CN105694790B - It is a kind of can the epoxy adhesive of rapid disassembling and its preparation and disassembling method - Google Patents
It is a kind of can the epoxy adhesive of rapid disassembling and its preparation and disassembling method Download PDFInfo
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- CN105694790B CN105694790B CN201610113331.5A CN201610113331A CN105694790B CN 105694790 B CN105694790 B CN 105694790B CN 201610113331 A CN201610113331 A CN 201610113331A CN 105694790 B CN105694790 B CN 105694790B
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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
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention provide it is a kind of can rapid disassembling epoxy adhesive, including following parts by weight each raw material composition：20~50 parts of epoxy resin；10~20 parts of epoxide diluent；50~80 parts of the mixture of the Maleimide adduct containing furans；40~70 parts of curing agent；0.5~2 part of amino modified carbon nanotube；5~20 parts of microspheres；Wherein, the mixture of the Maleimide adduct containing furans is the diglycidyl ether of the Maleimide adduct containing furans and the mixture of furans glycidol ether.Epoxy adhesive provided by the invention, adhesive strength is high at room temperature, and medium temperature is disassembled easily.
Description
Technical field
The present invention relates to adhesive materials, more particularly to a kind of for metal and metal, especially contain radioactive element
The epoxy adhesive of double-component cold curing of thin metal layer material bonding and its preparation and disassembling method.
Background technology
Epoxy adhesive is low, at low cost with excellent cementability, chemical stability, resistant of high or low temperature and shrinking percentage
The advantages that honest and clean, it is bonding with metal to be widely used in various metals, it has also become aerospace, automobile, military project and other field
In indispensable basic material.Per annual consumption more than 2,000,000 tons.Certain products being bonded using epoxy adhesive, work as bonding
When component is retired, need to recycle the metal base containing radioactive element.
However, epoxy adhesive is due to forming three-dimensional net structure after curing, and it is insoluble not melt, it disassembles extremely difficult.Mesh
Preceding industrial generally use pyrolysismethod or solvent decomposition method.Such as：Gleice etc. heats epoxy thermoset at 450 DEG C
It 2 hours, treats that epoxy curing compound is decomposed completely, could realize and disassemble.Liu et al. is faced in the presence of phenol and potassium hydroxide using super
Boundary's water decomposition epoxy curing compound, but need a large amount of phenol and potassium hydroxide.In short, these disassembling methods not only energy expenditure
Huge, environmental pollution frequently can lead to basis material to be recycled and generate destruction than more serious.If in epoxy matrix
Middle merging reversible covalent bonds by the disconnection of reversible covalent bonds, realize disassembling for epoxy adhesive, undoubtedly preferably selection.Example
Such as：Patent CN201510129184.6 discloses a kind of flip-chip with the quick capillary flow of room temperature and quick prosthetic
Underfill.The underfill can occur inverse Diels-Alder with furans end group polymer using maleimide and react
Realizing reduces bond matrix performance, improves the purpose for reprocessing performance.But the underfill needs intermediate temperature setting, it is impossible to meet one
As sheet metal bonding normal temperature cure requirement, and also not study the underfill bonding with metal base for the patent
Power.
In view of metal adhesive is needed with epoxy adhesive, room temperature curing, good to metal base wetability, bonding force is strong, and energy
The characteristics of rapid disassembling recycles, applicant will form the polyethyleneimine-modified carbon nanometer of stronger Van der Waals force with metal surface
Pipe, the glycidyl oxirane containing reversible covalent bonds and with epoxy matrix have preferable compatibility microspheres combined
Come, modified synergic epoxy adhesive, using three's respective reaction characteristics at different temperatures, invented and a kind of glued for metal
What is connect can the epoxy adhesive of rapid disassembling and its preparation and disassembling method.
Invention content
The purpose of the present invention is to solve common epoxy adhesive force difference Nian Jie with metal base, disassemble difficult, energy and disappear
Consume huge, the problems such as environmental pollution is serious, the process of disassembling is easy to cause components damage, provide it is a kind of for metal adhesive can
The epoxy adhesive of rapid disassembling and its preparation and disassembling method.Epoxy adhesive prepared by the present invention, bonding is strong at room temperature
Degree is high, and medium temperature is disassembled easily.
The technical scheme is that：It is a kind of can rapid disassembling epoxy adhesive, each raw material including following parts by weight
Composition：
20~50 parts of epoxy resin
10~20 parts of epoxide diluent
50~80 parts of mixture containing furans-Maleimide adduct
40~70 parts of curing agent
0.5~2 part of amino modified carbon nanotube
5~20 parts of microspheres.
Epoxy resin of the present invention is the epoxy resin containing at least two epoxy groups or preferably rubber cross
Modified epoxy more preferably selects the EP-4100HF epoxy resin or EPR-4023 carboxy nitrile rubber of ADEKA companies of Japan
Cross-linking modified epoxy resin.Rubber cross modified epoxy due to liquid nitrile rubber in advance and cross linking of epoxy resin, rubber
As stress concentration center, the toughness of epoxy resin can be dramatically increased, so as to increase the resistant of high or low temperature of composition epoxy resin.
The epoxide diluent is containing there are two the low molecular weight glycidol ether of epoxy group, preferentially selects Shang Haishu
The 6350 of fat factory, any one in the ED-506 glycidol ethers of ADEKA companies of Japan.Shanghai Resin Factory 6350, Japan
The ED-506 epoxide diluents of ADEKA companies are the diglycidyl ether containing aliphatic chain in strand, and viscosity is low, dilution effect
Fruit is good, and Chain Flexibility is good, is introduced into epoxy three-dimensional crosslinked network, can alleviate stress concentration, play the role of toughening.
The mixture containing furans-Maleimide adduct is two contractings containing furans-Maleimide adduct
The mixture of water glycerin ether (FDB) and furans glycidol ether (FGE).FDB is 1 with FGE molar ratios：(0.5-1.5), preferably
It is 1:1, which can be by adjusting furans glycidol ether (FGE) and N, N'- dimethyl tetraphenyl bismaleimide (BMI)
Molar ratio example controls, and the control of molar ratio example is 3:1~5:1, preferably 4:1.Wherein add containing furans-maleimide
Diglycidyl ether (FDB) structural formula into object is as follows：
Due to furans with the covalent bond that maleimide base group is formed for dynamic reversible covalent bond, the furans at 60~70 DEG C
Addition reaction occurs with maleimide base group, forms covalent bond, ensures the adhesive strength of epoxy adhesive, and 110~130
The covalent bond that furans is formed with maleimide base group at DEG C is broken, and reduces the crosslink density of epoxy cross-linking network, is reduced
The intensity and modulus of epoxy resin cured product, so as to be easy to disassemble.Furans glycidol ether contains the ring of furan group for one end
Oxygen diluent is reacted, not only favorably using excessive furans glycidol ether and N, N'- dimethyl tetraphenyl bismaleimide
It is carried out in opening to forward direction, improves conversion ratio, while play dilution in situ containing furans-Maleimide adduct
The effect of diglycidyl ether makes the diglycidyl ether containing furans-Maleimide adduct become modest viscosity from powder
Epoxy mixture, so as to conducive to being blended with other epoxy resin.But the addition of furans glycidol ether nor
It is The more the better, because furans glycidol ether is monoglycidyl ether of the one end containing glycidol ether, although in the curing process
Participate in addition reaction, but cross-linked network structure cannot be formed, thus in order to ensure furans glycidol ether can dilute containing furans-
The diglycidyl ether of Maleimide adduct makes it easier to use, and does not reduce the purpose of epoxy curing compound mechanical property,
Furans glycidol ether and the molar ratio of N, N'- dimethyl tetraphenyl bismaleimide must be controlled.In addition, single shrink
Glycerin ether cooperates with use with the diglycidyl ether containing aliphatic chain, can play and slow down stress contraction problem in solidification process, subtract
Since stress shrinks the probability cracked in few adhesive solidification process.
The curing agent selects any one in aliphatic amine or alicyclic amines curing agent, preferentially selects the U.S.
1618 epoxy curing agents of aerochemistry ANCAMINE.1618 curing agent viscosity of ANCAMINE is low, and volatility is small, cures
It will not lead to the albefaction of solidfied material surface because absorbing moisture content and carbon dioxide in air in journey, be a kind of curable epoxide of environment-friendly type
Agent.
The amino modified carbon nanotube is to hold the multi-walled carbon nanotube of amido polyethyleneimine-modified, wherein polyethylene
Imines grafting rate is 1-2wt%, preferably (1.5 ± 0.2) wt%；8~15 nanometers of carbon nanotube mean outside diameter, internal diameter 3~5 is received
Rice, the JCMT-99-11-50 multi-wall carbon nano-tubes of 30~50 microns of length, preferably Nanjing Ji Cang nanosecond science and technology Co., Ltd production
Pipe；Polyethyleneimine is the polyethyleneimine of ethylenediamine end-blocking, and number-average molecular weight is 600~2500, and structural formula is as follows：
Preferred molecular weight is the polyethyleneimine of 600~800 low molecular weight ethylenediamine end-blocking.Carbon nanotube has toughening
Humidification is confirmed in many ways.But carbon nanotube is directly added into epoxy adhesive, it is easy to cause carbon nanotube group
It is poly-, in addition, since the interface compatibility of carbon nanotube and epoxy resin is very poor, when epoxy matrix is by extraneous stress, it is difficult to
By in stress transfer to the higher carbon nanotube of intensity, so as to not have the effect of toughening enhancing.So in order to increase carbon nanometer
Dispersibility and interface compatibility of the pipe in epoxy matrix, it is necessary to which surface modification is carried out to carbon nanotube.Common surface is modified
Method includes amidation, silanization etc..The polyethyleneimine of ethylenediamine end-blocking is a kind of part for including primary amine, secondary amine and tertiary amine
Branched polymer.Polar Amides in polyethyleneimine can generate hydrogen bond with hydroxyl reaction so that polyethyleneimine can with it is bonding
Substrate surface has good wellability, increases bonding force；In addition, the Polar Amides in polyethyleneimine again can be anti-with carbonic acyl radical
Covalent bond should be generated, so as to realize that the surface of carbon nanotube is modified by amidation process；Third, containing anti-in polyethyleneimine
Answering property very strong primary amine and secondary amine, can be easy to react with epoxy resin, form covalent bond, make modified carbon nanometer
Pipe can be connect by covalent bond with epoxy matrix, increase the interface compatibility of carbon nanotube and epoxy resin；4th, using poly-
The carbon nanotube that aziridine is modified contains hydrophobic vinyl structure so that carbon nanotube is very easy to divide in epoxy matrix
It dissipates.But the dosage of the polyethyleneimine of ethylenediamine end-blocking, nor The more the better, when addition is excessive, it is extra to cause
Polyethyleneimine is accumulated by hydrogen bond on oxide/carbon nanometer tube surface, is added into epoxy matrix, is opened with epoxy resin
What ring reacted is the polyethyleneimine that carbon nano tube surface is dissociated, and when by extraneous stress, free polyethyleneimine is with connecing
Hydrogen bond dissociation of the branch between the polyethyleneimine of carbon nano tube surface, carbon nanotube cannot be effectively passed to so as to cause stress
On filler, mechanical property is caused to reduce；When addition is very few, make the binding site between carbon nanotube and epoxy matrix less,
Stress can not effectively be transmitted.Therefore it is necessary to ensure that polyethyleneimine and carbon nano tube surface carboxyl-content are in preferable ratio,
Stress could effectively be transmitted.In addition, the molecular weight of polyethyleneimine also has an impact stress transfer, when molecular weight is too big, by
In space steric effect so that the effective grafting site for being grafted on carbon nano tube surface is reduced, and then stress transfer efficiency is caused to drop
It is low.
The microspheres are that shell is butyl acrylate, methyl methacrylate and methyl propenoic acid glycidyl
Thermoplastic propene's acid ester polymer that ester is formed, globular powder particle of the kernel for alkanes gas composition, particle diameter 10
~30 microns, outer casing thickness is 2~15 microns, and microspheres expansion start temperature is 90~100 DEG C, and maximum blowing temperature is
125~135 DEG C, the F-48 microspheres of preferably Japanese Matsumoto Yushi-Seiyaku Co., Ltd.'s production.Due to microspheres
Thermoplastic propene's acid ester polymer that shell is formed for glycidyl methacrylate with acrylate, can be with curable epoxide
Agent crosslinks reaction, forms covalent bond, improves the dispersibility and interface compatibility of microspheres.The kernel of microspheres
For alkanes gas, since expansion start temperature is 90~100 DEG C, so during epoxy adhesive crosslinking curing (25 DEG C/
+ 60 DEG C/12 hours 4 days) it will not expand, so as to ensure that epoxy adhesive has preferable bonding force.Microspheres
Maximum blowing temperature is 125~135 DEG C, and the reversible covalent bonds that furans is formed with maleimide base group at 110~130 DEG C
It can be broken so that cross linking of epoxy resin density reduces, and matrix softening, the matrix of softening is in microspheres foaming and intumescing
In the process, due to the impetus of internal pressure so that furans is separated from each other with maleimide base group, further increases ring
The Discerptibility of oxygen adhesive.Using furans and the reversible covalent bonds that maleimide base group is formed combined at different temperatures with
The characteristic of fracture and the foam characteristics of microspheres ensure that the bonding of epoxy adhesive and disassemble performance.
The another technical solution that the present invention solves above-mentioned technical problem is as follows：It is a kind of can rapid disassembling epoxy adhesive
Preparation method, which is characterized in that it includes the following steps：
A. a certain amount of amino modified carbon nanotube and epoxy hardener are weighed by formula, ultrasound point is carried out after being sufficiently mixed
It dissipates, obtains curing agent pre-composition 1；
B. a certain amount of epoxy resin, epoxide diluent and mixing containing furans-Maleimide adduct are weighed by formula
Object is closed, microspheres is added in after being sufficiently mixed, continues to be sufficiently mixed, obtain epoxy pre-composition 2；
C. a certain amount of epoxy pre-composition 2 and epoxy hardener 1 are weighed by formula, is sufficiently mixed to obtain epoxy adhesive premix
Object 3；
D. epoxy adhesive pre-composition 3 is poured into be stirred under vacuum in kettle and stirs deaeration to get disassembled epoxy adhesive.
The another technical solution that the present invention solves above-mentioned technical problem is as follows：It is a kind of can rapid disassembling epoxy adhesive
Rapid disassembling method, which is characterized in that it includes the following steps：
Adhering part (such as bonding test sample plate) is toasted in (130 ± 5) DEG C baking oven, baking time was with 30 minutes
It is excellent, stretches or remove bonding adhering part and can be realized and disassemble；Or by adhering part immerse dimethyl sulfoxide (DMSO) in
Toasted in (120 ± 2) DEG C baking oven, baking time with 10~20 minutes to be excellent, the epoxy adhesive of bonding can be completely dissolved or
It is partly dissolved.
The another technical solution that the present invention solves above-mentioned technical problem is as follows：It is mixed containing furans-Maleimide adduct
Close the preparation method of object, which is characterized in that it includes the following steps：By N, N'- dimethyl tetraphenyl bismaleimide is dissolved in
In tetrahydrofuran, under nitrogen, stirring condition, excessive furans glycidol ether is slowly added to N, N'- dimethyl tetraphenyl spans
Come in acid imide-tetrahydrofuran solution, in 66 DEG C of back flow reactions for a period of time, be excellent with 24 hours, be then evaporated under reduced pressure out four
Hydrogen THF solvent is to get the mixture containing furans-Maleimide adduct.
The another technical solution that the present invention solves above-mentioned technical problem is as follows：The system of the carbon nanotube of polyethyleneimine-modified
Preparation Method, which is characterized in that it includes the following steps：
A. multi-walled carbon nanotube is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, stirring, in (65 ± 2) DEG C, heat preservation
Reaction a period of time was excellent with 90 minutes；Washing of Filter Cake after filtering obtains product oxide/carbon nanometer tube to neutrality after dry；
B. oxide/carbon nanometer tube is dispersed in n,N-Dimethylformamide solvent, obtains oxide/carbon nanometer tube-N, N- bis-
Methylformamide solution；By the polyethyleneimine of ethylenediamine end-blocking and O- (7- azepine benzos triazol-1-yl)-N, N, N ', N '-four
Methylurea hexafluorophosphoric acid ester (HATU) is added in n,N-Dimethylformamide solvent, obtains polyethylenimine solution；Then by poly- second
Alkene imide liquor is added in oxide/carbon nanometer tube-n,N-Dimethylformamide solution, stirring, when reacting one section in (120 ± 5) DEG C
Between, using 12h to be excellent；It filters and is washed with N,N-dimethylformamide into filtrate and detected without polyethyleneimine residue；It is dry
The carbon nanotube that product is polyethyleneimine-modified is obtained afterwards.
The beneficial effect comprise that：The epoxy adhesive preparation process of the present invention is simple, easy to use；Bonding force
By force, all there is excellent adhesive property with various metals base material；It toasts in an oven or adhering part is immersed into dimethyl sulfoxide (DMSO)
In toast in an oven, you can realize that metal adhesive component being disassembled and recycles.Therefore, epoxy adhesive of the invention, especially
Bonding suitable for sheet metal material, the especially metal material containing radioactive element and recycling is disassembled, realizing adhesive property
While, pressure of the radioactive metal material to environment is reduced, substantially increases resource recycling rate of waterused.
Description of the drawings
Fig. 1 is the schematic diagram that sample makes in tensile shear strength test process；
Fig. 2 is N, N'- dimethyl tetraphenyl bismaleimide (a), furans glycidol ether (b), both mixture (c)
With the infrared spectrum for reacting (d) for 24 hours；
Fig. 3 is N, N'- dimethyl tetraphenyl bismaleimide (a), furans glycidol ether (b), both mixture (c)
With reaction for 24 hours (d)1H nuclear magnetic spectrograms；
Fig. 4 is the shape appearance figure of the invention epoxy adhesive；
Fig. 5 is the microstructure schematic diagram of the invention epoxy adhesive.
Specific embodiment
The invention is further described below by with reference to attached drawing, but does not limit protection scope of the present invention.
The acquisition of component material
Epoxy resin selects the EP-4100HF epoxy resin of ADEKA companies of Japan or EPR-4023 carboxy nitrile rubber to hand over
Join modified epoxy.Epoxide diluent selects the 6350 of Shanghai Resin Factory or the ED-506 glycidols of ADEKA companies of Japan
Any one in ether.Mixture containing furans-Maleimide adduct is two contractings containing furans-Maleimide adduct
The mixture of water glycerin ether (FDB) and furans glycidol ether (FGE), FDB are 1 with FGE molar ratios：1, which passes through tune
Whole furans glycidol ether (FGE) and N, N'- dimethyl tetraphenyl bismaleimide (BMI) molar ratio example control, and throw
It is 4 to expect molar ratio control:1.Curing agent selects 1618 epoxy curing agents of U.S. aerochemistry ANCAMINE.Amido carbon
Nanotube be ethylenediamine end-blocking polyethyleneimine-modified multi-walled carbon nanotube, wherein grafting polyethylene imine rate be 1wt%, carbon
Nanotube selects the JCMT-99-11-50 of Nanjing Ji Cang Nanosolutions GmbH production, and polyethyleneimine selects ethylenediamine envelope
The polyethyleneimine at end, number-average molecular weight 600.Microspheres select the F- of Japanese Matsumoto Yushi-Seiyaku Co., Ltd.'s production
48.All compositions need to be stored in dry and ventilated shady place.
The test method of physical and chemical performance
(1) tensile shear strength
By 7124 standards of GB/T, the iron plate of 0.8mm thickness is positioned in ethanol solution and is ultrasonically treated 20 minutes, room temperature is done
It is dry；Surface is wiped with acetone again, is positioned in 50 DEG C of baking oven dry.Prepared epoxy adhesive is finally applied to sample sample
Plate cures 4 days at 25 DEG C, then cures 12 hours at 60 DEG C to get test sample plate.In order to control bondline thickness, prepare
Glue in be mixed into a small amount of 30 microns of glass microballoon.Sample makes as shown in Figure 1.
Bonding model at 130 DEG C is heated 30 minutes, is then rapidly cooled to room temperature to get model is disassembled.
Using the front and rear tensile shear strength of almighty test machine test sample plate heating, speed 50mm/min, contact surface
12.5 × 25mm of product2；The average value of 3 test sample plates is taken, is rounded up to integer, is represented with MPa.
(2) dissolubility
The epoxy adhesive after 0.1g curings is taken to be placed in dimethyl sulfoxide solvent, 4h is placed at room temperature for, then heats to 120
DEG C heating 20 minutes, the front and rear dissolubility of observation epoxy adhesive heating.
The preparation of mixture of the embodiment 1 containing furans-Maleimide adduct
7.14g (0.02 mole) N, N'- dimethyl tetraphenyl bismaleimide is dissolved in 20mL tetrahydrofurans, then
It pours into 100mL three-necked flasks, magnetic agitation, leads to nitrogen.Then it is 12.32g (0.08 mole) furans glycidol ether is slow
N is added in, in N'- dimethyl tetraphenyl bismaleimide-tetrahydrofuran solution, is flowed back 24 hours at 66 DEG C, then decompression is steamed
Tetrahydrofuran solvent is distillated to get the mixture containing furans-Maleimide adduct.In preparation process, each respective components
Infrared spectrum and1H nuclear magnetic spectrograms are as Figure 2-3.
The preparation of the carbon nanotube of 2 polyethyleneimine-modified of embodiment
A. weigh 2g multi-walled carbon nanotubes (Nanjing Ji Cang nanometers of model JCMT-99-11-50) add in 30 milliliters of concentrated sulfuric acids with
10 milliliters of concentrated nitric acid (volume ratios 3：1) in mixed solution, magnetic agitation, 600 turns per minute of mixing speed is warming up to 65 DEG C, protects
Temperature reaction 90 minutes；Then aperture is used as 0.45 micron of organic membrane filtration；Filter cake is disperseed in deionized water again
Filter cake, until being in neutrality, is finally dried in vacuo 6 hours, products therefrom is oxygen by washing, filtering in 110 DEG C of baking ovens
Carbon nano tube；
B. 1g oxide/carbon nanometer tubes are weighed, are added in 20 milliliters of n,N-Dimethylformamide solvents, are then surpassed at 80 DEG C
Sound disperses 30 minutes, ultrasonic power 100W, until oxide/carbon nanometer tube is thoroughly dispersed in n,N-Dimethylformamide solvent, obtains
To oxide/carbon nanometer tube-N,N-dimethylformamide solution；Then the polyethyleneimine and 0.02g of 0.2g ethylenediamine end-blockings are weighed
O- (7- azepine benzos triazol-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphoric acid ester (HATU) add in 20 milliliters of N, N- diformazans
In base formamide solvent, dissolving obtains polyethylenimine solution；Then polyethylenimine solution is added in into oxide/carbon nanometer tube-N,
In dinethylformamide solution, magnetic agitation, 600 turns per minute of mixing speed is warming up to 120 DEG C, insulation reaction 12h.So
Aperture is used to be washed repeatedly with n,N-Dimethylformamide for 0.45 micron of organic membrane filtration afterwards, until without poly- in filtrate
Aziridine residue detects.Gained filter cake is dried in vacuo 6 hours in 110 DEG C of baking ovens, products therefrom is polyethyleneimine
The multi-walled carbon nanotube that amine is modified.
Embodiment 3 can rapid disassembling epoxy adhesive preparation method
A. a certain amount of amino modified carbon nanotube (or polyethyleneimine-modified of the gained of embodiment 2 is weighed by formula
Carbon nanotube) and epoxy hardener, in the revolution rotation mixing deaeration machine of RN-500 20 are stirred with 1000 revs/min of speed
Minute, then ultrasonic disperse premixes for 30 minutes to get curing agent in the ultrasonic washing instrument that power is 100W, temperature is 60 DEG C
Object 1；
B. a certain amount of epoxy resin, epoxide diluent and mixing containing furans-Maleimide adduct are weighed by formula
Object is closed, is slowly heated to 70 DEG C, then high-speed stirred 20 minutes is slightly mixed 3 times with three-roll grinder, thin 3 times mixed；Add in thermal expansion
Microballoon, then with 1000 revs/min of speed in the revolution rotation mixing deaeration machine of the RN-500 of Japanese THINKY companies production
Degree stirring 10 minutes, obtains epoxy pre-composition 2；
C. a certain amount of epoxy pre-composition 2 and epoxy hardener 1 are weighed by formula, it is de- in the revolution rotation mixing of RN-500
10 minutes are stirred to get epoxy adhesive pre-composition 3 with 1000 revs/min of speed in bubble machine；
D. epoxy adhesive pre-composition 3 is poured into be stirred under vacuum in kettle and stirs deaeration, 300 turns per minute of mixing speed takes off
30 minutes time is steeped, vacuum degree -0.095MPa is to get disassembled epoxy adhesive, shape appearance figure and microstructure schematic diagram
Respectively as illustrated in figures 4-5.
Using the above process and method, obtaining following 4 formulas respectively, (additive amount of each component is with weight fraction in formula
Meter) epoxy adhesive product：
Formula one
Epoxy resin：ADEKA EP-4100HF 40
Epoxide diluent：Aliphatic diglycidylether (ADEKA ED-506) 20
Mixture containing furans-Maleimide adduct：(FDB and FGE molar ratios 1:1) 60
The multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified： 1
Microspheres：(Japanese Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 7
Curing agent：Alicyclic curing agent (U.S. aerochemistry ANCAMINE 1618) 48
Formula two
Epoxy resin：ADEKA EP-4100HF 45
Flexible epoxy diluent：Aliphatic diglycidylether (ADEKA ED506) 20
Mixture containing furans-Maleimide adduct：(FDB and FGE molar ratios 1:1) 55
The multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified： 1.5
Microspheres：(Japanese Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 6
Curing agent：Alicyclic curing agent (U.S. aerochemistry ANCAMINE 1618) 56
Formula three
Epoxy resin：ADEKA EP-4100HF 30
Epoxide diluent：Aliphatic diglycidylether (Shanghai Resin Factory 6350) 15
Mixture containing furans-Maleimide adduct：(FDB and FGE molar ratios 1:1) 70
The multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified： 2
Microspheres：(Japanese Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 5
Curing agent：Alicyclic curing agent (U.S. aerochemistry ANCAMINE 1618) 58
Formula four
Epoxy resin：Carboxy nitrile rubber cross-linked epoxy resin (ADEKA EPR-4023) 25
Flexible epoxy diluent：Aliphatic diglycidylether (Shanghai Resin Factory 6350) 20
Mixture containing furans-Maleimide adduct：(FDB and FGE molar ratios 1:1) 75
The multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified： 1
Microspheres：(Japanese Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 4
Curing agent：Alicyclic curing agent (U.S. aerochemistry ANCAMINE 1618) 54
Embodiment 4 can rapid disassembling epoxy adhesive rapid disassembling method
Adhering part in 130 DEG C of baking ovens is toasted 30 minutes, stretches or removes bonding adhering part and can be realized
It disassembles or will be toasted 10~20 minutes in 120 DEG C of baking ovens in adhering part immersion dimethyl sulfoxide (DMSO), the epoxy adhesive of bonding
It can be completely dissolved or be partly dissolved.
The offer of comparative example
In order to compare the effect for embodying the present invention, following two comparative examples are provided and are subject to comparative illustration.
Comparative example 1
Epoxy resin component includes following formulas by weight：
Epoxy resin：Wuxi resin processing plant E-51 100
Epoxide diluent：Aliphatic diglycidylether (Shanghai Resin Factory 6350) 20
Curing agent：Diethylenetriamine curing agent (DETA) 14
According to proportioning by all E-51 epoxy resin and 6350 aliphatic 2-glycidyls in above-mentioned 1 component of comparative example
Ether is stirred in the revolution rotation mixing deaeration machine of the RN-500 of Japanese THINKY companies production with 1000 revs/min of speed
10 minutes, obtain pre-composition 1；Then a certain amount of pre-composition 1 and all DETA epoxy hardeners are weighed by formula, in Japanese RN-
In 500 revolution rotation mixing deaeration machine with 1000 revs/min of speed stirring 10 minutes to get can rapid disassembling epoxy glue
Stick pre-composition 2；This pre-composition 2 is poured into be stirred under vacuum in kettle, deaeration 30 minutes, vacuum are stirred with 300 revs/min of speed
Degree -0.095MPa is to get epoxy adhesive.
Comparative example 2
Epoxy resin component includes following formulas by weight：
Epoxide diluent：Aliphatic diglycidylether (ADEKA ED506) 20
Mixture containing furans-Maleimide adduct： 100
Curing agent：Alicyclic curing agent (U.S. aerochemistry ANCAMINE 1618) 48
According to proportioning weigh in above-mentioned 2 component of comparative example all mixtures containing furans-Maleimide adduct and
6350 aliphatic diglycidylethers are slowly heated to 60 DEG C, then in the revolution of the RN-500 of Japanese THINKY companies production
It is stirred 10 minutes with 1000 revs/min of speed in rotation mixing deaeration machine, obtains epoxy pre-composition 1；Then all epoxies are added in
Curing agent stirs 10 minutes to get for gold in the revolution rotation mixing deaeration machine of RN-500 with 1000 revs/min of speed
Belong to the epoxy adhesive pre-composition of bonding.This epoxy adhesive pre-composition is poured into and is stirred under vacuum in kettle with 300 revs/min of speed
Degree stirring deaeration 30 minutes, vacuum degree -0.095MPa is to get disassembled type epoxy adhesive.
As a result it and analyzes
The epoxy adhesive that will be obtained in embodiment 3 and comparative example, using the test method point of above-mentioned physical and chemical performance
It is not detected, the results are shown in Table 1.
1 data of table are analyzed, we are it is seen that tensile shear strength is high before the heating of formula one~formula four
In comparative example 1, illustrate that adding in the multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified and microspheres helps to draw
Stretch the increase of shear strength, this is because the multi-walled carbon nanotube of ethylenediamine end-blocking polyethyleneimine-modified and microspheres with
Epoxy adhesive matrix can form covalent bond, have preferable interface compatibility with epoxy matrix, when epoxy adhesive is by outer
During boundary's stress, stress can be effectively passed in carbon nanotube and microspheres, dissipation energy, so as to increase epoxy adhesive
Tensile shear strength.In addition, with the diglycidyl ether containing furans-Maleimide adduct in formula one~formula four
Increase, tensile shear strength reduces seldom before epoxy adhesive heating, but heat post-tensioning shear strength reduce quickly, so as to
Epoxy adhesive is made to illustrate furans-Malaysia in heating process from insoluble to being partly dissolved and being completely dissolved after heating before heating
The reversible covalent bonds fracture that acid imide addition product is formed, under the action of microspheres expansive force, fast cooling after the heating
In the process, reversible covalent bonds have little time to re-form, and then the network cross-linked density of epoxy adhesive is caused to substantially reduce, even
Slabbing segment is decomposed, so that epoxy adhesive is partly dissolved or is completely dissolved after heating；And comparative example 1 can due to being free of
Inverse covalent bond and microspheres, so mechanical property is in a slight decrease after heating, it is impossible to dissolve, this further proves furans-horse
The expansive force of reversible covalent bonds and microspheres for carrying out the formation of acid imide addition product contributes to epoxy adhesive realization to disassemble.And
Epoxy adhesive (comparative example 2) is prepared using the diglycidyl ether containing furans-Maleimide adduct completely, although also can
Realize disassembling for epoxy adhesive, but tensile shear strength is relatively low before heating, to the applicability of metal adhesive requirement under room temperature
It is poor.
Claims (20)
1. it is a kind of can rapid disassembling epoxy adhesive, including following parts by weight each raw material composition：
20~50 parts of epoxy resin；
10~20 parts of epoxide diluent；
50~80 parts of mixture containing furans-Maleimide adduct；
40~70 parts of curing agent；
0.5~2 part of amino modified carbon nanotube；
5~20 parts of microspheres；
Wherein, the mixture containing furans-Maleimide adduct is two contractings containing furans-Maleimide adduct
The mixture of water glycerin ether and furans glycidol ether.
2. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the epoxy resin is
Epoxy resin containing at least two epoxy groups or rubber cross modified epoxy.
3. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that epoxy resin choosing
With the EP-4100HF epoxy resin of Japanese ADEKA companies or the cross-linking modified epoxy resin of EPR-4023 carboxy nitrile rubber.
4. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the epoxide diluent
To contain the low molecular weight glycidol ether there are two epoxy group.
5. it is according to claim 4 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the epoxide diluent
Select the diglycidyl ether containing aliphatic chain in strand.
6. it is according to claim 5 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the epoxide diluent
Select any one in the 6350 of Shanghai Resin Factory, the ED-506 glycidol ethers of ADEKA companies of Japan.
7. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that containing furans-Malaysia acyl
The diglycidyl ether of Imine adduct is 1 with the molar ratio of furans glycidol ether：(0.5-1.5)；Wherein contain furans-horse
The diglycidyl ether structural formula for carrying out acid imide addition product is as follows：
8. it is according to claim 7 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that containing furans-Malaysia acyl
The diglycidyl ether of Imine adduct is 1 with the molar ratio of furans glycidol ether:1.
9. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that described curing agent choosing
With any one in aliphatic amine or alicyclic amines curing agent.
10. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the curing agent
Select 1618 epoxy curing agents of U.S. aerochemistry ANCAMINE.
11. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the amido changes
Property carbon nanotube be hold amido polyethyleneimine-modified multi-walled carbon nanotube.
12. it is according to claim 11 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the amido changes
Property carbon nanotube in grafting polyethylene imine rate be 1-2wt%.
13. it is according to claim 11 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the amido changes
Property carbon nanotube in grafting polyethylene imine rate be (1.5 ± 0.2) wt%.
14. it is according to claim 11 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the amido changes
Property carbon nanotube in polyethyleneimine be ethylenediamine end-blocking polyethyleneimine, number-average molecular weight be 600~2500, structural formula is such as
Under：
15. it is according to claim 14 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the ethylenediamine
The number-average molecular weight of the polyethyleneimine of sealing end is 600-800.
16. it is according to claim 11 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the carbon nanotube
8~15 nanometers of mean outside diameter, 3~5 nanometers of internal diameter, 30~50 microns of length.
17. it is according to claim 11 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the carbon nanotube
Select the JCMT-99-11-50 multi-walled carbon nanotubes of Nanjing Ji Cang nanosecond science and technology Co., Ltd production.
18. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the thermal expansion
Microballoon is that shell is the thermoplastic acrylic that butyl acrylate, methyl methacrylate and glycidyl methacrylate are formed
Ester polymer, kernel are the globular powder particle of alkanes gas composition.
19. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the thermal expansion
A diameter of 10~30 microns of microsphere particle, outer casing thickness are 2~15 microns, and microspheres expansion start temperature is 90~100
DEG C, maximum blowing temperature is 125~135 DEG C.
20. it is according to claim 1 it is a kind of can rapid disassembling epoxy adhesive, which is characterized in that the thermal expansion
Microballoon selects the F-48 microspheres of Japanese Matsumoto Yushi-Seiyaku Co., Ltd.'s production.
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| JP6748999B2 (en) * | 2016-08-26 | 2020-09-02 | 国立大学法人横浜国立大学 | Adhesive composition |
| US10738171B2 (en) * | 2017-02-24 | 2020-08-11 | Toray Industries, Inc. | Sizing-coated carbon fiber bundle, thermoplastic resin composition, molded body, method for manufacturing sizing-coated carbon fiber bundle, and method for manufacturing molded body |
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| JP6874867B2 (en) * | 2018-02-09 | 2021-05-19 | Dic株式会社 | Adhesive tape, articles and methods of manufacturing articles |
| CN110734724B (en) * | 2018-10-19 | 2021-12-21 | 嘉兴学院 | Preparation method of epoxy resin heat-conducting adhesive |
| CN109401706B (en) * | 2018-10-31 | 2021-06-25 | 深圳广恒威科技有限公司 | High-reliability filling adhesive capable of being rapidly cured |
| CN109439254B (en) * | 2018-10-31 | 2021-05-04 | 深圳广恒威科技有限公司 | High-reliability filling adhesive capable of being repaired |
| CN110655816A (en) * | 2019-09-16 | 2020-01-07 | 江苏理工学院 | Self-repairing antibacterial crack sealer and preparation method thereof |
| JPWO2022202610A1 (en) * | 2021-03-23 | 2022-09-29 | ||
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| CN113388350B (en) * | 2021-06-30 | 2022-08-30 | 顺德职业技术学院 | Epoxy structural adhesive capable of being heated for repair and preparation method thereof |
| EP4148098A1 (en) | 2021-09-08 | 2023-03-15 | Sika Technology AG | Expandable one-component thermosetting epoxy adhesive with improved adhesion |
| JP7533821B2 (en) * | 2022-05-17 | 2024-08-14 | Dic株式会社 | Glycidyl ether group-containing compound, curable resin composition, cured product, and laminate |
| CN116239980A (en) * | 2023-02-23 | 2023-06-09 | 中南民族大学 | Visual epoxy resin adhesive for bonding process and preparation method thereof |
| CN117987061B (en) * | 2024-02-05 | 2024-10-11 | 青岛德聚胶接技术有限公司 | Photo-curing adhesive for bonding flexible printed circuit board and preparation method thereof |
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