CN111087958A - Room-temperature fast-curing epoxy adhesive and preparation method thereof - Google Patents
Room-temperature fast-curing epoxy adhesive and preparation method thereof Download PDFInfo
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- CN111087958A CN111087958A CN201911328035.7A CN201911328035A CN111087958A CN 111087958 A CN111087958 A CN 111087958A CN 201911328035 A CN201911328035 A CN 201911328035A CN 111087958 A CN111087958 A CN 111087958A
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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
- C08G59/18—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
- C08G59/44—Amides
- C08G59/46—Amides 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
- C08G59/50—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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a room-temperature fast curing epoxy adhesive and a preparation method thereof, wherein the adhesive consists of a component A and a component B, and the component A and the component B are used in a matching way according to the volume ratio of 100: 40-60; the component A comprises: 60-80 parts of epoxy resin, 20-40 parts of flexible epoxy resin, 40-60 parts of toughening agent, 4-6 parts of coupling agent, 40-60 parts of filler and 4-6 parts of hydrophobic fumed silica; the component B comprises: 20-40 parts of modified polyamide curing agent, 20-30 parts of modified aliphatic amine curing agent, 15-25 parts of modified alicyclic amine curing agent, 3-10 parts of toughening type accelerator, 5-10 parts of toughening agent, 20-30 parts of filler, 2-3 parts of hydrophobic fumed silica and 2-3 parts of coupling agent. The invention not only has proper operation time and rapid strength improvement capability, but also has high toughness and good mechanical strength, and has excellent adhesive force to metal and composite materials.
Description
Technical Field
The invention relates to the field of epoxy adhesives, in particular to a room-temperature fast curing epoxy adhesive for a toughened high-strength composite material and a preparation method thereof.
Background
With the rapid development of science and technology, the applications of various novel plastics and high-strength composite materials (SMC, GRP, CFRP) in the fields of aerospace, automobile industry, machine manufacturing, medical field, rail vehicles, smart homes and the like are gradually increased, and a large amount of metal and composite materials and the adhesion between the composite materials can be involved in the application process of the materials. And the composite material needs to be added with some release agent during the forming process, so that the composite material is difficult to have good bonding effect. Through continuous research and development, the acrylic adhesive and the epoxy adhesive are applied more in the field of composite material bonding.
The acrylic adhesive has the advantages of fast curing at room temperature, good adhesive force to composite materials, and is mainly used for vehicle interior trim and the like, but the acrylic adhesive has the defects of large smell in the using process of ①, certain influence on users and the environment, short operation time of ②, fast curing speed, violent reaction heat release, incapability of being used for large-area and large-gap bonding, and unsatisfactory ③ in the aspects of high temperature resistance, corrosion resistance and weather resistance.
The epoxy adhesive has the advantages of low price, long operation time, good high temperature resistance, corrosion resistance and weather resistance, and is mainly used for some applications needing large-area glue application, but the existing epoxy adhesive has the defects that the intensity of the epoxy adhesive with long operation time of ① is slowly improved, the operation time of the epoxy adhesive is mostly 1-2 h, the epoxy adhesive generally needs 10-15 h to be primarily cured, the production efficiency is seriously restricted, the process cost is increased, the epoxy adhesive with short initial curing time of ② is short, the operation time is short, and the toughness is poor, the operation time of the epoxy adhesive is 5-15 min, the primary curing time is 2-3 h, the intensity improving speed is still slow, the adaptability to large-size and special-shaped substrates is poor, and the toughness of the epoxy adhesive is poor, and the adhesive force of ③ epoxy adhesive to some demoulding-formed composite materials needs to be improved.
Therefore, the epoxy adhesive with proper operation time, rapid strength improvement and high adhesive force to the composite material is developed and has great application potential.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the room-temperature fast-curing epoxy adhesive and the preparation method thereof, which not only have proper operation time and fast strength improvement capability, but also have high toughness, good mechanical strength and excellent adhesive force to metal and composite materials.
The purpose of the invention is realized by the following technical scheme:
the room-temperature fast-curing epoxy adhesive consists of a component A and a component B, wherein the component A and the component B are used in a matching manner according to the volume ratio of 100: 40-60; wherein the content of the first and second substances,
the component A comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-40 parts of flexible epoxy resin, 40-60 parts of toughening agent, 4-6 parts of coupling agent, 40-60 parts of filler and 4-6 parts of hydrophobic fumed silica;
the component B comprises the following raw materials in parts by weight: 20-40 parts of modified polyamide curing agent, 20-30 parts of modified aliphatic amine curing agent, 15-25 parts of modified alicyclic amine curing agent, 3-10 parts of toughening type accelerator, 5-10 parts of toughening agent, 20-30 parts of filler, 2-3 parts of hydrophobic fumed silica and 2-3 parts of coupling agent.
Preferably, the epoxy resin is at least one of epoxy resin E-44, epoxy resin E-51, epoxy resin E-54, epoxy resin F-51 and epoxy resin F-44.
Preferably, the flexible epoxy resin adopts at least one of flexible epoxy resin NPER-174, flexible epoxy resin YD-171, flexible epoxy resin NPER-133L and flexible epoxy resin GY 298.
Preferably, the toughening agent in the component A adopts at least one of a Qishi toughening agent and a core-shell toughening agent; the toughening agent in the component B adopts at least one of terminal amino nitrile rubber and Qishi toughening agent; the Qishi toughening agent is at least one of a Qishi toughening agent VL-4 and a Qishi toughening agent VL-1; the core-shell toughening agent is a blend formed by uniformly dispersing core-shell rubber in epoxy resin; the core-shell rubber is a core-shell structure polymer with a shell made of polystyrene and a core made of a rubber elastomer.
Preferably, the coupling agent adopts at least one of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyl tris (β -methoxyethoxy) silane and aniline methyl triethoxysilane.
Preferably, the filler is at least one of calcium carbonate, talcum powder, silica powder, alumina, aluminum hydroxide and barium sulfate whisker.
Preferably, at least one of curing agent V140, curing agent XH429, curing agent XH351, curing agent D8140, curing agent 350A and curing agent ARADUR 283 is adopted as the modified polyamide curing agent.
Preferably, the modified fatty amine curing agent is at least one of curing agent JH5488, curing agent JH5472, curing agent JH5473, curing agent JH5432S, curing agent R-2011, curing agent R-2022B and curing agent 2958.
Preferably, the modified alicyclic amine curing agent adopts at least one of curing agent D650, curing agent R-3401, curing agent R-3400, curing agent R-3600 and curing agent 847.
Preferably, the toughening accelerator is at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, dimethyl dipropyl triamine, N' -bis (3-aminopropyl) -ethylene diamine, epoxy modified polyethyleneimine and N-aminoethyl piperazine.
A preparation method of an epoxy adhesive capable of being rapidly cured at room temperature comprises the following steps:
selecting raw materials according to the room-temperature fast curing epoxy adhesive;
preparation of component A: adding epoxy resin, flexible epoxy resin, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring, and defoaming for 30min after the stirring is finished, thereby preparing a component A;
preparation of the component B: adding a modified polyamide curing agent, a modified aliphatic amine curing agent, a modified alicyclic amine curing agent, a toughening type accelerator, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring, and defoaming for 30min after the stirring is finished, thereby preparing a component B;
and (3) matching the component A with the component B according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive.
Preferably, when the toughening type accelerator in the component B adopts epoxy modified polyethyleneimine, the preparation method of the epoxy modified polyethyleneimine comprises the following steps: mixing and dissolving 100 parts by weight of polyethyleneimine, 400 parts by weight of methanol, 15 parts by weight of bisphenol F type epoxy resin and 10 parts by weight of propylene oxide, refluxing and stirring at 40 ℃ for 24 hours, and evaporating and recovering the methanol to obtain the epoxy modified polyethyleneimine in a yellow transparent liquid.
Preferably, when the toughening agent in the component A adopts a core-shell toughening agent, the preparation method of the core-shell toughening agent comprises the following steps: and (3) fully stirring and mixing 100 parts by weight of epoxy resin and 30 parts by weight of core-shell rubber at 80 ℃ for 3 hours to prepare the core-shell toughening agent.
According to the technical scheme provided by the invention, the room-temperature fast-curing epoxy adhesive provided by the invention takes the rubber elastomer matched with the flexible epoxy resin as a toughening basis, realizes toughening and acceleration of the adhesive, controls proper operation time and improves the adhesive force of a composite material through the synergistic effect of the modified polyamide curing agent, the modified aliphatic amine curing agent, the modified alicyclic amine curing agent, the toughening type accelerator and the coupling agent, and realizes thixotropy and stability of the adhesive and enhancement of the mechanical property of the adhesive through the filler and hydrophobic fumed silica. The invention not only has proper operation time and rapid strength improvement capability, but also has high toughness and good mechanical strength, and has excellent adhesive force to metal and composite materials.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The room temperature fast curing epoxy adhesive and the preparation method thereof provided by the present invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
The room temperature fast curing epoxy adhesive for the toughened high-strength composite material consists of a component A and a component B, wherein the component A and the component B are matched according to the volume ratio of 100: 40-60.
Wherein the component A comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-40 parts of flexible epoxy resin, 40-60 parts of toughening agent, 4-6 parts of coupling agent, 40-60 parts of filler and 4-6 parts of hydrophobic fumed silica. The component B comprises the following raw materials in parts by weight: 20-45 parts of modified polyamide curing agent, 20-30 parts of modified aliphatic amine curing agent, 15-25 parts of modified alicyclic amine curing agent, 3-10 parts of toughening type accelerator, 5-10 parts of toughening agent, 20-30 parts of filler, 2-3 parts of hydrophobic fumed silica and 2-3 parts of coupling agent.
Specifically, the room temperature fast curing epoxy adhesive may include the following embodiments:
(1) the epoxy resin is at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin. The bisphenol A epoxy resin is at least one of epoxy resin E-44, epoxy resin E-51 and epoxy resin E-54. The bisphenol F epoxy resin adopts at least one of epoxy resin F-51 and epoxy resin F-44.
(2) The flexible epoxy resin adopts at least one of flexible epoxy resin NPER-174, flexible epoxy resin YD-171, flexible epoxy resin NPER-133L and flexible epoxy resin GY 298.
(3) The toughening agent in the component A adopts at least one of a Qishi toughening agent and a core-shell toughening agent; the toughening agent in the component B adopts at least one of amine-terminated nitrile rubber and Qishi toughening agent. The Qishi toughening agent is at least one of a Qishi toughening agent VL-4 and a Qishi toughening agent VL-1; the core-shell toughening agent is a blend formed by uniformly dispersing core-shell rubber in epoxy resin. The core-shell rubber is a core-shell structure polymer with a shell made of polystyrene and a core made of a rubber elastomer.
(4) The coupling agent adopts at least one of gamma-glycidoxypropyltrimethoxysilane (KH-560), gamma-aminopropyltriethoxysilane (KH-550), N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), vinyl tris (β -methoxyethoxy) silane (A172) and aniline methyl triethoxysilane (sj-42).
(5) The filler can adopt at least one of calcium carbonate, talcum powder, silica powder, alumina, aluminum hydroxide and barium sulfate whisker.
(6) The modified polyamide curing agent adopts at least one of curing agent V140, curing agent XH429, curing agent XH351, curing agent D8140, curing agent 350A and curing agent ARADUR 283.
(7) The modified fatty amine curing agent is at least one of curing agent JH5488, curing agent JH5472, curing agent JH5473, curing agent JH5432S, curing agent R-2011, curing agent R-2022B and curing agent 2958.
(8) The modified alicyclic amine curing agent is at least one of curing agent D650, curing agent R-3401, curing agent R-3400, curing agent R-3600 and curing agent 847.
(9) The toughening accelerator can adopt at least one of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), dimethyl dipropyl triamine, N' -bis (3-aminopropyl) -ethylene diamine, epoxy modified polyethyleneimine and N-aminoethyl piperazine.
Further, the preparation method of the room temperature fast curing epoxy adhesive can comprise the following steps:
(1) selecting the raw materials according to the room temperature fast curing epoxy adhesive.
(2) Preparation of component A: adding epoxy resin, flexible epoxy resin, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring that the filler and the fumed silica are uniformly dispersed, defoaming after the stirring is finished for 30min, and discharging to obtain the component A.
(3) Preparation of the component B: adding a modified polyamide curing agent, a modified aliphatic amine curing agent, a modified alicyclic amine curing agent, a toughening type accelerator, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring that the filler and the fumed silica are uniformly dispersed, defoaming after the stirring is finished for 30min, and discharging to obtain the component B.
(4) And (3) matching the component A with the component B according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive. In practical application, the component A and the component B can be subpackaged in a 2: 1 bi-component mixed rubber tube according to the volume ratio of 2: 1, and the room temperature fast curing epoxy adhesive for the toughened high-strength composite material is prepared.
Further, the method for preparing the room temperature fast curing epoxy adhesive may include the following embodiments:
(1) when the toughening type accelerant in the component B adopts epoxy modified polyethyleneimine, the preparation method of the epoxy modified polyethyleneimine comprises the following steps: mixing and dissolving 100 parts by weight of polyethyleneimine, 400 parts by weight of methanol, 15 parts by weight of bisphenol F type epoxy resin and 10 parts by weight of propylene oxide, refluxing and stirring at 40 ℃ for 24 hours, and evaporating and recovering the methanol to obtain the epoxy modified polyethyleneimine in a yellow transparent liquid.
(2) When the toughening agent in the component A adopts a core-shell toughening agent, the preparation method of the core-shell toughening agent comprises the following steps: 100 parts by weight of epoxy resin and 30 parts by weight of core-shell rubber are fully stirred and mixed for 3 hours at the temperature of 80 ℃, so that a smooth and fine blend, namely the core-shell toughening agent, is prepared.
In the process of the invention, the inventor finds that: the synergistic effect of the rubber elastomer and the flexible epoxy resin obviously improves the toughness of the adhesive and has excellent mechanical strength; the synergistic effect of the toughening type accelerant and the modified polyamide can effectively improve the strength improvement speed of the adhesive and the adhesive force to metal and nonmetal base materials. Therefore, the room-temperature fast-curing epoxy adhesive provided by the invention takes the rubber elastomer matched with the flexible epoxy resin as a toughening foundation, realizes toughening and acceleration of the adhesive, controls proper operation time and improves the adhesive force of a composite material through the synergistic effect of the modified polyamide curing agent, the modified aliphatic amine curing agent, the modified alicyclic amine curing agent, the toughening type accelerator and the coupling agent, and realizes thixotropy and stability of the adhesive and enhancement of the mechanical property of the adhesive through the filler and hydrophobic fumed silica.
In conclusion, the embodiment of the invention has the advantages of proper operation time, rapid strength improvement capability, high toughness, good mechanical strength and excellent adhesive force to metal and composite materials.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the room temperature fast curing epoxy adhesive and the preparation method thereof provided by the embodiments of the present invention are described in detail with specific embodiments below.
Example 1
A room temperature fast curing epoxy adhesive comprises the following steps (by weight parts):
preparation of component A: adding 80 parts of epoxy resin E-51, 20 parts of flexible epoxy resin NPER-174, 50 parts of core-shell toughening agent and 4 parts of coupling agent sj-42 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required in the stirring process, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 30 parts of calcium carbonate, 20 parts of barium sulfate whisker and 4 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of calcium carbonate, barium sulfate whiskers and hydrophobic fumed silica, defoaming after stirring for 30min, and discharging to obtain the component A.
Preparation of the component B: adding 20 parts of curing agent XH429, 5 parts of curing agent XH351, 15 parts of curing agent JH5473, 10 parts of curing agent R-2022B, 15 parts of curing agent R-3401, 3 parts of N, N' -bis (3-aminopropyl) -ethylene diamine, 5 parts of epoxy modified polyethylene imine, 5 parts of terminal amine nitrile rubber and 2 parts of coupling agent KH-550 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required in the stirring process, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 15 parts of calcium carbonate, 10 parts of barium sulfate whisker and 2 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of calcium carbonate, barium sulfate whiskers and hydrophobic fumed silica, defoaming after stirring for 30min, and discharging to obtain the component B.
And (3) matching the component A with the component B according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive for the toughened high-strength composite material.
Example 2
A room temperature fast curing epoxy adhesive comprises the following steps (by weight parts):
preparation of component A: adding 45 parts of epoxy resin E-44, 30 parts of epoxy resin F-51, 25 parts of flexible epoxy resin YD-171, 40 parts of core-shell toughening agent, 10 parts of Qishi toughening agent VL-4 and 4 parts of coupling agent A172 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required in the stirring process, and the pressure is kept between-0.095 MPa and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 30 parts of alumina, 20 parts of barium sulfate whisker and 4 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of the alumina, the barium sulfate whisker and the hydrophobic fumed silica, defoaming after the stirring is finished for 30min, and discharging to obtain the component A.
Preparation of the component B: adding 20 parts of curing agent V140, 10 parts of curing agent XH429, 20 parts of curing agent JH5432S, 15 parts of curing agent R-3400, 5 parts of dimethyl dipropyl triamine, 5 parts of epoxy modified polyethylene imine, 5 parts of Qishi toughening agent VL-1 and 2 parts of coupling agent KH-550 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required in the stirring process, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 15 parts of alumina, 10 parts of barium sulfate whisker and 2 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of the alumina, the barium sulfate whisker and the hydrophobic fumed silica, defoaming after the stirring is finished for 30min, and discharging to obtain the component B.
And (3) matching the component A with the component B according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive for the toughened high-strength composite material.
Example 3
A room temperature fast curing epoxy adhesive comprises the following steps (by weight parts):
preparation of component A: adding 60 parts of epoxy resin E-51, 10 parts of epoxy resin F-51, 30 parts of flexible epoxy resin YD-171, 50 parts of core-shell toughening agent and 4 parts of coupling agent KH-560 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 MPa and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 20 parts of alumina, 30 parts of barium sulfate whisker and 4 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of the alumina, the barium sulfate whisker and the hydrophobic fumed silica, defoaming after the stirring is finished for 30min, and discharging to obtain the component A.
Preparation of the component B: adding 40 parts of curing agent XH429, 5 parts of curing agent XH351, 20 parts of curing agent R-2022B, 15 parts of curing agent R-3401, 2 parts of dimethyl dipropyl triamine, 8 parts of epoxy modified polyethylene imine, 10 parts of terminal amino nitrile rubber and 2 parts of coupling agent KH-550 into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding 10 parts of alumina, 15 parts of barium sulfate whisker and 2 parts of hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring period, ensuring the uniform dispersion of the alumina, the barium sulfate whisker and the hydrophobic fumed silica, defoaming after the stirring is finished for 30min, and discharging to obtain the component B.
And (3) matching the component A with the component B according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive for the toughened high-strength composite material.
Performance detection
The room temperature fast curing epoxy adhesive prepared in examples 1 to 3 of the present invention was compared with 3 types of adhesives (i.e., comparative example 1, comparative example 2, and comparative example 3) in the prior art for performance test, and the test results are shown in table 1 below:
TABLE 1
As can be seen from table 1 above: compared with the adhesive in the prior art, the room temperature fast curing epoxy adhesive prepared in the embodiments 1 to 3 of the invention has obviously improved toughness through the synergistic effect of the flexible epoxy resin and the rubber elastomer, obviously improves the adhesive force to metal and composite materials through the synergistic effect of the coupling agent and the toughening type accelerator, and has excellent strength improvement speed.
The room temperature fast curing epoxy adhesive for the toughened high-strength composite material solves the problems of speed increase and toughening of the room temperature curing adhesive, has excellent adhesive force to various base materials, can be used for bonding composite materials such as metal materials, non-metal materials and the like, has excellent bonding strength to metal-metal, metal-composite materials and composite materials, and has failure modes of CF (metal) and SF (composite material).
In conclusion, the embodiment of the invention has the advantages of proper operation time, rapid strength improvement capability, high toughness, good mechanical strength and excellent adhesive force to metal and composite materials.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The room-temperature fast-curing epoxy adhesive is characterized by comprising a component A and a component B, wherein the component A and the component B are used in a matching manner according to the volume ratio of 100: 40-60; wherein the content of the first and second substances,
the component A comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-40 parts of flexible epoxy resin, 40-60 parts of toughening agent, 4-6 parts of coupling agent, 40-60 parts of filler and 4-6 parts of hydrophobic fumed silica;
the component B comprises the following raw materials in parts by weight: 20-40 parts of modified polyamide curing agent, 20-30 parts of modified aliphatic amine curing agent, 15-25 parts of modified alicyclic amine curing agent, 3-10 parts of toughening type accelerator, 5-10 parts of toughening agent, 20-30 parts of filler, 2-3 parts of hydrophobic fumed silica and 2-3 parts of coupling agent.
2. The room temperature fast curing epoxy adhesive according to claim 1, wherein the epoxy resin is at least one of epoxy resin E-44, epoxy resin E-51, epoxy resin E-54, epoxy resin F-51 and epoxy resin F-44;
the flexible epoxy resin adopts at least one of flexible epoxy resin NPER-174, flexible epoxy resin YD-171, flexible epoxy resin NPER-133L and flexible epoxy resin GY 298.
3. The room temperature fast curing epoxy adhesive according to claim 1 or 2, wherein the toughening agent in the component A is at least one of a Qishi toughening agent and a core-shell toughening agent; the toughening agent in the component B adopts at least one of terminal amino nitrile rubber and Qishi toughening agent;
wherein the Qishi toughening agent is at least one of a Qishi toughening agent VL-4 and a Qishi toughening agent VL-1; the core-shell toughening agent is a blend formed by uniformly dispersing core-shell rubber in epoxy resin; the core-shell rubber is a core-shell structure polymer with a shell made of polystyrene and a core made of a rubber elastomer.
4. The room temperature fast curing epoxy adhesive according to claim 1 or 2, wherein the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, and anilinomethyltriethoxysilane.
5. The room temperature fast curing epoxy adhesive according to claim 1 or 2, wherein the filler is at least one of calcium carbonate, talcum powder, silica powder, alumina, aluminum hydroxide and barium sulfate whisker.
6. The room temperature fast-curing epoxy adhesive as claimed in claim 1 or 2, wherein the modified polyamide curing agent is at least one of curing agent V140, curing agent XH429, curing agent XH351, curing agent D8140, curing agent 350A and curing agent ARADUR 283;
the modified fatty amine curing agent is at least one of a curing agent JH5488, a curing agent JH5472, a curing agent JH5473, a curing agent JH5432S, a curing agent R-2011, a curing agent R-2022B and a curing agent 2958;
the modified alicyclic amine curing agent is at least one of curing agent D650, curing agent R-3401, curing agent R-3400, curing agent R-3600 and curing agent 847.
7. The room temperature fast curing epoxy adhesive according to claim 1 or 2, wherein the toughening type accelerator is at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, dimethyl dipropyl triamine, N' -bis (3-aminopropyl) -ethylene diamine, epoxy modified polyethylene imine, and N-aminoethyl piperazine.
8. A preparation method of the room-temperature fast curing epoxy adhesive is characterized by comprising the following steps:
selecting raw materials according to the room-temperature fast-curing epoxy adhesive of any one of the claims 1 to 7;
preparation of component A:
adding epoxy resin, flexible epoxy resin, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring, and defoaming for 30min after the stirring is finished, thereby preparing a component A;
preparation of the component B:
adding a modified polyamide curing agent, a modified aliphatic amine curing agent, a modified alicyclic amine curing agent, a toughening type accelerator, a toughening agent and a coupling agent into a reaction kettle, stirring at normal temperature, wherein the planetary rotation speed is 15-20 Hz, the dispersion rotation speed is 650rpm, vacuumizing is required during stirring, and the pressure is kept between-0.095 and-0.1 MPa; after stirring for 30min, reducing the dispersion rotation speed to 250rpm, adding the filler and the hydrophobic fumed silica, then increasing the dispersion rotation speed to 650rpm, vacuumizing, and keeping the pressure between-0.095 MPa and-0.1 MPa; stirring for 2h, cleaning the kettle once every 30min during the stirring, and defoaming for 30min after the stirring is finished, thereby preparing a component B;
the component A and the component B are used together according to the volume ratio of 100: 40-60 to form the room-temperature fast curing epoxy adhesive as claimed in any one of the claims 1 to 7.
9. The preparation method of the room temperature fast curing epoxy adhesive according to claim 8, wherein when the toughening type accelerator in the component B is epoxy modified polyethyleneimine, the preparation method of the epoxy modified polyethyleneimine is as follows: mixing and dissolving 100 parts by weight of polyethyleneimine, 400 parts by weight of methanol, 15 parts by weight of bisphenol F type epoxy resin and 10 parts by weight of propylene oxide, refluxing and stirring at 40 ℃ for 24 hours, and evaporating and recovering the methanol to obtain the epoxy modified polyethyleneimine in a yellow transparent liquid.
10. The preparation method of the room temperature fast curing epoxy adhesive according to claim 8 or 9, wherein when the toughening agent in the component A adopts a core-shell toughening agent, the preparation method of the core-shell toughening agent comprises the following steps: and (3) fully stirring and mixing 100 parts by weight of epoxy resin and 30 parts by weight of core-shell rubber at 80 ℃ for 3 hours to prepare the core-shell toughening agent.
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Application publication date: 20200501 |
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