CN107474770A - A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof - Google Patents

A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof Download PDF

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CN107474770A
CN107474770A CN201710658394.3A CN201710658394A CN107474770A CN 107474770 A CN107474770 A CN 107474770A CN 201710658394 A CN201710658394 A CN 201710658394A CN 107474770 A CN107474770 A CN 107474770A
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added
silane
blocked isocyanate
prepare
parts
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李娜
李峰
贺国新
张利文
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Yantai Seayu New Materials Corp Ltd
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Yantai Seayu New Materials Corp Ltd
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to a kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof, epoxy resin, modified epoxy and toughener and coupling agent part are added sequentially in double-planet power mixing kettle, revolution stirring is opened and high speed is scattered, at a certain temperature, 1h is stirred, modified heat-conductive insulation filling is added, stirs 1h, add latent curing agent, 1h is stirred, adds aerosil, stirs 1h, 1h is kept under a certain pressure, produces one-component high heat conductive insulating structural adhesive.The present invention has the characteristics of viscosity is low, and trickling property is good, high temperature resistant and excellent heat conductivility.

Description

A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof
Technical field
The present invention relates to a kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof.
Background technology
At this stage, in electromechanics trade, with development in science and technology require more and more higher, it is desirable to motor can the duration of runs increasingly Long, motor operating produces substantial amounts of heat, thus it requires motor temperature tolerance more and more higher.Protect the glue temperature tolerance of motor coil poor And it is more crisp, easily cause glue to ftracture, coil breakage.Therefore the heat resistance of glue, flexible shock resistance, the industry is fettered Development.In order to improve the temperature tolerance of adhesive system and pliability, expensive raw material is often selected, causes the increase of production cost.
On the thermal fatigue life for improving protection motor coil structure glue, the good heat conductivility of glue is slowly gone Industry is considered as an important index, can greatly prolong the service life of motor, and motor epoxy structural rubber is led at this stage Hot property is simultaneously bad.
Improve thermal conductivity on the market at this stage and use aluminum oxide, aluminium nitride, boron nitride etc. more, although can reach higher Thermal conductivity, but during the containing ratio by improving such filler, viscosity steeply rises when causing to produce shaping, and mobility declines, sternly The application field of product is limited again.There is the spherical BN of production in foreign vendor, and product cut size is big, and specific surface area is small, and filling rate is high, no Easily thickening, and price is high, it is difficult to be widely used.Therefore finished product is increased by improving the content of inorganic filling material Thermal conductivity is conditional.
Most of structure glues are Bi-component adhesive, to be well mixed before use, cumbersome with respect to single-component glue, effect Rate is low.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of one pack system high heat conductive insulating structural adhesive and its preparation Method, the present invention solve the problem of structure adhesiveness is high, and trickling property is poor, heat conductivility difference.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof, it is characterised in that：
10~30 parts of epoxy resin, 10~20 parts of modified epoxy, 2~10 parts of toughener, coupling agent 0.5-2 parts are added successively Enter into double-planet power mixing kettle, open revolution stirring and high speed is scattered, under the conditions of temperature is 15~30 DEG C, stir 1h, Modified 30~70 parts of heat-conductive insulation filling is added, stirs 1h, adds 5~20 parts of latent curing agent, stirs 1h, adds gas phase two 0~2 part of silica, 1h is stirred, open vavuum pump and vacuumize 1h, vacuum pressure is -0.098, produces one-component high heat conductive insulating Structural adhesive；The revolution speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, be heated to 118 DEG C, is returned to the epoxychloropropane distilled out using circulation distillation mode Into round-bottomed flask, 1h is reacted, cooling removes circulation distilling apparatus, is heated to 118 DEG C, epoxychloropropane is distilled off, adds 560g methyl iso-butyl ketone (MIBK)s, are washed, and add 48% sodium hydroxide 13.5g, and 1h is stirred under the conditions of being 85 DEG C in temperature, then Washed with 40 DEG C of warm water of 200ml, be heated to 117 DEG C -118 DEG C and methyl iso-butyl ketone (MIBK) is distilled off, produce modified epoxy tree Fat；
The epoxy resin be 3,4- epoxycyclohexyls formic acid esters, 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, Bisphenol A epoxide resin, bisphenol F epoxy resin and phenolic resin one or several kinds therein；
The toughener be nitrile rubber, core-shell tougheners Kane Ace@MX-125, Initialcreate@ICAM-8627 and One kind or arbitrary proportion in ring figured woven silk material chemical industry S-2001 it is two or more；
The latent curing agent is dicyandiamide, Ai Di sections EH-4360S, EH-4357S, the taste of Changzhou common calla Resins Corporation Plain PN-H, aginomoto PN-23 and one kind in Fuji's chemistry 1020 or arbitrary proportion it is two or more；
The aerosil is from R202 the and Ying Chuan companies of TS-720, EH-5, Ying Chuan company of Cabot Co., Ltd One kind or arbitrary proportion in A200 it is two or more；
The coupling agent is from a kind of or any in γ aminopropyltriethoxy silane and glycidoxy trimethoxy silane Two kinds of ratio；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：Blocked isocyanate silane is added in ethanol solution, blocked isocyanate silane and ethanol Mol ratio 1:3, the volume ratio of ethanol solution reclaimed water and ethanol is 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Add acetic acid in obtained mixed liquor, adjust pH be 3.5~ 5.5,30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Preferably, alumina powder footpath size is 15~30 μm.
Preferably, by 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 15 parts of modified epoxy, Core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane is added sequentially to double-planet power and mixes Close in kettle, unlatching revolution is stirred and disperseed at a high speed, under the conditions of temperature is 25 DEG C, stirring 1h, adds modified heat-conductive insulation filling 57.5 parts, 1h is stirred, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, opens vacuum pumping Vacuum 1h, vacuum pressure are -0.098, produce one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/ Min, scattered rotating speed is 800r/min at a high speed.
Invention has following advantageous effects：
1. the present invention uses the silane-modified heat-conductive insulation filling of blocked isocyanate, system is set to form three-dimensional netted thermal conducting path, Thermal conductivity is high, and low with thermal coefficient of expansion, the good excellent properties of temperature tolerance.
2. the characteristics of preparation method of the present invention is that filler surface there occurs the merging of chemical bond, forms one after treatment Organic coating layer, cause filler surface to become hydrophobic by hydrophilic, it is also better with matrix compatibility, therefore addition it is higher when Time viscosity is relatively low, and glue can be glued by voluntarily permeating, good to the covered effect of motor coil, and can significantly be carried High workload efficiency, synthesis process simply easily operate, and cost is low, and product application is extensive.
Embodiment
Embodiment 1
By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 10 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 62.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, continues to be heated to 118 DEG C of distillations, the epoxychloropropane distilled out returns to round-bottomed flask In, continue to react 1h, kept for 118 DEG C, epoxychloropropane is distilled off, add 560g methyl iso-butyl ketone (MIBK)s, washed, then add Enter 48% sodium hydroxide 13.5g, 1h is stirred under the conditions of being 85 DEG C in temperature, then washed with 40 DEG C of 200ml warm water, is heated to 117 DEG C -118 DEG C are distilled off methyl iso-butyl ketone (MIBK), produce modified epoxy；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Embodiment 2
By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 20 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 52.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, continues to be heated to 118 DEG C of distillations, the epoxychloropropane distilled out returns to round-bottomed flask In, continue to react 1h, kept for 118 DEG C, epoxychloropropane is distilled off, add 560g methyl iso-butyl ketone (MIBK)s, washed, then add Enter 48% sodium hydroxide 13.5g, 1h is stirred under the conditions of being 85 DEG C in temperature, then washed with 40 DEG C of 200ml warm water, is heated to 117 DEG C -118 DEG C are distilled off methyl iso-butyl ketone (MIBK), produce modified epoxy；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Embodiment 3
By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 15 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 57.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, continues to be heated to 118 DEG C of distillations, the epoxychloropropane distilled out returns to round-bottomed flask In, continue to react 1h, kept for 118 DEG C, epoxychloropropane is distilled off, add 560g methyl iso-butyl ketone (MIBK)s, washed, then add Enter 48% sodium hydroxide 13.5g, 1h is stirred under the conditions of being 85 DEG C in temperature, then washed with 40 DEG C of 200ml warm water, is heated to 117 DEG C -118 DEG C are distilled off methyl iso-butyl ketone (MIBK), produce modified epoxy；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Embodiment 4
By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 12 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 60.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, continues to be heated to 118 DEG C of distillations, the epoxychloropropane distilled out returns to round-bottomed flask In, continue to react 1h, kept for 118 DEG C, epoxychloropropane is distilled off, add 560g methyl iso-butyl ketone (MIBK)s, washed, then add Enter 48% sodium hydroxide 13.5g, 1h is stirred under the conditions of being 85 DEG C in temperature, then washed with 40 DEG C of 200ml warm water, is heated to 117 DEG C -118 DEG C are distilled off methyl iso-butyl ketone (MIBK), produce modified epoxy；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Embodiment 5
By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 18 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 54.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min；
The modified epoxy follows the steps below：
Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, continues to be heated to 118 DEG C of distillations, the epoxychloropropane distilled out returns to round-bottomed flask In, continue to react 1h, kept for 118 DEG C, epoxychloropropane is distilled off, add 560g methyl iso-butyl ketone (MIBK)s, washed, then add Enter 48% sodium hydroxide 13.5g, 1h is stirred under the conditions of being 85 DEG C in temperature, then washed with 40 DEG C of 200ml warm water, is heated to 117 DEG C -118 DEG C are distilled off methyl iso-butyl ketone (MIBK), produce modified epoxy；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
Embodiment 6
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, bisphenol-A 5 parts of epoxy resin, 18 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:2 parts, 1.5 parts of nitrile rubber, epoxy 1 part of propoxyl group trimethoxy silane is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, in temperature Spend under the conditions of 25 DEG C, to stir 1h, add modified 54.5 parts of heat-conductive insulation filling, stir 1h, add 8 parts of dicyandiamide, stir 1h, Open vavuum pump and vacuumize 1h, vacuum pressure is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed；
The modified epoxy follows the steps below：Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added to In round-bottomed flask, and nitrogen is continually fed into, adds epoxychloropropane 1200g and 180g diethylene glycol dimethyl ether, be heated to 60 DEG C, add Enter 21.2g48% potassium hydroxide aqueous solutions, stir 1h, be heated to 100 DEG C of distillations and remove moisture removal, continue to be heated to 118 DEG C of steamings Evaporate, the epoxychloropropane distilled out is returned in round-bottomed flask, is continued to react 1h, is kept for 118 DEG C, epoxy chloropropionate is distilled off Alkane, 560g methyl iso-butyl ketone (MIBK)s are added, is washed, adds 48% sodium hydroxide 13.5g, stirred under the conditions of being 85 DEG C in temperature Mix 1h, then washed with 40 DEG C of 200ml warm water, be heated to 117 DEG C -118 DEG C and methyl iso-butyl ketone (MIBK) is distilled off, produce modification Epoxy resin；
The modified heat-conductive insulation filling follows the steps below：
1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
6）Prepare mixed liquor：By blocked isocyanate silane according to the mol ratio 1 with ethanol:3 are added in ethanol solution, ethanol Solution reclaimed water and the volume ratio of ethanol are 1:2, obtain mixed liquor；
7）Prepare blocked isocyanate solution of silane：To step 6）Acetic acid is added in obtained mixed liquor, it is 3.5~5.5 to adjust pH, 30min is stood, obtains blocked isocyanate solution of silane；
8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
The present invention is further illustrated with reference to instantiation：
Beneficial effects of the present invention are further illustrated with reference to experimental data：
1 materials and methods：
1.1 test site：Yantai Xin You new materials limited company laboratory.
1.2 experiment detections：
1.2.1 tensile-sbear strength：Three groups are taken, the good AL pieces of frosted, gluing area is 12.5cm*20mm, is solidified after overlap joint at 120 DEG C After 30min, shear strength, record data are tested on tensile testing machine.
1.2.2 heatproof is tested：Take three groups, the good AL pieces of frosted, gluing area is 12.5cm*20mm, at 120 DEG C after overlap joint After solidifying 30min, three groups of AL/AL overlap joint exemplars are taken out after 180 DEG C of baking ovens place 30min, heat surveys shear strength at 180 DEG C. Record data.
1.2.3 the test of thermal conductivity：The making of exemplar：70 degrees Celsius of solidification 1h exemplars, it is desirable to which sample must not have crackle, become Shape, fusion hole, fall the defects of side and gas cell distribution are uneven.Specimen size is 0.5 above and below diameter 180mm, and thickness is on 10-25mm Lower 0.5 circular specimen.Experiment takes a data every time, when sample puts dry 3h, side thickness under 110-120 degrees Celsius before experiment, A data are surveyed every 120 ° at sample edge, are taken the mean.
Tester：NETZSCH thermal conductivity meters.
1.2.4 extrusion rate is tested：From 3mm steel glue discharging mouth, the test 30s gel quantity under 0.4Mpa pressure, Extrusion rate is calculated, it is parallel to do three groups, take the mean.
1.3 material to be tested：For embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, contrast 1（Self-control changes Property heatproof epoxy resin is substituted by common bisphenol A epoxide resin, and other preparation methods are consistent with embodiment 3）With contrast 2（Except changing Property heat-conductive insulation filling replaced using aluminum oxide outer, other preparation methods are consistent with embodiment 3）Effect is done to compare.
In addition to experiment process is different, other operations are consistent for this experiment.
2 results and analysis：
Conclusion：From above example test result it is seen that the best results of embodiment 3.

Claims (3)

  1. A kind of 1. one pack system high heat conductive insulating structural adhesive and preparation method thereof, it is characterised in that：
    10~30 parts of epoxy resin, 10~20 parts of modified epoxy, 2~10 parts of toughener, coupling agent 0.5-2 parts are added successively Enter into double-planet power mixing kettle, open revolution stirring and high speed is scattered, under the conditions of temperature is 15~30 DEG C, stir 1h, Modified 30~70 parts of heat-conductive insulation filling is added, stirs 1h, adds 5~20 parts of latent curing agent, stirs 1h, adds gas phase two 0~2 part of silica, 1h is stirred, open vavuum pump and vacuumize 1h, vacuum pressure is -0.098, produces one-component high heat conductive insulating Structural adhesive；The revolution speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed；
    The modified epoxy follows the steps below：
    Hydroquinones 125g and 4,4- dihydroxybiphenyl 25g are added in round-bottomed flask, and are continually fed into nitrogen, adds epoxy Chloropropane 1200g and 180g diethylene glycol dimethyl ether, 60 DEG C are heated to, add 21.2g48% potassium hydroxide aqueous solutions, stir 1h, then It is heated to 100 DEG C of distillations and removes moisture removal, be heated to 118 DEG C, is returned to the epoxychloropropane distilled out using circulation distillation mode Into round-bottomed flask, 1h is reacted, cooling removes circulation distilling apparatus, is heated to 118 DEG C, epoxychloropropane is distilled off, adds 560g methyl iso-butyl ketone (MIBK)s, are washed, and add 48% sodium hydroxide 13.5g, and 1h is stirred under the conditions of being 85 DEG C in temperature, then Washed with 40 DEG C of warm water of 200ml, be heated to 117 DEG C -118 DEG C and methyl iso-butyl ketone (MIBK) is distilled off, produce modified epoxy tree Fat；
    The epoxy resin be 3,4- epoxycyclohexyls formic acid esters, 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, Bisphenol A epoxide resin, bisphenol F epoxy resin and phenolic resin one or several kinds therein；
    The toughener be nitrile rubber, core-shell tougheners Kane Ace@MX-125, Initialcreate@ICAM-8627 and One kind or arbitrary proportion in ring figured woven silk material chemical industry S-2001 it is two or more；
    The latent curing agent is dicyandiamide, Ai Di sections EH-4360S, EH-4357S, the taste of Changzhou common calla Resins Corporation Plain PN-H, aginomoto PN-23 and one kind in Fuji's chemistry 1020 or arbitrary proportion it is two or more；
    The aerosil is from R202 the and Ying Chuan companies of TS-720, EH-5, Ying Chuan company of Cabot Co., Ltd One kind or arbitrary proportion in A200 it is two or more；
    The coupling agent is from a kind of or any in γ aminopropyltriethoxy silane and glycidoxy trimethoxy silane Two kinds of ratio；
    The modified heat-conductive insulation filling follows the steps below：
    1）Prepare dry toluene：It is aobvious that 100ml toluene solutions, 25g metallic sodiums and 3~5 drops are sequentially added into 150ml round-bottomed flasks Toner benzophenone, 150ml round-bottomed flasks are connected in reflux, are heated to 130 DEG C, constant temperature backflow, when molten in flask Liquid is changed into blueness, makes backflow into rectification, 130 DEG C of rectification 2h, cooling, obtains dry toluene；
    2）Prepare isocyanatomethyl triethoxysilane toluene solution：15g isocyanatomethyl triethoxysilanes are added to 25ml
    Dissolved in dry toluene, obtain isocyanatomethyl triethoxysilane toluene solution；
    3）Load flask：Isocyanatomethyl triethoxysilane toluene solution is added to equipped with 100ml constant pressure funnels and In the 250ml three-necked flasks of spherical condensation tube；
    4）Prepare sample：23.6g diacetylmonoximes are added in 25ml dry toluenes and dissolved, 100ml constant pressures drop is transferred to after dissolving In liquid funnel, it is added drop-wise in three-necked flask, controls during dropwise addition solution temperature in three-necked flask to be no more than 40 DEG C, 0.5h is dripped Finish, 35 DEG C of constant temperature 0.5h, be warming up to 80 DEG C of reaction 4h, obtain sample；
    5）Prepare blocked isocyanate silane：By step 4）Obtained sample is added in Rotary Evaporators, pressure for- 0.1MPa, under the conditions of temperature is 60 DEG C, 2h is evaporated, obtains blocked isocyanate silane；
    6）Prepare mixed liquor：Blocked isocyanate silane is added in ethanol solution, blocked isocyanate silane and ethanol Mol ratio 1:3, the volume ratio of ethanol solution reclaimed water and ethanol is 1:2, obtain mixed liquor；
    7）Prepare blocked isocyanate solution of silane：To step 6）Add acetic acid in obtained mixed liquor, adjust pH be 3.5~ 5.5,30min is stood, obtains blocked isocyanate solution of silane；
    8）Prepare preheating alumina powder：Alumina powder is added in high-speed mixer, under the conditions of temperature is 100 DEG C, in advance Hot 10min, obtain preheating alumina powder；
    9）Prepare the silane-modified heat-conductive insulation filling of pre- blocked isocyanate：Respectively by step 8）Gained preheat alumina powder and Step 7）Obtained blocked isocyanate solution of silane in mass ratio 1000:5 are added in high-speed mixer, 100 DEG C of temperature, High-speed stirred 1h under conditions of rotating speed 1000r/min, static 30min, obtain the silane-modified heat conductive insulating of pre- blocked isocyanate and fill out Material；
    10）Prepare modified heat-conductive insulation filling：By step 9）The silane-modified heat conductive insulating of pre- blocked isocyanate prepared is filled out Material, is placed in 80 DEG C of drying boxes and dries 4h, obtain being modified heat-conductive insulation filling.
  2. 2. one pack system high heat conductive insulating structural adhesive as claimed in claim 1 and preparation method thereof, it is characterised in that：It is described Alumina powder footpath size is 15~30 μm.
  3. 3. one pack system high heat conductive insulating structural adhesive as claimed in claim 1 and preparation method thereof, it is characterised in that：
    By 10 parts of 3,4- epoxycyclohexyls formic acid esters, 5 parts of bisphenol A epoxide resin, 15 parts of modified epoxy, core-shell tougheners Kane Ace@MX-125:3 parts, 1 part of glycidoxy trimethoxy silane be added sequentially in double-planet power mixing kettle, open Open revolution stirring and disperse at a high speed, under the conditions of temperature is 25 DEG C, stir 1h, add modified 57.5 parts of heat-conductive insulation filling, stir 1h is mixed, adds 8 parts of dicyandiamide, stirs 1h, adds 0.5 part of aerosil, stirs 1h, vavuum pump is opened and vacuumizes 1h, very Pneumatics power is -0.098, produces one-component high heat conductive insulating structural adhesive；The revolution speed of agitator is 20r/min, at a high speed Scattered rotating speed is 800r/min.
CN201710658394.3A 2017-08-04 2017-08-04 A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof Pending CN107474770A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109722197A (en) * 2019-02-28 2019-05-07 宁国市奇博电器有限公司 A kind of encapsulating insulation silica gel of capacitor and preparation method thereof
CN112409971A (en) * 2020-11-20 2021-02-26 湖北三选科技有限公司 Liquid mold sealing adhesive for protecting five sides of semiconductor chip and preparation method
CN114507333A (en) * 2021-12-27 2022-05-17 烟台信友新材料有限公司 High-toughness and high-weather-resistance photo-thermal dual-curing resin, preparation method and application thereof, and epoxy adhesive containing dual-curing resin

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102083881A (en) * 2008-03-03 2011-06-01 新日铁化学株式会社 Modified epoxy resin, epoxy resin compositions and cured articles
CN103773298A (en) * 2014-01-24 2014-05-07 临安金奥科技有限公司 High thermal-conductive and insulating adhesive for high-power LED lamp and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102083881A (en) * 2008-03-03 2011-06-01 新日铁化学株式会社 Modified epoxy resin, epoxy resin compositions and cured articles
CN103773298A (en) * 2014-01-24 2014-05-07 临安金奥科技有限公司 High thermal-conductive and insulating adhesive for high-power LED lamp and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙芳: "导热绝缘尼龙6复合材料的性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109722197A (en) * 2019-02-28 2019-05-07 宁国市奇博电器有限公司 A kind of encapsulating insulation silica gel of capacitor and preparation method thereof
CN112409971A (en) * 2020-11-20 2021-02-26 湖北三选科技有限公司 Liquid mold sealing adhesive for protecting five sides of semiconductor chip and preparation method
CN114507333A (en) * 2021-12-27 2022-05-17 烟台信友新材料有限公司 High-toughness and high-weather-resistance photo-thermal dual-curing resin, preparation method and application thereof, and epoxy adhesive containing dual-curing resin
CN114507333B (en) * 2021-12-27 2024-02-23 烟台信友新材料有限公司 High-toughness high-weather-resistance photo-thermal dual-curing resin, preparation method and application thereof, and epoxy adhesive containing dual-curing resin

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Application publication date: 20171215