CN106753100B - Inorganic nano particle hybrid phenolic resin adhesive and preparation method thereof - Google Patents
Inorganic nano particle hybrid phenolic resin adhesive and preparation method thereof Download PDFInfo
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- C08K2003/0862—Nickel
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses an inorganic nanoparticle hybrid phenolic resin adhesive and a preparation method thereof, relates to a high-temperature-resistant phenolic resin adhesive and a preparation method thereof, and aims to solve the problems of low working temperature and poor adhesive property of the existing modified phenolic resin. The inorganic nanoparticle hybrid phenolic resin adhesive is prepared from 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nanoparticles and 1-5 parts by weight of coupling agent, wherein the nanoparticles are silicon dioxide, silicon carbide, metal oxide powder or metal powder, and the thermosetting nitrile-based phenolic resin is prepared from thermosetting phenolic resin and 4-nitrophthalonitrile through chemical reaction. The shear strength of the phenolic resin adhesive reaches about 10MPa at room temperature and about 7MPa at 350 ℃, and the phenolic resin adhesive shows good temperature resistance and toughness.
Description
Technical Field
The invention relates to a high-temperature-resistant phenolic resin adhesive and a preparation method thereof.
Background
The phenolic resin is a polymer resin variety with low price and excellent comprehensive performance, has good mechanical strength and heat resistance, particularly has outstanding instantaneous high-temperature ablation resistance, and can be used for manufacturing adhesives, coatings, composite materials and the like. For example, the product can be used as a structural composite material with instantaneous high temperature resistance and ablation for the aspects of space aircrafts, missiles and the like, and can be widely applied to the fields of aviation, aerospace, automobiles and the like as an adhesive. However, when the working temperature exceeds 300 ℃, the phenolic resin has problems of severe oxidative decomposition and the like, and the application range is limited.
Phenolic resin is divided into thermosetting and thermoplastic, and the thermoplastic phenolic resin can be crosslinked and cured by adding a curing agent. The thermosetting phenolic resin can be crosslinked into high polymer by direct heating without adding a curing agent, and has the advantages of low viscosity, strong infiltration capacity, good bonding property, large volume density, low porosity and the like. The phthalonitrile resin is a novel high-temperature resistant resin, the glass transition temperature of a condensate is more than 450 ℃, the condensate has excellent mechanical property and excellent moisture resistance and chemical corrosion resistance, and the like, and the high-temperature performance of the phenolic resin can be obviously improved by introducing the structure into a phenolic structure. For example, the heat resistance of the phthalonitrile modified thermoplastic phenolic resin which is researched more at present is obviously improved. The nano particles have the physical characteristics of unique surface effect, small size effect, quantum effect and the like, so that the properties of the nano particles, such as optical, electric, magnetic, thermal and chemical activities, are obviously different from those of a bulk substance, in addition, the surface activation centers of the nano particles are more, the performance of the polymer can be effectively improved, and the effects of strengthening, toughening, improving heat resistance and endowing special functions to the polymer are achieved.
Disclosure of Invention
The invention provides an inorganic nano particle hybrid phenolic resin adhesive and a preparation method thereof, aiming at solving the problems of low working temperature and poor adhesive property of the existing modified phenolic resin.
The inorganic nano particle hybrid phenolic resin adhesive is prepared from 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nano particles and 1-5 parts by weight of coupling agent; wherein the nano particles are one or a mixture of silicon dioxide, silicon carbide, metal oxide powder or metal powder.
Wherein the thermosetting nitrile-based phenolic resin is prepared by the chemical reaction of thermosetting phenolic resin and 4-nitrophthalonitrile.
The preparation method of the inorganic nano particle hybrid phenolic resin adhesive is realized according to the following steps:
firstly, mixing phenol and formaldehyde according to a molar ratio of 1: 1.2-2.0, adding the mixture into a reactor, starting stirring, heating to 90-100 ℃, adding an alkaline catalyst a according to 0.5-5% of the amount of phenol substances, keeping the reaction temperature at 90-100 ℃, finishing the reaction when the cloud point temperature of the reaction liquid reaches 60-80 ℃, then washing the reaction liquid for multiple times by using water, adjusting the vacuum degree to 10-5 kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain a thermosetting phenolic resin;
secondly, the molar ratio of the raw materials is 1: 3.0-7.0 adding thermosetting phenolic resin and 4-nitrophthalonitrile into a reactor, adding N, N-dimethylformamide, heating to 60-80 ℃, stirring for dissolving, adding an alkaline catalyst b, controlling the pH of the system to be 9-11, keeping the temperature for reaction for 12-18 h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to 10-5 kPa, heating for vacuum desolventizing, cooling the resin to room temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain the thermosetting nitrile-based phenolic resin;
weighing 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nano particles and 1-5 parts by weight of coupling agent;
fourthly, mixing and stirring the thermosetting nitrile-based phenolic resin, the nano particles and the coupling agent weighed in the third step uniformly to obtain an inorganic nano particle hybrid phenolic resin adhesive;
and the nano particles in the step three are one or a mixture of silicon dioxide, silicon carbide, metal oxide powder or metal powder.
The nitrile resin in the inorganic nano particle hybrid phenolic resin adhesive has good thermal stability and rigidity after being cured, and the thermosetting phenolic resin can promote the curing reaction of the nitrile resin. The inorganic nano particles endow the resin with higher toughness, so the phenolic resin adhesive has higher temperature resistance and toughness and also has good use technological performance. The inorganic nano particle hybrid phenolic resin adhesive has the shear strength of about 10MPa at room temperature, the strength improved by more than 60 percent compared with the common phenolic resin, the shear strength of about 7MPa at 350 ℃ and the adhesive bonding strength improved by more than 200 percent compared with the common phenolic resin.
Detailed Description
The first embodiment is as follows: the inorganic nanoparticle hybrid phenolic resin adhesive is prepared from 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nanoparticles and 1-5 parts by weight of coupling agent; wherein the nano particles are one or a mixture of silicon dioxide, silicon carbide, metal oxide powder or metal powder.
The thermosetting phenolic resin is phenolic resin containing a phthalonitrile structure, and inorganic nanoparticles are used for carrying out blending toughening modification on the thermosetting phenolic resin, so that the modified resin has high bonding performance and heat resistance. In this embodiment, the metal oxide powder may be titanium dioxide, zirconium oxide, or aluminum oxide, and the metal powder may be nickel, iron, or aluminum.
The second embodiment is as follows: the preparation method of the inorganic nanoparticle hybrid phenolic resin adhesive is implemented according to the following steps:
firstly, mixing phenol and formaldehyde according to a molar ratio of 1: 1.2-2.0, adding the mixture into a reactor, starting stirring, heating to 90-100 ℃, adding an alkaline catalyst a according to 0.5-5% of the amount of phenol substances, keeping the reaction temperature at 90-100 ℃, finishing the reaction when the cloud point temperature of the reaction liquid reaches 60-80 ℃, then washing the reaction liquid for multiple times by using water, adjusting the vacuum degree to 10-5 kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain a thermosetting phenolic resin;
secondly, the molar ratio of the raw materials is 1: 3.0-7.0 adding thermosetting phenolic resin and 4-nitrophthalonitrile into a reactor, adding N, N-dimethylformamide, heating to 60-80 ℃, stirring for dissolving, adding an alkaline catalyst b, controlling the pH of the system to be 9-11, keeping the temperature for reaction for 12-18 h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to 10-5 kPa, heating for vacuum desolventizing, cooling the resin to room temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain the thermosetting nitrile-based phenolic resin;
weighing 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nano particles and 1-5 parts by weight of coupling agent;
fourthly, mixing and stirring the thermosetting nitrile-based phenolic resin, the nano particles and the coupling agent weighed in the third step uniformly to obtain an inorganic nano particle hybrid phenolic resin adhesive;
and the nano particles in the step three are one or a mixture of silicon dioxide, silicon carbide, metal oxide powder or metal powder.
In the first step of the embodiment, the solid content of the thermosetting phenolic resin is controlled to be 50% -70%, and in the second step, the solid content of the thermosetting nitrile phenolic resin is controlled to be 50% -70%.
The third concrete implementation mode: the difference between the present embodiment and the second embodiment is that the basic catalyst a in the first step is one or a mixture of more of ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, zinc oxide, sodium carbonate, magnesium hydroxide and calcium hydroxide. Other steps and parameters are the same as those in the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the second or third embodiment in that the reaction solution is washed with water at 60 to 90 ℃ for 2 times. Other steps and parameters are the same as those in the second or third embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that the alkali catalyst b is added in an amount of 1-5% of the amount of the thermosetting phenol resin substance after the second embodiment is stirred and dissolved. Other steps and parameters are the same as those of one of the second to fourth embodiments.
The sixth specific implementation mode: this embodiment differs from one of the second to fifth embodiments in that the basic catalyst b in the second step is potassium carbonate, sodium carbonate or a mixture of both. Other steps and parameters are the same as those of one of the second to fifth embodiments.
The seventh embodiment: the difference between the present embodiment and one of the second to sixth embodiments is that the solvent in the first and second steps is one or more of butanone, acetone, and ethyl acetate. Other steps and parameters are the same as those of the second to sixth embodiments.
The specific implementation mode is eight: the difference between the second embodiment and the seventh embodiment is that in the third step, 100 parts by weight of thermosetting nitrile-based phenolic resin, 7-8 parts by weight of nanoparticles and 1 part by weight of coupling agent are weighed. Other steps and parameters are the same as those of the second to seventh embodiments.
The specific implementation method nine: this embodiment differs from one of the second to eighth embodiments in that the coupling agent described in step three is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacrylate) propyltrimethoxysilane, phenylaminomethyltriethoxysilane, beta-aminoethyl-gamma-aminopropyltrimethoxysilane, isopropyltrioleate acyloxytitanate titanate, a mixture of tristearate titanate isopropyl ester, tetraisopropylbis (dioctylphosphite acyloxy) titanate. Other steps and parameters are the same as those of the second to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and the second to ninth embodiments is that the nanoparticles are metal oxide powder, the metal oxide is titanium dioxide, zirconium oxide or aluminum oxide, and the particle size of the powder is 10 to 30 nm. Other steps and parameters are the same as those in one of the second to ninth embodiments.
The concrete implementation mode eleven: the second to tenth embodiments are different from the second to tenth embodiments in that the nanoparticles are metal powder, the metal powder is nickel, iron or aluminum, and the particle size of the powder is 10 to 30 nm. Other steps and parameters are the same as those in one of the second to tenth embodiments.
The specific implementation mode twelve: the difference between this embodiment and the second to the eleventh embodiment is that step four is performed by using an ultrasonic or electric stirrer to mix and stir uniformly. Other steps and parameters are the same as those in one of the second to eleventh embodiments.
The first embodiment is as follows: the preparation method of the inorganic nanoparticle hybrid phenolic resin adhesive is implemented according to the following steps:
adding 94g of phenol and 125g of formaldehyde into a reactor, starting stirring, heating to 100 ℃, adding 1g of zinc oxide, keeping the reaction temperature at 100 ℃ (reflux temperature), finishing the reaction when the cloud point temperature of the reaction solution reaches 65 ℃ (the reaction time is 5h), washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 6kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gel time of the resin reaches 180 seconds, adding an ethyl acetate solvent to obtain thermosetting phenolic resin (a tan solution), wherein the yield is 102%;
adding 40g of thermosetting phenolic resin (with a solid content of 67%) and 32g of 4-nitrophthalonitrile into a reactor, adding 160ml of N, N-dimethylformamide, controlling the pH value of a reaction solution to be 10, heating to 70 ℃, stirring to dissolve, adding 23g of alkaline catalyst potassium carbonate, keeping the temperature for reaction for 15h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid (with the concentration of 5%), separating by a separating funnel, adjusting the vacuum degree to be 6kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 180 seconds, adding the solvent to obtain the thermosetting nitrile-based phenolic resin (dark green solution), wherein the yield is 84%;
weighing 100 parts of thermosetting nitrile-based phenolic resin, 5 parts of silicon dioxide and 1 part of coupling agent gamma-aminopropyltriethoxysilane according to parts by weight;
and fourthly, mixing the thermosetting nitrile-based phenolic resin weighed in the third step, the nano particles and the coupling agent, and then uniformly stirring to obtain the inorganic nano particle hybrid phenolic resin adhesive.
The cured thermosetting nitrile-based phenolic resin obtained in the second step of the embodiment (cured at 220 ℃ for 4 hours) has a rapid thermal weight loss temperature of 620 ℃ in an air atmosphere and a residual carbon rate of 75% in a nitrogen atmosphere at 800 ℃.
The test piece for testing the performance of the inorganic nanoparticle hybrid phenolic resin adhesive in the embodiment is a carbon steel sheet, the curing temperature is 220 ℃ and the curing time is 4 hours, and the shear strength is 10.5MPa at room temperature and 7.2MPa at 350 ℃ through testing. While the shear strength of the common zinc oxide thermosetting phenolic resin is 5.68MPa at room temperature and 2.35MPa at 350 ℃. The shear strength of the nitrile-based phenolic resin which is not modified by the added nanoparticles is 7.62MPa at room temperature, and the shear strength at 350 ℃ is 4.42 MPa.
Example two: the preparation method of the inorganic nanoparticle hybrid phenolic resin adhesive is implemented according to the following steps:
adding 94g of phenol and 141g of formaldehyde into a reactor, starting stirring, heating to 100 ℃, adding 1g of zinc oxide, keeping the reaction temperature at 100 ℃ (reflux temperature), finishing the reaction when the cloud point temperature of the reaction solution reaches 65 ℃ (the reaction time is 5h), washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 6kPa, heating to perform vacuum dehydration, gradually increasing the temperature, reducing the temperature of the resin to normal temperature when the gelation time of the resin reaches 180 seconds, adding ethyl acetate serving as a solvent to obtain thermosetting phenolic resin (a tan solution), wherein the yield is 104%;
adding 58g of thermosetting phenolic resin (with a solid content of 67%) and 52g of 4-nitrophthalonitrile into a reactor, adding 160ml of N, N-dimethylformamide, controlling the pH value of a reaction solution to be 10, heating to 70 ℃, stirring to dissolve, adding 38g of alkaline catalyst potassium carbonate, keeping the temperature for reaction for 15h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid (with the concentration of 5%), separating by a separating funnel, adjusting the vacuum degree to be 6kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 180 seconds, adding the solvent to obtain the thermosetting nitrile-based phenolic resin (dark green solution), wherein the yield is 85%;
weighing 100 parts of thermosetting nitrile-based phenolic resin, 7 parts of nano particle silicon carbide and 1 part of coupling agent gamma-aminopropyl triethoxysilane according to parts by weight;
and fourthly, mixing the thermosetting nitrile-based phenolic resin weighed in the third step, the nano particles and the coupling agent, and then uniformly stirring to obtain the inorganic nano particle hybrid phenolic resin adhesive.
The cured thermosetting nitrile-based phenolic resin obtained in the second step of the embodiment (cured at 220 ℃ for 4 hours) has a rapid thermal weight loss temperature of 630 ℃ in an air atmosphere and a residual carbon rate of 78% in a nitrogen atmosphere at 800 ℃.
The inorganic nanoparticle hybrid phenolic resin adhesive of the present example has a shear strength of 9.5MPa at room temperature and a shear strength of 8.1MPa at 350 ℃.
Example three: the preparation method of the inorganic nanoparticle hybrid phenolic resin adhesive is implemented according to the following steps:
adding 94g of phenol and 168g of formaldehyde into a reactor, starting stirring, heating to 100 ℃, adding 1g of zinc oxide, keeping the reaction temperature at 100 ℃ (reflux temperature), finishing the reaction when the cloud point temperature of the reaction liquid reaches 65 ℃ (the reaction time is 5h), washing the reaction liquid for 2 times by using water, adjusting the vacuum degree to 6kPa, heating for vacuum dehydration, gradually increasing the temperature, reducing the temperature of the resin to normal temperature when the gelation time of the resin reaches 180 seconds, adding a solvent butanone to obtain a thermosetting phenolic resin (a tan solution), wherein the yield is 106%;
adding 60g of thermosetting phenolic resin (with a solid content of 67%) and 60g of 4-nitrophthalonitrile into a reactor, adding 180ml of N, N-dimethylformamide, controlling the pH value of a reaction solution to be 10, heating to 70 ℃, stirring to dissolve, adding 44g of alkaline catalyst sodium carbonate, keeping the temperature for reaction for 15h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid (with a concentration of 5%), separating with a separating funnel, adjusting the vacuum degree to 6kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 180 seconds, adding the solvent to obtain the thermosetting nitrile-based phenolic resin (dark green solution), wherein the yield is 85%;
weighing 100 parts of thermosetting nitrile-based phenolic resin, 8 parts of nano particle silicon dioxide and 1 part of coupling agent gamma-aminopropyl triethoxysilane according to parts by weight;
and fourthly, mixing the thermosetting nitrile-based phenolic resin weighed in the third step, the nano particles and the coupling agent, and then uniformly stirring to obtain the inorganic nano particle hybrid phenolic resin adhesive.
The cured thermosetting nitrile-based phenolic resin obtained in the second step of the embodiment (cured at 220 ℃ for 4 hours) has a rapid thermal weight loss temperature of 640 ℃ in an air atmosphere and a residual carbon rate of 79% in a nitrogen atmosphere at 800 ℃.
The shear strength of the inorganic nanoparticle hybrid phenolic resin adhesive of the embodiment at room temperature is 10.8MPa, and the shear strength at 350 ℃ is 7.7MPa, which shows that the adhesive has good adhesive bonding performance, and the preparation method of the adhesive is simple.
Claims (7)
1. The inorganic nanoparticle hybrid phenolic resin adhesive is characterized by being prepared from 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nanoparticles and 1-5 parts by weight of coupling agent;
the preparation method of the inorganic nano particle hybrid phenolic resin adhesive comprises the following steps:
firstly, mixing phenol and formaldehyde according to a molar ratio of 1: 1.2-2.0, adding the mixture into a reactor, starting stirring, heating to 90-100 ℃, adding an alkaline catalyst a according to 0.5-5% of the amount of phenol substances, keeping the reaction temperature at 90-100 ℃, finishing the reaction when the cloud point temperature of the reaction liquid reaches 60-80 ℃, then washing the reaction liquid for multiple times by using water, adjusting the vacuum degree to 10-5 kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain a thermosetting phenolic resin;
secondly, the molar ratio of the raw materials is 1: 3.0-7.0 adding thermosetting phenolic resin and 4-nitrophthalonitrile into a reactor, adding N, N-dimethylformamide, heating to 60-80 ℃, stirring for dissolving, adding an alkaline catalyst b, controlling the pH of the system to be 9-11, keeping the temperature for reaction for 12-18 h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to 10-5 kPa, heating for vacuum desolventizing, cooling the resin to room temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain the thermosetting nitrile-based phenolic resin;
weighing 100 parts by weight of thermosetting nitrile-based phenolic resin, 5-10 parts by weight of nano particles and 1-5 parts by weight of coupling agent;
fourthly, mixing and stirring the thermosetting nitrile-based phenolic resin, the nano particles and the coupling agent weighed in the third step uniformly to obtain an inorganic nano particle hybrid phenolic resin adhesive;
wherein the alkaline catalyst b in the second step is potassium carbonate, sodium carbonate or a mixture of the potassium carbonate and the sodium carbonate, and the alkaline catalyst b is added according to 1-5% of the amount of the thermosetting phenolic resin substances after stirring and dissolving in the second step; and step three, the nano particles are one or a mixture of silicon dioxide, silicon carbide, metal oxide powder or metal powder.
2. The inorganic nanoparticle hybrid phenolic resin adhesive according to claim 1, wherein the alkaline catalyst a in step one is one or more of ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, zinc oxide, sodium carbonate, magnesium hydroxide and calcium hydroxide.
3. The inorganic nanoparticle hybrid phenolic resin adhesive according to claim 1, wherein the solvent in the first step and the second step is one or more of butanone, acetone and ethyl acetate.
4. The inorganic nanoparticle hybrid phenolic resin adhesive according to claim 1, wherein in step three, 100 parts by weight of thermosetting nitrile-based phenolic resin, 7-8 parts by weight of nanoparticles and 1 part by weight of coupling agent are weighed.
5. The inorganic nanoparticle hybrid phenolic resin adhesive according to claim 1, wherein the coupling agent in step three is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacrylate) propyltrimethoxysilane, phenylaminomethyltriethoxysilane, beta-aminoethyl-gamma-aminopropyltrimethoxysilane, isopropyltrioleate acyloxy titanate, a mixture of isopropyl tristearate titanate and isopropyl ester, and tetraisopropyl bis (dioctylphosphite acyloxy) titanate.
6. The inorganic nanoparticle hybrid phenolic resin adhesive as claimed in claim 1, wherein the nanoparticles are metal oxide powder, the metal oxide is titanium dioxide, zirconium oxide or aluminum oxide, and the particle size of the powder is 10-30 nm.
7. The inorganic nanoparticle hybrid phenolic resin adhesive according to claim 1, wherein the step four is performed by mixing and stirring uniformly by using an ultrasonic or electric stirrer.
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