CN108314987B - High-temperature-resistant adhesive containing graphite powder and preparation method thereof - Google Patents

High-temperature-resistant adhesive containing graphite powder and preparation method thereof Download PDF

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CN108314987B
CN108314987B CN201810144696.3A CN201810144696A CN108314987B CN 108314987 B CN108314987 B CN 108314987B CN 201810144696 A CN201810144696 A CN 201810144696A CN 108314987 B CN108314987 B CN 108314987B
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graphite powder
temperature
phenolic resin
preparation
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CN108314987A (en
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陈瑞
陈庚
韩玉凤
陈硕
张岩
崔广宏
王景柱
韩玉芝
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Heilongjiang Aoxing Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention belongs to the field of adhesives, and particularly relates to a high-temperature-resistant adhesive containing graphite powder and a preparation method thereof. The preparation method of the adhesive comprises the following steps: preparing modified boron phenolic resin, and step two: weighing the following raw materials: methyl phenyl silicone resin containing hydroxyl, modified boron phenolic resin, curing paste, graphite powder, high-temperature-resistant filler, liquid toughening agent, inorganic toughening agent, ethyl orthosilicate and filler, and the third step is that: grinding treatment, step four: preparing the high-temperature-resistant adhesive containing graphite powder. The invention takes methyl phenyl silicon resin containing hydroxyl and modified phenol formaldehyde resin as the base materials of the adhesive, adds high temperature carbonization material-graphite powder and high temperature resistant filler, and utilizes a cross-linking agent-tetraethoxysilane to cross-link organic resin and inorganic material at the curing temperature, thereby improving the bonding strength of the adhesive under the normal temperature and high temperature environment, and the adhesive can still maintain the shear strength of 1.6Mpa under the high temperature condition of more than 1000 ℃.

Description

High-temperature-resistant adhesive containing graphite powder and preparation method thereof
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a high-temperature-resistant adhesive containing graphite powder and a preparation method thereof.
Background
The phenolic resin adhesive is prepared by performing polycondensation, neutralization and washing on phenol and formaldehyde under the condition of a catalyst, has the characteristics of high carbon forming property, good bonding capability, water resistance, heat resistance and chemical resistance, and is mainly used for bonding wood, foamed plastics and other porous materials. However, the phenolic resin adhesive needs to be heated and pressurized for curing in the using process, the glue line of the cured phenolic resin adhesive is brittle, the heat stability and the high temperature resistance of the pure phenolic resin adhesive are not high enough, and other high molecular compounds are commonly used for improving the performance of the phenolic resin adhesive so as to improve the heat resistance and the bonding strength of the phenolic resin adhesive.
Compared with the common phenolic resin, the boron phenolic resin has more excellent heat resistance, instantaneous high temperature resistance and mechanical property, and is an excellent ablation-resistant material. Boron phenolic resin as an organic adhesive has high bonding strength and good toughness, but cannot meet the technical requirement of resisting heat of more than 1000 ℃, and the heat resistance of an adhesive taking boron phenolic as a base material is only 500 ℃.
In addition, the curing temperature of the boron phenolic resin is generally higher than 160 ℃, which limits the application of the boron phenolic resin in the field of low-temperature curing.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a high-temperature-resistant adhesive containing graphite powder and a preparation method thereof.
The technical scheme of the invention is as follows:
the preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting a phenolic compound, an aldehyde compound and a catalyst at 50-70 ℃ for 8-10 h, dehydrating the reaction system to 0.5-1.0 ten thousand centipoise at 95-100 ℃, adding a certain amount of the same phenolic compound into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing the phenolic aldehyde prepolymer and a boron compound according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to prepare modified boron phenolic resin;
step two: weighing the following raw materials in parts by mass:
methyl phenyl silicone resin containing hydroxyl, modified boron phenolic resin, curing paste, graphite powder, high-temperature-resistant filler, liquid-state toughening agent, inorganic toughening agent, ethyl orthosilicate and filler;
step three: grinding treatment:
putting graphite powder and high-temperature-resistant filler into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then putting inorganic toughening agent and filler into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid flexibilizer and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
Further, the active phenolic compound in the step one (1) is one or a mixture of more of phenol, resorcinol, methyl phenol, catechol, alkyl resorcinol, phloroglucinol or hydroquinone; the aldehyde compound is one or a mixture of more of formaldehyde, furfural, salicylaldehyde or acetaldehyde; the mass ratio of the phenolic compound to the aldehyde compound is 2: 1-3; the catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide or ammonium chloride, and the mass of the catalyst is 1-2% of that of the phenolic compound; the boron compound in the step one (2) is one or a mixture of boric acid, phenyl boric acid, 3-methoxy phenyl boric acid or p-bromo phenyl boric acid, and the mass ratio of the phenolic aldehyde prepolymer to the boron compound is 20: 3-5.
Further, the raw materials in the second step are as follows in parts by mass: 100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder, 5-10 parts of high-temperature-resistant filler, 10-20 parts of liquid toughening agent, 30-50 parts of inorganic toughening agent, 10-20 parts of ethyl orthosilicate and 50-180 parts of filler.
Further, the concentration of polyvinyl alcohol in the curing paste in the second step is 3-8%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with polymerization degree of 1000-2000 and alcohol solubility of 88% into formaldehyde solution at 20 ℃ in batches, controlling stirring speed to be 200rmp, and stirring for 18 hours.
Further, the particle size of the graphite powder in the second step is 150 meshes; the high-temperature-resistant filler is a mixture of titanium carbide and one of zirconia or yttria, wherein the mass ratio of the titanium carbide to the zirconia or yttria is 2: 1.
Further, the liquid toughening agent in the second step is one or a mixture of more of liquid nitrile rubber, liquid polyisoprene rubber, CTBN, ATBN or HTBN; the inorganic toughening agent is one or a mixture of more of silicon carbide chopped fibers, carbon fibers, glass fibers or quartz fibers.
Further, the filler in the second step is one or a mixture of more of zinc oxide, iron powder, mica powder, talcum powder, calcium carbonate, calcium sulfate whisker, tin powder, light magnesium oxide, zinc powder, calcium oxide, aluminum powder, fossil powder, titanium dioxide, aluminum oxide, kaolin, antimony trioxide, wollastonite, calcite, ceramic powder, boron nitride or boron carbide.
The high-temperature-resistant adhesive containing graphite powder is prepared by a preparation method of the high-temperature-resistant adhesive containing graphite powder, and is characterized by comprising the following components in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder, 5-10 parts of a mixture of titanium carbide and zirconium oxide or yttrium oxide in a mass ratio of 2:1, 10-20 parts of liquid nitrile rubber, 30-50 parts of silicon carbide chopped fibers, 10-20 parts of ethyl orthosilicate, and 50-180 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide;
the preparation method of the modified boron phenolic resin comprises the following steps:
(1) reacting 100 parts of phenol, 50-150 parts of formaldehyde and 1-2 parts of sodium hydroxide at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of phenol into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boric acid according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to obtain the modified boron phenolic resin.
The high-temperature-resistant adhesive containing graphite powder is prepared by a preparation method of the high-temperature-resistant adhesive containing graphite powder, and is characterized by comprising the following components in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron-phenolic resin, 30 parts of curing paste, 15 parts of graphite powder, 4 parts of titanium carbide, 2 parts of zirconia or yttria, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped fiber, 15 parts of tetraethoxysilane, 80 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide;
the preparation method of the modified boron phenolic resin comprises the following steps:
(1) reacting 100 parts of phenol, 50-150 parts of formaldehyde and 1-2 parts of sodium hydroxide at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of phenol into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boric acid according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to obtain the modified boron phenolic resin.
The invention has the beneficial effects that:
the adhesive uses methyl phenyl silicon resin containing hydroxyl and modified boron phenolic resin as base materials of the adhesive, is added with high-temperature carbonized material-graphite powder and high-temperature resistant filler, and utilizes the action of a cross-linking agent-tetraethoxysilane to cross-link organic resin and inorganic material at a curing temperature, so that the bonding strength of the adhesive under normal temperature and high temperature environment is improved, and the adhesive can still maintain the shear strength of 1.6Mpa under the high temperature condition of more than 1000 ℃.
Secondly, in the process of preparing the adhesive, a large amount of free formaldehyde contained in the curing paste is utilized to carry out normal-temperature curing on the boron phenolic resin, and the prepared adhesive can be cured under the normal-temperature condition and obtains good bonding strength.
The methyl phenyl silicone resin containing hydroxyl, the boron phenolic resin and the inorganic toughening agent are crosslinked at the curing temperature under the action of the crosslinking agent-tetraethoxysilane, and the inorganic toughening agent and the liquid toughening agent are compounded for use, so that the adhesive has higher toughness at normal temperature and can still maintain good toughness in a high-temperature environment of 1000 ℃.
The adhesive shows excellent bonding performance of the organic adhesive at the temperature of below 500 ℃ by combining the organic resin with inorganic materials such as graphite powder, high-temperature-resistant filler and the like; the inorganic adhesive has heat resistance at a high temperature of more than 500 ℃, has good toughness at a high temperature, and can meet the requirements of good toughness and high bonding strength of the adhesive at the high temperature.
The preparation method of the high-temperature-resistant adhesive containing graphite powder has the advantages of low cost of raw materials, simple process and easy operation, and the prepared high-temperature-resistant adhesive containing graphite powder has strong adaptability to a curing environment in the use process, low operation requirement and convenient use, and can be normally coated by only uniformly mixing the components of the adhesive.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting a phenolic compound, an aldehyde compound and a catalyst at 50-70 ℃ for 8-10 h, dehydrating the reaction system to 0.5-1.0 ten thousand centipoise at 95-100 ℃, adding a certain amount of the same phenolic compound into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing the phenolic aldehyde prepolymer and a boron compound according to the mass part, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to prepare modified boron phenolic resin;
step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder, 5-10 parts of high-temperature-resistant filler, 10-20 parts of liquid toughening agent, 30-50 parts of inorganic toughening agent, 10-20 parts of ethyl orthosilicate and 50-180 parts of filler;
step three: grinding treatment:
putting graphite powder and high-temperature-resistant filler into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then putting inorganic toughening agent and filler into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid flexibilizer and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive-1 containing graphite powder is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
Example 2
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenolic compound, 50-150 parts of aldehyde compound and 1-2 parts of catalyst at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of the same phenolic compound into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
the active phenolic compound is one or a mixture of more of phenol, resorcinol, methyl phenol, catechol, alkyl resorcinol, phloroglucinol or hydroquinone; the aldehyde compound is one or a mixture of more of formaldehyde, furfural, salicylaldehyde or acetaldehyde; the catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide or ammonium chloride;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boron compound according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to prepare modified boron phenolic resin; the boron compound is one or a mixture of boric acid, phenyl boric acid, 3-methoxy phenyl boric acid or p-bromo phenyl boric acid.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder with the particle size of 150 meshes, 5-10 parts of high-temperature-resistant filler, 10-20 parts of liquid toughening agent, 30-50 parts of inorganic toughening agent, 10-20 parts of ethyl orthosilicate and 50-180 parts of filler.
The concentration of polyvinyl alcohol in the curing paste is 3-8%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with polymerization degree of 1000-2000 and alcohol solubility of 88% into formaldehyde solution at 20 ℃ in batches, controlling stirring speed to be 200rmp, and stirring for 18 hours;
the high-temperature-resistant filler is a mixture of titanium carbide and one of zirconia or yttria, wherein the mass ratio of the titanium carbide to the zirconia or yttria is 2: 1;
the liquid toughening agent is one or a mixture of more of liquid nitrile rubber, liquid polyisoprene rubber, CTBN, ATBN or HTBN; the inorganic toughening agent is one or a mixture of more of silicon carbide chopped fibers, carbon fibers, glass fibers or quartz fibers;
the filler is one or a mixture of more of zinc oxide, iron powder, mica powder, talcum powder, calcium carbonate, calcium sulfate whisker, tin powder, light magnesium oxide, zinc powder, calcium oxide, aluminum powder, fossil powder, titanium dioxide, aluminum oxide, kaolin, antimony trioxide, wollastonite, calcite, ceramic powder, boron nitride or boron carbide;
step three: grinding treatment:
putting graphite powder and high-temperature-resistant filler into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then putting inorganic toughening agent and filler into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid flexibilizer and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive-2 containing graphite powder is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
Example 3
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenol, 50-150 parts of formaldehyde and 1-2 parts of sodium hydroxide at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of phenol into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boric acid according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to obtain the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder with the particle size of 150 meshes, 5-10 parts of a mixture of titanium carbide and zirconia or yttria in a mass ratio of 2:1, 10-20 parts of liquid nitrile rubber, 30-50 parts of silicon carbide chopped fibers, 10-20 parts of ethyl orthosilicate, and 50-180 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 3-8%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with polymerization degree of 1000-2000 and alcohol solubility of 88% into formaldehyde solution at 20 ℃ in batches, controlling stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
placing the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then placing the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder-3 is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
Example 4
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenol, 50 parts of formaldehyde and 1 part of sodium hydroxide at 50 ℃ for 8 hours, dehydrating the reaction system at 95 ℃ to 0.5 ten thousand centipoise, adding 10 parts of phenol into the reaction system, and reacting at 50 ℃ for 5 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15 parts of boric acid according to the mass parts, reacting for 5 hours at 85 ℃, and dehydrating the reaction system to 3.0 ten thousand centipoise under the pressure of 65mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15 parts of modified boron phenolic resin, 25 parts of curing paste, 10 parts of graphite powder with the particle size of 150 meshes, 5 parts of a mixture of titanium carbide and zirconia or yttria in a mass ratio of 2:1, 10 parts of liquid nitrile rubber, 30 parts of silicon carbide chopped fibers, 10 parts of ethyl orthosilicate, and 50 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 3%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1000 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
placing the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then placing the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder-4 is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
Example 5
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxide at 60 ℃ for 9 hours, dehydrating the reaction system to 0.8 ten thousand centipoise at 96 ℃, adding 20 parts of phenol into the reaction system, and reacting at 55 ℃ for 6 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 20 parts of boric acid according to the mass parts, reacting for 5 hours at 90 ℃, and dehydrating the reaction system to 3.5 ten thousand centipoise under the pressure of 68mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron phenolic resin, 30 parts of curing paste, 15 parts of graphite powder with the particle size of 150 meshes, 4 parts of titanium carbide, 2 parts of a mixture of zirconium oxide or yttrium oxide, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped fibers, 15 parts of ethyl orthosilicate, and 80 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 4%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1500 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
placing the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine according to the mass parts for grinding for 30min, and then placing the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder is 5.
Example 6
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of resorcinol, 150 parts of furfural and 2 parts of potassium hydroxide at 70 ℃ for 10 hours, dehydrating a reaction system at 97 ℃ to 1.0 ten thousand centipoise, adding 30 parts of resorcinol into the reaction system, and reacting at 60 ℃ for 7 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 25 parts of phenyl boric acid according to the mass parts, reacting for 5 hours at the temperature of 95 ℃, and dehydrating a reaction system to 4 ten thousand centipoise under the pressure of 70mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 25 parts of modified boron phenolic resin, 35 parts of curing paste, 20 parts of graphite powder with the particle size of 150 meshes, 7 parts of a mixture of titanium carbide and zirconia in a mass ratio of 2:1, 20 parts of liquid polyisoprene rubber, 40 parts of carbon fiber, 20 parts of ethyl orthosilicate, and 100 parts of a mixture of iron oxide, calcium carbonate and calcium oxide.
The concentration of polyvinyl alcohol in the curing paste is 5%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 2000 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
grinding the mixture of graphite powder, titanium carbide and zirconium oxide in a star-shaped grinding machine for 30min, and then grinding the mixture of carbon fibers, iron oxide, calcium carbonate and calcium oxide in the star-shaped grinding machine for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding methyl phenyl silicone resin containing hydroxyl, modified boron phenolic resin, curing paste, liquid polyisoprene rubber and tetraethoxysilane in parts by mass, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder, which is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder in the embodiment, is the-6.
Example 7
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of methylphenol, 50 parts of salicylaldehyde and 1 part of lithium hydroxide at 50 ℃ for 8 hours, dehydrating the reaction system at 98 ℃ to 0.5 ten thousand centipoise, adding 10 parts of methylphenol into the reaction system, and reacting at 50 ℃ for 8 hours to obtain a phenolic aldehyde prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15 parts of 3-methoxyphenylboronic acid in parts by mass, reacting for 5 hours at 85 ℃, and dehydrating a reaction system to 3 ten thousand centipoise under the pressure of 65mmHg after the reaction is finished to obtain the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 30 parts of modified boron phenolic resin, 40 parts of curing paste, 10 parts of graphite powder with the particle size of 150 meshes, 8 parts of a mixture of titanium carbide and yttrium oxide with the mass ratio of 2:1, 8 parts of CTBN10 parts, 45 parts of glass fiber, 10 parts of ethyl orthosilicate, and 130 parts of a mixture of aluminum oxide, wollastonite and boron nitride.
The concentration of polyvinyl alcohol in the curing paste is 6%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1000 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
grinding the mixture of graphite powder, titanium carbide and yttrium oxide in parts by mass in a star-shaped grinding machine for 30min, and then grinding the mixture of glass fiber, alumina, wollastonite and boron nitride in the star-shaped grinding machine for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, CTBN and ethyl orthosilicate in parts by mass, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder is 7.
Example 8
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of catechol, 100 parts of acetaldehyde and 1.5 parts of magnesium hydroxide at 60 ℃ for 9 hours, dehydrating the reaction system at 100 ℃ to 0.8 ten thousand centipoise, adding 20 parts of catechol into the reaction system, and reacting at 55 ℃ for 5 hours to obtain a phenolic aldehyde prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 20 parts of p-bromophenyl boric acid according to the mass parts, reacting for 5 hours at 90 ℃, and dehydrating a reaction system to 3.5 ten thousand centipoise under the pressure of 68mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15 parts of modified boron phenolic resin, 45 parts of curing paste, 15 parts of graphite powder with the particle size of 150 meshes, 9 parts of a mixture of titanium carbide and zirconia in a mass ratio of 2:1, 15 parts of ATBN, 50 parts of quartz fiber, 15 parts of ethyl orthosilicate, and 150 parts of a mixture of boron carbide, zinc oxide and talcum powder.
The concentration of polyvinyl alcohol in the curing paste is 7%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1500 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
grinding the mixture of graphite powder, titanium carbide and zirconia in a star-shaped grinding machine for 30min, and then grinding the mixture of quartz fiber, boron carbide, zinc oxide and talcum powder in the star-shaped grinding machine for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, ATBN and ethyl orthosilicate in parts by mass, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder-8 is provided by the embodiment.
Example 9
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of alkyl resorcinol, 150 parts of formaldehyde and 2 parts of barium hydroxide at 70 ℃ for 10 hours, dehydrating a reaction system at 95 ℃ to 0.5 ten thousand centipoise, adding 30 parts of alkyl resorcinol into the reaction system, and reacting at 60 ℃ for 6 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 25 parts of boric acid according to the mass parts, reacting for 5 hours at 95 ℃, and dehydrating the reaction system to 4 ten thousand centipoise under the pressure of 70mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron phenolic resin, 50 parts of curing paste, 20 parts of graphite powder with the particle size of 150 meshes, 10 parts of a mixture of titanium carbide and zirconia in a mass ratio of 2:1, 20 parts of HTBN, 30 parts of silicon carbide chopped fibers, 20 parts of ethyl orthosilicate and 180 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 8%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 2000 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
putting the graphite powder, the mixture of titanium carbide and zirconia into a star-shaped grinding machine according to the mass parts, grinding for 30min, putting the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine, and continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the HTBN and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder-9 is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
Example 10
The preparation method of the high-temperature-resistant adhesive containing graphite powder comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phloroglucinol, 50 parts of formaldehyde and 1 part of calcium hydroxide at 50 ℃ for 8 hours, dehydrating a reaction system at 98 ℃ to 1 ten thousand centipoise, adding 10 parts of phloroglucinol into the reaction system, and reacting at 50 ℃ for 7 hours to obtain a phenolic aldehyde prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15 parts of boric acid according to the mass parts, reacting for 5 hours at 85 ℃, and dehydrating the reaction system to 3 ten thousand centipoise under the pressure of 65mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 25 parts of modified boron phenolic resin, 25 parts of curing paste, 10 parts of graphite powder with the particle size of 150 meshes, 8 parts of a mixture of titanium carbide and zirconia in a mass ratio of 2:1, 10 parts of liquid nitrile rubber, 35 parts of carbon fiber, 10 parts of ethyl orthosilicate, and 100 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 5%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 2000 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
grinding the graphite powder, the mixture of titanium carbide and zirconia in a star-shaped grinding machine for 30min, and then putting the mixture of carbon fibers, zinc oxide, aluminum oxide and light magnesium oxide in the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder is-10.
Comparative example 1:
the difference between the comparative example and the example 5 is that the raw material formula of the comparative example does not contain graphite powder and high-temperature-resistant filler, and the preparation method of the specific adhesive comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxide at 60 ℃ for 9 hours, dehydrating the reaction system to 0.8 ten thousand centipoise at 96 ℃, adding 20 parts of phenol into the reaction system, and reacting at 55 ℃ for 6 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 20 parts of boric acid according to the mass parts, reacting for 5 hours at 90 ℃, and dehydrating the reaction system to 3.5 ten thousand centipoise under the pressure of 68mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron phenolic resin, 30 parts of curing paste, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped fiber, 15 parts of tetraethoxysilane, and 80 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 4%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1500 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
placing the mixture of the silicon carbide chopped fibers and the zinc oxide, the aluminum oxide and the light magnesium oxide into a star-shaped grinding machine to continuously grind for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The high-temperature-resistant adhesive containing graphite powder-I is prepared by the preparation method of the high-temperature-resistant adhesive containing graphite powder.
The adhesives prepared in example 4, example 5, example 6, and comparative example 1 were used to bond silicon carbide and wood, respectively, and the pre-shear strength of each adhesive was tested at different temperatures after curing for 5 days at 25 ℃ with the results shown in table 1:
TABLE 1
Figure GDA0002662542560000131
As can be seen from the comparison of the shear strength of the adhesives in the table 1 at different temperatures, the invention takes the methyl phenyl silicone resin containing hydroxyl and the modified boron phenolic resin as the base materials of the adhesives, adds the high-temperature carbonized material-graphite powder and the high-temperature resistant filler, and utilizes the action of the cross-linking agent-tetraethoxysilane to cross-link the organic resin and the inorganic material at the curing temperature, thereby improving the bonding strength of the adhesives at normal temperature and high temperature, and the adhesives of the invention can still maintain the shear strength of 1.6Mpa at the high temperature of more than 1000 ℃.
Comparative example 2:
the difference between the comparative example and the example 5 is that the raw material formula of the comparative example does not contain an inorganic toughening agent, and the preparation method of the specific adhesive comprises the following steps:
the method comprises the following steps: preparing modified boron phenolic resin:
(1) reacting 100 parts of phenol, 100 parts of formaldehyde and 1.5 parts of sodium hydroxide at 60 ℃ for 9 hours, dehydrating the reaction system to 0.8 ten thousand centipoise at 96 ℃, adding 20 parts of phenol into the reaction system, and reacting at 55 ℃ for 6 hours to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 20 parts of boric acid according to the mass parts, reacting for 5 hours at 90 ℃, and dehydrating the reaction system to 3.5 ten thousand centipoise under the pressure of 68mmHg after the reaction is finished to prepare the modified boron phenolic resin.
Step two: weighing the following raw materials in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron phenolic resin, 30 parts of curing paste, 15 parts of graphite powder with the particle size of 150 meshes, 4 parts of titanium carbide, 2 parts of a mixture of zirconium oxide or yttrium oxide, 15 parts of liquid nitrile rubber, 15 parts of ethyl orthosilicate, and 80 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide.
The concentration of polyvinyl alcohol in the curing paste is 4%; the preparation method of the solidified paste comprises the steps of adding powdery polyvinyl alcohol with the polymerization degree of 1500 and the alcohol solubility of 88% into formaldehyde solution at the temperature of 20 ℃ in batches, controlling the stirring speed to be 200rmp, and stirring for 18 hours;
step three: grinding treatment:
putting the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine according to the mass parts for grinding for 30min, and putting the mixture of zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min;
step four: preparing a high-temperature-resistant adhesive containing graphite powder:
and taking out the ground material obtained in the third step, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid butadiene-acrylonitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing graphite powder.
The embodiment provides a high-temperature-resistant adhesive-II containing graphite powder, which is prepared by a preparation method of the high-temperature-resistant adhesive containing graphite powder.
The adhesives prepared in example 4, example 5, example 6, and comparative example 2 were used to bond silicon carbide and wood, respectively, and the elongation at break of each adhesive was measured at different temperatures after curing at 25 ℃ for 5 days, and the results are shown in table 2:
TABLE 2
Figure GDA0002662542560000141
As can be seen from the comparison of the elongation at break of the adhesives in Table 2 at different temperatures, the invention enables the methyl phenyl silicone resin containing hydroxyl, the boron phenolic resin and the inorganic toughening agent to be crosslinked at the curing temperature under the action of the crosslinking agent-tetraethoxysilane, and the inorganic toughening agent and the liquid toughening agent are compounded for use, so that the adhesive has higher toughness at normal temperature and can still maintain good toughness at the high temperature of 1000 ℃.

Claims (2)

1. The high-temperature-resistant adhesive containing graphite powder is characterized by comprising the following components in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 15-30 parts of modified boron phenolic resin, 25-50 parts of curing paste, 10-20 parts of graphite powder with the particle size of 150 meshes, 5-10 parts of a mixture of titanium carbide and zirconia or yttria in a mass ratio of 2:1, 10-20 parts of liquid nitrile rubber, 30-50 parts of silicon carbide chopped fibers, 10-20 parts of ethyl orthosilicate, and 50-180 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide;
the preparation method of the modified boron phenolic resin comprises the following steps:
(1) reacting 100 parts of phenol, 50-150 parts of formaldehyde and 1-2 parts of sodium hydroxide at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of phenol into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boric acid according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to prepare modified boron phenolic resin;
the concentration of polyvinyl alcohol in the curing paste is 3-8%; the preparation method of the curing paste comprises the steps of adding powdery polyvinyl alcohol with polymerization degree of 1000-2000 and alcohol solubility of 88% into formaldehyde solution at 20 ℃ in batches, controlling stirring speed to be 200rpm, and stirring for 18 hours;
the preparation method of the adhesive comprises the following steps: placing the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine for grinding for 30min, and then placing the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min; and taking out the obtained ground substance, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid nitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing the graphite powder.
2. The high-temperature-resistant adhesive containing graphite powder is characterized by comprising the following components in parts by mass:
100 parts of hydroxyl-containing methyl phenyl silicone resin, 20 parts of modified boron-phenolic resin, 30 parts of curing paste, 15 parts of graphite powder with the particle size of 150 meshes, 4 parts of titanium carbide, 2 parts of zirconia or yttria, 15 parts of liquid nitrile rubber, 35 parts of silicon carbide chopped fiber, 15 parts of ethyl orthosilicate, and 80 parts of a mixture of zinc oxide, aluminum oxide and light magnesium oxide;
the preparation method of the modified boron phenolic resin comprises the following steps:
(1) reacting 100 parts of phenol, 50-150 parts of formaldehyde and 1-2 parts of sodium hydroxide at 50-70 ℃ for 8-10 h, dehydrating the reaction system at 95-100 ℃ to 0.5-1.0 ten thousand centipoise, adding 10-30 parts of phenol into the reaction system, and reacting at 50-60 ℃ for 5-8 h to obtain a phenolic prepolymer;
(2) mixing 100 parts of phenolic aldehyde prepolymer and 15-25 parts of boric acid according to the mass parts, reacting for 5 hours at 85-95 ℃, and dehydrating a reaction system to 3.0-4.0 ten thousand centipoise under the pressure of 65-70 mmHg after the reaction is finished to prepare modified boron phenolic resin;
the concentration of polyvinyl alcohol in the curing paste is 3-8%; the preparation method of the curing paste comprises the steps of adding powdery polyvinyl alcohol with polymerization degree of 1000-2000 and alcohol solubility of 88% into formaldehyde solution at 20 ℃ in batches, controlling stirring speed to be 200rpm, and stirring for 18 hours;
the preparation method of the adhesive comprises the following steps: placing the mixture of graphite powder, titanium carbide and zirconium oxide or yttrium oxide into a star-shaped grinding machine for grinding for 30min, and then placing the mixture of silicon carbide chopped fibers and zinc oxide, aluminum oxide and light magnesium oxide into the star-shaped grinding machine for continuously grinding for 30 min; and taking out the obtained ground substance, adding the methyl phenyl silicone resin containing hydroxyl, the modified boron phenolic resin, the curing paste, the liquid nitrile rubber and the ethyl orthosilicate according to the mass parts, and uniformly mixing to obtain the high-temperature-resistant adhesive containing the graphite powder.
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