CN109233711A - A kind of preparation method of high-temperature adhesives - Google Patents
A kind of preparation method of high-temperature adhesives Download PDFInfo
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- CN109233711A CN109233711A CN201810669043.7A CN201810669043A CN109233711A CN 109233711 A CN109233711 A CN 109233711A CN 201810669043 A CN201810669043 A CN 201810669043A CN 109233711 A CN109233711 A CN 109233711A
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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
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- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention discloses a kind of preparation methods of high-temperature adhesives, belong to technical field of polymer materials.According to parts by weight, successively weigh 20~30 parts of epoxy resin, 1~3 part of curing agent, 5~8 parts of additives, 5~8 parts of modified graphene oxides and 30~50 mixed solvents, epoxy resin and mixed solvent are mixed in blender, and curing agent is added into blender, additive and modified graphene oxide, in temperature be 45~65 DEG C, after revolving speed is stirred 30~50min under conditions of being 300~400r/min, high-temperature adhesives are obtained.The high-temperature adhesives of technical solution of the present invention preparation have the characteristics that excellent high temperature resistance, have broad prospects in the development of macromolecule material industry.
Description
Technical field
The invention discloses a kind of preparation methods of high-temperature adhesives, belong to technical field of polymer materials.
Background technique
Resistance to quotient's temperature bonding agent is mainly used in terms of being bonded heat-resisting material, is connection, seals the effective of heat-resisting material
Mode.It is typically used in the high-tech areas such as Aeronautics and Astronautics and military project.It, can the resistance to height of effective solution using high temperature resistant adhesive
The connectivity problem of adiabator.The disadvantages such as that there are solidification temperatures is high for general high temperature resistant adhesive, high temperature resistance is low.With science
The progress of technology, adhesive technology is as a kind of method for connecting different material, by more and more extensive use.Adhesive technology, no
It is same as other connection methods.It connects, other connection methods such as clamping connection, has the advantages that lower compared to welding, guiding principle:
(1) small to the destruction of adhesives, do not damage adhesives;
(2) light weight only just will need originally the different components fixed with steel nail, skilful silk etc. by a small amount of bonding agent, be connected to
Together;
(3) at low cost, the expense of adhesive technology has the advantages that at low cost for other interconnection techniques;
(4) easy to operate, as long as bonding agent is coated in bonded object surface, adherend is docked, after centainly handling, just
It can be bonded together;
(5) it is connected firmly, adhesive technology General Mechanics is had excellent performance, and can well be connected together adherend, and prolonged
It is durable since adhesive technology has the advantages that many other interconnection techniques are incomparable, from Aeronautics and Astronautics to our daily people
With life, all it can be seen that the figure of adhesive technology.The key factor for determining adhesive technology, is bonding agent.Adhesive performance it is good
It is bad, it is directly related to adhesive property, is that cannot be neglected a bit.It, can be according to the side such as selection, application field for bonding agent
Face is divided into many types.For high temperature resistant field, bonding agent has also played its due effect.In order under the high temperature conditions, make
Bonding agent is still able to maintain adhesive property, for the bonding agent used under conditions of high humidity --- and grinding for high temperature resistant adhesive is ingeniously also got over
More to attract attention.High temperature adhesive due to its property in terms of heat resistance, at present oneself be widely used in it is a variety of from
Sciemtifec and technical sphere, especially in the fields such as Aeronautics and Astronautics and automobile, high-temperature resistance adhesive plays irreplaceable important function.
And traditional high-temperature adhesives the shortcomings that can not being further increased there is also high temperature resistance.
Therefore, how to improve the shortcomings that high temperature resistance existing for traditional high-temperature adhesives can not further increase, with
Asking exploration to develop the high-temperature adhesives with good comprehensive performance is problem to be solved.
Summary of the invention
The present invention solves the technical problem of: for conventional high-temperature adhesive high temperature resistance can not be further
The shortcomings that raising, provides a kind of preparation method of high-temperature adhesives.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of high-temperature adhesives, specific preparation step are as follows:
(1) by graphene oxide molecular sieve dehydration, and dewatered graphene oxide and n,N-Dimethylformamide are pressed into matter
Amount is mixed than 1:10~1:12, after ultrasonic disperse, obtains graphene oxide dispersion, and graphene oxide dispersion and toluene two is different
Cyanate 15:1~20:1 in mass ratio is mixed, and after ultrasonic disperse, is added 0.08~0.12 times of toluene di-isocyanate(TDI) quality
Dibutyl tin dilaurate after being stirred to react, obtains graphene oxide mixture, by graphene oxide mixture graphene oxide
After the acetone washing that 2~3 times of volume of mixture, centrifuge separation obtains modified graphene oxide blank, by modified graphene oxide base
Material vacuum drying, obtains modified graphene oxide；
(2) epoxy resin is mixed with water 1:5~1:8 in mass ratio, and 0.5~0.8 times of epoxy resin quality of benzene first is added
The mixed surfactant of 0.3~0.6 times of pure and mild epoxy resin quality, after being stirred, obtains epoxy resin latex, by asphalt mixtures modified by epoxy resin
Fat liquor is mixed with styrene 5:1~5:3 in mass ratio, and 0.02~0.10 times of epoxy resin latex quality of azo two is added
Isobutyronitrile, the initiator and 0.1~0.2 times of epoxy resin latex quality of poly- second that 0.05~0.12 times of epoxy resin latex quality
Alkene pyrrolidone obtains epoxy resin composition after being stirred under nitrogen atmosphere, by epoxy resin composition and potassium peroxydisulfate
The mixing of 100:1~100:2 in mass ratio, continues after being stirred to react, and is freeze-dried, obtains polystyrene microsphere, and polystyrene is micro-
Ball is mixed with water 1:10~1:20 in mass ratio, and 1~2 times of polystyrene microsphere quality of mix acid liquor is added, and is stirred to react
Afterwards, it filters, washing to cleaning solution is neutrality, it is dry, pretreatment polystyrene microsphere is obtained, by pretreatment polystyrene microsphere and hydrogen
Potassium oxide solution 1:5~1:8 in mass ratio mixing, and the thio sulphur of 0.2~0.3 times of polystyrene microsphere quality of pretreatment is added
Sour sodium, after being stirred to react, filtering, washing to cleaning solution is neutrality, dry, obtains Modified polystyrene spheres；
(3) graphene oxide is mixed, ultrasonic disperse with water 1:8~1:10 in mass ratio, graphene oxide mixing must be pre-processed
Pretreatment graphene oxide mixture is mixed with hydrazine hydrate 10:1~10:2 in mass ratio, after being stirred to react, filters, do by object
It is dry, redox graphene is obtained, Modified polystyrene spheres are mixed with water 1:8~1:10 in mass ratio, and is added modified poly-
The redox graphene and 0.3~0.4 times of Modified polystyrene spheres quality of nano oxygen that 2~3 times of phenylethylene micro ball quality
Change aluminum fiber, filters, obtain additive；
(4) according to parts by weight, 20~30 parts of epoxy resin are successively weighed, 1~3 part of curing agent, 5~8 parts of additives, 5~8 parts
Epoxy resin is mixed with mixed solvent, and curing agent is added by modified graphene oxide and 30~50 mixed solvents, additive and
Modified graphene oxide after being stirred, obtains high-temperature adhesives.
The epoxy resin is any one in epoxy resin E-44 or epoxy resin E-51.
Step (2) mixed surfactant is to mix neopelex and Arabic gum 3:1 in mass ratio
It closes, obtains mixed surfactant.
Step (2) initiator is any one in benzoyl peroxide or lauroyl peroxide.
Step (2) described mix acid liquor be 40~60% by mass fraction sulfuric acid and mass fraction be 30~50% nitre
Acid 3:1 in mass ratio mixing, obtains mix acid liquor.
Step (4) curing agent is ethylenediamine, any one in diethylenetriamine or triethylene tetramine.
Step (4) mixed solvent is to mix dimethylbenzene with toluene 3:1~5:1 in mass ratio, obtains mixed solvent.
The beneficial effects of the present invention are:
(1) additive is added when preparing high-temperature adhesives by the present invention, firstly, having the polyphenyl second with amino on the outside of additive
Alkene, after mixing with redox graphene, redox graphene can be under the action of electrostatic force, in polystyrene surface shape
At one layer of clad, to make additive that there is preferable heat-conducting effect, the heat-resisting quantity of product can be made after being added in product
It improves, secondly, the polystyrene in additive can be dissolved by toluene, to make inside after additive is added in product
Epoxy resin exposure, and then improve the compatibility between additive and matrix resin, additive can be uniformly distributed in product,
The heat-resisting quantity of product is improved, and since the redox graphene of outside cladding is porous structure, epoxy can be interspersed in
In the cross-linked network of resin, and then further increase the heat-resisting quantity of product；
(2) modified graphene oxide is added when preparing high-temperature adhesives by the present invention, on the one hand, graphene oxide is by being modified
Hydrophily reduces afterwards, improves, can be uniformly distributed in product after being added in product, and then make product with the compatibility of organic matter
Heat-resisting quantity further increase, on the other hand, modified graphene oxide can form in spherical additive in interiors of products good
Good thermal conducting path, so that the heat-resisting quantity of product be made to improve.
Specific embodiment
Matter is pressed by graphene oxide molecular sieve dehydration, and by dewatered graphene oxide and n,N-Dimethylformamide
Amount is mixed than 1:10~1:12, under conditions of frequency is 45~55kHz after 20~30min of ultrasonic disperse, obtains graphene oxide
Dispersion liquid mixes graphene oxide dispersion with toluene di-isocyanate(TDI) 15:1~20:1 in mass ratio, in frequency be 45~
Under conditions of 50kHz after 15~25min of ultrasonic disperse, in the mixture of graphene oxide dispersion and toluene di-isocyanate(TDI)
0.08~0.12 times of toluene di-isocyanate(TDI) quality of dibutyl tin dilaurate is added, is 50~80 DEG C in temperature, revolving speed is
After the item of 280~350r/min is stirred to react 1~3h under, graphene oxide mixture is obtained, graphene oxide mixture is used
After the acetone washing that 2~3 times of graphene oxide volume of mixture, the centrifugation point under conditions of revolving speed is 2000~3000r/min
From rear, modified graphene oxide blank is obtained, modified graphene oxide blank is dried in vacuo, modified graphene oxide is obtained；By ring
Oxygen resin and water 1:5~1:8 in mass ratio are mixed in beaker, and 0.5~0.8 times of epoxy resin quality is added into beaker
Benzyl alcohol and 0.3~0.6 times of epoxy resin quality of mixed surfactant, in temperature be 45~55 DEG C, revolving speed be 300~
After being stirred 30~60min under conditions of 600r/min, epoxy resin latex is obtained, epoxy resin latex and styrene are pressed into matter
Amount is mixed in three-necked flask than 5:1~5:3, and 0.02~0.10 times of epoxy resin latex quality is added into three-necked flask
Azodiisobutyronitrile, the initiator that 0.05~0.12 times of epoxy resin latex quality and 0.1~0.2 times of epoxy resin latex quality
Polyvinylpyrrolidone, nitrogen is passed through with the rate of 5~18mL/min into three-necked flask, in temperature be 55~85 DEG C, turn
Speed be 300~400r/min under conditions of be stirred 1~3h after, obtain epoxy resin composition, by epoxy resin composition with
Potassium peroxydisulfate 100:1~100:2 in mass ratio mixing, continuing at temperature is 55~85 DEG C, and revolving speed is the item of 300~400r/min
After being stirred to react 40~80min under part, freeze-drying obtains polystyrene microsphere, by polystyrene microsphere and water in mass ratio 1:
10~1:20 is mixed, and the mixed acid of 1~2 times of polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water
Liquid is 50~60 DEG C in temperature, and after revolving speed is stirred to react under conditions of being 300~350r/min after 2~3h, filtering obtains filter cake,
After filter cake is washed with water to cleaning solution as neutrality, dry 15~30min under conditions of being 30~40 DEG C in temperature must be pre-processed
Polystyrene microsphere will pre-process the potassium hydroxide solution 1:5 in mass ratio that polystyrene microsphere and mass fraction are 8~10%
~1:8 mixing, and addition pretreatment polystyrene is micro- into the mixture of pretreatment polystyrene microsphere and potassium hydroxide solution
The sodium thiosulfate that 0.2~0.3 times of ball quality is 70~80 DEG C in temperature, and revolving speed stirs under conditions of being 300~320r/min
After reacting 2~3h, filtering obtains filter residue, and filter residue is washed with water to cleaning solution for neutrality, under conditions of temperature is 30~40 DEG C
It is dry, obtain Modified polystyrene spheres；Graphene oxide is mixed with water 1:8~1:10 in mass ratio, in frequency be 40~
20~30min of ultrasonic disperse under conditions of 50kHz must pre-process graphene oxide mixture, and pretreatment graphene oxide is mixed
It closes object to mix with hydrazine hydrate 10:1~10:2 in mass ratio, is 45~55 DEG C in temperature, revolving speed is the condition of 300~400r/min
Under be stirred to react 1~2h after, filtering, obtain redox graphene blank, by redox graphene blank in temperature be 60~
Dry 20~30min, obtains redox graphene, by Modified polystyrene spheres and water 1:8 in mass ratio under conditions of 880 DEG C
~1:10 mixing, and 2~3 times of Modified polystyrene spheres quality is added into the mixture of Modified polystyrene spheres and water
Redox graphene and 0.3~0.4 times of Modified polystyrene spheres quality of nano-alumina fiber filter, obtain additive；
According to parts by weight, 20~30 parts of epoxy resin, 1~3 part of curing agent, 5~8 parts of additives, 5~8 parts of modified oxygen are successively weighed
Epoxy resin and mixed solvent are mixed in blender, and are added into blender by graphite alkene and 30~50 mixed solvents
Curing agent, additive and modified graphene oxide are 45~65 DEG C in temperature, and revolving speed stirs under conditions of being 300~400r/min
After mixing 30~50min of mixing, high-temperature adhesives are obtained.The epoxy resin is any in epoxy resin E-44 or epoxy resin E-51
It is a kind of.The mixed surfactant is to mix neopelex with Arabic gum 3:1 in mass ratio, obtains mixture table
Face activating agent.The initiator is any one in benzoyl peroxide or lauroyl peroxide.The mix acid liquor is by matter
The sulfuric acid that amount score is 40~60% is mixed with the nitric acid 3:1 in mass ratio that mass fraction is 30~50%, obtains mix acid liquor.It is described
Curing agent is ethylenediamine, any one in diethylenetriamine or triethylene tetramine.The mixed solvent is by dimethylbenzene and toluene
The mixing of 3:1~5:1 in mass ratio, obtains mixed solvent.
Matter is pressed by graphene oxide molecular sieve dehydration, and by dewatered graphene oxide and n,N-Dimethylformamide
Amount is mixed than 1:12, under conditions of frequency is 55kHz after ultrasonic disperse 30min, is obtained graphene oxide dispersion, will be aoxidized stone
Black alkene dispersion liquid is mixed with toluene di-isocyanate(TDI) 20:1 in mass ratio, the ultrasonic disperse 25min under conditions of frequency is 50kHz
Afterwards, 0.12 times of toluene di-isocyanate(TDI) quality is added into the mixture of graphene oxide dispersion and toluene di-isocyanate(TDI)
Dibutyl tin dilaurate is 80 DEG C in temperature, and revolving speed is after the item of 350r/min is stirred to react 3h under, to obtain graphene oxide
Mixture, after 3 times of graphene oxide volume of mixture of acetone washing of graphene oxide mixture, in revolving speed be 3000r/
After being centrifugated under conditions of min, modified graphene oxide blank is obtained, modified graphene oxide blank is dried in vacuo, must be changed
Property graphene oxide；Epoxy resin and water 1:8 in mass ratio are mixed in beaker, and epoxy resin quality is added into beaker
0.8 times of benzyl alcohol and 0.6 times of epoxy resin quality of mixed surfactant, in temperature be 55 DEG C, revolving speed 600r/min
Under conditions of be stirred 60min after, obtain epoxy resin latex, epoxy resin latex mixed with styrene 5:3 in mass ratio
In three-necked flask, and 0.10 times of epoxy resin latex quality of azodiisobutyronitrile, epoxy resin are added into three-necked flask
The initiator and 0.2 times of epoxy resin latex quality of polyvinylpyrrolidone that 0.12 times of quality of the emulsion, into three-necked flask with
The rate of 18mL/min is passed through nitrogen, is 85 DEG C in temperature, after revolving speed is stirred 3h under conditions of being 400r/min, obtains epoxy
Resin compound mixes epoxy resin composition with potassium peroxydisulfate 100:2 in mass ratio, and continuing at temperature is 85 DEG C, revolving speed
After being stirred to react 80min under conditions of 400r/min, freeze-drying obtains polystyrene microsphere, by polystyrene microsphere and water
1:20 in mass ratio is mixed, and the mixing of 2 times of polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water
Acid solution is 60 DEG C in temperature, and after revolving speed is stirred to react rear 3h under conditions of being 350r/min, filtering obtains filter cake, by filter cake water
After washing is neutral to cleaning solution, dry 30min under conditions of being 40 DEG C in temperature obtains pretreatment polystyrene microsphere, will be pre-
The potassium hydroxide solution 1:8 in mass ratio that processing polystyrene microsphere and mass fraction are 10% is mixed, and to pre-processing polyphenyl second
The sodium thiosulfate of 0.3 times of polystyrene microsphere quality of pretreatment is added in the mixture of alkene microballoon and potassium hydroxide solution, in
Temperature is 80 DEG C, and after revolving speed is stirred to react 3h under conditions of being 320r/min, filtering obtains filter residue, filter residue is washed with water to and is washed
Liquid is washed as neutrality, drying under conditions of being 40 DEG C in temperature obtains Modified polystyrene spheres；Graphene oxide and water are pressed into quality
It is mixed than 1:10, the ultrasonic disperse 30min under conditions of frequency is 50kHz must pre-process graphene oxide mixture, will locate in advance
Reason graphene oxide mixture is mixed with hydrazine hydrate 10:2 in mass ratio, is 55 DEG C in temperature, revolving speed is the condition of 400r/min
Under be stirred to react 2h after, filtering obtains redox graphene blank, by redox graphene blank in temperature be 880 DEG C
Under the conditions of dry 30min, obtain redox graphene, Modified polystyrene spheres mixed with water 1:10 in mass ratio, and to
The redox graphene of 3 times of Modified polystyrene spheres quality is added in the mixture of Modified polystyrene spheres and water and changes
Property 0.4 times of quality of polystyrene microsphere of nano-alumina fiber, filter, obtain additive；According to parts by weight, 30 are successively weighed
Part epoxy resin, 3 parts of curing agent, 8 parts of additives, 8 parts of modified graphene oxides and 50 mixed solvents, by epoxy resin with mix
Solvent is mixed in blender, and curing agent is added into blender, additive and modified graphene oxide, in temperature be 65
DEG C, after revolving speed is stirred 50min under conditions of being 400r/min, obtain high-temperature adhesives.The epoxy resin is epoxy resin
E-44.The mixed surfactant is to mix neopelex with Arabic gum 3:1 in mass ratio, obtains mixture table
Face activating agent.The initiator is benzoyl peroxide.The mix acid liquor is that the sulfuric acid for being 60% by mass fraction divides with quality
Number mixes for 50% nitric acid 3:1 in mass ratio, obtains mix acid liquor.The curing agent is ethylenediamine.The mixed solvent is by two
Toluene is mixed with toluene 5:1 in mass ratio, obtains mixed solvent.
Epoxy resin and water 1:8 in mass ratio are mixed in beaker, and 0.8 times of epoxy resin quality is added into beaker
Benzyl alcohol and 0.6 times of epoxy resin quality of mixed surfactant, in temperature be 55 DEG C, revolving speed be 600r/min condition
Under be stirred 60min after, obtain epoxy resin latex, epoxy resin latex and styrene 5:3 in mass ratio be mixed in three mouthfuls
In flask, and 0.10 times of epoxy resin latex quality of azodiisobutyronitrile, epoxy resin latex matter are added into three-necked flask
0.12 times of initiator and 0.2 times of epoxy resin latex quality of polyvinylpyrrolidone are measured, into three-necked flask with 18mL/
The rate of min is passed through nitrogen, is 85 DEG C in temperature, after revolving speed is stirred 3h under conditions of being 400r/min, obtains epoxy resin
Mixture mixes epoxy resin composition with potassium peroxydisulfate 100:2 in mass ratio, and continuing at temperature is 85 DEG C, and revolving speed is
After being stirred to react 80min under conditions of 400r/min, freeze-drying obtains polystyrene microsphere, polystyrene microsphere and water is pressed
Mass ratio 1:20 is mixed, and the mixed acid of 2 times of polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water
Liquid is 60 DEG C in temperature, and after revolving speed is stirred to react rear 3h under conditions of being 350r/min, filtering obtains filter cake, filter cake is washed with water
It washs after being neutral to cleaning solution, dry 30min under conditions of being 40 DEG C in temperature obtains pretreatment polystyrene microsphere, will locate in advance
The potassium hydroxide solution 1:8 in mass ratio that reason polystyrene microsphere and mass fraction are 10% is mixed, and to pre-processing polystyrene
The sodium thiosulfate of 0.3 times of polystyrene microsphere quality of pretreatment, Yu Wen are added in the mixture of microballoon and potassium hydroxide solution
Degree is 80 DEG C, and after revolving speed is stirred to react 3h under conditions of being 320r/min, filtering obtains filter residue, filter residue is washed with water to washing
Liquid is neutrality, dry under conditions of being 40 DEG C in temperature, obtains Modified polystyrene spheres；In mass ratio by graphene oxide and water
1:10 mixing, the ultrasonic disperse 30min under conditions of frequency is 50kHz, must pre-process graphene oxide mixture, will pre-process
Graphene oxide mixture is mixed with hydrazine hydrate 10:2 in mass ratio, is 55 DEG C in temperature, revolving speed is under conditions of 400r/min
After being stirred to react 2h, filtering obtains redox graphene blank, the item for being 880 DEG C in temperature by redox graphene blank
Dry 30min, obtains redox graphene, Modified polystyrene spheres is mixed with water 1:10 in mass ratio under part, and to changing
Property polystyrene microsphere and water mixture in be added 3 times of Modified polystyrene spheres quality redox graphene and modification
The nano-alumina fiber that 0.4 times of polystyrene microsphere quality filters, obtains additive；According to parts by weight, 30 parts are successively weighed
Epoxy resin, 3 parts of curing agent, 8 parts of additives, 8 parts of graphene oxides and 50 mixed solvents, epoxy resin and mixed solvent are mixed
Together in blender, and curing agent is added into blender, additive and graphene oxide are 65 DEG C in temperature, and revolving speed is
After being stirred 50min under conditions of 400r/min, high-temperature adhesives are obtained.The epoxy resin is epoxy resin E-44.It is described
Mixed surfactant is to mix neopelex with Arabic gum 3:1 in mass ratio, obtains mixed surfactant.
The initiator is benzoyl peroxide.The mix acid liquor be 60% by mass fraction sulfuric acid and mass fraction be 50%
Nitric acid 3:1 in mass ratio mixing, obtains mix acid liquor.The curing agent is ethylenediamine.The mixed solvent is by dimethylbenzene and first
Benzene 5:1 in mass ratio mixing, obtains mixed solvent.
Matter is pressed by graphene oxide molecular sieve dehydration, and by dewatered graphene oxide and n,N-Dimethylformamide
Amount is mixed than 1:12, under conditions of frequency is 55kHz after ultrasonic disperse 30min, is obtained graphene oxide dispersion, will be aoxidized stone
Black alkene dispersion liquid is mixed with toluene di-isocyanate(TDI) 20:1 in mass ratio, the ultrasonic disperse 25min under conditions of frequency is 50kHz
Afterwards, 0.12 times of toluene di-isocyanate(TDI) quality is added into the mixture of graphene oxide dispersion and toluene di-isocyanate(TDI)
Dibutyl tin dilaurate is 80 DEG C in temperature, and revolving speed is after the item of 350r/min is stirred to react 3h under, to obtain graphene oxide
Mixture, after 3 times of graphene oxide volume of mixture of acetone washing of graphene oxide mixture, in revolving speed be 3000r/
After being centrifugated under conditions of min, modified graphene oxide blank is obtained, modified graphene oxide blank is dried in vacuo, must be changed
Property graphene oxide；Graphene oxide is mixed with water 1:10 in mass ratio, the ultrasonic disperse under conditions of frequency is 50kHz
30min must pre-process graphene oxide mixture, and pretreatment graphene oxide mixture is mixed with hydrazine hydrate 10:2 in mass ratio
It closing, is 55 DEG C in temperature, after revolving speed is stirred to react 2h under conditions of being 400r/min, filtering obtains redox graphene blank,
Dry 30min under conditions of being 880 DEG C in temperature by redox graphene blank, obtains redox graphene, by polyphenyl second
Alkene microballoon is mixed with water 1:10 in mass ratio, and polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water
3 times of redox graphene and 0.4 times of polystyrene microsphere quality of nano-alumina fiber filter, obtain additive；By weight
Number meter is measured, successively weighs 30 parts of epoxy resin, 3 parts of curing agent, 8 parts of additives, 8 parts of modified graphene oxides and 50 mixing are molten
Epoxy resin and mixed solvent are mixed in blender, and curing agent are added into blender by agent, additive and modified oxidized
Graphene is 65 DEG C in temperature, after revolving speed is stirred 50min under conditions of being 400r/min, obtains high-temperature adhesives.The ring
Oxygen resin is epoxy resin E-44.The mixed surfactant be by neopelex and Arabic gum in mass ratio
3:1 mixing, obtains mixed surfactant.The initiator is benzoyl peroxide.The mix acid liquor is to be by mass fraction
60% sulfuric acid is mixed with the nitric acid 3:1 in mass ratio that mass fraction is 50%, obtains mix acid liquor.The curing agent is ethylenediamine.
The mixed solvent is to mix dimethylbenzene with toluene 5:1 in mass ratio, obtains mixed solvent.
Matter is pressed by graphene oxide molecular sieve dehydration, and by dewatered graphene oxide and n,N-Dimethylformamide
Amount is mixed than 1:12, under conditions of frequency is 55kHz after ultrasonic disperse 30min, is obtained graphene oxide dispersion, will be aoxidized stone
Black alkene dispersion liquid is mixed with toluene di-isocyanate(TDI) 20:1 in mass ratio, the ultrasonic disperse 25min under conditions of frequency is 50kHz
Afterwards, 0.12 times of toluene di-isocyanate(TDI) quality is added into the mixture of graphene oxide dispersion and toluene di-isocyanate(TDI)
Dibutyl tin dilaurate is 80 DEG C in temperature, and revolving speed is after the item of 350r/min is stirred to react 3h under, to obtain graphene oxide
Mixture, after 3 times of graphene oxide volume of mixture of acetone washing of graphene oxide mixture, in revolving speed be 3000r/
After being centrifugated under conditions of min, modified graphene oxide blank is obtained, modified graphene oxide blank is dried in vacuo, must be changed
Property graphene oxide；Epoxy resin and water 1:8 in mass ratio are mixed in beaker, and epoxy resin quality is added into beaker
0.8 times of benzyl alcohol and 0.6 times of epoxy resin quality of mixed surfactant, in temperature be 55 DEG C, revolving speed 600r/min
Under conditions of be stirred 60min after, obtain epoxy resin latex, epoxy resin latex mixed with styrene 5:3 in mass ratio
In three-necked flask, and 0.10 times of epoxy resin latex quality of azodiisobutyronitrile, epoxy resin are added into three-necked flask
The initiator and 0.2 times of epoxy resin latex quality of polyvinylpyrrolidone that 0.12 times of quality of the emulsion, into three-necked flask with
The rate of 18mL/min is passed through nitrogen, is 85 DEG C in temperature, after revolving speed is stirred 3h under conditions of being 400r/min, obtains epoxy
Resin compound mixes epoxy resin composition with potassium peroxydisulfate 100:2 in mass ratio, and continuing at temperature is 85 DEG C, revolving speed
After being stirred to react 80min under conditions of 400r/min, freeze-drying obtains polystyrene microsphere, by polystyrene microsphere and water
1:20 in mass ratio is mixed, and the mixing of 2 times of polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water
Acid solution is 60 DEG C in temperature, and after revolving speed is stirred to react rear 3h under conditions of being 350r/min, filtering obtains filter cake, by filter cake water
After washing is neutral to cleaning solution, dry 30min under conditions of being 40 DEG C in temperature obtains pretreatment polystyrene microsphere, will be pre-
The potassium hydroxide solution 1:8 in mass ratio that processing polystyrene microsphere and mass fraction are 10% is mixed, and to pre-processing polyphenyl second
The sodium thiosulfate of 0.3 times of polystyrene microsphere quality of pretreatment is added in the mixture of alkene microballoon and potassium hydroxide solution, in
Temperature is 80 DEG C, and after revolving speed is stirred to react 3h under conditions of being 320r/min, filtering obtains filter residue, filter residue is washed with water to and is washed
Liquid is washed as neutrality, drying under conditions of being 40 DEG C in temperature obtains Modified polystyrene spheres；By Modified polystyrene spheres and water
The mixing of 1:10 in mass ratio, and Modified polystyrene spheres quality 3 is added into the mixture of Modified polystyrene spheres and water
0.4 times of Modified polystyrene spheres quality of nano-alumina fiber again filters, obtains additive；According to parts by weight, successively
30 parts of epoxy resin, 3 parts of curing agent, 8 parts of additives, 8 parts of modified graphene oxides and 50 mixed solvents are weighed, by epoxy resin
It is mixed in blender with mixed solvent, and curing agent is added into blender, additive and modified graphene oxide, in temperature
It is 65 DEG C, after revolving speed is stirred 50min under conditions of being 400r/min, obtains high-temperature adhesives.The epoxy resin is epoxy
Resin E-44.The mixed surfactant is to mix neopelex with Arabic gum 3:1 in mass ratio, is obtained mixed
Close surfactant.The initiator is benzoyl peroxide.The mix acid liquor be 60% by mass fraction sulfuric acid and matter
It measures the nitric acid 3:1 in mass ratio that score is 50% to mix, obtains mix acid liquor.The curing agent is ethylenediamine.The mixed solvent is
Dimethylbenzene is mixed with toluene 5:1 in mass ratio, obtains mixed solvent.
Comparative example: the high-temperature adhesives of Shandong Science and Technology Ltd. production.
Example 1 to the resulting high-temperature adhesives of example 4 and comparative example product are subjected to performance detection, specific detection method is such as
Under:
Thermal coefficient is detected according to ASTM E1461.After being coated with the sample solidification of test specimen, at constant temperature in 200 DEG C of insulating boxs
Reason 7 days, the shear strength of sample.
Specific testing result is as shown in table 1:
1 high-temperature adhesives performance test results of table
By 1 testing result of table it is found that the high-temperature adhesives of technical solution of the present invention preparation have the spy of excellent high temperature resistance
Point has broad prospects in the development of macromolecule material industry.
Claims (7)
1. a kind of preparation method of high-temperature adhesives, which is characterized in that specific preparation step are as follows:
(1) by graphene oxide molecular sieve dehydration, and dewatered graphene oxide and n,N-Dimethylformamide are pressed into matter
Amount is mixed than 1:10~1:12, after ultrasonic disperse, obtains graphene oxide dispersion, and graphene oxide dispersion and toluene two is different
Cyanate 15:1~20:1 in mass ratio is mixed, and after ultrasonic disperse, is added 0.08~0.12 times of toluene di-isocyanate(TDI) quality
Dibutyl tin dilaurate after being stirred to react, obtains graphene oxide mixture, by graphene oxide mixture graphene oxide
After the acetone washing that 2~3 times of volume of mixture, centrifuge separation obtains modified graphene oxide blank, by modified graphene oxide base
Material vacuum drying, obtains modified graphene oxide；
(2) epoxy resin is mixed with water 1:5~1:8 in mass ratio, and 0.5~0.8 times of epoxy resin quality of benzene first is added
The mixed surfactant of 0.3~0.6 times of pure and mild epoxy resin quality, after being stirred, obtains epoxy resin latex, by asphalt mixtures modified by epoxy resin
Fat liquor is mixed with styrene 5:1~5:3 in mass ratio, and 0.02~0.10 times of epoxy resin latex quality of azo two is added
Isobutyronitrile, the initiator and 0.1~0.2 times of epoxy resin latex quality of poly- second that 0.05~0.12 times of epoxy resin latex quality
Alkene pyrrolidone obtains epoxy resin composition after being stirred under nitrogen atmosphere, by epoxy resin composition and potassium peroxydisulfate
The mixing of 100:1~100:2 in mass ratio, continues after being stirred to react, and is freeze-dried, obtains polystyrene microsphere, and polystyrene is micro-
Ball is mixed with water 1:10~1:20 in mass ratio, and 1~2 times of polystyrene microsphere quality of mix acid liquor is added, and is stirred to react
Afterwards, it filters, washing to cleaning solution is neutrality, it is dry, pretreatment polystyrene microsphere is obtained, by pretreatment polystyrene microsphere and hydrogen
Potassium oxide solution 1:5~1:8 in mass ratio mixing, and the thio sulphur of 0.2~0.3 times of polystyrene microsphere quality of pretreatment is added
Sour sodium, after being stirred to react, filtering, washing to cleaning solution is neutrality, dry, obtains Modified polystyrene spheres；
(3) graphene oxide is mixed, ultrasonic disperse with water 1:8~1:10 in mass ratio, graphene oxide mixing must be pre-processed
Pretreatment graphene oxide mixture is mixed with hydrazine hydrate 10:1~10:2 in mass ratio, after being stirred to react, filters, do by object
It is dry, redox graphene is obtained, Modified polystyrene spheres are mixed with water 1:8~1:10 in mass ratio, and is added modified poly-
The redox graphene and 0.3~0.4 times of Modified polystyrene spheres quality of nano oxygen that 2~3 times of phenylethylene micro ball quality
Change aluminum fiber, filters, obtain additive；
(4) according to parts by weight, 20~30 parts of epoxy resin are successively weighed, 1~3 part of curing agent, 5~8 parts of additives, 5~8 parts
Epoxy resin is mixed with mixed solvent, and curing agent is added by modified graphene oxide and 30~50 mixed solvents, additive and
Modified graphene oxide after being stirred, obtains high-temperature adhesives.
2. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: the epoxy resin is ring
Any one in oxygen resin E-44 or epoxy resin E-51.
3. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: step (2) described mixing
Surfactant is to mix neopelex with Arabic gum 3:1 in mass ratio, obtains mixed surfactant.
4. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: step (2) described initiation
Agent is any one in benzoyl peroxide or lauroyl peroxide.
5. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: step (2) described mixing
Acid solution is that the sulfuric acid for being 40~60% by mass fraction is mixed with the nitric acid 3:1 in mass ratio that mass fraction is 30~50%, is obtained mixed
Close acid solution.
6. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: step (4) described solidification
Agent is ethylenediamine, any one in diethylenetriamine or triethylene tetramine.
7. a kind of preparation method of high-temperature adhesives according to claim 1, it is characterised in that: step (4) described mixing
Solvent is to mix dimethylbenzene with toluene 3:1~5:1 in mass ratio, obtains mixed solvent.
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