electricity, military industry, medical treatment, aviation, high-speed rail and the like, and is particularly suitable for insulating packaging of power electronic containers related to large steel, copper and other special metal materials.
Background
The epoxy pouring sealant is mainly used for strengthening the integrity of electronic components, increasing the insulativity between internal elements and circuits and improving the resistance to external impact and vibration, thereby achieving the purposes of insulation protection, confidentiality, water resistance, moisture resistance and the like, and being widely applied to the fields of electronics, electricity, war industry, medical treatment, aviation, high-speed rail and the like.
With the development of science and technology, the performance requirement of the encapsulation device is higher and higher, the design is more and more complex, and the requirement of higher matching performance is provided for the encapsulation glue. Especially, for some special equipment, such as power capacitors applied to large-sized locomotives and ships, the device size is huge, the shell is made of metals with extremely low coefficient of linear expansion, such as stainless steel and the like which are difficult to surface treat, the materials with large CTE difference, such as copper, aluminum, PP plastics and the like, exist inside the special equipment, and sharp chamfers exist. After encapsulation is completed, the encapsulated device is also subjected to tests such as high and low temperature impacts of-55 ℃/1h to 100 ℃/1h for multiple times, considering that the encapsulated device can operate under extreme climatic conditions. In the prior art, epoxy pouring sealants, silicone sealants and polyurethane sealants are mainstream, and in the special application, the silicone sealants and polyurethane sealants cannot meet the requirements due to low bonding strength, insufficient heat resistance, low body strength, insufficient long-term reliability and the like, and the epoxy pouring sealants cannot meet the protection requirements due to the problems of stress cracking and peeling of colloids and metal shells after high and low temperature impact caused by the brittleness.
In order to solve the problem that epoxy pouring sealants are large in brittleness and easy to crack, in the prior art, toughening technologies such as rubber and the like are mostly used for modifying epoxy resin or curing agents. For example: CN106281174A, CN107573882A, CN106318298A, CN102898993A, etc. all use rubber, polyurethane or polyurethane to modify epoxy and flexible amine or anhydride curing agents to improve the cracking resistance of the epoxy body, and these methods essentially reduce the modulus of the cured product at low temperature to reduce stress, but the modified product hardly participates in the reaction, the CTE of the cured product itself increases, the CTE difference between the pouring sealant and the metal device increases, and the risk of cracking still exists; in addition, this method greatly reduces the heat resistance of the cured product, lowers the usable temperature thereof, and lowers the reliability.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-strength cracking-resistant liquid pouring sealant and a preparation method thereof. According to the invention, the low-viscosity epoxy resin is toughened and modified by the high-molecular-weight thermoplastic resin, a large number of hydroxyl groups can participate in the reaction of epoxy groups to form an interpenetrating network structure so as to provide good toughness and bonding performance, and the low-stress spherical silicon with high filling content is matched, so that the problems of high stress of an epoxy condensate, body cracking under high and low temperature impact and easiness in cracking of a contact part with a metal part are solved.
The content of the invention is as follows: the utility model provides a high strength crack resistant liquid pouring sealant which characterized by: the high-strength cracking-resistant liquid pouring sealant is formed by mixing 70-110 parts by weight of a component A and 10-30 parts by weight of a component B (when in use);
the component A is formed by mixing 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, 40-80 parts by weight of (low-stress) spherical silicon micro powder and 0-5 parts by weight of reinforcing chopped fibers;
the component B is formed by mixing 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator.
The content of the invention is better as follows: the utility model provides a high strength crack resistant liquid pouring sealant which characterized by: the high-strength cracking-resistant liquid pouring sealant is formed by mixing 90-100 parts by weight of a component A and 13-18 parts by weight of a component B (when in use);
the component A is formed by mixing 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, 40-80 parts by weight of (low-stress) spherical silicon micro powder and 0.1-5 parts by weight of reinforcing chopped fibers;
the component B is formed by mixing 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator.
The component A of the high-strength cracking-resistant liquid pouring sealant disclosed by the invention can also contain (add) various dyes according to the needs.
The invention comprises the following steps: the toughened liquid epoxy resin is prepared by blending and modifying a high-molecular-weight thermoplastic resin and a low-viscosity epoxy resin, and the preparation method comprises the following steps: heating the low-viscosity epoxy resin to 130-150 ℃, adding the high-molecular-weight thermoplastic resin in a stirring state (slowly), preserving heat, and keeping stirring until the high-molecular-weight thermoplastic resin is completely dissolved to obtain toughened liquid epoxy resin; the toughening liquid epoxy resin contains 4-13 wt% of high molecular weight thermoplastic resin;
the low-viscosity epoxy resin is one or a mixture of two or more of phenyl glycidyl ether modified epoxy resin (such as YD-112 of national institute of chemical (Kunshan) Co., Ltd.), cardanol glycidyl ether modified epoxy resin (such as YD-113 of national institute of chemical (Kunshan) Co., Ltd.), butyl glycidyl ether modified epoxy resin (such as YD-115CA of national institute of chemical (Kunshan) Co., Ltd.), and C12-C14 alkyl glycidyl ether modified epoxy resin (such as YD-114 of national institute of chemical (Kunshan)) and has a viscosity of 400-2000 mPas at 25 ℃ and an epoxy equivalent of 170-230 g/eq;
the high molecular weight thermoplastic resin has a chemical structural formula (characteristic) shown in formula (I):
in formula (I): x, y and z are 0.85, 0, 0.15-0.5, 0.25 and 0.25, x + y + z is less than or equal to 1, x is less than or equal to 0.5 and less than or equal to 0.85, y is less than or equal to 0 and less than or equal to 0.25, and z is less than or equal to 0.15 and less than or equal to 0.25; n is more than or equal to 100 and less than or equal to 2000, and the weight average molecular weight (between) is 6-30 ten thousand;
R1one selected from the following chemical structures: -CH2—、—CH2CH2—、—CH2CH2CH2CH2—；
R2One selected from the following chemical structures: -OH, -COOCH3。
The production providing enterprises and models of the high molecular weight thermoplastic resin products are as follows: SEKISUI S-LEC BX-1, Monsanto Butvar B-90, and the like.
The invention comprises the following steps: the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin (bisphenol A type glycidyl ether, bisphenol F glycidyl ether, polyphenol type glycidyl ether and aliphatic glycidyl ether) (such as Nantong star 0164), glycidyl ester type epoxy resin (such as TDE-85 manufactured by Tianjin synthetic materials), glycidyl amine type epoxy resin (such as huntsman Araldite MY720) and alicyclic epoxy resin (such as Daicel 2021P), the epoxy equivalent of the epoxy resin is 240g/eq at 120-.
The invention comprises the following steps: the epoxy reactive diluent is one or a mixture of two or more of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether, and preferably 1, 4-butanediol diglycidyl ether. (e.g., Anhui Xinyuan XY 622).
The invention comprises the following steps: the defoaming agent is one or a mixture of two or more of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent, and the organic silicon polymer compound defoaming agent is preferably selected. (e.g., BYK-A530).
The invention comprises the following steps: the (low-stress) spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5-5 parts by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5-75 parts by weight; preferably, the small-particle spherical silicon micro powder has the particle sizes of D500.5-1 mu m and D901.5-2.5 mu m, and the large-particle spherical silicon micro powder has the particle sizes of D5020-26 mu m and D9060-70 mu m, and the spherical silicon micro powder is formed by mixing 1-3 parts by weight of small-particle spherical silicon micro powder and 55-65 parts by weight of large-particle spherical silicon micro powder. (e.g., Birapi material DQ1010, NQ 1175D).
The invention comprises the following steps: the anhydride curing agent is one or a mixture of two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyazelaic anhydride and polysebacic anhydride, preferably methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride (such as Hitachi chemical HN-2000NT, HN-7000A).
The invention comprises the following steps: the accelerator is any one of DMP-30, N-dimethylbenzylamine, toluene dimethylamine, 2-ethyl-4-methylimidazole and cyanoethyl modified 2-ethyl-4-methylimidazole, and preferably N, N-dimethylbenzylamine or cyanoethyl modified 2-ethyl-4-methylimidazole (such as BDMA (New Dian chemical) and 2E4MZ-CN (four kingdoms chemical).
The invention comprises the following steps: the aluminum hydroxide is preferably aluminum hydroxide obtained by a common Bayer process, and the particle size is D501-3.5 μm or D904-15 μm; preferably D501-3 μm and D904-10 μm (e.g., Anhui Yi Shi Tong JATH-0030E).
The invention comprises the following steps: the chopped reinforced fiber can be one or a mixture of two or more of chopped glass fiber, chopped aramid fiber, chopped carbon fiber and chopped polyester fiber, and the chopped reinforced fiber has the diameter of 3-15 mu m and the length of 0.1-2 mm; preferably: chopped glass fiber and aramid fiber (such as Hangzhou high-tech composite material MQ-50) subjected to surface treatment by a coupling agent.
Another aspect of the invention is: a preparation method of a high-strength cracking-resistant liquid pouring sealant is characterized by comprising the following steps:
a. preparing a component A:
preparing materials: taking raw materials of 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, (40-80 parts by weight of low-stress) spherical silicon micro powder and 0-5 parts by weight of reinforcing chopped fiber;
the (low-stress) spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5-5 parts by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5-75 parts by weight; preferably, the small-particle spherical silicon micropowder D500.5-1 μm and D901.5-2.5 μm, and the large-particle spherical silicon micropowder D5020-26 μm and D9060-70 μm, and is prepared by mixing 1-3 parts by weight of small-particle spherical silicon micropowder and 55-65 parts by weight of large-particle spherical silicon micropowder (such as Birexina DQ1010 and NQ 1175D).
Mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the material temperature at 95-120 ℃, stirring for 5-20min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 10-30 min at the rotating speed of 1000-3000 rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 0.5-1.5 h at the rotating speed of 1000-3000 rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator;
mixing: and adding the anhydride curing agent and the accelerator into a reaction container, starting stirring for 20-60 min, and uniformly mixing to obtain the component B.
Further, when the high-strength cracking-resistant liquid pouring sealant is used, the component A and the component B are mixed according to the weight ratio of 70-110 parts (preferably 90-100 parts) by weight of the component A to 10-30 parts (preferably 13-18 parts) by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; potting fill seal for gaps in the device.
In another aspect of the invention: the reinforced chopped fiber is preferably replaced by 0.1-5 parts by weight of the reinforced chopped fiber.
In another aspect of the invention: the component A of the high-strength cracking-resistant liquid pouring sealant can also contain (add) various dyes according to the needs.
In another aspect of the invention: the toughened liquid epoxy resin is prepared by blending and modifying a high-molecular-weight thermoplastic resin and a low-viscosity epoxy resin, and the preparation method comprises the following steps: heating the low-viscosity epoxy resin to 130-150 ℃, adding the high-molecular-weight thermoplastic resin in a stirring state (slowly), preserving heat, and keeping stirring until the high-molecular-weight thermoplastic resin is completely dissolved to obtain toughened liquid epoxy resin; the toughening liquid epoxy resin contains 4-13% of high molecular weight thermoplastic resin by weight:
the low-viscosity epoxy resin is one or a mixture of two or more of phenyl glycidyl ether modified epoxy resin, cardanol glycidyl ether modified epoxy resin, butyl glycidyl ether modified epoxy resin and C12-C14 alkyl glycidyl ether modified epoxy resin, and the viscosity of the low-viscosity epoxy resin at 25 ℃ is 400-2000 mPa & s, and the epoxy equivalent is 170-230 g/eq;
the high molecular weight thermoplastic resin has a chemical structural formula (characteristic) shown in formula (I):
in formula (I): x, y and z are 0.85, 0, 0.15-0.5, 0.25 and 0.25, x + y + z is less than or equal to 1, x is less than or equal to 0.5 and less than or equal to 0.85, y is less than or equal to 0 and less than or equal to 0.25, and z is less than or equal to 0.15 and less than or equal to 0.25; n is more than or equal to 100 and less than or equal to 2000, and the weight average molecular weight (between) is 6-30 ten thousand;
R1one selected from the following chemical structures: -CH2—、—CH2CH2—、—CH2CH2CH2CH2—；
R2One selected from the following chemical structures: -OH, -COOCH3。
In another aspect of the invention: the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin (bisphenol A type glycidyl ether, bisphenol F glycidyl ether, polyphenol type glycidyl ether and aliphatic glycidyl ether), glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and alicyclic epoxy, the epoxy equivalent of the epoxy resin is 240g/eq at 120-.
In another aspect of the invention: the epoxy reactive diluent is one or a mixture of two or more of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether, and preferably 1, 4-butanediol diglycidyl ether.
In another aspect of the invention: the defoaming agent is one or a mixture of two or more of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent, and the organic silicon polymer compound defoaming agent is preferably selected.
In another aspect of the invention: the anhydride curing agent is one or a mixture of two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyazelaic anhydride and polysebacic anhydride, preferably methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride;
in another aspect of the invention: the accelerator is any one of DMP-30, N-dimethylbenzylamine, toluene dimethylamine, 2-ethyl-4-methylimidazole and cyanoethyl-modified 2-ethyl-4-methylimidazole, and preferably N, N-dimethylbenzylamine or cyanoethyl-modified 2-ethyl-4-methylimidazole.
In another aspect of the invention: the aluminum hydroxide is preferably aluminum hydroxide obtained by a common Bayer process, and the particle size is D501-3.5 μm or D904-15 μm; preferably D501 to 3 μm and D904 to 10 μm.
In another aspect of the invention: the chopped reinforced fiber can be one or a mixture of two or more of chopped glass fiber, chopped aramid fiber, chopped carbon fiber and chopped polyester fiber, and the chopped reinforced fiber has the diameter of 3-15 mu m and the length of 0.1-2 mm; chopped glass fiber and aramid fiber which are subjected to surface treatment by a coupling agent are preferred.
The invention relates to a use method of a high-strength cracking-resistant liquid pouring sealant (or called dual-component epoxy pouring sealant), which comprises the following steps: preheating a device to be glue-filled at 90-120 ℃ for 1-4 h, simultaneously preheating the component A at 60-80 ℃ for 2-10 h, and mixing the component A and the component B according to the weight ratio [ namely: mixing 70-110 parts (preferably 90-100 parts) by weight of the component A and 10-30 parts (preferably 13-18 parts) by weight of the component B, uniformly stirring, pouring the mixed glue solution into a device to be glue-filled in batches after vacuum defoaming, performing vacuum defoaming to realize infiltration filling of gaps, curing at 75-85 ℃ for 3-5 hours and at 95-125 ℃ for 3-6 hours in sequence, and then slowly cooling at the speed of 0.5-1.5 ℃/min.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the high-strength cracking-resistant liquid pouring sealant (a heating curing type bi-component epoxy pouring sealant) comprises a component A and a component B, wherein the component A contains high-filling-amount low-stress spherical silica micro powder and reactive high-molecular-weight thermoplastic resin, the high-molecular-weight thermoplastic resin, epoxy and anhydride curing agent form an interpenetrating network in the curing reaction, the stress and the shrinkage are reduced under the condition of not increasing the CTE, meanwhile, a large number of hydroxyl groups increase the bonding with the device material, so that the cracking resistance of a cured product is improved, particularly the low-temperature brittleness is improved, and the strength of the cured product is obviously improved;
(2) the high-strength cracking-resistant liquid pouring sealant disclosed by the invention is moderate in viscosity, can be used for pouring large metal devices with a larger difference in thermal expansion coefficient with epoxy resin, is smooth and good in surface, has Shore D hardness of more than 80, does not crack after being subjected to cold and heat impact for 10 times of-55 ℃/1 h-100 ℃/1h, and has no crack at a bonding interface with metal;
(3) the product of the invention has simple preparation process, excellent product performance and convenient use, has high bonding strength, low thermal expansion coefficient, low stress, high strength, excellent insulativity and excellent high and low temperature impact resistance after being heated and cured, is particularly suitable for the insulation packaging of power electronic containers related to special metal materials such as large steel, copper and the like, and has strong practicability.
Drawings
Fig. 1 is a schematic structural diagram of a cold-thermal shock potted sample device in an embodiment of the invention; the specifications of the cold and hot impact encapsulation sample device are as follows: length, width, height 50, 20, 10 cm.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Preparation of first part toughened epoxy resin
Example 1: preparation of toughened epoxy resin
The implementation steps are as follows: weighing 92-95 parts of low-viscosity epoxy resin, adding the weighed low-viscosity epoxy resin into a reaction kettle, starting electric heating and stirring, gradually adding 5-8 parts of high-molecular-weight thermoplastic resin powder into the reaction kettle in a manner of slowly adding and dissolving when the temperature is raised to 145 ℃, keeping the temperature and stirring until the powder is completely dissolved, and then stirring for 0.5h to obtain the toughened epoxy resin. The steps are repeated by adopting different raw materials to prepare the toughened epoxy resin of the embodiment 1-4.
The low-viscosity epoxy resin is selected from one or more of phenyl glycidyl ether modified epoxy resin, cardanol glycidyl ether modified epoxy resin, butyl glycidyl ether modified epoxy resin or C12-C14 alkyl glycidyl ether modified epoxy resin.
Table 1: examples 1-1 to 1-4 the toughened epoxy resin comprises the following components in percentage by weight:
preparation and application of second part high-strength cracking-resistant epoxy pouring sealant
Example 2: preparation and application of high-strength cracking-resistant epoxy pouring sealant
The implementation steps are as follows:
(1) preparation of component A
Sequentially adding 8-15 parts of toughened liquid epoxy resin, 10-12 parts of epoxy resin, 0.1-5 parts of epoxy active diluent, 0.01-1 part of defoaming agent and 0-1 part of dye into a reaction kettle, starting heating and stirring at the rotating speed of 60-200 rpm, keeping the material temperature at 95-120 ℃, stirring for 5-20min, then slowly adding 0.5-5 parts of low-stress small-particle-size spherical silicon micro powder with D500.2-1 mu m and D901.5-5 mu m and 9-14 parts of aluminum hydroxide with D501-3.5 mu m and D904-15 mu m, starting high-speed stirring and shearing for emulsification for 10-30 min, rotating at the rotating speed of 1000-3000 rpm, then respectively adding 39.5-75 parts of D5018-28 mu m, D9055-75 mu m large-particle-size low-stress spherical silicon micro powder and 0-5 parts of short reinforcing fiber with the diameter of 3-15 mu m and the length of 0.1-2 mm, keeping the temperature and stirring at the high speed for 0.5-1.5 h, and keeping the vacuum degree of vacuum at the vacuum degree of defoaming less than or less than 0.09, cooling to obtain the component A.
(2) Preparation of component B
Adding 13-25 parts of anhydride curing agent and 0.1-1 part of accelerator into a reaction kettle, starting stirring for 15-30 min, and uniformly mixing to obtain a component B.
(3) Application of pouring sealant
Preheating the component A at 60-80 ℃ for 2-10 h, respectively taking 70-110 parts of the component A and 10-30 parts of the component B, uniformly stirring and mixing, pouring the mixed glue solution into a mold or a device (shown in figure 1) preheated at 90-120 ℃ in a plurality of times after vacuum defoaming, realizing infiltration and filling of gaps through vacuum defoaming, curing at 75-85 ℃/3-5 h + 95-125 ℃/3-6 h, and slowly cooling to room temperature at the speed of 0.5-1.5 ℃/min to obtain the required sample.
The raw materials used in the examples:
a1: the toughened epoxy resin prepared in example 1-1;
a2: toughened epoxy resins prepared in examples 1-2;
a3: toughened epoxy resins prepared in examples 1-3;
a4: toughened epoxy resins prepared in examples 1-4;
b1: YD-128, bisphenol A epoxy resin in Kunshan, with an epoxy equivalent of 184-190 g/eq;
b2: 0164, the Nantong star bisphenol A epoxy resin has the epoxy equivalent of 183-plus 190 g/eq;
c1: diluent XY622, Anhui Xin Yuan 1, 4-butanediol diglycidyl ether;
c2: diluent XY669, anshin ethylene glycol diglycidyl ether;
d1: defoamer BYK-a 530, birk chemical;
d2: defoamer BYK-a 535, birk chemical;
e: aluminum hydroxide JATH-0030E, Anhui Yi Shitong;
f1: spherical silica DQ1010, jagsu birry;
f2: spherical silica NQ1175D, jagsu dirough;
g: chopped reinforced glass fiber MQ-50, a Hangzhou high-tech composite material;
h1: WNY-1008 parts of methyltetrahydrophthalic anhydride, Jiaxing south ocean everything prosperizing chemical;
h2: methylhexahydrophthalic anhydride HN-7000A, Hitachi formation;
i: modified imidazole accelerator 2E4MZ-CN, formed in four japan.
Table 2: the resin solution of the embodiment 2-1 to 2-8 comprises the following components in percentage by weight:
note: the curing condition is that the temperature is reduced to room temperature at 80 ℃/4h +110 ℃/6h +0.5 ℃/min.
Table 3: examples 2-1 to 2-8 Table of Performance parameters:
note that after the cold and hot impact, the surface of the sample device was not cracked, and no peeling of the resin from the metal case was represented as ◎, the surface of the sample device was slightly cracked, or slight peeling of the resin from the metal case was represented as ○ (defects with a length of < 1cm and a number of < 5 were considered slight), the surface of the sample device was severely cracked, or severe peeling of the resin from the metal case was represented as △ (defects with a length of > 1cm or a number of > 5 were considered severe).
Comparative example of the third section
Comparative example a low viscosity epoxy resin in component a was prepared in the same way as in example, without toughening modification.
Raw materials used in comparative examples:
a1: butyl glycidyl ether modified epoxy YD-115CA, national institutes of chemical (Kunshan);
a2: phenyl glycidyl ether modified epoxy YD-112, national institutes of chemical (Kunshan);
a3: cardanol glycidyl ether modified epoxy YD-113, national chemical (Kunshan);
a4: C12-C14 glycidyl ether modified epoxy YD-114, national chemical (Kunshan);
b1: YD-128, bisphenol A epoxy resin in Kunshan, with an epoxy equivalent of 184-190 g/eq;
b2: 0164, the Nantong star bisphenol A epoxy resin has the epoxy equivalent of 183-plus 190 g/eq;
c1: diluent XY622, Anhui Xin Yuan 1, 4-butanediol diglycidyl ether;
c2: diluent XY669, anshin ethylene glycol diglycidyl ether;
d1: defoamer BYK-a 530, birk chemical;
d2: defoamer BYK-a 535, birk chemical;
e: aluminum hydroxide JATH-0030E, Anhui Yi Shitong;
f1: spherical silica DQ1010, jagsu birry;
f2: spherical silica NQ1175D, jagsu dirough;
g: chopped reinforced glass fiber MQ-50, a Hangzhou high-tech composite material;
h1: WNY-1008 parts of methyltetrahydrophthalic anhydride, Jiaxing south ocean everything prosperizing chemical;
h2: methylhexahydrophthalic anhydride HN-7000A, Hitachi formation;
i: modified imidazole accelerator 2E4MZ-CN, formed in four japan.
Table 4: comparative examples 3-1 to 3-8 resin solution components and ratios:
note: the curing condition is that the temperature is reduced to room temperature at 80 ℃/4h +110 ℃/6h +0.5 ℃/min
Table 5: comparative examples 3-1 to 3-8 Performance parameter tables:
note that after the cold and hot impact, the surface of the sample device was not cracked, and no peeling of the resin from the metal case was represented as ◎, the surface of the sample device was slightly cracked, or slight peeling of the resin from the metal case was represented as ○ (defects with a length of < 1cm and a number of < 5 were considered slight), the surface of the sample device was severely cracked, or severe peeling of the resin from the metal case was represented as △ (defects with a length of > 1cm or a number of > 5 were considered severe).
Example 4:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 110 parts by weight of a component A and 30 parts by weight of a component B (when in use);
the component A is formed by mixing 15 parts by weight of toughened liquid epoxy resin, 12 parts by weight of epoxy resin, 5 parts by weight of epoxy active diluent, 1 part by weight of defoaming agent, 14 parts by weight of aluminum hydroxide, 80 parts by weight of (low-stress) spherical silicon micro powder and 5 parts by weight of reinforcing chopped fibers;
the component B is formed by mixing 25 parts by weight of anhydride curing agent and 1 part by weight of accelerator.
Example 5:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 70 parts by weight of a component A and 15 parts by weight of a component B (when in use);
the component A is formed by mixing 8 parts by weight of toughened liquid epoxy resin, 10 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 0.01 part by weight of defoaming agent, 9 parts by weight of aluminum hydroxide, 40 parts by weight of (low-stress) spherical silicon micro powder and 1 part by weight of reinforcing chopped fiber;
the component B is formed by mixing 13 parts by weight of anhydride curing agent and 0.1 part by weight of accelerator.
Example 6:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 90 parts by weight of a component A and 20 parts by weight of a component B (when in use);
the component A is formed by mixing 12 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 2.5 parts by weight of epoxy active diluent, 0.5 part by weight of defoaming agent, 12 parts by weight of aluminum hydroxide, 60 parts by weight of (low-stress) spherical silicon micro powder and 1.5 parts by weight of reinforcing chopped fiber;
the component B is formed by mixing 19 parts by weight of anhydride curing agent and 0.5 part by weight of accelerator.
Example 7:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 75 parts by weight of a component A and 15 parts by weight of a component B (when in use);
the component A is formed by mixing 9 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 1 part by weight of epoxy active diluent, 0.3 part by weight of defoaming agent, 10 parts by weight of aluminum hydroxide and 50 parts by weight of (low-stress) spherical silicon micro powder;
the component B is formed by mixing 16 parts by weight of anhydride curing agent and 0.3 part by weight of accelerator.
Example 8:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 100 parts by weight of a component A and 22 parts by weight of a component B (when in use);
the component A is formed by mixing 14 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 4 parts by weight of epoxy active diluent, 0.8 part by weight of defoaming agent, 13 parts by weight of aluminum hydroxide and 70 parts by weight of (low-stress) spherical silicon micro powder;
the component B is formed by mixing 21 parts by weight of anhydride curing agent and 0.8 part by weight of accelerator.
Example 9:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 90 parts by weight of a component A and 20 parts by weight of a component B (when in use);
the component A is formed by mixing 11 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 2.5 parts by weight of epoxy active diluent, 0.5 part by weight of defoaming agent, 11.5 parts by weight of aluminum hydroxide and 60 parts by weight of (low-stress) spherical silicon micro powder;
the component B is formed by mixing 19 parts by weight of anhydride curing agent and 0.55 part by weight of accelerator.
Example 10:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 90 parts by weight of a component A and 18 parts by weight of a component B (when in use);
the component A is formed by mixing 8 parts by weight of toughened liquid epoxy resin, 10 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 0.01 part by weight of defoaming agent, 9 parts by weight of aluminum hydroxide, 40 parts by weight of (low-stress) spherical silicon micro powder and 0.1 part by weight of reinforcing chopped fiber;
the component B is formed by mixing 13 parts by weight of anhydride curing agent and 0.1 part by weight of accelerator.
Example 11:
a high-strength cracking-resistant liquid pouring sealant is formed by mixing 95 parts by weight of a component A and 20.2 parts by weight of a component B (when in use);
the component A is formed by mixing 11.5 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 2.5 parts by weight of epoxy active diluent, 0.55 part by weight of defoaming agent, 11.5 parts by weight of aluminum hydroxide, 60 parts by weight of (low-stress) spherical silicon micro powder and 2.5 parts by weight of reinforcing chopped fiber;
the component B is formed by mixing 19 parts by weight of anhydride curing agent and 0.5 part by weight of accelerator.
In examples 4 to 11 above: the toughened liquid epoxy resin is prepared by blending and modifying a high-molecular-weight thermoplastic resin and a low-viscosity epoxy resin, and the preparation method comprises the following steps: heating the low-viscosity epoxy resin to 130-150 ℃, adding the high-molecular-weight thermoplastic resin in a stirring state (slowly), preserving heat, and keeping stirring until the high-molecular-weight thermoplastic resin is completely dissolved to obtain toughened liquid epoxy resin; the toughening liquid epoxy resin contains 4-13 wt% of high molecular weight thermoplastic resin;
the low-viscosity epoxy resin is one or a mixture of two or more of phenyl glycidyl ether modified epoxy resin, cardanol glycidyl ether modified epoxy resin, butyl glycidyl ether modified epoxy resin and C12-C14 alkyl glycidyl ether modified epoxy resin, and the viscosity of the low-viscosity epoxy resin at 25 ℃ is 400-2000 mPa & s, and the epoxy equivalent is 170-230 g/eq;
the high molecular weight thermoplastic resin has a chemical structural formula (characteristic) shown in formula (I):
in formula (I): x, y and z are 0.85, 0, 0.15-0.5, 0.25 and 0.25, x + y + z is less than or equal to 1, x is less than or equal to 0.5 and less than or equal to 0.85, y is less than or equal to 0 and less than or equal to 0.25, and z is less than or equal to 0.15 and less than or equal to 0.25; n is more than or equal to 100 and less than or equal to 2000, and the weight average molecular weight (between) is 6-30 ten thousand;
R1one selected from the following chemical structures: -CH2—、—CH2CH2—、—CH2CH2CH2CH2—；
R2One selected from the following chemical structures: -OH, -COOCH3；
In examples 4 to 11 above: the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin (bisphenol A type glycidyl ether, bisphenol F glycidyl ether, polyphenol type glycidyl ether and aliphatic glycidyl ether), glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and alicyclic epoxy, the epoxy equivalent of the epoxy resin is 240g/eq at 120-.
In examples 4 to 11 above: the epoxy reactive diluent is one or a mixture of two or more of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether, and preferably 1, 4-butanediol diglycidyl ether.
In examples 4 to 11 above: the defoaming agent is one or a mixture of two or more of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent, and the organic silicon polymer compound defoaming agent is preferably selected.
In examples 4 to 11 above: the (low-stress) spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5-5 parts by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5-75 parts by weight; preferably, the small-particle spherical silicon micro powder has the particle sizes of D500.5-1 μm and D901.5-2.5 μm, and the large-particle spherical silicon micro powder has the particle sizes of D5020-26 μm and D9060-70 μm, and is formed by mixing 1-3 parts by weight of small-particle spherical silicon micro powder and 55-65 parts by weight of large-particle spherical silicon micro powder.
In examples 4 to 11 above: the anhydride curing agent is one or a mixture of two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyazelaic anhydride and polysebacic anhydride, preferably methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride;
the accelerator is any one of DMP-30, N-dimethylbenzylamine, toluene dimethylamine, 2-ethyl-4-methylimidazole and cyanoethyl modified 2-ethyl-4-methylimidazole, and preferably N, N-dimethylbenzylamine or cyanoethyl modified 2-ethyl-4-methylimidazole;
the aluminum hydroxide is aluminum hydroxide obtained by a common Bayer process, and has particle sizes of D501-3.5 μm and D904-15 μm; d501-3 μm and D904-10 μm are preferred;
the chopped reinforced fibers are one or a mixture of two or more of chopped glass fibers, chopped aramid fibers, chopped carbon fibers and chopped polyester fibers, and the chopped reinforced fibers have the diameter of 3-15 mu m and the length of 0.1-2 mm; chopped glass fiber and aramid fiber which are subjected to surface treatment by a coupling agent are preferred.
Example 12:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking 11 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 2.5 parts by weight of epoxy active diluent, 0.5 part by weight of defoaming agent, 11.5 parts by weight of aluminum hydroxide, 60 parts by weight of (low-stress) spherical silicon micro powder and 2.5 parts by weight of reinforcing chopped fiber;
the (low-stress) spherical silicon micro powder is a mixture of two spherical silicon micro powders with different particle sizes; wherein the small-particle spherical silicon micro powder is D500.5-1 μm and D901.5-2.5 μm, the large-particle spherical silicon micro powder is D5020-26 μm and D9060-70 μm, and the small-particle spherical silicon micro powder is formed by mixing 2 parts by weight of small-particle spherical silicon micro powder and 60 parts by weight of large-particle spherical silicon micro powder;
mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the temperature of the material at 110 ℃ for 20min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 20min at the rotating speed of 2000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 1h at the rotating speed of 2000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 19 weight parts of anhydride curing agent and 0.5 weight part of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 40min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 90 parts by weight of the component A to 20 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 13:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking raw materials of 8 parts by weight of toughened liquid epoxy resin, 10 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 0.01 part by weight of defoaming agent, 9 parts by weight of aluminum hydroxide, 40 parts by weight of (low-stress) spherical silicon micro powder and 0.5 part by weight of reinforcing chopped fiber;
the (low-stress) spherical silicon micro powder is a mixture of two spherical silicon micro powders with different particle sizes, wherein the small-particle size spherical silicon micro powder is D500.5-1 mu m and D901.5-2.5 mu m, the large-particle size spherical silicon micro powder is D5020-26 mu m and D9060-70 mu m, and the (low-stress) spherical silicon micro powder is formed by mixing 1 part by weight of small-particle size spherical silicon micro powder and 55 parts by weight of large-particle size spherical silicon micro powder.
Mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the material temperature at 95 ℃ and stirring for 20min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 10min at the rotating speed of 1000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 1.5h at the rotating speed of 1000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 13 weight parts of anhydride curing agent and 0.1 weight part of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 20min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 70 parts by weight of the component A to 10 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 14:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking raw materials of 15 parts by weight of toughened liquid epoxy resin, 12 parts by weight of epoxy resin, 5 parts by weight of epoxy active diluent, 1 part by weight of defoaming agent, 14 parts by weight of aluminum hydroxide, 80 parts by weight of (low-stress) spherical silicon micro powder and 5 parts by weight of reinforcing chopped fiber;
the (low-stress) spherical silicon micro powder is a mixture of spherical silicon micro powders with different particle sizes, wherein the spherical silicon micro powder with small particle size is D500.5-1 mu m, D901.5-2.5 mu m and the spherical silicon micro powder with large particle size is D5020-26 mu m and D9060-70 mu m, and is formed by mixing 3 parts by weight of spherical silicon micro powder with small particle size and 65 parts by weight of spherical silicon micro powder with large particle size.
Mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the temperature of the material at 120 ℃ for 5min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 30min at the rotating speed of 3000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 0.5h at the rotating speed of 3000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 25 parts by weight of anhydride curing agent and 1 part by weight of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 60min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 110 parts by weight of the component A to 30 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 15:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking raw materials of 8 parts by weight of toughened liquid epoxy resin, 10 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 0.01 part by weight of defoaming agent, 9 parts by weight of aluminum hydroxide and 40 parts by weight of (low-stress) spherical silicon micro powder;
the (low-stress) spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5 part by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5 parts by weight;
mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the material temperature at 95 ℃ and stirring for 20min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 10min at the rotating speed of 1000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 1.5h at the rotating speed of 1000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 13 weight parts of anhydride curing agent and 0.1 weight part of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 20min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 90 parts by weight of the component A to 13 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 16:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking the raw materials of 15 parts by weight of toughened liquid epoxy resin, 12 parts by weight of epoxy resin, 5 parts by weight of epoxy active diluent, 1 part by weight of defoaming agent, 14 parts by weight of aluminum hydroxide and 80 parts by weight of (low-stress) spherical silicon micro powder;
the (low-stress) spherical silicon micro powder is a mixture consisting of two spherical silicon micro powders with different particle sizes of D500.2-1 mu m, D901.5-5 mu m, D5018-28 mu m and D9055-75 mu m, wherein the spherical silicon micro powder with small particle size accounts for 5 parts by weight, and the spherical silicon micro powder with large particle size accounts for 75 parts by weight; mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the temperature of the material at 120 ℃ for 5min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 30min at the rotating speed of 3000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 0.5h at the rotating speed of 3000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 25 parts by weight of anhydride curing agent and 1 part by weight of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 60min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 100 parts by weight of the component A to 18 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 17:
a preparation method of a high-strength cracking-resistant liquid pouring sealant comprises the following steps:
a. preparing a component A:
preparing materials: taking 11.5 parts by weight of toughened liquid epoxy resin, 11 parts by weight of epoxy resin, 0.55 part by weight of epoxy active diluent, 0.51 part by weight of defoaming agent, 11.5 parts by weight of aluminum hydroxide and 60 parts by weight of (low-stress) spherical silicon micro powder;
the (low-stress) spherical silicon micro powder is a mixture consisting of two spherical silicon micro powders with different particle sizes of D500.2-1 mu m, D901.5-5 mu m, D5018-28 mu m and D9055-75 mu m, wherein the spherical silicon micro powder with small particle size is 2.7 parts by weight, and the spherical silicon micro powder with large particle size is 57 parts by weight;
mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the temperature of the material at 108 ℃ for 13min, then respectively (slowly) adding small-particle-size (low-stress) spherical silicon micro powder and aluminum hydroxide, starting (high-speed) stirring, shearing and emulsifying for 20min at the rotating speed of 2000rpm, then adding large-particle-size (low-stress) spherical silicon micro powder and reinforcing chopped fibers, stirring for 1h at the rotating speed of 2000rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 19 weight parts of anhydride curing agent and 0.55 weight part of accelerator; mixing: and adding the anhydride curing agent and the accelerator into a reaction vessel, starting stirring for 40min, and uniformly mixing to obtain the component B.
Further, when in use, the component A and the component B are mixed according to the weight ratio of 95 parts by weight of the component A to 15.5 parts by weight of the component B, and the high-strength cracking-resistant liquid pouring sealant is obtained; for potting filling of gaps in the device.
Example 18:
the application method of the high-strength cracking-resistant liquid pouring sealant (or called dual-component epoxy pouring sealant) comprises the following steps: preheating a device to be encapsulated at 105 ℃ for 2.5h, simultaneously preheating the component A at 70 ℃ for 6h, and mixing the component A and the component B according to the weight ratio [ namely: mixing the component A and the component B according to the weight ratio of 90 parts by weight of the component A to 20 parts by weight of the component B, uniformly stirring, pouring the mixed glue solution into a device to be glue-filled in batches after vacuum defoaming, soaking and filling gaps by vacuum defoaming, curing at 80 ℃ for 4 hours and at 110 ℃ for 4.5 hours in sequence, and then slowly cooling at the speed of 1 ℃/min.
Example 19:
the application method of the high-strength cracking-resistant liquid pouring sealant (or called dual-component epoxy pouring sealant) comprises the following steps: preheating a device to be encapsulated at 90 ℃ for 4h, simultaneously preheating the component A at 60 ℃ for 10h, and mixing the component A and the component B according to the weight ratio [ namely: mixing the component A and the component B according to the weight ratio of 70 parts by weight of the component A to 10 parts by weight of the component B, uniformly stirring, pouring the mixed glue solution into a device to be glue-filled in batches after vacuum defoaming, soaking and filling gaps by vacuum defoaming, curing at 75 ℃ for 5 hours and at 95 ℃ for 6 hours in sequence, and then slowly cooling at the speed of 0.5 ℃/min.
Example 20:
the application method of the high-strength cracking-resistant liquid pouring sealant (or called dual-component epoxy pouring sealant) comprises the following steps: preheating a device to be encapsulated at 120 ℃ for 1h, simultaneously preheating the component A at 80 ℃ for 2h, and mixing the component A and the component B according to the weight ratio [ namely: mixing the component A and the component B according to the weight ratio of 110 parts by weight of the component A to 30 parts by weight of the component B, uniformly stirring, pouring the mixed glue solution into a device to be glue-filled in batches after vacuum defoaming, soaking and filling gaps by vacuum defoaming, curing at 85 ℃ for 3 hours and 125 ℃ for 3 hours in sequence, and then slowly cooling at the speed of 1.5 ℃/min.
In examples 12 to 17 above: the toughened liquid epoxy resin is prepared by blending and modifying a high-molecular-weight thermoplastic resin and a low-viscosity epoxy resin, and the preparation method comprises the following steps: heating the low-viscosity epoxy resin to 130-150 ℃, adding the high-molecular-weight thermoplastic resin in a stirring state (slowly), preserving heat, and keeping stirring until the high-molecular-weight thermoplastic resin is completely dissolved to obtain toughened liquid epoxy resin; the toughening liquid epoxy resin contains 4-13% of high molecular weight thermoplastic resin by weight:
the low-viscosity epoxy resin is one or a mixture of two or more of phenyl glycidyl ether modified epoxy resin, cardanol glycidyl ether modified epoxy resin, butyl glycidyl ether modified epoxy resin and C12-C14 alkyl glycidyl ether modified epoxy resin, and the viscosity of the low-viscosity epoxy resin at 25 ℃ is 400-2000 mPa & s, and the epoxy equivalent is 170-230 g/eq;
the high molecular weight thermoplastic resin has a chemical structural formula (characteristic) shown in formula (I):
in formula (I): x, y and z are 0.85, 0, 0.15-0.5, 0.25 and 0.25, x + y + z is less than or equal to 1, x is less than or equal to 0.5 and less than or equal to 0.85, y is less than or equal to 0 and less than or equal to 0.25, and z is less than or equal to 0.15 and less than or equal to 0.25; n is more than or equal to 100 and less than or equal to 2000, and the weight average molecular weight (between) is 6-30 ten thousand;
R1one selected from the following chemical structures: -CH2—、—CH2CH2—、—CH2CH2CH2CH2—；
R2One selected from the following chemical structures: -OH, -COOCH3。
In examples 12 to 17 above: the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin (bisphenol A type glycidyl ether, bisphenol F glycidyl ether, polyphenol type glycidyl ether and aliphatic glycidyl ether), glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and alicyclic epoxy, the epoxy equivalent of the epoxy resin is 240g/eq at 120-.
In examples 12 to 17 above: the epoxy reactive diluent is one or a mixture of two or more of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether, and preferably 1, 4-butanediol diglycidyl ether.
In examples 12 to 17 above: the defoaming agent is one or a mixture of two or more of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent, and the organic silicon polymer compound defoaming agent is preferably selected.
In examples 12 to 17 above: the anhydride curing agent is one or a mixture of two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyazelaic anhydride and polysebacic anhydride, preferably methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride;
the accelerator is any one of DMP-30, N-dimethylbenzylamine, toluene dimethylamine, 2-ethyl-4-methylimidazole and cyanoethyl modified 2-ethyl-4-methylimidazole, and preferably N, N-dimethylbenzylamine or cyanoethyl modified 2-ethyl-4-methylimidazole;
the aluminum hydroxide is aluminum hydroxide obtained by a common Bayer process, and the particle size of the product is D501-3.5 μm and D904-15 μm; d501-3 μm and D904-10 μm are preferred;
the chopped reinforced fibers are one or a mixture of two or more of chopped glass fibers, chopped aramid fibers, chopped carbon fibers and chopped polyester fibers, and the chopped reinforced fibers have the diameter of 3-15 mu m and the length of 0.1-2 mm; chopped glass fiber and aramid fiber which are subjected to surface treatment by a coupling agent are preferred.
In the above embodiment: the component A of the high-strength cracking-resistant liquid pouring sealant can also contain (add) various dyes according to the needs.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, concentration, rotating speed and the like) and the numerical values of the components in each step are in a range, and any point can be applicable.
The technical indexes adopted in the patent application document of the invention have the following relevant standards:
glass transition temperature measured according to ISO11357-3, Differential Scanning Calorimetry (DSC) part 3, determination of melting and crystallization enthalpies and temperatures;
coefficient of thermal expansion: tested according to ISO11359-2, section 2 of thermomechanical analysis (TMA), determination of the linear thermal expansion coefficient and the glass transition temperature;
water absorption: testing according to GB/T1034 and 2008 'Plastic Water absorption test method';
shore D hardness: testing according to GB/T2411-2008 using a hardness tester for testing indentation hardness of plastics and hard rubber;
shear adhesion strength: testing according to GB/T7124-;
bending strength: testing according to GB/T9341-2008 'determination of Plastic bending Property';
impact strength: according to GB/T1043.1-2008' determination of impact performance of plastic simply supported beam part 1: non-instrumented impact test;
cold and hot impact: according to GB/T2423.22-2012 environmental test part 2: test methods test N: temperature variation test, the switching is completed within 2min at high temperature and low temperature, wherein the temperature is 55 ℃/1h to 100 ℃/1 h.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (12)
1. The utility model provides a high strength crack resistant liquid pouring sealant which characterized by: the high-strength cracking-resistant liquid pouring sealant is formed by mixing 70-110 parts by weight of a component A and 10-30 parts by weight of a component B;
the component A is formed by mixing 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, 40-80 parts by weight of spherical silicon micro powder and 0-5 parts by weight of reinforcing chopped fibers;
the component B is formed by mixing 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator.
2. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1, which is characterized in that: the high-strength cracking-resistant liquid pouring sealant is formed by mixing 90-100 parts by weight of a component A and 13-18 parts by weight of a component B;
the component A is formed by mixing 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, 40-80 parts by weight of spherical silicon micro powder and 0.1-5 parts by weight of reinforcing chopped fibers;
the component B is formed by mixing 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator.
3. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the toughened liquid epoxy resin is prepared by blending and modifying a high-molecular-weight thermoplastic resin and a low-viscosity epoxy resin, and the preparation method comprises the following steps: heating the low-viscosity epoxy resin to 130-150 ℃, adding the high-molecular-weight thermoplastic resin under a stirring state, preserving heat, and keeping stirring until the high-molecular-weight thermoplastic resin is completely dissolved to obtain toughened liquid epoxy resin; the toughening liquid epoxy resin contains 4-13% of high molecular weight thermoplastic resin by weight:
the low-viscosity epoxy resin is one or a mixture of two or more of phenyl glycidyl ether epoxy resin, cardanol glycidyl ether epoxy resin, butyl glycidyl ether epoxy resin and C12-C14 alkyl glycidyl ether epoxy resin;
the high molecular weight thermoplastic resin has a chemical formula shown in formula (I):
in formula (I): x, y and z are 0.85, 0, 0.15-0.5, 0.25 and 0.25, x + y + z is less than or equal to 1, x is less than or equal to 0.5 and less than or equal to 0.85, y is less than or equal to 0 and less than or equal to 0.25, and z is less than or equal to 0.15 and less than or equal to 0.25; n is more than or equal to 100 and less than or equal to 2000, and the weight average molecular weight is 6-30 ten thousand;
R1one selected from the following chemical structures: -CH2—、—CH2CH2—、—CH2CH2CH2CH2—；
R2One selected from the following chemical structures: -OH, -COOCH3。
4. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and alicyclic epoxy.
5. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the epoxy reactive diluent is one or a mixture of two or more of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether.
6. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the defoaming agent is one or a mixture of two or more of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent.
7. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5-5 parts by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5-75 parts by weight.
8. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the aluminum hydroxide is aluminum hydroxide obtained by a common Bayer process, and the particle size of the aluminum hydroxide is D501-3.5 μm and D904-15 μm.
9. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the chopped reinforced fiber is one or a mixture of two or more of chopped glass fiber, chopped aramid fiber, chopped carbon fiber and chopped polyester fiber, and the chopped reinforced fiber has the diameter of 3-15 mu m and the length of 0.1-2 mm.
10. The high-strength crack-resistant liquid pouring sealant as claimed in claim 1 or 2, which is characterized in that: the anhydride curing agent is one or a mixture of two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyazelaic anhydride and polysebacic anhydride;
the accelerator is any one of DMP-30, N-dimethylbenzylamine, toluene dimethylamine, 2-ethyl-4-methylimidazole and cyanoethyl modified 2-ethyl-4-methylimidazole.
11. A preparation method of a high-strength cracking-resistant liquid pouring sealant is characterized by comprising the following steps:
a. preparing a component A:
preparing materials: taking raw materials of 8-15 parts by weight of toughened liquid epoxy resin, 10-12 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 0.01-1 part by weight of defoaming agent, 9-14 parts by weight of aluminum hydroxide, 40-80 parts by weight of spherical silicon micro powder and 0-5 parts by weight of reinforcing chopped fiber; the spherical silicon micro powder is a mixture consisting of small-particle-size spherical silicon micro powder with the particle size of D500.2-1 mu m and D901.5-5 mu m and large-particle-size spherical silicon micro powder with the particle size of D5018-28 mu m and D9055-75 mu m, wherein the small-particle-size spherical silicon micro powder accounts for 0.5-5 parts by weight, and the large-particle-size spherical silicon micro powder accounts for 39.5-75 parts by weight;
mixing: adding toughened liquid epoxy resin, epoxy active diluent and defoaming agent into a reaction container, starting heating and stirring, keeping the temperature of the material at 95-120 ℃, stirring for 5-20min, then respectively adding small-particle-size spherical silicon micropowder and aluminum hydroxide, starting stirring, shearing and emulsifying for 10-30 min at the rotating speed of 1000-3000 rpm, then adding large-particle-size spherical silicon micropowder and reinforcing chopped fiber, stirring for 0.5-1.5 h at the rotating speed of 1000-3000 rpm, keeping the vacuum degree at less than or equal to-0.09 MPa for defoaming, and then cooling to obtain a component A;
b. preparing a component B:
preparing materials: taking 13-25 parts by weight of an anhydride curing agent and 0.1-1 part by weight of an accelerator;
mixing: and adding the anhydride curing agent and the accelerator into a reaction container, starting stirring for 20-60 min, and uniformly mixing to obtain the component B.
12. The method for preparing the high-strength cracking-resistant liquid pouring sealant as claimed in claim 11, wherein the method comprises the following steps: and 0-5 parts by weight of the reinforced chopped fibers are replaced by 0.1-5 parts by weight of the reinforced chopped fibers.
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| CN202010229339.4A Pending CN111234751A (en) | 2020-03-27 | 2020-03-27 | High-strength cracking-resistant liquid pouring sealant and preparation method thereof |
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| CN115260704A (en) * | 2022-08-10 | 2022-11-01 | 重庆科技学院 | Carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| CN115785856A (en) * | 2022-12-14 | 2023-03-14 | 科建高分子材料（上海）股份有限公司 | Composite pressure-sensitive adhesive, epoxy adhesive and preparation method thereof |
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| CN115093827A (en) * | 2022-06-23 | 2022-09-23 | 厦门捌斗新材料科技有限公司 | Organic silicon pouring sealant and preparation method thereof |
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