CN110128982B - Normal-temperature fast-curing structural adhesive and preparation method thereof - Google Patents
Normal-temperature fast-curing structural adhesive and preparation method thereof Download PDFInfo
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- CN110128982B CN110128982B CN201910260192.2A CN201910260192A CN110128982B CN 110128982 B CN110128982 B CN 110128982B CN 201910260192 A CN201910260192 A CN 201910260192A CN 110128982 B CN110128982 B CN 110128982B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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Abstract
The invention discloses a normal-temperature fast-curing structural adhesive and a preparation method thereof, wherein the structural adhesive comprises a component A and a component B, wherein the component A is a resin adhesive, and the component B is a curing agent; the resin adhesive comprises the following components in percentage by weight: 25-55% of epoxy resin, 0-20% of epoxy resin diluent, 0-10% of epoxy resin toughening agent, 0-10% of coupling agent, 10-25% of flame-retardant filler, 10-30% of heat-conducting filler and 0-7.5% of solvent; the curing agent comprises the following components in percentage by weight: 20-25% of modified fatty amine, 22-35% of modified phenolic aldehyde amine, 1-5% of curing accelerator, 0.5-3% of dispersant and 27-40% of flame-retardant filler. The structural adhesive has the high strength and good heat resistance of the epoxy adhesive, is also provided with the fast-curing epoxy adhesive, can be cured within minutes and tens of minutes, is very suitable for application in positioning, assembling, repairing, sealing, encapsulating and the like, and can improve the efficiency and reduce the pollution.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a normal-temperature fast-curing structural adhesive and a preparation method thereof.
Background
At present, the adhesive is more widely applied in the fields of aerospace, automobiles, electronics, military industry, mechanical manufacturing and the like, is generally used for bonding and packaging electronic components, and keeps certain flame retardant performance and heat conduction performance. However, with continuous progress of the technology, electronic components are continuously developed towards thinning and miniaturization, which inevitably leads to continuous improvement of the assembly density of the electronic components, and accordingly, the requirements on the flame retardant property and the thermal conductivity of the adhesive are higher, and the curing property, the adhesion property, the high temperature resistance and the flame retardant property of the adhesive are especially important under the condition of the electronic components. Therefore, the development of the normal-temperature fast-curing flame-retardant (V0) heat-conducting epoxy electronic structural adhesive with excellent comprehensive performance is of great significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the normal-temperature fast-curing structural adhesive with flame retardance and heat conduction and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that the normal-temperature fast-curing structural adhesive comprises a component A and a component B, wherein the component A is a resin adhesive, and the component B is a curing agent;
the resin adhesive comprises the following components in percentage by weight: 25-55% of epoxy resin, 0-20% of epoxy resin diluent, 0-10% of epoxy resin toughening agent, 0-10% of coupling agent, 10-25% of flame-retardant filler, 10-30% of heat-conducting filler and 0-7.5% of solvent;
the curing agent comprises the following components in percentage by weight: the curing agent comprises the following components in percentage by weight: 20-30% of modified fatty amine, 22-35% of modified phenolic aldehyde amine, 1-5% of curing accelerator, 0.5-3% of dispersant and 27-40% of flame-retardant filler.
The invention selects the epoxy resin, the epoxy resin diluent, the epoxy resin toughening agent, the flame retardant filler, the heat conducting filler and the curing agent in the resin adhesive, the modified aliphatic amine, the modified phenolic amine, the flame retardant filler and the content thereof, and obtains the normal-temperature fast-curing structural adhesive which has flame retardance, heat conduction, high bonding strength and high insulation strength in the daily life of industrial production, wherein, the addition of the flame retardant filler can play a role in increasing the compactness of the network structure of the resin, the epoxy resin can generate a great deal of stress in the curing process, and the increase of the proper filler proportion can form a 'sea-island' structure in the curing system, thereby greatly reducing the destructiveness of the curing stress on the crystal structure, achieving the purposes of increasing the strength of a resin curing piece, slowing the curing rate of the filler and increasing the effective epoxy resin proportion (the effective epoxy resin refers to the resin with active groups participating in the curing reaction), the curing rate will increase accordingly; the heat-conducting filler can improve the heat-conducting effect, has the high-strength and good heat-resisting performance of epoxy adhesive, is quick-curing epoxy adhesive, can be cured within minutes and tens of minutes, is very suitable for positioning, assembling, repairing, sealing, encapsulating and other applications, and can improve the efficiency and reduce the pollution.
In a preferred embodiment of the room-temperature fast-curing structural adhesive of the present invention, the epoxy resin is at least one of bisphenol a epoxy resin, modified bisphenol epoxy resin, bisphenol F epoxy resin, modified bisphenol F epoxy resin, bisphenol a/F epoxy resin, and modified bisphenol a/F epoxy resin. When the epoxy value of the bis-A epoxy resin is between 0.4 and 0.52, the performance is better. Such as B-44 and/or E-44.
In a preferred embodiment of the room temperature fast setting structural adhesive of the present invention, the epoxy resin diluent is at least one of benzyl glycidyl ether, n-butyl glycidyl ether, octyl glycidyl ether, C12-C14 alkyl glycidyl ether, glycidyl methacrylate, glycidyl benzoate, diglycidyl ether, ethylene glycol glycidyl ether, 1, 4-butanediol glycidyl ether, hexanediol glycidyl ether, neopentyl glycol glycidyl ether, resorcinol glycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether.
In a preferred embodiment of the room-temperature fast-curing structural adhesive of the present invention, the epoxy resin toughening agent is at least one of carboxyl group liquid nitrile rubber, carboxyl group-terminated liquid nitrile rubber, polysulfide rubber, polyether, polyimide, polyurethane epoxy resin, and polyether epoxy resin. In order to obtain a good fast curing effect and an adaptive balance to the ambient temperature, in a more preferred embodiment, carboxyl-terminated liquid nitrile rubber is selected.
In a preferred embodiment of the room-temperature quick-setting adhesive according to the present invention, at least one of the following (a) to (c):
(a) the coupling agent is KH-560 and/or KH-550;
(b) the flame-retardant filler is at least one of 300-500-mesh aluminium hydroxide, magnesium hydroxide and a silicon-containing inorganic filler type flame retardant;
(c) the heat-conducting filler is at least one of micron-sized spherical alumina, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide and micron-sized silicon micro powder.
As a preferred embodiment of the normal-temperature fast-curing structural adhesive, the modified aliphatic amine has an amine value of 200-400 mgKOH/g, an active hydrogen equivalent of 150-200 and a viscosity of 1000-30000 centipoises at 25 ℃. More preferably, the modified fatty amine has an amine value of 200 to 300mgKOH/g, an active hydrogen equivalent of 160 to 200, and a viscosity of 1000 to 4000 centipoises at 25 ℃. The phenolic aldehyde amine curing agent is singly used, and the explosion polymerization is easily caused when the using amount is too large or the using environment temperature is too high, so that the modified aliphatic amine is added into the curing agent, the activity of the modified aliphatic amine is lower than that of the modified phenolic aldehyde amine, and the modified phenolic aldehyde amine is slowly balanced.
As a preferred embodiment of the normal-temperature fast-curing structural adhesive, the modified phenolic aldehyde amine is Mannich basic modified phenolic aldehyde amine, the amine value is 500-600mgKOH/g, the active equivalent hydrogen amount is 50-85, and the viscosity at 25 ℃ is 2000-10000 centipoises; or cardanol modified phenolic aldehyde amine with an amine value of 300-400 mgKOH/g, an active hydrogen equivalent of 80-100 and a viscosity of 1000-10000 centipoises at 25 ℃. Compared with Mannich alkaline modified phenolic aldehyde amine which is used as a modified phenolic amine agent, the cardanol modified phenolic amine has better performances of toughening, strengthening adhesion, electrical property and the like; mannich base-modified phenol aldehyde amines have high activity but high brittleness and often contain much water; more preferably, the cardanol modified phenolic aldehyde amine is selected, so that the cardanol modified phenolic aldehyde amine has high activity, good toughness and low water content.
In a preferred embodiment of the room-temperature fast-curing structural adhesive of the present invention, the curing accelerator is at least one of 2,4, 6-tris (dimethylaminomethyl) -phenol, dicyandiamide, maleic anhydride, phthalic anhydride, and 1, 2-dimethylimidazole. The use of the accelerator can accelerate the initial reaction rate.
In a preferred embodiment of the room temperature fast setting structural adhesive of the present invention, the dispersant is a polycarboxylic amine salt, a polyacrylic acid type or polyurethane type high molecular block copolymer with an anchoring group and containing a pigment-philic group.
In a preferred embodiment of the room temperature fast setting structural adhesive of the present invention, the solvent is at least one of cyclohexane, methyl ethyl ketone, ethylene glycol diethyl ether, monoethylhexyl phthalate, ethylene glycol ethyl ether acetate, methyl nylon acid, methyl mixed acid, and diethylene glycol ethyl ether acetate.
As a preferred embodiment of the normal-temperature fast-curing structural adhesive, the weight ratio of the resin adhesive to the curing agent is 1-10: 0-1. Preferably, the ratio of curing agent to epoxy resin has an effect on the curing rate and the adhesive strength within a certain range, and the curing rate and the adhesive strength are optimal when the weight ratio of resin to curing agent is 4: 1.
In a normal-temperature construction environment, after resin glue and a curing agent are mixed uniformly according to a ratio, the construction time can be operated for 15 minutes, the initial curing time at the normal temperature of 25 ℃ is 25 minutes, the construction time is greatly superior to that of the traditional electronic structural glue with the dry time of 60 minutes, the maximum bonding force can be reached in two hours, and the index strength can meet the requirements of GB 50728-2011.
The invention provides a preparation method of a normal-temperature fast-curing structural adhesive, which comprises the following steps:
(1) preparing a resin adhesive: sequentially adding epoxy resin, an epoxy resin diluent and an epoxy resin toughening agent in a planetary mixer, fully stirring at 80-110 ℃, cooling to normal temperature, respectively adding a coupling agent, a flame-retardant filler, a heat-conducting filler and a solvent, continuously stirring, then closing a cylinder cover of the planetary mixer, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and then discharging to obtain a resin adhesive;
(2) preparing a curing agent: in the planet stirring blade, according to the curing agent, sequentially modifying fatty amine, modified phenolic amine, curing accelerator, dispersant and the solvent, stirring, vacuumizing and defoaming; and then adding the flame-retardant filler treated by the coupling agent, closing a cylinder cover of the planetary stirrer after stirring and stopping, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and discharging to obtain the curing agent.
The invention has the beneficial effects that:
according to the invention, by selecting the epoxy resin, the epoxy resin diluent, the epoxy resin toughening agent, the flame-retardant filler, the heat-conducting filler and the modified aliphatic amine, the modified phenolic amine, the flame-retardant filler in the curing agent and the content thereof in the resin adhesive, the obtained structural adhesive has flame retardance and heat conduction, and has the rapidly-cured epoxy adhesive in daily life of industrial production, besides the high strength and good heat resistance of the epoxy adhesive, the structural adhesive can be cured within minutes and tens of minutes, and is very suitable for application in positioning, assembling, repairing, sealing, encapsulating and the like, so that the efficiency can be improved, and the pollution can be reduced.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The raw materials in the following examples are all commercially available general-purpose materials unless otherwise specified.
Example 1
The normal-temperature fast-curing structural adhesive with flame retardance and heat conduction comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E5120%, modified bisphenol F epoxy resin 15%, benzyl glycidyl ether 3%, carboxyl-terminated liquid nitrile rubber 6%, KH 5603%, spherical alumina powder (average particle size 30um) 30%, montmorillonite 20% and cyclohexane 3%.
The component B is a curing agent which comprises the following components in percentage by weight: 22% of modified fatty amine, 35% of cardanol modified phenolic aldehyde amine, 5% of 2,4, 6-tris (dimethylaminomethyl) -phenol, 1.5% of polyurethane type high-molecular block copolymer and 36.5% of diatomite.
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The epoxy resin of the resin adhesive component of this embodiment is epoxy resin E51 and modified bisphenol F epoxy resin; the epoxy resin diluent is benzyl glycidyl ether; the epoxy resin toughening agent is carboxyl-terminated liquid butadiene-acrylonitrile rubber; the coupling agent is KH 560; the flame-retardant filler is montmorillonite; the heat-conducting filler is spherical alumina powder; the solvent is cyclohexane.
The curing accelerator of the curing agent component is 2,4, 6-tris (dimethylaminomethyl) -phenol; the dispersant is polyurethane type high molecular block copolymer; the flame-retardant filler is diatomite.
The preparation method of the flame-retardant and heat-conducting normal-temperature fast-curing structural adhesive comprises the following steps:
(1) preparing a resin adhesive: sequentially adding epoxy resin, epoxy resin diluent and epoxy resin toughening agent in a planetary mixer, fully stirring at 80-110 ℃, cooling to normal temperature, respectively adding coupling agent, flame-retardant filler, heat-conducting filler and solvent, continuously stirring, closing a cylinder cover of the planetary mixer, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and discharging to obtain the resin adhesive with the viscosity of 45000cps (25 ℃);
(2) preparing a curing agent: in the planet stirring blade, according to the curing agent, sequentially modifying fatty amine, modified phenolic amine, curing accelerator, dispersant and the solvent, stirring, vacuumizing and defoaming; and then adding the flame-retardant filler treated by the coupling agent, closing a cylinder cover of the planetary stirrer after stirring and stopping, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and discharging to obtain the curing agent.
Example 2
The normal-temperature fast-curing structural adhesive with flame retardance and heat conduction comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E4415%, bisphenol F epoxy resin 12.5%, octyl glycidyl ether 10%, carboxyl liquid nitrile rubber 10%, KH 56010%, magnesium oxide 10%, aluminum hydroxide (500 meshes) 25% and methyl ethyl ketone 7.5%.
The component B is a curing agent which comprises the following components in percentage by weight: 20% of modified fatty amine, 34.5% of Mannich basic modified phenolic aldehyde amine, 2.5% of dicyandiamide, 3% of polycarboxylic amine salt and 40% of aluminum hydroxide (500 meshes).
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The epoxy resin of the resin adhesive component of this embodiment is epoxy resin E44 and bisphenol F epoxy resin; the epoxy resin diluent is octyl glycidyl ether; the epoxy resin toughening agent is carboxyl liquid butadiene-acrylonitrile rubber; the coupling agent is KH 560; the flame-retardant filler is aluminum hydroxide; the heat-conducting filler is magnesium oxide; the solvent is methyl ethyl ketone.
The curing accelerator of the curing agent component is dicyandiamide; the dispersant is polycarboxylic amine salt; the flame-retardant filler is aluminum hydroxide.
The preparation method of the structural adhesive of this example is the same as that of example 1, and will not be described in detail here.
Example 3
The normal-temperature fast-curing structural adhesive with flame retardance and heat conduction comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: the epoxy resin B4430%, the bisphenol A/F epoxy resin 25%, KH 5501%, micron-sized silicon micropowder 30%, magnesium hydroxide (500 meshes) 10% and ethylene glycol diethyl ester 4%.
The component B is a curing agent which comprises the following components in percentage by weight: 25% of modified fatty amine, 33.5% of Mannich basic modified phenolic aldehyde amine, 1% of maleic anhydride, 0.25% of polyacrylic acid type with anchoring group and containing pigment-philic group, 0.25% of polyurethane type high-molecular block copolymer and 40% of magnesium hydroxide (500 meshes).
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The epoxy resin of the resin adhesive component of this embodiment is epoxy resin B44 and bisphenol A/F epoxy resin; the coupling agent is KH 550; the flame-retardant filler is magnesium hydroxide; the heat-conducting filler is micron-sized silicon micropowder; the solvent is ethylene glycol diethyl ether.
The curing accelerator of the curing agent component is maleic anhydride; the dispersant is polyacrylic acid type or polyurethane type high molecular block copolymer with anchoring group and pigment-philic group; the flame-retardant filler is magnesium hydroxide.
The preparation method of the structural adhesive of this example is the same as that of example 1, and will not be described in detail here.
Example 4
The normal-temperature fast-curing structural adhesive with flame retardance and heat conduction comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E4420%, modified bisphenol A/F epoxy resin 15%, resorcinol glycidyl ether 7.5%, glycerol triglycidyl ether 7.5%, polyether epoxy resin 5%, silicon carbide 25% and montmorillonite (500 mesh) 20%.
The component B is a curing agent which comprises the following components in percentage by weight: 30% of modified fatty amine, 35% of cardanol modified phenolic aldehyde amine, 5% of 2,4, 6-tris (dimethylaminomethyl) -phenol, 3% of polyurethane type high-molecular block copolymer and 27% of montmorillonite (500 meshes).
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The epoxy resin of the resin adhesive component of this embodiment is epoxy resin E44 and modified bisphenol A/F epoxy resin; the flame-retardant filler is montmorillonite; the heat conducting filler is silicon carbide.
The curing accelerator of the curing agent component is 2,4, 6-tris (dimethylaminomethyl) -phenol; the dispersant is polyurethane type high molecular block copolymer; the flame-retardant filler is montmorillonite.
The preparation method of the structural adhesive of this example is the same as that of example 1, and will not be described in detail here.
Example 5
The normal-temperature fast-curing structural adhesive with flame retardance and heat conduction comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E5120%, modified bisphenol F epoxy resin 15%, benzyl glycidyl ether 3%, carboxyl liquid butadiene acrylonitrile rubber 3%, carboxyl-terminated liquid butadiene acrylonitrile rubber 3%, KH 5603%, aluminum nitride 15%, boron nitride 15%, montmorillonite 10%, diatomite 10%, methyl ester mixed acid 1.5% and diethylene glycol ethyl ether acetate 1.5%.
The component B is a curing agent which comprises the following components in percentage by weight: 30% of modified fatty amine, 22% of cardanol modified phenolic aldehyde amine, 3% of phthalic anhydride, 2% of 1, 2-dimethyl imidazole, 3% of polyurethane type high-molecular block copolymer and 40% of diatomite.
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The epoxy resin of the resin adhesive component of this embodiment is epoxy resin E51 and modified bisphenol F epoxy resin; the epoxy resin diluent is benzyl glycidyl ether; the epoxy resin toughening agent is carboxyl liquid butadiene-acrylonitrile rubber and carboxyl-terminated liquid butadiene-acrylonitrile rubber; the coupling agent is KH 560; the flame-retardant filler is montmorillonite and diatomite; the heat conducting filler is aluminum nitride and boron nitride; the solvent is cyclohexane.
The curing accelerator of the curing agent component is phthalic anhydride and 1, 2-dimethyl imidazole; the dispersant is polyurethane type high molecular block copolymer; the flame-retardant filler is diatomite.
Example 6
The difference between the embodiment and the embodiment 1 is only that the weight ratio of the resin adhesive to the curing agent is 1: 1.
Example 7
The difference between the embodiment and the embodiment 1 is only that the weight ratio of the resin glue to the curing agent is 2: 1.
Example 8
The difference between the embodiment and the embodiment 1 is only that the weight ratio of the resin glue to the curing agent is 8: 1.
Example 9
The difference between the embodiment and the embodiment 1 is only that the weight ratio of the resin adhesive to the curing agent is 10: 1.
Comparative example 1
The structural adhesive of the comparative example comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E5135%, modified bisphenol F epoxy resin 17%, benzyl glycidyl ether 17%, carboxyl-terminated liquid nitrile rubber 8%, KH 5605%, spherical alumina powder (average particle size 30um) 5%, montmorillonite 8% and cyclohexane 5%.
The component B is a curing agent which comprises the following components in percentage by weight: 22% of modified fatty amine, 35% of cardanol modified phenolic aldehyde amine, 5% of 2,4, 6-tris (dimethylaminomethyl) -phenol, 1.5% of polyurethane type high-molecular block copolymer and 36.5% of diatomite.
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The preparation method of the structural adhesive is the same as that of the embodiment 1.
Comparative example 2
The structural adhesive of the comparative example comprises a component A and a component B, wherein the weight ratio of the component A to the component B is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E5113%, modified bisphenol F epoxy resin 12%, benzyl glycidyl ether 5%, carboxyl-terminated liquid nitrile rubber 5%, KH 5602%, spherical alumina powder (average particle size 30um) 32%, montmorillonite 28% and cyclohexane 3%.
The component B is a curing agent which comprises the following components in percentage by weight: 22% of modified fatty amine, 35% of cardanol modified phenolic aldehyde amine, 5% of 2,4, 6-tris (dimethylaminomethyl) -phenol, 1.5% of polyurethane type high-molecular block copolymer and 36.5% of diatomite.
The modified phenolic aldehyde amine has amine value of 300mgKOH/g, active hydrogen equivalent of 80, viscosity of 1000 centipoises at 25 deg.c and water content not higher than 1%.
The amine value of the modified aliphatic amine is 200KOH/g, the active hydrogen equivalent is 160, and the viscosity at 25 ℃ is 1000 centipoises.
The preparation method of the structural adhesive is the same as that of the embodiment 1.
Comparative example 3
This comparative example differs from example 1 only in that the weight ratio of resin glue to curing agent is 0.5: 1.
Example 10
The structural adhesives prepared in the examples 1-9 and the comparative examples 1-3 are subjected to performance tests, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the structural adhesive of the present invention has the advantages of short curing time, strong shearing force, high thermal conductivity, high flame retardancy, high adhesive strength and high insulating strength. The curing agent can be cured within minutes and dozens of minutes, and is very suitable for application in positioning, assembling, repairing, sealing, encapsulating and the like, so that the efficiency can be improved, and the pollution can be reduced. The content of the flame-retardant filler and the heat-conducting filler in the resin adhesive components in the comparative examples 1 and 2 is out of the scope of the invention, the addition of the flame-retardant filler can increase the compactness of the network structure of the resin, the epoxy resin can generate a great deal of stress in the curing process, and the proper filler proportion is increased to form a 'sea-island' structure in the curing system, so that the destructiveness of the curing stress on the crystal structure is greatly reduced, and the strength of a cured resin is increased; as can be seen from examples 1, 6 to 9 and comparative example 3, the ratio of the curing agent to the epoxy resin has an influence on the curing rate, the adhesive strength and the like, and when the weight ratio of the epoxy resin to the curing agent is 1 to 10:1, the performance is better, and when the curing agent is excessive, the performance is reduced, which shows that the best effect can be achieved only by the epoxy resin and the curing agent in a certain proportion.
Example 11
In this example, the influence of characteristic parameters in modified fatty amine and modified phenol aldehyde amine in the curing agent on the performance of the structural adhesive prepared by the present invention is discussed, and the weight ratio of the component a to the component B in the structural adhesive in example 1 is 4: 1;
wherein the component A is a resin adhesive which comprises the following components in percentage by weight: epoxy resin E5120%, modified bisphenol F epoxy resin 15%, benzyl glycidyl ether 3%, carboxyl-terminated liquid nitrile rubber 6%, KH 5603%, spherical alumina powder (average particle size 30um) 30%, montmorillonite 20% and cyclohexane 3%.
The component B is a curing agent which comprises the following components in percentage by weight: 22% of modified fatty amine, 35% of modified phenolic aldehyde amine, 5% of 2,4, 6-tri (dimethylaminomethyl) -phenol, 1.5% of polyurethane type high molecular block copolymer and 36.5% of diatomite.
The preparation method of the structural adhesive is the same as that of the embodiment 1.
In the embodiment, experimental groups 1 to 5 are respectively arranged as shown in table 2, and the performance test is performed according to the test method of the embodiment 1, and the test results are shown in table 2:
TABLE 2
As can be seen from table 2, the amine value, the active hydrogen equivalent and the viscosity of the modified fatty amine mainly affect the curing time, and as can be seen from the table, when the amine value of the modified fatty amine is 200-300 mgKOH/g, the active hydrogen equivalent is 160-200, and the viscosity at 25 ℃ is 1000-4000 centipoises, the curing time can be accelerated, and compared with the experimental group 5, the cardanol modified phenolic amine is adopted as the modified phenolic amine agent, compared with the mannich basic modified phenolic amine, the mannich basic modified phenolic amine has better performances such as toughening, adhesion strengthening and electrical performance, and the mannich basic modified phenolic amine has high activity, but large brittleness and often contains more water; more preferably, the cardanol modified phenolic aldehyde amine is selected, so that the cardanol modified phenolic aldehyde amine has high activity, good toughness and low water content.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (11)
1. The normal-temperature fast-curing structural adhesive is characterized by comprising a component A and a component B, wherein the component A is a resin adhesive, and the component B is a curing agent;
the resin adhesive comprises the following components in percentage by weight: 25-55% of epoxy resin, 0-20% of epoxy resin diluent, 0-10% of epoxy resin toughening agent, 0-10% of coupling agent, 10-25% of flame-retardant filler, 10-30% of heat-conducting filler and 0-7.5% of solvent;
the curing agent comprises the following components in percentage by weight: 20-30% of modified fatty amine, 22-35% of modified phenolic aldehyde amine, 1-5% of curing accelerator, 0.5-3% of dispersant and 27-40% of flame-retardant filler;
the weight ratio of the resin adhesive to the curing agent is (1-10) to 1;
the flame-retardant filler is at least one of 300-500 meshes of aluminum hydroxide, magnesium hydroxide, montmorillonite and diatomite;
the heat-conducting filler is at least one of micron-sized spherical alumina, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide and micron-sized silicon micro powder.
2. The normal-temperature fast-curing structural adhesive according to claim 1, wherein the epoxy resin is at least one of bisphenol a epoxy resin, modified bisphenol F epoxy resin, and bisphenol a/F epoxy resin.
3. The normal-temperature fast-curing structural adhesive as claimed in claim 1, wherein the epoxy resin diluent is at least one of benzyl glycidyl ether, n-butyl glycidyl ether, octyl glycidyl ether, C12-C14 alkyl glycidyl ether, glycidyl methacrylate, glycidyl benzoate, diglycidyl ether, ethylene glycol glycidyl ether, 1, 4-butanediol glycidyl ether, hexanediol glycidyl ether, neopentyl glycol glycidyl ether, resorcinol glycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether.
4. The normal-temperature fast-curing structural adhesive as claimed in claim 1, wherein the epoxy resin toughening agent is at least one of carboxyl liquid nitrile rubber, polysulfide rubber, polyether, polyimide, polyurethane epoxy resin and polyether epoxy resin.
5. The ambient-temperature fast-curing structural adhesive according to claim 1, wherein the coupling agent is KH-560 and/or KH-550.
6. The normal-temperature fast-curing structural adhesive as claimed in claim 1, wherein the modified fatty amine has an amine value of 200-400 mgKOH/g, an active hydrogen equivalent of 150-200, and a viscosity of 1000-30000 cps at 25 ℃.
7. The normal-temperature fast-curing structural adhesive as claimed in claim 1, wherein the modified phenolic aldehyde amine is a Mannich basic modified phenolic aldehyde amine, the amine value is 500-600mgKOH/g, the active equivalent hydrogen amount is 50-85, and the viscosity at 25 ℃ is 2000-10000 centipoise; or cardanol modified phenolic aldehyde amine with an amine value of 300-400 mgKOH/g, an active hydrogen equivalent of 80-100 and a viscosity of 1000-10000 centipoises at 25 ℃.
8. The adhesive according to claim 1, wherein the curing accelerator is at least one of 2,4, 6-tris (dimethylaminomethyl) -phenol, dicyandiamide, maleic anhydride, phthalic anhydride, and 1, 2-dimethylimidazole.
9. The room temperature fast-curing structural adhesive according to claim 1, wherein the dispersant is a polycarboxylic amine salt, a polyacrylic acid type or polyurethane type high-molecular block copolymer having an anchoring group and containing a pigment-philic group.
10. The adhesive according to claim 1, wherein the solvent is at least one selected from cyclohexane, methyl ethyl ketone, ethylene glycol diethyl ether, mono-ethylhexyl phthalate, ethylene glycol ethyl ether acetate, methyl nylon acid, methyl mixed acid, and diethylene glycol ethyl ether acetate.
11. A method for preparing an ambient fast-curing structural adhesive according to any one of claims 1 to 10, comprising the following steps:
(1) preparing a resin adhesive: sequentially adding epoxy resin, epoxy resin diluent and epoxy resin toughening agent components in a planetary mixer, fully stirring at 80-110 ℃, cooling to normal temperature, respectively adding coupling agent, flame-retardant filler, heat-conducting filler and solvent, continuously stirring, closing a cylinder cover of the planetary mixer, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and discharging to obtain resin adhesive;
(2) preparing a curing agent: sequentially adding modified fatty amine, modified phenolic amine, a curing accelerator, a dispersant and a solvent into a planetary stirrer, stirring, vacuumizing and defoaming; and adding the flame-retardant filler treated by the coupling agent, closing a cylinder cover of the planetary stirrer after stirring and stopping, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, uniformly stirring, and discharging to obtain the curing agent.
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