CN108314987A - A kind of high-temperature resistance adhesive and preparation method thereof containing graphite powder - Google Patents
A kind of high-temperature resistance adhesive and preparation method thereof containing graphite powder Download PDFInfo
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- CN108314987A CN108314987A CN201810144696.3A CN201810144696A CN108314987A CN 108314987 A CN108314987 A CN 108314987A CN 201810144696 A CN201810144696 A CN 201810144696A CN 108314987 A CN108314987 A CN 108314987A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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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- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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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
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to adhesive field more particularly to a kind of high-temperature resistance adhesives and preparation method thereof containing graphite powder.The preparation method of invention adhesive includes step 1：Prepare modified boron containing phenolic resin, step 2：Weigh following raw material：Methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification cream, graphite powder, high temperature resistant filler, liquid toughener, inorganic toughener, ethyl orthosilicate and filler, step 3：Milled processed, step 4：Prepare the high-temperature resistance adhesive containing graphite powder.The present invention touches phenolic resin as the base-material of adhesive using the methyl phenyl silicone resin for containing hydroxyl and modification, it is added to high temperature cabonization material graphite powder and high temperature resistant filler, organic resin is set mutually to be crosslinked with inorganic material at curing temperatures using crosslinking agent ethyl orthosilicate, adhesive strength of the adhesive under room temperature and hot environment is improved, invention adhesive remains to keep under 1000 DEG C or more of hot conditions the shear strength of 1.6Mpa.
Description
Technical field
The invention belongs to adhesive area more particularly to a kind of containing the high-temperature resistance adhesive of graphite powder and its preparation side
Method.
Background technology
Synvaren be phenol and formaldehyde under catalysts conditions through polycondensation, in and washing and made of tree
The characteristics of fat has into carbon height, and cementability is good, water-fast, heat-resisting and chemical resistance, is mainly used for being bonded timber, foam plastic
Material and other porous materials.But synvaren needs temperature-pressure to cure in use, cured glue layer
Property is crisp, and pure synvaren thermal stability and heat-resisting quantity are not high enough, commonly use other high-molecular compounds to improve it
Performance, to improve its heat resistance and adhesive strength.
Boron bakelite resin has more excellent heat resistance, resistance to TRANSIENT HIGH TEMPERATURE and mechanical performance than phenolic resin, is
A kind of excellent ablation resistant material.Although boron bakelite resin high, good toughness as organic adhesion agent adhesive strength, cannot be satisfied
Heat-resisting 1000 DEG C or more of technology requirement, usually using boron phenolic as heat-resisting only 500 DEG C of the adhesive of base-material.
In addition, the solidification temperature of boron bakelite resin is generally greater than 160 DEG C, its application in low-temperature setting field is limited.
Invention content
To solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of high-temperature resistance adhesive containing graphite powder and its
Preparation method.
Technical scheme of the present invention：
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) phenolic compound, aldehyde compound and catalyst are reacted to 8~10h under the conditions of 50-70 DEG C, 95~100
So that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises at DEG C, a certain amount of identical phenolic compound added into reaction system,
5~8h is reacted under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) mass parts are pressed to mix phenolic aldehyde prepolymer and boron compound, 5h, reaction knot is reacted under the conditions of 85~95 DEG C
So that reaction system is dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after beam, modified boron containing phenolic resin is made；
Step 2：Following raw material is weighed by certain mass part：
Methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification cream, graphite powder, high temperature resistant filler, liquid
Toughener, inorganic toughener, ethyl orthosilicate and filler；
Step 3：Milled processed：
Graphite powder and high temperature resistant filler are put into star grinder by mass parts and grind 30min, then by inorganic toughener
It is put into star grinder with filler and continues to grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid toughener and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
Further, step 1 (1) described reactive phenolic compounds are phenol, resorcinol, methylphenol, adjacent benzene two
The mixture of one or more of phenol, alkyl-resorcin, phloroglucin or hydroquinone；The aldehyde compound is first
The mixture of one or more of aldehyde, furfural, salicylide or acetaldehyde；The matter of the phenolic compound and the aldehyde compound
Amount is than being 2:1~3；The catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, hydroxide
The mixture of one or more of calcium or ammonium chloride, the quality of the catalyst are the 1~2% of phenolic compound quality；Step
Rapid one (2) boron compound is boric acid, phenylboric acid, 3- methoxyphenyl-boronic acids or to one kind in bromo phenylboric acid
Or several mixtures, the mass ratio of the phenolic aldehyde prepolymer and boron compound is 20:3~5.
Further, each material quality part described in step 2 is as follows：100 parts of the methyl phenyl silicone resin containing hydroxyl changes
Property 15~30 parts of boron bakelite resin, solidification 25~50 parts of cream, 10~20 parts of graphite powder, 5~10 parts of high temperature resistant filler, liquid toughening
50~180 parts of 10~20 parts of agent, 30~50 parts of inorganic toughener, 10~20 parts of ethyl orthosilicate and filler.
Further, it is 3~8% to cure polyvinyl alcohol concentration in cream described in step 2；The preparation method of the solidification cream
Be by the degree of polymerization be 1000~2000, alcohol solubility be 88% polyethylene powder alcohol be added portionwise into 20 DEG C of formalin,
Control mixing speed is 200rmp, stirs 18h.
Further, the grain size of graphite powder described in step 2 is 150 mesh；The high temperature resistant filler is titanium carbide and zirconium oxide
Or a kind of mixture of composition in yttrium oxide, wherein titanium carbide is 2 than the mass ratio of zirconium oxide or yttrium oxide:1.
Further, liquid toughener described in step 2 be liquid nitrile rubber, liquid polyisoprene rubber, CTBN,
The mixture of one or more of ATBN or HTBN；Inorganic toughener be silicon carbide chopped strand, carbon fiber, glass fibre or
The mixture of one or more of quartz fibre.
Further, filler described in step 2 is zinc oxide, iron oxide, iron powder, mica powder, talcum powder, calcium carbonate, sulfuric acid
Calcium pyroborate, glass putty, light magnesium oxide, zinc powder, calcium oxide, aluminium powder, fossil meal, titanium dioxide, aluminium oxide, kaolin, three oxidations two
The mixture of one or more of antimony, wollastonite, calcite, ceramic powder, boron nitride or boron carbide.
A kind of a kind of high-temperature plastic containing graphite powder prepared by the preparation method of the high-temperature resistance adhesive containing graphite powder
Stick, it is characterised in that the adhesive includes the component of following mass parts：
15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification 25~50 parts of cream,
10~20 parts of graphite powder, mass ratio 2:5~10 parts of mixture, the fine rubber of liquid fourth of 1 titanium carbide and zirconium oxide or yttrium oxide
10~20 parts of glue, 30~50 parts of silicon carbide chopped strand, 10~20 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and lightweight oxidation
50~180 parts of the mixture of magnesium；
The preparation method of the modified boron containing phenolic resin is as follows：
(1) 100 parts of phenol, 50~150 parts of formaldehyde and 1~2 part of sodium hydroxide are reacted 8 under the conditions of 50-70 DEG C~
10h makes reaction system be dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, and 10-30 parts of benzene are added into reaction system
Phenol reacts 5~8h under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boric acid, be reacted under the conditions of 85~95 DEG C
5h makes reaction system be dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, and modified boron phenol is made
Urea formaldehyde.
A kind of a kind of high-temperature plastic containing graphite powder prepared by the preparation method of the high-temperature resistance adhesive containing graphite powder
Stick, it is characterised in that the adhesive includes the component of following mass parts：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 30 parts of cream of solidification, graphite powder 15
Part, 4 parts of titanium carbide, zirconium oxide or 2 parts of yttrium oxide, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped strand, ethyl orthosilicate
15 parts, 80 parts of the mixture of zinc oxide, aluminium oxide and light magnesium oxide；
The preparation method of the modified boron containing phenolic resin is as follows：
(1) 100 parts of phenol, 50~150 parts of formaldehyde and 1~2 part of sodium hydroxide are reacted 8 under the conditions of 50-70 DEG C~
10h makes reaction system be dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, and 10-30 parts of benzene are added into reaction system
Phenol reacts 5~8h under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boric acid, be reacted under the conditions of 85~95 DEG C
5h makes reaction system be dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, and modified boron phenol is made
Urea formaldehyde.
Beneficial effects of the present invention：
One, the present invention using contain hydroxyl methyl phenyl silicone resin and modified boron containing phenolic resin as adhesive base-material,
Be added to high temperature cabonization material-graphite powder and high temperature resistant filler, using crosslinking agent-ethyl orthosilicate effect at curing temperatures
So that organic resin is mutually crosslinked with inorganic material, improves adhesive strength of the adhesive under room temperature and hot environment, glue of the present invention
Stick remains to keep under 1000 DEG C or more of hot conditions the shear strength of 1.6Mpa.
Two, the present invention prepare during adhesive using a large amount of free formaldehydes contained in solidification cream to boron bakelite resin into
Row normal temperature cure, adhesive obtained is i.e. curable under normal temperature condition and obtains good adhesive strength.
Three, the present invention makes the methyl phenyl silicone resin containing hydroxyl, boron phenolic by the effect of crosslinking agent-ethyl orthosilicate
Resin is mutually crosslinked at curing temperatures with inorganic toughener, and inorganic toughener makes gluing of the present invention with liquid toughener
Agent has higher toughness at normal temperatures, remains to keep good toughness under 1000 DEG C of hot environments.
Four, the present invention makes adhesive exist by the combination of the inorganic material such as organic resin and graphite powder, high temperature resistant filler
500 DEG C hereinafter, show the superior adhesion energy of organic adhesion agent；Under 500 DEG C or more hot conditions, inorganic gluing is shown
The heat resistance of agent, and still have good toughness at high temperature can meet for adhesive good toughness, viscous at high temperature
Connect the high requirement of intensity.
Five, the preparation method of the high-temperature resistance adhesive of the invention containing graphite powder is raw materials used at low cost, simple for process, easily
In operation, the high-temperature resistance adhesive obtained containing graphite powder is adaptable to curing environment in use, is wanted to operation
Ask low, it is easy to use, it only need to be by adhesive each component normal gluing after mixing.
Specific implementation mode
With reference to embodiment, the following further describes the technical solution of the present invention, and however, it is not limited to this, every right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be contained
It covers in protection scope of the present invention.
Embodiment 1
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) phenolic compound, aldehyde compound and catalyst are reacted to 8~10h under the conditions of 50-70 DEG C, 95~100
So that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises at DEG C, a certain amount of identical phenolic compound added into reaction system,
5~8h is reacted under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix phenolic aldehyde prepolymer and boron compound, reacts 5h under the conditions of 85~95 DEG C, react
After so that reaction system is dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg, be made modified boron containing phenolic resin；
Step 2：Following raw material is weighed by certain mass part：
15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification 25~50 parts of cream,
10~20 parts of graphite powder, 5~10 parts of high temperature resistant filler, 10~20 parts of liquid toughener, 30~50 parts of inorganic toughener, positive silicic acid
50~180 parts of 10~20 parts of ethyl ester and filler；
Step 3：Milled processed：
Graphite powder and high temperature resistant filler are put into star grinder by mass parts and grind 30min, then by inorganic toughener
It is put into star grinder with filler and continues to grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid toughener and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -1.
Embodiment 2
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) by 100 parts of phenolic compounds, 50~150 parts of aldehyde compounds and 1~2 part of catalyst under the conditions of 50-70 DEG C
8~10h is reacted, so that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, 10- is added into reaction system
30 parts of identical phenolic compounds react 5~8h under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
The reactive phenolic compounds are phenol, resorcinol, methylphenol, catechol, alkyl-resorcin, isophthalic
The mixture of one or more of triphenol or hydroquinone；The aldehyde compound is in formaldehyde, furfural, salicylide or acetaldehyde
One or more of mixtures；The catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, hydroxide
The mixture of one or more of barium, calcium hydroxide or ammonium chloride；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boron compounds, in 85~95 DEG C of conditions
Lower reaction 5h makes reaction system be dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, is made and changes
Property boron bakelite resin；The boron compound is boric acid, phenylboric acid, 3- methoxyphenyl-boronic acids or in bromo phenylboric acid
One or more of mixtures.
Step 2：Following raw material is weighed by certain mass part：
15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification 25~50 parts of cream,
Grain size is 10~20 parts of 5~10 parts of 10~20 parts of graphite powder, high temperature resistant filler, liquid toughener, the inorganic toughener 30 of 150 mesh
50~180 parts of~50 parts, 10~20 parts of ethyl orthosilicate and filler.
Polyvinyl alcohol concentration is 3~8% in the solidification cream；It is 1000 that the preparation method of the solidification cream, which is by the degree of polymerization,
~2000, the polyethylene powder alcohol that alcohol solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is
200rmp stirs 18h；
The high temperature resistant filler is titanium carbide and zirconium oxide or a kind of mixture of composition in yttrium oxide, wherein titanium carbide
It is 2 than the mass ratio of zirconium oxide or yttrium oxide:1；
The liquid toughener is one in liquid nitrile rubber, liquid polyisoprene rubber, CTBN, ATBN or HTBN
Kind or several mixtures；Inorganic toughener is one kind in silicon carbide chopped strand, carbon fiber, glass fibre or quartz fibre
Or several mixture；
The filler is zinc oxide, iron oxide, iron powder, mica powder, talcum powder, calcium carbonate, calcium sulfate crystal whiskers, glass putty, light
Matter magnesia, zinc powder, calcium oxide, aluminium powder, fossil meal, titanium dioxide, aluminium oxide, kaolin, antimony oxide, wollastonite, Fang Xie
The mixture of one or more of stone, ceramic powder, boron nitride or boron carbide；
Step 3：Milled processed：
Graphite powder and high temperature resistant filler are put into star grinder by mass parts and grind 30min, then by inorganic toughener
It is put into star grinder with filler and continues to grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid toughener and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -2.
Embodiment 3
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phenol, 50~150 parts of formaldehyde and 1~2 part of sodium hydroxide are reacted 8 under the conditions of 50-70 DEG C~
10h makes reaction system be dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, and 10-30 parts of benzene are added into reaction system
Phenol reacts 5~8h under the conditions of 50~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boric acid, be reacted under the conditions of 85~95 DEG C
5h makes reaction system be dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, and modified boron phenol is made
Urea formaldehyde.
Step 2：Following raw material is weighed by certain mass part：
15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification 25~50 parts of cream,
Grain size is 10~20 parts of graphite powder, the mass ratio 2 of 150 mesh:1 titanium carbide and zirconium oxide or the mixture 5~10 of yttrium oxide
Part, 10~20 parts of liquid nitrile rubber, 30~50 parts of silicon carbide chopped strand, 10~20 parts of ethyl orthosilicate, zinc oxide, oxidation
50~180 parts of the mixture of aluminium and light magnesium oxide.
Polyvinyl alcohol concentration is 3~8% in the solidification cream；It is 1000 that the preparation method of the solidification cream, which is by the degree of polymerization,
~2000, the polyethylene powder alcohol that alcohol solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is
200rmp stirs 18h；
Step 3：Milled processed：
The mixture of graphite powder and titanium carbide and zirconium oxide or yttrium oxide is put into star grinder by mass parts and is ground
30min, then the mixture of silicon carbide chopped strand and zinc oxide, aluminium oxide and light magnesium oxide is put into star grinder relaying
Continuous grinding 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -3.
Embodiment 4
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phenol, 50 parts of formaldehyde and 1 part of sodium hydroxide are reacted into 8h under the conditions of 50 DEG C, makes reaction at 95 DEG C
System is dehydrated to 0.5 ten thousand centipoises, and 10 parts of phenol are added into reaction system, reacts 5h under the conditions of 50 DEG C, and it is pre- that phenolic aldehyde is made
Polymers；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15 parts of boric acid, reacts 5h under the conditions of 85 DEG C, react
After so that reaction system is dehydrated to 3.0 ten thousand centipoises under the pressure of 65mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
15 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 25 parts of cream of solidification, grain size 150
10 parts of purpose graphite powder, mass ratio 2:1 titanium carbide and zirconium oxide or 5 parts of mixture, the liquid nitrile rubber 10 of yttrium oxide
Part, 30 parts of silicon carbide chopped strand, 10 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide 50 parts of mixture.
Polyvinyl alcohol concentration is 3% in the solidification cream；It is 1000 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
The mixture of graphite powder and titanium carbide and zirconium oxide or yttrium oxide is put into star grinder by mass parts and is ground
30min, then the mixture of silicon carbide chopped strand and zinc oxide, aluminium oxide and light magnesium oxide is put into star grinder relaying
Continuous grinding 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -4.
Embodiment 5
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxides are reacted into 9h under the conditions of 60 DEG C, made at 96 DEG C
Reaction system is dehydrated to 0.8 ten thousand centipoises, and 20 parts of phenol are added into reaction system, reacts 6h under the conditions of 55 DEG C, and phenol is made
Aldehyde prepolymer；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 20 parts of boric acid, reacts 5h under the conditions of 90 DEG C, react
After so that reaction system is dehydrated to 3.5 ten thousand centipoises under the pressure of 68mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 30 parts of cream of solidification, grain size 150
15 parts of purpose graphite powder, 4 parts of titanium carbide, 15 parts of 2 parts of mixture, liquid nitrile rubber, the silicon carbide of zirconium oxide or yttrium oxide are short
Cut 80 parts of the mixture of 35 parts of fiber, 15 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide.
Polyvinyl alcohol concentration is 4% in the solidification cream；It is 1500 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
The mixture of graphite powder and titanium carbide and zirconium oxide or yttrium oxide is put into star grinder by mass parts and is ground
30min, then the mixture of silicon carbide chopped strand and zinc oxide, aluminium oxide and light magnesium oxide is put into star grinder relaying
Continuous grinding 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -5.
Embodiment 6
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of resorcinols, 150 parts of furfurals and 2 parts of potassium hydroxide are reacted into 10h under the conditions of 70 DEG C, at 97 DEG C
So that reaction system is dehydrated to 1.0 ten thousand centipoises, 30 parts of resorcinols added into reaction system, reacts 7h under the conditions of 60 DEG C,
Phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 25 parts of phenylboric acids, reacts 5h under the conditions of 95 DEG C,
So that reaction system is dehydrated to 40,000 centipoises under the pressure of 70mmHg after reaction, modified boron containing phenolic resin is made.
Step 2：Following raw material is weighed by certain mass part：
25 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 35 parts of cream of solidification, grain size 150
20 parts of purpose graphite powder, mass ratio 2:7 parts of 1 titanium carbide and the mixture of zirconium oxide, 20 parts of liquid polyisoprene rubber,
100 parts of the mixture of 40 parts of carbon fiber, 20 parts of ethyl orthosilicate, iron oxide, calcium carbonate and calcium oxide.
Polyvinyl alcohol concentration is 5% in the solidification cream；It is 2000 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
Graphite powder and titanium carbide are put into zirconia blend in star grinder by mass parts and grind 30min, then will
Carbon fiber and iron oxide, calcium carbonate and calcium oxide mixture be put into star grinder continue grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid polyisoprene rubber and ethyl orthosilicate, are made the resistance to height containing graphite powder after mixing
Warm adhesive.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -6.
Embodiment 7
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of methylphenols, 50 parts of salicylides and 1 part of lithium hydroxide are reacted into 8h under the conditions of 50 DEG C, at 98 DEG C
So that reaction system is dehydrated to 0.5 ten thousand centipoises, 10 parts of methylphenols added into reaction system, reacts 8h under the conditions of 50 DEG C,
Phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15 parts of 3- methoxyphenyl-boronic acids, under the conditions of 85 DEG C
5h is reacted, reaction system is made to be dehydrated to 30,000 centipoises under the pressure of 65mmHg after reaction, modified boron containing phenolic resin is made.
Step 2：Following raw material is weighed by certain mass part：
30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 40 parts of cream of solidification, grain size 150
10 parts of purpose graphite powder, mass ratio 2:8 parts of 1 titanium carbide and the mixture of yttrium oxide, CTBN10 parts, 45 parts of glass fibre,
130 parts of the mixture of 10 parts of ethyl orthosilicate, aluminium oxide, wollastonite and boron nitride.
Polyvinyl alcohol concentration is 6% in the solidification cream；It is 1000 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
Graphite powder and titanium carbide are put into yttrium oxide mixture in star grinder by mass parts and grind 30min, then will
Glass fibre and aluminium oxide, wollastonite and boron nitride mixture be put into star grinder continue grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, CTBN and ethyl orthosilicate, are made the high-temperature resistance adhesive containing graphite powder after mixing.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -7.
Embodiment 8
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of catechols, 100 parts of acetaldehyde and 1.5 parts of magnesium hydroxides are reacted into 9h under the conditions of 60 DEG C, at 100 DEG C
Under so that reaction system is dehydrated to 0.8 ten thousand centipoises, 20 parts of catechols are added into reaction system, are reacted under the conditions of 55 DEG C
Phenolic aldehyde prepolymer is made in 5h；
(2) mass fraction is pressed to mix bromo phenylboric acid 100 parts of phenolic aldehyde prepolymers and 20 parts, it is anti-under the conditions of 90 DEG C
5h is answered, reaction system is made to be dehydrated to 3.5 ten thousand centipoises under the pressure of 68mmHg after reaction, modified boron containing phenolic resin is made.
Step 2：Following raw material is weighed by certain mass part：
15 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 45 parts of cream of solidification, grain size 150
15 parts of purpose graphite powder, mass ratio 2:9 parts of 1 titanium carbide and the mixture of zirconium oxide, ATBN15 parts, 50 parts of quartz fibre,
150 parts of the mixture of 15 parts of ethyl orthosilicate, boron carbide, zinc oxide and talcum powder.
Polyvinyl alcohol concentration is 7% in the solidification cream；It is 1500 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
Graphite powder and titanium carbide are put into zirconia blend in star grinder by mass parts and grind 30min, then will
Quartz fibre and boron carbide, zinc oxide and talcum powder mixture be put into star grinder continue grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, ATBN and ethyl orthosilicate, are made the high-temperature resistance adhesive containing graphite powder after mixing.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -8.
Embodiment 9
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of alkyl-resorcins, 150 parts of formaldehyde and 2 parts of barium hydroxides are reacted into 10h under the conditions of 70 DEG C, 95
So that reaction system is dehydrated to 0.5 ten thousand centipoises at DEG C, 30 parts of alkyl-resorcins are added into reaction system, under the conditions of 60 DEG C
6h is reacted, phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 25 parts of boric acid, reacts 5h under the conditions of 95 DEG C, react
After so that reaction system is dehydrated to 40,000 centipoises under the pressure of 70mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 50 parts of cream of solidification, grain size 150
20 parts of purpose graphite powder, mass ratio 2:1 titanium carbide and 10 parts of the mixture of zirconium oxide, HTBN20 parts, the chopped fibre of silicon carbide
180 parts of the mixture of 30 parts of dimension, 20 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide.
Polyvinyl alcohol concentration is 8% in the solidification cream；It is 2000 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
Graphite powder and titanium carbide are put into zirconia blend in star grinder by mass parts and grind 30min, then will
Silicon carbide chopped strand and zinc oxide, aluminium oxide and light magnesium oxide mixture be put into star grinder and continue to grind
30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, HTBN and ethyl orthosilicate, are made the high-temperature resistance adhesive containing graphite powder after mixing.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -9.
Embodiment 10
Steps are as follows for a kind of preparation method of the high-temperature resistance adhesive containing graphite powder：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phloroglucins, 50 parts of formaldehyde and 1 part of calcium hydroxide are reacted into 8h under the conditions of 50 DEG C, made at 98 DEG C
Reaction system is dehydrated to 10,000 centipoises, and 10 parts of phloroglucins are added into reaction system, reacts 7h under the conditions of 50 DEG C, is made
Phenolic aldehyde prepolymer；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15 parts of boric acid, reacts 5h under the conditions of 85 DEG C, react
After so that reaction system is dehydrated to 30,000 centipoises under the pressure of 65mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
25 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 25 parts of cream of solidification, grain size 150
10 parts of purpose graphite powder, mass ratio 2:1 titanium carbide and 8 parts of the mixture of zirconium oxide, 10 parts of liquid nitrile rubber, carbon fiber
35 parts, 100 parts of the mixture of 10 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide.
Polyvinyl alcohol concentration is 5% in the solidification cream；It is 2000 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
Graphite powder and titanium carbide are put into zirconia blend in star grinder by mass parts and grind 30min, then will
Carbon fiber and zinc oxide, aluminium oxide and light magnesium oxide mixture be put into star grinder continue grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive -10.
Comparative example 1：
This comparative example is differed only in embodiment 5, and graphite powder and high temperature resistant are not contained in this comparative example composition of raw materials
Filler, steps are as follows for the preparation method of specific adhesive：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxides are reacted into 9h under the conditions of 60 DEG C, made at 96 DEG C
Reaction system is dehydrated to 0.8 ten thousand centipoises, and 20 parts of phenol are added into reaction system, reacts 6h under the conditions of 55 DEG C, and phenol is made
Aldehyde prepolymer；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 20 parts of boric acid, reacts 5h under the conditions of 90 DEG C, react
After so that reaction system is dehydrated to 3.5 ten thousand centipoises under the pressure of 68mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 30 parts of cream of solidification, liquid fourth are fine
The mixture of 15 parts of rubber, 35 parts of silicon carbide chopped strand, 15 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide
80 parts.
Polyvinyl alcohol concentration is 4% in the solidification cream；It is 1500 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
The mixture of silicon carbide chopped strand and zinc oxide, aluminium oxide and light magnesium oxide is put into star grinder relaying
Continuous grinding 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive-I.
It is bonded silicon carbide and timber respectively with adhesive made from embodiment 4, embodiment 5, embodiment 6 and comparative example 1,
25 DEG C of solidifications test intensity before the shearing of each adhesive at different temperatures after 5 days, and test result is as shown in table 1：
Table 1
By the shear strength comparison of each adhesive in table 1 at different temperatures as can be seen that of the invention to contain hydroxyl
Base-material as adhesive of methyl phenyl silicone resin and modified boron containing phenolic resin, be added to high temperature cabonization material-graphite powder and
High temperature resistant filler makes organic resin be mutually crosslinked with inorganic material at curing temperatures using the effect of crosslinking agent-ethyl orthosilicate,
Adhesive strength of the adhesive under room temperature and hot environment is improved, invention adhesive is under 1000 DEG C or more of hot conditions
Remain to keep the shear strength of 1.6Mpa.
Comparative example 2：
This comparative example is differed only in embodiment 5, inorganic toughener is not contained in this comparative example composition of raw materials, specifically
Steps are as follows for the preparation method of adhesive：
Step 1：Prepare modified boron containing phenolic resin：
(1) 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxides are reacted into 9h under the conditions of 60 DEG C, made at 96 DEG C
Reaction system is dehydrated to 0.8 ten thousand centipoises, and 20 parts of phenol are added into reaction system, reacts 6h under the conditions of 55 DEG C, and phenol is made
Aldehyde prepolymer；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 20 parts of boric acid, reacts 5h under the conditions of 90 DEG C, react
After so that reaction system is dehydrated to 3.5 ten thousand centipoises under the pressure of 68mmHg, be made modified boron containing phenolic resin.
Step 2：Following raw material is weighed by certain mass part：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 30 parts of cream of solidification, grain size 150
15 parts of 2 parts of mixture, liquid nitrile rubber, the positive silicic acid second of 15 parts of purpose graphite powder, 4 parts of titanium carbide, zirconium oxide or yttrium oxide
80 parts of the mixture of 15 parts of ester, zinc oxide, aluminium oxide and light magnesium oxide.
Polyvinyl alcohol concentration is 4% in the solidification cream；It is 1500 that the preparation method of the solidification cream, which is by the degree of polymerization, alcohol
The polyethylene powder alcohol that solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is 200rmp, stirring
18h；
Step 3：Milled processed：
The mixture of graphite powder and titanium carbide and zirconium oxide or yttrium oxide is put into star grinder by mass parts and is ground
30min, then the mixture of zinc oxide, aluminium oxide and light magnesium oxide is put into star grinder and continues to grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron is added by mass parts
Phenolic resin, solidification cream, liquid nitrile rubber and ethyl orthosilicate, are made the high temperature resistant gluing containing graphite powder after mixing
Agent.
The preparation method of high-temperature resistance adhesive containing graphite powder of the present embodiment a kind of is prepared a kind of containing graphite powder
High-temperature resistance adhesive-II.
It is bonded silicon carbide and timber respectively with adhesive made from embodiment 4, embodiment 5, embodiment 6 and comparative example 1,
25 DEG C of solidifications test the elongation at break of each adhesive at different temperatures after 5 days, and test result is as shown in table 2：
Table 2
By the elongation at break comparison of each adhesive in table 2 at different temperatures as can be seen that the present invention passes through crosslinking
The effect of agent-ethyl orthosilicate makes the methyl phenyl silicone resin containing hydroxyl, boron bakelite resin with inorganic toughener in solidification temperature
Degree is lower to be mutually crosslinked, and inorganic toughener makes invention adhesive at normal temperatures with higher tough with liquid toughener
Property, it remains to keep good toughness under 1000 DEG C of hot environments.
Claims (9)
1. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder, it is characterised in that the adhesive preparation method step
It is as follows：
Step 1：Prepare modified boron containing phenolic resin：
(1) phenolic compound, aldehyde compound and catalyst are reacted to 8~10h under the conditions of 50-70 DEG C, at 95~100 DEG C
So that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises, a certain amount of identical phenolic compound is added into reaction system, 50
5~8h is reacted under the conditions of~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) mass parts are pressed to mix phenolic aldehyde prepolymer and boron compound, reacts 5h under the conditions of 85~95 DEG C, after reaction
So that reaction system is dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg, modified boron containing phenolic resin is made；
Step 2：Following raw material is weighed by certain mass part：
Methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, solidification cream, graphite powder, high temperature resistant filler, liquid toughening
Agent, inorganic toughener, ethyl orthosilicate and filler；
Step 3：Milled processed：
Graphite powder and high temperature resistant filler are put into star grinder by mass parts and grind 30min, then by inorganic toughener and is filled out
Material, which is put into star grinder, to be continued to grind 30min；
Step 4：Prepare the high-temperature resistance adhesive containing graphite powder：
The abrasive material that step 3 obtains is taken out and the methyl phenyl silicone resin containing hydroxyl, modified boron phenolic is added by mass parts
Resin, solidification cream, liquid toughener and ethyl orthosilicate, are made the high-temperature resistance adhesive containing graphite powder after mixing.
2. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 1, it is characterised in that step
One (1) reactive phenolic compounds are phenol, resorcinol, methylphenol, catechol, alkyl-resorcin, isophthalic three
The mixture of one or more of phenol or hydroquinone；The aldehyde compound is in formaldehyde, furfural, salicylide or acetaldehyde
One or more of mixtures；The mass ratio of the phenolic compound and the aldehyde compound is 2:1~3；The catalyst
For one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide or ammonium chloride
Mixture, the quality of the catalyst is the 1~2% of phenolic compound quality；Step 1 (2) described boron compound is boron
Acid, phenylboric acid, 3- methoxyphenyl-boronic acids or the mixture to one or more of bromo phenylboric acid, the phenolic aldehyde are pre-
The mass ratio of polymers and boron compound is 20:3~5.
3. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 2, it is characterised in that step
Two each material quality parts are as follows：15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl,
Cure 25~50 parts of cream, 10~20 parts of graphite powder, 5~10 parts of high temperature resistant filler, 10~20 parts of liquid toughener, inorganic toughener
50~180 parts of 30~50 parts, 10~20 parts of ethyl orthosilicate and filler.
4. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 3, it is characterised in that step
Polyvinyl alcohol concentration is 3~8% in the two solidification cream；It is described solidification cream preparation method be by the degree of polymerization be 1000~
2000, the polyethylene powder alcohol that alcohol solubility is 88% is added portionwise into 20 DEG C of formalin, and control mixing speed is
200rmp stirs 18h.
5. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 4, it is characterised in that step
The grain size of two graphite powders is 150 mesh；The high temperature resistant filler is titanium carbide and a kind of composition in zirconium oxide or yttrium oxide
Mixture, wherein titanium carbide than the mass ratio of zirconium oxide or yttrium oxide be 2:1.
6. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 5, it is characterised in that step
The two liquid toughener are liquid nitrile rubber, liquid polyisoprene rubber, one kind in CTBN, ATBN or HTBN or several
The mixture of kind；Inorganic toughener is one or more of silicon carbide chopped strand, carbon fiber, glass fibre or quartz fibre
Mixture.
7. a kind of preparation method of the high-temperature resistance adhesive containing graphite powder according to claim 6, it is characterised in that step
Two fillers are zinc oxide, iron oxide, iron powder, mica powder, talcum powder, calcium carbonate, calcium sulfate crystal whiskers, glass putty, lightweight oxidation
Magnesium, zinc powder, calcium oxide, aluminium powder, fossil meal, titanium dioxide, aluminium oxide, kaolin, antimony oxide, wollastonite, calcite, ceramics
The mixture of one or more of powder, boron nitride or boron carbide.
8. one kind prepared by the preparation method based on any high-temperature resistance adhesives containing graphite powder of claim 1-7 contains
The high-temperature resistance adhesive of graphite powder, it is characterised in that the adhesive includes the component of following mass parts：
15~30 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 25~50 parts of cream of solidification, graphite
10~20 parts of powder, mass ratio 2:1 titanium carbide and zirconium oxide or 5~10 parts of mixture, the liquid nitrile rubber 10 of yttrium oxide
~20 parts, 30~50 parts of silicon carbide chopped strand, 10~20 parts of ethyl orthosilicate, zinc oxide, aluminium oxide and light magnesium oxide
50~180 parts of mixture；
The preparation method of the modified boron containing phenolic resin is as follows：
(1) 100 parts of phenol, 50~150 parts of formaldehyde and 1~2 part of sodium hydroxide are reacted into 8~10h under the conditions of 50-70 DEG C,
So that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, 10-30 parts of phenol is added into reaction system, 50
5~8h is reacted under the conditions of~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boric acid, reacts 5h under the conditions of 85~95 DEG C,
So that reaction system is dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, modified boron phenolic tree is made
Fat.
9. one kind prepared by the preparation method based on any high-temperature resistance adhesives containing graphite powder of claim 1-7 contains
The high-temperature resistance adhesive of graphite powder, it is characterised in that the adhesive includes the component of following mass parts：
20 parts of 100 parts of methyl phenyl silicone resin, modified boron containing phenolic resin containing hydroxyl, 30 parts of cream of solidification, 15 parts of graphite powder, carbon
Change 4 parts of titanium, 2 parts of zirconium oxide or yttrium oxide, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped strand, 15 parts of ethyl orthosilicate,
80 parts of the mixture of zinc oxide, aluminium oxide and light magnesium oxide；
The preparation method of the modified boron containing phenolic resin is as follows：
(1) 100 parts of phenol, 50~150 parts of formaldehyde and 1~2 part of sodium hydroxide are reacted into 8~10h under the conditions of 50-70 DEG C,
So that reaction system is dehydrated to 0.5~1.0 ten thousand centipoises at 95~100 DEG C, 10-30 parts of phenol is added into reaction system, 50
5~8h is reacted under the conditions of~60 DEG C, and phenolic aldehyde prepolymer is made；
(2) it presses mass fraction to mix 100 parts of phenolic aldehyde prepolymers and 15~25 parts of boric acid, reacts 5h under the conditions of 85~95 DEG C,
So that reaction system is dehydrated to 3.0~4.0 ten thousand centipoises under the pressure of 65~70mmHg after reaction, modified boron phenolic tree is made
Fat.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110093142A (en) * | 2019-05-29 | 2019-08-06 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of the organosilicon adhesive for being resistant to 1500 DEG C of ablations of normal temperature cure |
| CN115322699A (en) * | 2022-07-26 | 2022-11-11 | 成都航天明江科技实业有限公司 | Pressure-sensitive adhesive tape with instant high temperature resistance of 550 DEG C |
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| CN115322699A (en) * | 2022-07-26 | 2022-11-11 | 成都航天明江科技实业有限公司 | Pressure-sensitive adhesive tape with instant high temperature resistance of 550 DEG C |
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