CN114045133A - Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant - Google Patents

Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant Download PDF

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CN114045133A
CN114045133A CN202111407151.5A CN202111407151A CN114045133A CN 114045133 A CN114045133 A CN 114045133A CN 202111407151 A CN202111407151 A CN 202111407151A CN 114045133 A CN114045133 A CN 114045133A
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thermal
parts
flame
pouring sealant
modified unsaturated
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王亚飞
程浩
尚保仁
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Wuhan Institute of Marine Electric Propulsion China Shipbuilding Industry Corp No 712 Institute CSIC
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Wuhan Institute of Marine Electric Propulsion China Shipbuilding Industry Corp No 712 Institute CSIC
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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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a preparation method of a high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant, which is prepared from dibasic acid, dihydric alcohol, acid anhydride, a heat-conducting material and a flame retardant in an in-situ polymerization manner. According to the invention, an in-situ polymerization mode is adopted, the heat conduction material is added in a synthesis stage, so that the heat conduction material and the synthetic raw materials are fully infiltrated, and the heat conduction material is peeled by using polymerization heat and exists in the resin in a delamination mode, so that the problem of poor heat conduction and flame retardant performance caused by the fact that the conventional pouring sealant containing the heat conduction material and the flame retardant is uneven in distribution and easy to agglomerate is solved.

Description

Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant
Technical Field
The invention relates to the technical field of unsaturated resins, in particular to a preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin.
Background
With the rapid development of high-voltage large motors and variable frequency motors in China, the motor design gradually pursues higher power density, the requirement on insulating materials is gradually improved, the comprehensive performances such as electrical performance, mechanical performance and the like are required to be excellent, and meanwhile, higher requirements are provided for the heat-conducting performance and the flame retardant performance of the insulating materials.
At present, heat-conducting fillers are widely applied in the field of pouring sealant, but the problems of poor performance consistency caused by uneven dispersion, easy agglomeration and sedimentation of heat-conducting materials in a resin matrix exist.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a preparation method of a high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant, and solves the technical problems of poor performance caused by poor dispersion, easy agglomeration and sedimentation of a thermal conductive material in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant is prepared from dibasic acid, dihydric alcohol, anhydride, a heat conduction material and a flame retardant in an in-situ polymerization manner, and comprises the following steps:
pretreating the heat conducting material, namely adding the weighed heat conducting material into a silane coupling agent/ethanol solution, ultrasonically oscillating, carrying out vacuum filtration, washing and drying after heating reaction to obtain the heat conducting material treated by the silane coupling agent: adding 5-10 parts of heat conducting material powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4-10%, ultrasonically vibrating for 1-2 h, stirring and reacting for 1-4 h at 50-90 ℃, cooling, vacuum filtering and washing, placing the washed solid in a drying oven at 60-80 ℃ for drying for 16-24 h to obtain the pretreated heat conducting material;
in-situ polymerization: firstly adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, then adding 10-20 parts of pretreated heat conducting material, heating to 140-160 ℃ after ultrasonic vibration for 4 hours, carrying out reflux reaction for 1-3 hours, and continuously heating to 180 ℃: EReacting at 190 deg.C for 4 hr, cooling to 100 deg.C, adding 20 parts maleic anhydride, 20 parts propylene glycol and flame retardant, and reacting at 160 deg.C and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃ and carrying out normal pressure distillation reaction for 2h, then cooling to 100 ℃, adding an epoxy resin diluent and zinc isooctate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
The preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant comprises the following steps of (1) mixing the heat-conducting material powder with the silane coupling agent/absolute ethyl alcohol by mass ratio of 0.01-0.1: 1.
according to the preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant, the thermal conductive material is aluminum nitride, boron nitride or the combination of the aluminum nitride and the boron nitride.
The preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant comprises the following steps of, in the second step, the mass ratio of the pretreated heat-conducting material to the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant is 0.04-0.4: 1.
according to the preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant, the mass ratio of the flame retardant to the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant is 0.001-0.05: 1.
the preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant comprises the step of preparing a flame retardant from one or more of hexabromocyclododecane, antimony trioxide, dicumyl peroxide, red phosphorus, aluminum hydroxide and magnesium hydroxide.
According to the preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant, the epoxy resin diluent is phenyl glycidyl ether or 1, 6-hexanediol diglycidyl ether or the combination of the phenyl glycidyl ether and the 1, 6-hexanediol diglycidyl ether.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method provided by the invention adopts an in-situ polymerization mode, the heat conduction material is directly mixed in at the synthesis stage of the matrix resin, and the heat conduction material is stripped by utilizing polymerization heat release after small molecular acid and alcohol are fully soaked and enter the interlayer of the heat conduction material, so that the heat conduction material is uniformly dispersed in the matrix resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a preparation method of a high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Adding the heat conducting material powder into a silane coupling agent/absolute ethyl alcohol solution with the mass concentration of the silane coupling agent of 1-10%, ultrasonically vibrating for 0.5-2 h, stirring and reacting for 1-4 h at 50-90 ℃, cooling, vacuum filtering and washing with water, and drying the washed solid in an oven at 60-80 ℃ for 12-24 h to obtain the pretreated heat conducting material. Wherein the mass ratio of the heat conducting material powder to the silane coupling agent/absolute ethyl alcohol is (0.01-0.1): 1.
the heat conducting material is one or more of aluminum nitride, boron nitride, aluminum oxide, silicon carbide and beryllium oxide; the silane coupling agent is one or more of trichlorosilane, trimethoxy vinylsilane, triethoxy vinylsilane, gamma-aminopropyl triethoxysilane, trichloropropenyl silane, 3- (2, 3-glycidoxy) propyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, 3- (2, 3-glycidoxy) propyl triethoxysilane and 3- (2, 3-glycidoxy) propyl methyl diethoxy silane.
Step two is in-situ polymerization. Adding dibasic acid, dihydric alcohol and acid anhydride, heating until the solid is completely dissolved, and adding pretreated catalystHeating the thermal material, performing ultrasonic vibration for 2-4 h, heating to 140-160 ℃, performing reflux reaction for 1-3 h, continuously heating to 180-190 ℃, reacting for 2-4 h, then cooling to 100 ℃, adding anhydride, dihydric alcohol and a flame retardant, and performing ultrasonic vibration at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 1-4 h, then gradually heating to 200-210 ℃, carrying out atmospheric distillation reaction for 2-3 h, then cooling to 100-120 ℃, adding an epoxy resin diluent and an accelerant, continuing the reaction for 1-5 h, and adding an acrylate active diluent, an initiator, a polymerization inhibitor and an accelerant when the temperature is reduced to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
In the second step, the molar ratio of the dibasic acid, the anhydride and the dihydric alcohol is more than 1 so as to ensure that enough terminal carboxyl groups are further reacted with the epoxy resin diluent for end capping; the dibasic acid is one or more of terephthalic acid, isophthalic acid and adipic acid; the dihydric alcohol is one or more of ethylene glycol, propylene glycol, neopentyl glycol and diethylene glycol; the acid anhydride is one or more of maleic anhydride, nadic anhydride and phthalic anhydride.
The mass ratio of the heat conduction material pretreated in the step two to the high-heat-conduction flame-retardant epoxy modified unsaturated resin pouring sealant is (0.04-0.4): 1.
in the second step, the mass ratio of the flame retardant to the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant is (0.001-0.05): 1; the flame retardant is one or more of hexabromocyclododecane, antimony trioxide, dicumyl peroxide, red phosphorus, aluminum hydroxide and magnesium hydroxide.
In the second step, the epoxy resin diluent is one or more of alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and neopentyl glycol diglycidyl ether; the accelerant is one or more of 2, 4, 6-tri (dimethylaminomethyl) phenol, N-dimethylbenzylamine, N-dimethylaniline, zinc isooctanoate, zinc naphthenate, dimethyl imidazole and boron trifluoride ethylamine.
The acrylate reactive diluent is one or more of benzyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, butylene glycol diacrylate and hexanediol diacrylate; the initiator is one or more of dicumyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl cumene peroxide and 1, 1-di-tert-butyl cyclohexane peroxide; the polymerization inhibitor is one or more of hydroquinone, tert-butyl catechol, copper naphthenate and p-methoxyphenol.
Examples 1-7 and comparative example 1 provide preparation methods of eight different high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealants.
Example 1
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 10 parts of AlN powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4%, ultrasonically vibrating for 2h, stirring and reacting for 4h at 50 ℃, cooling, vacuum filtering and washing, and drying the washed solid in a 60 ℃ drying oven for 24h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 2
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 10 parts of AlN powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4%, ultrasonically vibrating for 2h, stirring and reacting for 4h at 50 ℃, cooling, vacuum filtering and washing, and drying the washed solid in a 60 ℃ drying oven for 24h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding 1, 6-hexanediol diglycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-heat-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 3
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 5 parts of AlN powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4%, ultrasonically vibrating for 2h, stirring and reacting for 4h at 50 ℃, cooling, vacuum filtering and washing, and drying the washed solid in a 60 ℃ drying oven for 24h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, the reaction is further refluxed for 2 hours, and then the reaction is gradually carried outHeating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing to react for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 4
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 10 parts of AlN powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 10%, ultrasonically vibrating for 1h, stirring and reacting for 1h at 90 ℃, cooling, then carrying out vacuum filtration and washing, and drying the washed solid in an oven at 80 ℃ for 16h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 5
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 10 parts of AlN powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 10%, ultrasonically vibrating for 1h, stirring and reacting for 1h at 90 ℃, cooling, then carrying out vacuum filtration and washing, and drying the washed solid in an oven at 80 ℃ for 16h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding firstAdding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 20 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 6
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 5 parts of AlN powder and 5 parts of BN into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4%, ultrasonically vibrating for 2h, stirring and reacting for 4h at 50 ℃, cooling, vacuum filtering and washing, and drying the washed solid in a 60 ℃ drying oven for 24h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Example 7
The method comprises the following steps: and (4) pretreating the heat conduction material. Adding 5 parts of AlN powder and 5 parts of BN into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4%, ultrasonically vibrating for 2h, stirring and reacting for 4h at 50 ℃, cooling, vacuum filtering and washing, and drying the washed solid in a 60 ℃ drying oven for 24h to obtain the pretreated heat conduction material.
Step two: and (3) in-situ polymerization. Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 20 parts of pretreated heat conducting material, carrying out ultrasonic vibration for 4 hours, heating to 140-160 ℃, carrying out reflux reaction for 1-3 hours, continuously heating to 180-190 ℃, carrying out reaction for 4 hours, then cooling to 100 ℃, adding 20 parts of maleic anhydride, 20 parts of propylene glycol and a flame retardant, and carrying out reaction at 160 ℃ and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Comparative example 1
Adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating to 140-160 ℃, performing reflux reaction for 1-3 h, continuously heating to 180-190 ℃, reacting for 4h, cooling to 100 ℃, adding 20 parts of maleic anhydride and 20 parts of propylene glycol, and performing reflux reaction at 160 ℃ and N2And under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃, carrying out distillation reaction for 2h under normal pressure, then cooling to 100 ℃, adding phenyl glycidyl ether and zinc isooctanoate, continuing the reaction for 3h, and adding 10 parts of AlN, ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine trifluoride when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
Performance testing
The performances of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant in the embodiments 1-7 and the comparative example 1 are tested, and the test results are shown in the following table.
Figure DEST_PATH_IMAGE001
As can be seen from the table above, the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant obtained in the embodiments 1 to 7 has good dispersibility of the thermal conductive material and the flame retardant, the thermal conductivity coefficient is obviously higher than that of the comparative example 1, the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant does not settle after being placed for a long time, the stability is good, and the flame retardant grade reaches V0 grade.
The invention has the characteristics of good heat conduction material and flame retardant dispersibility, difficult sedimentation, higher heat conduction coefficient and better flame retardant grade under the condition of the same addition proportion.
The high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant provided by the invention can be universally used for end part pouring and sealing treatment of equipment such as high-voltage motors, wind power, variable frequency motors, low-voltage high-power motors and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A preparation method of a high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant is characterized by comprising the following steps: comprises the following steps
Pretreatment of heat conducting materials: adding 5-10 parts of heat conducting material powder into 100 parts of silane coupling agent/absolute ethyl alcohol solution with the mass concentration of 3- (2, 3-epoxypropoxy) propyltriethoxysilane of 4-10%, ultrasonically vibrating for 1-2 h, stirring and reacting for 1-4 h at 50-90 ℃, cooling, vacuum filtering and washing, placing the washed solid in a drying oven at 60-80 ℃ for drying for 16-24 h to obtain the pretreated heat conducting material;
in-situ polymerization: adding 20 parts of isophthalic acid, 30 parts of propylene glycol and 20 parts of maleic anhydride, heating until the solid is completely dissolved, adding 10-20 parts of pretreated heat conducting material, ultrasonically vibrating for 4 hours, heating to 140-160 ℃, and returningReacting for 1-3 h, heating to 180-190 deg.C, reacting for 4h, cooling to 100 deg.C, adding 20 parts maleic anhydride, 20 parts propylene glycol and flame retardant, reacting at 160 deg.C and N2Under the protection condition, carrying out further reflux reaction for 2h, then gradually heating to 200-210 ℃ and carrying out normal pressure distillation reaction for 2h, then cooling to 100 ℃, adding an epoxy resin diluent and zinc isooctate, continuing the reaction for 3h, and adding ethylene glycol diacrylate, benzyl acrylate, dibenzoyl peroxide, hydroquinone and boron trifluoride ethylamine when cooling to 70 ℃ to obtain the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant.
2. The preparation method of the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant as claimed in claim 1, wherein the mass ratio of the thermal conductive material powder to the silane coupling agent/absolute ethyl alcohol is 0.01-0.1: 1.
3. the preparation method of the epoxy modified unsaturated resin pouring sealant with high thermal conductivity and flame retardance as claimed in claim 2, wherein the thermal conductive material is aluminum nitride, boron nitride or a combination of the aluminum nitride and the boron nitride.
4. The preparation method of the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant as claimed in claim 1, wherein the mass ratio of the pretreated thermal conductive material to the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant in the second step is 0.04-0.4: 1.
5. the preparation method of the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant as claimed in claim 1, wherein the mass ratio of the flame retardant to the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant is 0.001-0.05: 1.
6. the preparation method of the epoxy modified unsaturated resin pouring sealant with high thermal conductivity and flame retardance as claimed in claim 5, wherein the flame retardant is one or more of hexabromocyclododecane, antimony trioxide, dicumyl peroxide, red phosphorus, aluminum hydroxide and magnesium hydroxide.
7. The preparation method of the high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant as claimed in claim 1, wherein the molar ratio of the isophthalic acid, the propylene glycol and the maleic anhydride is greater than 1.
8. The preparation method of the high-thermal-conductivity flame-retardant epoxy-modified unsaturated resin pouring sealant as claimed in claim 1, wherein the epoxy resin diluent is phenyl glycidyl ether or 1, 6-hexanediol diglycidyl ether or a combination of the phenyl glycidyl ether and the 1, 6-hexanediol diglycidyl ether.
CN202111407151.5A 2021-11-24 2021-11-24 Preparation method of high-thermal-conductivity flame-retardant epoxy modified unsaturated resin pouring sealant Pending CN114045133A (en)

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