CN114539959A - Epoxy resin adhesive and preparation method thereof - Google Patents
Epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN114539959A CN114539959A CN202210307889.2A CN202210307889A CN114539959A CN 114539959 A CN114539959 A CN 114539959A CN 202210307889 A CN202210307889 A CN 202210307889A CN 114539959 A CN114539959 A CN 114539959A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Abstract
The invention relates to an epoxy resin adhesive and a preparation method thereof, wherein the epoxy resin adhesive comprises A, B components, and the A component comprises the following raw materials in parts by weight: 85-110 parts of epoxy resin, 15-25 parts of toughening filler, 5-10 parts of glycol glycidyl ether and 1-3 parts of kaolin; the epoxy resin has higher crosslinking density after being cured as a matrix, and further has good thermal stability, in addition, the epoxy resin also contains flexible group ether bonds, the molecular toughness is good, the defect of high brittleness of the epoxy resin can be overcome, the toughening filler is prepared, the toughening filler is liquid gutta-percha, the molecular structure contains epoxy groups, the chain ends are aldehyde groups and ketone groups, and the toughening filler has good compatibility with the epoxy resin, and when the liquid gutta-percha is uniformly dispersed in the epoxy resin matrix in micron-level spherical rubber particles after blending and curing, the impact strength and the shear strength of epoxy resin crosslinking grids can be improved, and the toughening effect is improved.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an epoxy resin adhesive and a preparation method thereof.
Background
The epoxy adhesive is a liquid or solid adhesive composed of epoxy resin, a curing agent, an accelerant, a modifier and the like. Because the epoxy resin contains various polar groups and epoxy groups with high activity, the epoxy resin has strong adhesive force with various polar materials such as metal, glass, cement, wood, plastics and the like, and simultaneously the cohesive strength of an epoxy cured product is also high, so the adhesive strength is high. The epoxy resin adhesive is widely applied to the industrial and living fields due to the excellent comprehensive performance of the epoxy resin adhesive. However, the epoxy resin is a linear thermoplastic substance, and a cured product obtained by adding the curing agent is in a three-dimensional network structure and is hard and brittle in nature; and the epoxy resin generates internal stress due to shrinkage in the process of forming a cured product through heating, curing and cooling, and cracks are easily generated in the cured product. Therefore, the existing epoxy resin adhesive has the great defects of poor mechanical property, particularly poor toughness, and in addition, the development of modern scientific technologies such as aviation, aerospace, electronics and the like puts higher requirements on the temperature resistance of the adhesive.
Disclosure of Invention
In order to solve the technical problems, the invention provides an epoxy resin adhesive and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an epoxy resin adhesive comprises A, B components, wherein the A component comprises the following raw materials in parts by weight: 85-110 parts of epoxy resin, 15-25 parts of toughening filler, 5-10 parts of glycol glycidyl ether and 1-3 parts of kaolin;
the component B comprises 60-70 parts of composite curing agent and 0.1-0.3 part of curing accelerator;
the epoxy resin is prepared by the following steps:
adding epoxy chloropropane and an auxiliary agent into a three-neck flask, stirring at a constant speed, heating to 65 ℃, adding 4, 4 '-diaminodiphenyl ether in equal amount twice, continuing to stir for 15min, heating to 75-80 ℃, carrying out heat preservation reaction for 4h, adding a sodium hydroxide aqueous solution with the mass fraction of 15% after the reaction is finished, cooling to 45-50 ℃, carrying out heat preservation reaction for 30min, adding an extracting agent, stirring uniformly, standing for 15min, filtering, removing water-soluble salt and an excessive sodium hydroxide solution, washing with deionized water until a washing solution is neutral, then carrying out reduced pressure, distillation and devolatilization to obtain the epoxy resin, controlling the molar ratio of epoxy chloropropane to 4, 4' -diaminodiphenyl ether to be 4: 1, controlling the amount of the auxiliary agent to be 1-1.5% of the weight of epoxy chloropropane, and controlling the molar ratio of sodium hydroxide to the epoxy chloropropane to be 6-8: 1.
Firstly, epichlorohydrin and 4, 4 '-diaminodiphenyl ether react under the action of an auxiliary agent, the epichlorohydrin is subjected to ring opening, one amino group on the 4, 4' -diaminodiphenyl ether reacts with two epoxy groups to generate an intermediate, then sodium hydroxide is added, and the two sides of the intermediate are subjected to ring closing reaction to generate epoxy resin.
Further: the toughening filler is prepared by the following steps:
sequentially adding gutta-percha and petroleum ether into a three-neck flask, heating to 55 ℃, uniformly stirring for 1h, then adding deionized water, stirring for 5min to form gutta-percha emulsion, adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, carrying out heat preservation reaction for 2h, carrying out ethanol precipitation, deionized water washing and vacuum drying after the reaction is finished to obtain modified gutta-percha, then adding the modified gutta-percha into tetrahydrofuran, uniformly stirring for 1h at room temperature, adding periodic acid, uniformly stirring and reacting for 6h, carrying out methanol precipitation, deionized water washing and vacuum drying to obtain a toughening filler, wherein the using amount ratio of the gutta-percha, the petroleum ether and the deionized water is controlled to be 5 g: 50-70 mL: 30-50mL, the molar ratio of the formic acid to the hydrogen peroxide is 1: 2, and the molar ratio of the carbon-carbon double bond to the formic acid is 1: 1;
firstly adding gutta-percha into petroleum ether, adding deionized water to prepare emulsion, then adding formic acid and hydrogen peroxide to epoxidize the gutta-percha, introducing an epoxy group into a molecular structure, then adding periodic acid to oxidize and degrade the epoxidized gutta-percha, and preparing the toughening filler, wherein the toughening filler is liquid gutta-percha, the molecular structure contains an epoxy group, and the chain end contains an aldehyde group and a ketone group, so that the toughening filler has good compatibility with epoxy resin.
Further: the composite curing agent is prepared by the following steps:
adding 2, 2 '-dimercaptoethyl sulfide, trimethylolpropane triacrylate and triethylamine into a three-neck flask, introducing nitrogen, heating to 65-75 ℃, preserving the temperature for reaction for 8 hours to obtain a reactant, adding condensed amine-105, continuously preserving the temperature and reacting for 2 hours to obtain the composite curing agent, wherein the weight ratio of the 2, 2' -dimercaptoethyl sulfide, the trimethylolpropane triacrylate, the triethylamine and the condensed amine-105 is controlled to be 7.5-10: 0.3-0.5: 50.
In the reaction process, 2' -dimercaptoethylsulfide and trimethylolpropane triacrylate are mixed, triethylamine is added as a catalyst, the reaction temperature is increased, a reactant which is polythiol with a multi-branched structure is prepared, and then an amine-105 curing agent is added for compounding, so that the composite curing agent is prepared.
The thixotropic agent is kaolin.
A preparation method of an epoxy resin adhesive comprises the following steps:
uniformly mixing the epoxy resin, the toughening filler and the kaolin, magnetically stirring for 30min, then adding ethylene glycol glycidyl ether, stirring at a high speed, heating to 55-65 ℃, carrying out heat preservation reaction for 30min, cooling and discharging to obtain a component A;
adding the composite curing agent and the curing accelerator into a stirring kettle, heating to 60-80 ℃, and stirring at a high speed for 30min to obtain the component B.
The invention has the beneficial effects that:
the epoxy resin adhesive takes epoxy resin and other raw materials as a component A, the epoxy resin is subjected to ring opening by epoxy chloropropane in the preparation process, one amino group on 4, 4' -diaminodiphenyl ether reacts with two epoxy groups to generate an intermediate, then sodium hydroxide is added, the ring closing reaction is carried out on two sides of the intermediate to generate the epoxy resin, the epoxy resin has phenyl and higher epoxy functional groups in structure, so that the epoxy resin has higher crosslinking density after being cured as a substrate, and further has good thermal stability, and in addition, the epoxy resin adhesive also contains flexible group ether bonds, has better molecular toughness, can make up the defect of high brittleness of the epoxy resin, and prepares a toughening filler which is liquid gutta-percha, contains epoxy groups in the molecular structure, and has good compatibility with the epoxy resin because the chain ends are aldehyde groups and ketone groups, after blending and curing, the liquid gutta-percha is uniformly dispersed in the epoxy resin matrix in the form of micron-level spherical rubber particles, so that the impact strength and the shear strength of the epoxy resin cross-linked grid can be improved, and the toughening effect is improved; in addition, the invention also provides a compound curing agent which is polythiol with a multi-branched structure, and then the amine-105 curing agent is added for compounding to form the compound curing agent, and the compound curing agent can play a role in fast curing by matching with the curing accelerator triethylene diamine.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The epoxy resin is prepared by the following steps:
adding epoxy chloropropane and an auxiliary agent CAT-18 into a three-neck flask, stirring at a constant speed, heating to 65 ℃, adding 4, 4 '-diaminodiphenyl ether in equal amount twice, continuing stirring for 15min, heating to 75 ℃, carrying out heat preservation reaction for 4h, adding a sodium hydroxide aqueous solution with the mass fraction of 15% after the reaction is finished, cooling to 45 ℃, carrying out heat preservation reaction for 30min, adding an extracting agent, standing for 15min after uniform stirring, filtering, removing water-soluble salt and an excessive sodium hydroxide solution, washing with deionized water until a washing solution is neutral, then carrying out reduced pressure, distillation and devolatilization to obtain the epoxy resin, controlling the molar ratio of epoxy chloropropane to 4, 4' -diaminodiphenyl ether to be 4: 1, the amount of the auxiliary agent to be 1 percent of the weight of epoxy chloropropane, and the molar ratio of sodium hydroxide to epoxy chloropropane to be 6: 1.
The toughening filler is prepared by the following steps:
sequentially adding gutta-percha and petroleum ether into a three-neck flask, heating to 55 ℃, uniformly stirring for 1h, then adding deionized water, stirring for 5min to form gutta-percha emulsion, adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, carrying out heat preservation reaction for 2h, carrying out ethanol precipitation, deionized water washing and vacuum drying after the reaction is finished to prepare modified gutta-percha, then adding the modified gutta-percha into tetrahydrofuran, uniformly stirring for 1h at room temperature, adding periodic acid, uniformly stirring and reacting for 6h, carrying out methanol precipitation, deionized water washing and vacuum drying to prepare toughening filler, controlling the dosage ratio of the gutta-percha, the petroleum ether and the deionized water to be 5 g: 50 mL: 30mL, the molar ratio of the formic acid to the hydrogen peroxide to be 1: 2, and the molar ratio of carbon-carbon double bonds to the formic acid to be 1: 1;
the composite curing agent is prepared by the following steps:
adding 2, 2 '-dimercaptoethyl sulfide, trimethylolpropane triacrylate and triethylamine into a three-neck flask, introducing nitrogen, heating to 65 ℃, preserving heat for reacting for 8 hours to obtain a reactant, adding condensed amine-105, continuously preserving heat and reacting for 2 hours to obtain a composite curing agent, wherein the weight ratio of the 2, 2' -dimercaptoethyl sulfide, the trimethylolpropane triacrylate, the triethylamine and the condensed amine-105 is controlled to be 7.5: 10: 0.3: 50.
Example 2
The epoxy resin is prepared by the following steps:
adding epoxy chloropropane and an auxiliary agent CAT-18 into a three-neck flask, stirring at a constant speed, heating to 65 ℃, adding 4, 4 '-diaminodiphenyl ether in equal amount twice, continuing stirring for 15min, heating to 75 ℃, carrying out heat preservation reaction for 4h, adding a sodium hydroxide aqueous solution with the mass fraction of 15% after the reaction is finished, cooling to 48 ℃, carrying out heat preservation reaction for 30min, adding an extracting agent, standing for 15min after uniform stirring, filtering, removing water-soluble salt and an excessive sodium hydroxide solution, washing with deionized water until a washing solution is neutral, then carrying out reduced pressure, distillation and devolatilization to obtain the epoxy resin, controlling the molar ratio of epoxy chloropropane to 4, 4' -diaminodiphenyl ether to be 4: 1, the amount of the auxiliary agent to be 1.2% of the weight of epoxy chloropropane, and the molar ratio of sodium hydroxide to epoxy chloropropane to be 7: 1.
The toughening filler is prepared by the following steps:
sequentially adding gutta-percha and petroleum ether into a three-neck flask, heating to 55 ℃, uniformly stirring for 1h, then adding deionized water, stirring for 5min to form gutta-percha emulsion, adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, carrying out heat preservation reaction for 2h, carrying out ethanol precipitation, deionized water washing and vacuum drying after the reaction is finished to prepare modified gutta-percha, then adding the modified gutta-percha into tetrahydrofuran, uniformly stirring for 1h at room temperature, adding periodic acid, uniformly stirring and reacting for 6h, carrying out methanol precipitation, deionized water washing and vacuum drying to prepare toughening filler, controlling the dosage ratio of the gutta-percha, the petroleum ether and the deionized water to be 5 g: 60 mL: 40mL, the molar ratio of the formic acid to the hydrogen peroxide to be 1: 2, and the molar ratio of carbon-carbon double bonds to the formic acid to be 1: 1;
the composite curing agent is prepared by the following steps:
adding 2, 2 '-dimercaptoethyl sulfide, trimethylolpropane triacrylate and triethylamine into a three-neck flask, introducing nitrogen, heating to 70 ℃, preserving heat for reacting for 8 hours to obtain a reactant, adding condensed amine-105, continuously preserving heat and reacting for 2 hours to obtain a composite curing agent, wherein the weight ratio of the 2, 2' -dimercaptoethyl sulfide, the trimethylolpropane triacrylate, the triethylamine and the condensed amine-105 is controlled to be 9: 10: 0.4: 50.
Example 3
The epoxy resin is prepared by the following steps:
adding epoxy chloropropane and an auxiliary agent CAT-18 into a three-neck flask, stirring at a constant speed, heating to 65 ℃, adding 4, 4 '-diaminodiphenyl ether in equal amount twice, continuing stirring for 15min, heating to 80 ℃, carrying out heat preservation reaction for 4h, adding a sodium hydroxide aqueous solution with the mass fraction of 15% after the reaction is finished, cooling to 50 ℃, carrying out heat preservation reaction for 30min, adding an extracting agent, standing for 15min after uniform stirring, filtering, removing water-soluble salt and an excessive sodium hydroxide solution, washing with deionized water until a washing solution is neutral, then carrying out reduced pressure, distillation and devolatilization to obtain the epoxy resin, controlling the molar ratio of epoxy chloropropane to 4, 4' -diaminodiphenyl ether to be 4: 1, the amount of the auxiliary agent to be 1.5% of the weight of epoxy chloropropane, and the molar ratio of sodium hydroxide to epoxy chloropropane to be 8: 1.
The toughening filler is prepared by the following steps:
sequentially adding gutta-percha and petroleum ether into a three-neck flask, heating to 55 ℃, uniformly stirring for 1h, then adding deionized water, stirring for 5min to form gutta-percha emulsion, adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, carrying out heat preservation reaction for 2h, carrying out ethanol precipitation, deionized water washing and vacuum drying after the reaction is finished to prepare modified gutta-percha, then adding the modified gutta-percha into tetrahydrofuran, uniformly stirring for 1h at room temperature, adding periodic acid, uniformly stirring and reacting for 6h, carrying out methanol precipitation, deionized water washing and vacuum drying to prepare toughening filler, wherein the dosage ratio of the gutta-percha, the petroleum ether and the deionized water is controlled to be 5 g: 70 mL: 50mL, the molar ratio of the formic acid to the hydrogen peroxide is 1: 2, and the molar ratio of carbon-carbon double bonds to the formic acid is 1: 1;
the composite curing agent is prepared by the following steps:
adding 2, 2 '-dimercaptoethyl sulfide, trimethylolpropane triacrylate and triethylamine into a three-neck flask, introducing nitrogen, heating to 75 ℃, keeping the temperature for reacting for 8 hours to obtain a reactant, adding condensed amine-105, keeping the temperature continuously and reacting for 2 hours to obtain a composite curing agent, wherein the weight ratio of the 2, 2' -dimercaptoethyl sulfide, the trimethylolpropane triacrylate, the triethylamine and the condensed amine-105 is controlled to be 10: 0.5: 50.
Example 4
An epoxy resin adhesive comprises A, B components, wherein the A component comprises the following raw materials in parts by weight: 85 parts of epoxy resin, 15 parts of toughening filler, 5 parts of glycol glycidyl ether and 1 part of kaolin;
the component B comprises 60 parts of a composite curing agent and 0.1 part of triethylene diamine;
uniformly mixing the epoxy resin, the toughening filler and the kaolin, magnetically stirring for 30min, then adding ethylene glycol glycidyl ether, stirring at a high speed, heating to 55 ℃, carrying out heat preservation reaction for 30min, cooling and discharging to obtain a component A;
and adding the composite curing agent and triethylene diamine into a stirring kettle, heating to 60 ℃, and stirring at a high speed for 30min to obtain the component B.
Example 5
An epoxy resin adhesive comprises A, B components, wherein the A component comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 20 parts of toughening filler, 8 parts of glycol glycidyl ether and 2 parts of kaolin;
the component B comprises 65 parts of a composite curing agent and 0.2 part of triethylene diamine;
uniformly mixing the epoxy resin, the toughening filler and the kaolin, magnetically stirring for 30min, then adding ethylene glycol glycidyl ether, stirring at a high speed, heating to 60 ℃, carrying out heat preservation reaction for 30min, cooling and discharging to obtain a component A;
adding the composite curing agent and triethylene diamine into a stirring kettle, heating to 70 ℃, and stirring at a high speed for 30min to obtain the component B.
Example 6
An epoxy resin adhesive comprises A, B components, wherein the A component comprises the following raw materials in parts by weight: 110 parts of epoxy resin, 25 parts of toughening filler, 10 parts of glycol glycidyl ether and 3 parts of kaolin;
the component B comprises 70 parts of composite curing agent and 0.3 part of triethylene diamine;
uniformly mixing the epoxy resin, the toughening filler and the kaolin, magnetically stirring for 30min, then adding ethylene glycol glycidyl ether, stirring at a high speed, heating to 65 ℃, carrying out heat preservation reaction for 30min, cooling and discharging to obtain a component A;
and adding the composite curing agent and triethylene diamine into a stirring kettle, heating to 80 ℃, and stirring at a high speed for 30min to obtain the component B.
Comparative example 1
This comparative example compares to example 4 with a bisphenol a epoxy resin in place of the epoxy resin prepared according to the present invention.
Comparative example 2
In comparison with example 4, this comparative example uses ethylene propylene diene monomer instead of the toughening filler.
Comparative example 3
This comparative example was compared to example 4, using the amine acetal-105 in place of the composite curing agent.
The mechanical properties of the adhesives prepared in examples 4-6 and comparative examples 1-2 were tested by GB/T1040-2006, and the results are shown in the following table;
it can be seen from the above table that the epoxy adhesives prepared in examples 4-6 of the present invention have excellent toughness.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. An epoxy resin adhesive, comprising A, B components, characterized in that: the component A comprises the following raw materials in parts by weight: 85-110 parts of epoxy resin, 15-25 parts of toughening filler, 5-10 parts of glycol glycidyl ether and 1-3 parts of thixotropic agent;
the component B comprises 60-70 parts of composite curing agent and 0.1-0.3 part of curing accelerator;
the epoxy resin is prepared by the following steps:
adding epoxy chloropropane and an auxiliary agent into a three-neck flask, stirring at a constant speed, heating to 65 ℃, adding 4, 4' -diaminodiphenyl ether in equal amount twice, continuing stirring for 15min, heating to 75-80 ℃, carrying out heat preservation reaction for 4h, adding a sodium hydroxide aqueous solution with the mass fraction of 15% after the reaction is finished, cooling to 45-50 ℃, carrying out heat preservation reaction for 30min, adding an extracting agent, stirring uniformly, standing for 15min, filtering, washing with deionized water until the washing solution is neutral, and then carrying out reduced pressure, distillation and devolatilization to obtain the epoxy resin.
2. The epoxy resin adhesive as set forth in claim 1, wherein: controlling the mol ratio of epoxy chloropropane to 4, 4' -diaminodiphenyl ether to be 4: 1, controlling the dosage of the auxiliary agent to be 1-1.5% of the weight of the epoxy chloropropane, and controlling the mol ratio of sodium hydroxide to the epoxy chloropropane to be 6-8: 1.
3. The epoxy resin adhesive as set forth in claim 1, wherein: the toughening filler is prepared by the following steps:
sequentially adding gutta-percha and petroleum ether into a three-neck flask, heating to 55 ℃, stirring at a constant speed for 1h, then adding deionized water, stirring for 5min to form gutta-percha emulsion, adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, reacting for 2h while keeping the temperature, performing ethanol precipitation, deionized water washing and vacuum drying after the reaction is finished to prepare modified gutta-percha, then adding the modified gutta-percha into tetrahydrofuran, stirring at a constant speed for 1h at room temperature, adding periodic acid, stirring at a constant speed and reacting for 6h, performing methanol precipitation and deionized water washing, and performing vacuum drying to prepare the toughening filler.
4. The epoxy resin adhesive as set forth in claim 3, wherein: the dosage ratio of the gutta-percha, the petroleum ether and the deionized water is controlled to be 5 g: 50-70 mL: 30-50mL, the molar ratio of the formic acid to the hydrogen peroxide is 1: 2, and the molar ratio of the carbon-carbon double bond to the formic acid on the gutta-percha is 1: 1.
5. The epoxy resin adhesive as set forth in claim 1, wherein: the thixotropic agent is kaolin.
6. The epoxy resin adhesive as set forth in claim 1, wherein: the composite curing agent is prepared by the following steps:
adding 2, 2 '-dimercaptoethyl sulfide, trimethylolpropane triacrylate and triethylamine into a three-neck flask, introducing nitrogen, heating to 65-75 ℃, preserving the temperature for reaction for 8 hours to obtain a reactant, adding condensed amine-105, continuously preserving the temperature and reacting for 2 hours to obtain the composite curing agent, wherein the weight ratio of the 2, 2' -dimercaptoethyl sulfide, the trimethylolpropane triacrylate, the triethylamine and the condensed amine-105 is controlled to be 7.5-10: 0.3-0.5: 50.
7. The method for preparing the epoxy resin adhesive according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
uniformly mixing the epoxy resin, the toughening filler and the thixotropic agent, magnetically stirring for 30min, then adding ethylene glycol glycidyl ether, stirring at a high speed, heating to 55-65 ℃, carrying out heat preservation reaction for 30min, cooling and discharging to obtain a component A;
adding the composite curing agent and the curing accelerator into a stirring kettle, heating to 60-80 ℃, and stirring at a high speed for 30min to obtain the component B.
8. The method for preparing an epoxy resin adhesive according to claim 7, wherein: the curing accelerator is any one of triethylamine and triethylene diamine.
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| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
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| CN116285814A (en) * | 2023-03-03 | 2023-06-23 | 山东凯恩新材料科技有限公司 | Modified epoxy adhesive for optical fibers and preparation method thereof |
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| CN115010402A (en) * | 2022-07-04 | 2022-09-06 | 杭州每步材料科技有限公司 | Anti-abrasion epoxy mortar with low thermal linear expansion coefficient and preparation method thereof |
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| CN116285814A (en) * | 2023-03-03 | 2023-06-23 | 山东凯恩新材料科技有限公司 | Modified epoxy adhesive for optical fibers and preparation method thereof |
| CN116285814B (en) * | 2023-03-03 | 2023-09-19 | 山东凯恩新材料科技有限公司 | Modified epoxy adhesive for optical fibers and preparation method thereof |
| CN116162441A (en) * | 2023-03-29 | 2023-05-26 | 广州宝捷电子材料科技有限公司 | Composite modified epoxy resin adhesive and preparation method thereof |
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Application publication date: 20220527 |