CN105694790A - Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof - Google Patents
Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof Download PDFInfo
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- CN105694790A CN105694790A CN201610113331.5A CN201610113331A CN105694790A CN 105694790 A CN105694790 A CN 105694790A CN 201610113331 A CN201610113331 A CN 201610113331A CN 105694790 A CN105694790 A CN 105694790A
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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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- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
The invention provides an epoxy adhesive capable of being removed quickly. The epoxy adhesive is prepared from, by weight, 20-50 parts of epoxy resin, 10-20 parts of epoxy diluent, 50-80 parts of mixture containing a furan-maleimide addition product, 40-70 parts of curing agent, 0.5-2 parts of amido modified carbon nano tube and 5-20 parts of thermal expansion microsphere, wherein the mixture containing the furan-maleimide addition product is the diglycidyl ether and furan glycidyl ether mixture containing the furan-maleimide addition product. The epoxy adhesive is high in bonding strength at room temperature and is easy to remove at medium temperature.
Description
Technical field
The present invention relates to adhesive material, particularly to one for metal and metal, especially contain the epoxy adhesive of the bonding double-component cold curing of the thin metal layer material of radioelement and preparation thereof and disassembling method。
Background technology
Epoxy adhesive has the cementability of excellence, chemical stability, resistant of high or low temperature, and the advantage such as shrinkage factor is low, with low cost, it is widely used in various metals bonding with metal, it has also become indispensable basic material in Aero-Space, automobile, military project and other field。Every annual consumption is more than 2,000,000 tons。Some adopts the product that epoxy adhesive is bonding, when adhering part is retired, it is necessary to reclaim the metal base containing radioelement。
But, epoxy adhesive, owing to forming three-dimensional net structure after solidifying, insoluble does not melt, and it disassembles extremely difficult。Current industrial usual employing pyrolysismethod or solvent decomposition method。Such as: epoxy thermoset is heated 2 hours by Gleice etc. at 450 DEG C, treat that curable epoxide thing decomposes completely, could realize disassembling。Liu etc., under phenol and potassium hydroxide exist, utilize supercritical water decomposition curable epoxide thing, however it is necessary that substantial amounts of phenol and potassium hydroxide。In a word, these disassembling methods not only energy expenditure is huge, and environmental pollution ratio is more serious, and frequently can lead to matrix material to be recycled and produce to destroy。If inserting reversible covalent bonds in epoxy matrix, by the disconnection of reversible covalent bonds, it is achieved disassembling of epoxy adhesive, better select beyond doubt。Such as: patent CN201510129184.6 discloses a kind of flip-chip underfill with the quick capillary flow of room temperature and quick prosthetic。This underfill utilizes maleimide and furan end group polymer that inverse Diels-Alder can be occurred to react realization reduction bond matrix performance, improves the purpose reprocessing performance。But this underfill needs intermediate temperature setting, it is impossible to meet the requirement of the bonding normal temperature cure of general sheet metal, and this patent does not study the bonding force of this underfill and metal base yet。
In view of metal adhesive epoxy adhesive needs cold curing, metal base wettability is good, bonding force is strong, and the feature that energy rapid disassembling reclaims, applicant by can with metal surface formed stronger Van der Waals force polyethyleneimine-modified CNT, glycidyl oxirane containing reversible covalent bonds and there is with epoxy matrix the microspheres of the better compatibility combine, modified synergic epoxy adhesive, utilize three's respective reaction characteristics at different temperatures, invented a kind of for metal adhesive can the epoxy adhesive of rapid disassembling and preparation thereof and disassembling method。
Summary of the invention
It is poor with metal base bonding force to it is an object of the invention to as solving common epoxy adhesive, disassemble difficulty, energy expenditure huge, environmental pollution is serious, the process of disassembling is easily caused the problems such as components damage, it is provided that a kind of for metal adhesive can the epoxy adhesive of rapid disassembling and preparation thereof and disassembling method。Epoxy adhesive prepared by the present invention, under room temperature, adhesive strength is high, and middle temperature is disassembled easily。
The technical scheme is that a kind of can the epoxy adhesive of rapid disassembling, each raw material including following weight portion forms:
Epoxy resin 20～50 parts
Epoxide diluent 10～20 parts
50～80 parts of mixture containing furan-Maleimide adduct
40～70 parts of firming agent
Amino modified CNT 0.5～2 part
Microspheres 5～20 parts。
Epoxy resin of the present invention is the epoxy resin containing at least two epoxide group or is preferably rubber cross modified epoxy, more preferably selects EP-4100HF epoxy resin or the cross-linking modified epoxy resin of EPR-4023 carboxy terminated nitrile rubber of ADEKA company of Japan。Rubber cross modified epoxy due to LNBR in advance with cross linking of epoxy resin, rubber concentrates center as stress, can dramatically increase the toughness of epoxy resin, thus increasing the resistant of high or low temperature of composition epoxy resin。
Described epoxide diluent is the low-molecular-weight glycidyl ether containing two epoxide groups, preferential selects the 6350 of Shanghai Resin Factory, any one in the ED-506 glycidyl ether of ADEKA company of Japan。The 6350 of Shanghai Resin Factory, the diglycidyl ether that the ED-506 epoxide diluent of ADEKA company of Japan is in strand containing aliphatic chain, viscosity is low, and dilution effect is good, and Chain Flexibility is good, it is introduced in epoxy three-dimensional crosslinked network, stress can be alleviated and concentrate, play toughness reinforcing effect。
The described mixture containing furan-Maleimide adduct is the mixture of the diglycidyl ether (FDB) containing furan-Maleimide adduct and furan glycidyl ether (FGE)。FDB and FGE molar ratio is 1:(0.5-1.5), it is preferably 1:1, this ratio can be passed through to adjust furan glycidyl ether (FGE) and N, N'-dimethyl tetraphenyl BMI (BMI) molar ratio example controls, molar ratio example controls as 3:1～5:1, it is preferred to 4:1。Wherein diglycidyl ether (FDB) structural formula containing furan-Maleimide adduct is as follows:
The covalent bond formed due to furan and maleimide base group is dynamic reversible covalent bond, furan and maleimide base group generation additive reaction at 60～70 DEG C, form covalent bond, ensure the adhesive strength of epoxy adhesive, and the covalent bond that furan and maleimide base group are formed at 110～130 DEG C ruptures, reducing the crosslink density of epoxy cross-linking network, reducing intensity and the modulus of epoxy resin cured product, thus being prone to disassemble。Furan glycidyl ether is the epoxide diluent that furan group is contained in one end, adopt excessive furan glycidyl ether and N, N'-dimethyl tetraphenyl BMI reacts, not only contribute to opening carry out to forward, improve conversion ratio, simultaneously work as the effect of the original position dilution diglycidyl ether containing furan-Maleimide adduct, making the diglycidyl ether containing furan-Maleimide adduct be become the epoxy mixture of modest viscosity from powder, carrying out blended thus being beneficial to other epoxy resin。But, the addition of furan glycidyl ether neither be The more the better, because furan glycidyl ether is the one end monoglycidyl ether containing glycidyl ether, although participating in additive reaction in the curing process, but cross-linked network structure can not be formed, so in order to ensure that furan glycidyl ether can dilute the diglycidyl ether containing furan-Maleimide adduct, make it easier to use, do not reduce again the purpose of curable epoxide thing mechanical property, furan glycidyl ether and the molar ratio of N, N'-dimethyl tetraphenyl BMI must be controlled。Use it addition, monoglycidyl ether is collaborative with the diglycidyl ether containing aliphatic chain, can play and slow down stress contraction problem in solidification process, reduce in adhesive solidification process owing to stress shrinks the probability cracked。
Described firming agent selects any one in aliphatic amine or alicyclic amine curing agent, preferential selection US Air chemistry ANCAMINE1618 epoxy curing agent。ANCAMINE1618 firming agent viscosity is low, and volatility is little, will not cause the albefaction of solidfied material surface because of absorption water in air part and carbon dioxide, be the epoxy hardener of a kind of environment-friendly type in solidification process。
Described amino modified CNT is the multi-walled carbon nano-tubes of end amido polyethyleneimine-modified, and wherein grafting polyethylene imine rate is 1-2wt%, it is preferred to (1.5 ± 0.2) wt%；CNT mean outside diameter 8～15 nanometers, internal diameter 3～5 nanometers, length 30～50 microns, it is preferable that the JCMT-99-11-50 multi-walled carbon nano-tubes that Nanjing Ji Cang nanosecond science and technology company limited produces；Polymine is the polymine of ethylenediamine end-blocking, and number-average molecular weight is 600～2500, and structural formula is as follows:
Preferred molecular weight is the polymine of the low-molecular-weight ethylenediamine end-blocking of 600～800。CNT has toughness reinforcing potentiation, is in many ways confirmed。But CNT is directly added in epoxy adhesive, it is easily caused CNT to reunite, additionally, owing to the interface compatibility of CNT Yu epoxy resin is very poor, when epoxy matrix is subject to extraneous stress, it is difficult on CNT higher for Stress Transfer to intensity, thus not having the effect of toughness reinforcing enhancing。So, in order to increase CNT dispersibility in epoxy matrix and interface compatibility, it is necessary to CNT is carried out surface modification。Conventional surface modifying method includes amidatioon, silanization etc.。The polymine of ethylenediamine end-blocking is a kind of part branch polymer comprising primary amine, secondary amine and tertiary amine。Polar Amides in polymine can generate hydrogen bond with hydroxyl reaction so that polymine can have good wellability with bonding substrate surface, increases bonding force；It addition, the Polar Amides in polymine can react generation covalent bond with carbonic acyl radical again, realize the surface modification of CNT thereby through amidation process；3rd, containing reactive very strong primary amine and secondary amine in polymine, it is possible to be easy to react with epoxy resin, form covalent bond, enable modified CNT to be connected with epoxy matrix by covalent bond, increase the interface compatibility of CNT and epoxy resin；4th, adopt the CNT of polyethyleneimine-modified to contain hydrophobic vinyl structure so that CNT is very easy to dispersion in epoxy matrix。But, the consumption of the polymine of ethylenediamine end-blocking neither be The more the better, when addition is too much, cause unnecessary polymine by hydrogen bond at oxide/carbon nanometer tube surface sediment, it is added in epoxy matrix, with epoxy resin generation ring-opening reaction be the free polymine of carbon nano tube surface, when being subject to extraneous stress, the free hydrogen bond between polymine and the polymine being grafted on carbon nano tube surface dissociates, thus causing that stress can not be effectively passed in carbon nanotube filler, cause that mechanical property reduces；When addition is very few, make the binding site between CNT and epoxy matrix less, can not effectively transmit stress。Therefore it is necessary to ensure that polymine and carbon nano tube surface carboxyl-content are in better ratio, could effectively transmit stress。It addition, the molecular weight counter stress transmission of polymine also has impact, when molecular weight is too big, due to space steric effect so that the effective grafting site being grafted on carbon nano tube surface reduces, and then causes that Stress Transfer efficiency reduces。
Described microspheres is shell is thermoplastic propene's acid ester polymer of being formed of butyl acrylate, methyl methacrylate and glycidyl methacrylate, kernel is the globular powder granule of alkanes gas composition, particle diameter is 10～30 microns, outer casing thickness is 2～15 microns, microspheres expansion start temperature is 90～100 DEG C, maximum blowing temperature is 125～135 DEG C, it is preferable that the F-48 microspheres that Matsumoto Yushi-Seiyaku Co., Ltd. of Japan produces。Owing to the shell of microspheres is thermoplastic propene's acid ester polymer that glycidyl methacrylate is formed with acrylate, it is possible to epoxy hardener generation cross-linking reaction, formation covalent bond, the dispersibility of raising microspheres and interface compatibility。The kernel of microspheres is alkanes gas, owing to expansion start temperature is 90～100 DEG C, so (25 DEG C/4 days+60 DEG C/12 hours) will not expand in epoxy adhesive crosslinking curing process, thus ensureing that epoxy adhesive has good bonding force。The maximum blowing temperature of microspheres is 125～135 DEG C, and the reversible covalent bonds that furan and maleimide base group are formed at 110～130 DEG C can rupture, make cross linking of epoxy resin decrease in density, matrix softens, the matrix of softening is in the process of microspheres foaming and intumescing, impetus due to internal pressure so that furan and maleimide base group are separated from each other, and further increase the Discerptibility of epoxy adhesive。The reversible covalent bonds that furan is formed with maleimide base group is utilized to be combined the foam characteristics with the characteristic ruptured and microspheres at different temperatures, it is ensured that epoxy adhesive bonding and disassemble performance。
This invention address that the another technical scheme of above-mentioned technical problem is as follows: a kind of can the preparation method of epoxy adhesive of rapid disassembling, it is characterised in that it comprises the following steps:
A. weigh a certain amount of amino modified CNT and epoxy hardener by formula, carry out ultrasonic disperse after being sufficiently mixed, obtain firming agent pre-composition 1；
B. weigh a certain amount of epoxy resin, epoxide diluent and the mixture containing furan-Maleimide adduct by formula, add microspheres after being sufficiently mixed, continue to be sufficiently mixed, obtain epoxy pre-composition 2；
C. weigh a certain amount of epoxy pre-composition 2 and epoxy hardener 1 by formula, be sufficiently mixed to obtain epoxy adhesive pre-composition 3；
D. epoxy adhesive pre-composition 3 is poured into stirring deaeration in vacuum stirring still, obtains disassembled epoxy adhesive。
This invention address that the another technical scheme of above-mentioned technical problem is as follows: a kind of can the rapid disassembling method of epoxy adhesive of rapid disassembling, it is characterised in that it comprises the following steps:
Being toasted in (130 ± 5) DEG C baking oven by adhering part (test sample plate as bonding), baking time, with 30 minutes for excellent, stretches or peels off bonding adhering part and can realize disassembling；Or adhering part is immersed baking in (120 ± 2) DEG C baking oven in dimethyl sulfoxide, baking time is with 10～20 minutes for excellent, and bonding epoxy adhesive can be completely dissolved or be partly dissolved。
This invention address that the another technical scheme of above-mentioned technical problem is as follows: containing the preparation method of the mixture of furan-Maleimide adduct, it is characterized in that, it comprises the following steps: by N, N'-dimethyl tetraphenyl BMI is dissolved in oxolane, nitrogen, under stirring condition, excessive furan glycidyl ether is slowly added to N, in N'-dimethyl tetraphenyl BMI-tetrahydrofuran solution, 66 DEG C of back flow reaction a period of times, with 24 hours for excellent, then decompression distills out tetrahydrofuran solvent, obtain the mixture containing furan-Maleimide adduct。
This invention address that the another technical scheme of above-mentioned technical problem is as follows: the preparation method of the CNT of polyethyleneimine-modified, it is characterised in that it comprises the following steps:
A., multi-walled carbon nano-tubes adding concentrated sulphuric acid with the mixed solution of concentrated nitric acid, stirring, in (65 ± 2) DEG C, insulation reaction a period of time, with 90 minutes for excellent；Cake Wash after filtration, to neutral, obtains product oxide/carbon nanometer tube after drying；
B. oxide/carbon nanometer tube is dispersed in DMF solvent, obtains oxide/carbon nanometer tube-DMF solution；The polymine and O-(7-azepine benzo triazol-1-yl)-N, N, N ', N '-tetramethylureas hexafluorophosphoric acid ester (HATU) that terminate ethylenediamine add in DMF solvent, obtain polyethylenimine solution；Then polyethylenimine solution is added in oxide/carbon nanometer tube-DMF solution, stirring, in (120 ± 5) DEG C reaction a period of time, with 12h for excellent；Filter and detect without polymine residue with in N,N-dimethylformamide washing to filtrate；The dried product that obtains is the CNT of polyethyleneimine-modified。
The beneficial effect comprise that: the epoxy adhesive preparation technology of the present invention is simple, easy to use；Bonding force is strong, all has excellent adhesive property with various metals base material；Toast in an oven, or adhering part is immersed in dimethyl sulfoxide toast in an oven, disassembling and reclaiming of metal adhesive parts can be realized。Therefore, the epoxy adhesive of the present invention, it is particularly well-suited to sheet metal material, especially containing the bonding of radioelement metal material and disassemble recovery, while realizing adhesive property, reduce the radioactive metal material pressure to environment, substantially increase resource recycling rate of waterused。
Accompanying drawing explanation
Fig. 1 is the schematic diagram of sample production in tensile shear strength test process；
Fig. 2 is the infrared spectrum of N, N'-dimethyl tetraphenyl BMI (a), furan glycidyl ether (b), the two mixture (c) and reaction 24h (d)；
Fig. 3 is N, N'-dimethyl tetraphenyl BMI (a), furan glycidyl ether (b), the two mixture (c) and reaction 24h (d)1H nuclear magnetic spectrogram；
Fig. 4 is the shape appearance figure of the invention epoxy adhesive；
Fig. 5 is the microstructure schematic diagram of the invention epoxy adhesive。
Detailed description of the invention
Below by conjunction with accompanying drawing, the invention is further described, but does not limit protection scope of the present invention。
The acquisition of component material
Epoxy resin selects EP-4100HF epoxy resin or the cross-linking modified epoxy resin of EPR-4023 carboxy terminated nitrile rubber of ADEKA company of Japan。Epoxide diluent selects any one in the 6350 of Shanghai Resin Factory or the ED-506 glycidyl ether of ADEKA company of Japan。Mixture containing furan-Maleimide adduct is the mixture of the diglycidyl ether (FDB) containing furan-Maleimide adduct and furan glycidyl ether (FGE), FDB and FGE molar ratio is 1:1, this ratio is by adjusting furan glycidyl ether (FGE) and N, N'-dimethyl tetraphenyl BMI (BMI) molar ratio example controls, and molar ratio example controls as 4:1。US Air chemistry ANCAMINE1618 epoxy curing agent selected by firming agent。Amido CNT is the multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified, wherein grafting polyethylene imine rate is 1wt%, CNT selects the JCMT-99-11-50 that Nanjing Ji Cang Nanosolutions GmbH produces, polymine selects the polymine of ethylenediamine end-blocking, and number-average molecular weight is 600。Microspheres selects the F-48 that Matsumoto Yushi-Seiyaku Co., Ltd. of Japan produces。All compositions need to leave dry ventilating and cooling place in。
The method of testing of physical and chemical performance
(1) tensile shear strength
By GB/T7124 standard, it is positioned in alcoholic solution by the iron plate that 0.8mm is thick supersound process 20 minutes, drying at room temperature；Again with acetone wiping surface, it is positioned in the baking oven of 50 DEG C dry。Finally the epoxy adhesive prepared is applied to sample model, solidifies 4 days at 25 DEG C, then solidify 12 hours at 60 DEG C, obtain test sample plate。In order to control bondline thickness, the glue prepared is mixed into the glass microballoon of a small amount of 30 microns。Sample production is as shown in Figure 1。
Bonding model is heated 30 minutes at 130 DEG C, is then rapidly cooled to room temperature, model must be disassembled。
Adopt the tensile shear strength before and after the heating of almighty test machine test sample plate, speed 50mm/min, contact area 12.5 × 25mm2；Take the meansigma methods of 3 test sample plate, be rounded up to integer, represent with MPa。
(2) dissolubility
Taking the epoxy adhesive after 0.1g solidifies and be placed in dimethyl sulfoxide solvent, room temperature places 4h, then heats to 120 DEG C and heats 20 minutes, observes the dissolubility before and after epoxy adhesive heating。
Embodiment 1 is containing the preparation of the mixture of furan-Maleimide adduct
7.14g (0.02 mole) N, N'-dimethyl tetraphenyl BMI is dissolved in 20mL oxolane, is subsequently poured in 100mL there-necked flask, magnetic agitation, logical nitrogen。Then 12.32g (0.08 mole) furan glycidyl ether is slowly added to N, in N'-dimethyl tetraphenyl BMI-tetrahydrofuran solution, refluxing 24 hours at 66 DEG C, then decompression distills out tetrahydrofuran solvent, obtains the mixture containing furan-Maleimide adduct。In preparation process, the infrared spectrum of each respective components and1H nuclear magnetic spectrogram is as Figure 2-3。
The preparation of the CNT of embodiment 2 polyethyleneimine-modified
A. weigh 2g multi-walled carbon nano-tubes (Ji Cang nanometer of Nanjing model JCMT-99-11-50) and add in 30 milliliters of concentrated sulphuric acids and 10 milliliters of concentrated nitric acid (volume ratio 3:1) mixed solutions, magnetic agitation, 600 turns per minute of mixing speed, is warming up to 65 DEG C, insulation reaction 90 minutes；Then the organic membrane filtration adopting aperture to be 0.45 micron；Again disperse filter cake to wash in deionized water, filter, until in neutrality, finally by filter cake vacuum drying 6 hours in 110 DEG C of baking ovens, products therefrom is oxide/carbon nanometer tube；
B. 1g oxide/carbon nanometer tube is weighed, add 20 milliliters of N, in dinethylformamide solvent, then ultrasonic disperse 30 minutes at 80 DEG C, ultrasonic power 100W, until oxide/carbon nanometer tube is thoroughly dispersed in DMF solvent, obtain oxide/carbon nanometer tube-DMF solution；Then polymine and 0.02gO-(7-azepine benzo triazol-1-yl)-N, N, the N ' of 0.2g ethylenediamine end-blocking are weighed, N '-tetramethylurea hexafluorophosphoric acid ester (HATU) adds 20 milliliters of N, in dinethylformamide solvent, dissolve, obtain polyethylenimine solution；Then polyethylenimine solution is added in oxide/carbon nanometer tube-DMF solution, magnetic agitation, 600 turns per minute of mixing speed, be warming up to 120 DEG C, insulation reaction 12h。Then the organic membrane filtration adopting aperture to be 0.45 micron, uses DMF cyclic washing, until detecting without polymine residue in filtrate。By gained filter cake vacuum drying 6 hours in 110 DEG C of baking ovens, products therefrom is the multi-walled carbon nano-tubes of polyethyleneimine-modified。
Embodiment 3 can the preparation method of epoxy adhesive of rapid disassembling
A. a certain amount of amino modified CNT (or CNT of the polyethyleneimine-modified of embodiment 2 gained) and epoxy hardener is weighed by formula, in the revolution rotation mixing deaeration machine of RN-500, the speed with 1000 revs/min stirs 20 minutes, then ultrasonic disperse 30 minutes in power to be 100W, temperature the be ultrasonic washing instrument of 60 DEG C, obtain firming agent pre-composition 1；
B. weigh a certain amount of epoxy resin, epoxide diluent and the mixture containing furan-Maleimide adduct by formula, be slowly heated to 70 DEG C, high-speed stirred 20 minutes, then slightly mix 3 times with three-roll grinder, thin mixed 3 times；Add microspheres, the revolution rotation mixing deaeration machine of the RN-500 then produced in THINKY company of Japan stirs 10 minutes with the speed of 1000 revs/min, obtains epoxy pre-composition 2；
C. weigh a certain amount of epoxy pre-composition 2 and epoxy hardener 1 by formula, in the revolution rotation mixing deaeration machine of RN-500, the speed with 1000 revs/min stirs 10 minutes, obtains epoxy adhesive pre-composition 3；
D., epoxy adhesive pre-composition 3 being poured into stirring deaeration, 300 turns per minute of mixing speed, inclined heated plate 30 minutes, vacuum-0.095MPa in vacuum stirring still, obtains disassembled epoxy adhesive, its shape appearance figure and microstructure schematic diagram are respectively as illustrated in figures 4-5。
Adopt said process and method, obtain the epoxy adhesive product of following 4 formula (in formula, the addition of each component is in weight fraction) respectively:
Formula one
Epoxy resin: ADEKAEP-4100HF40
Epoxide diluent: aliphatic diglycidylether (ADEKAED-506) 20
Mixture containing furan-Maleimide adduct: (FDB and FGE mol ratio 1:1) 60
The multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified: 1
Microspheres: (Japan Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 7
Firming agent: alicyclic firming agent (US Air chemistry ANCAMINE1618) 48
Formula two
Epoxy resin: ADEKAEP-4100HF45
Flexible epoxy diluent: aliphatic diglycidylether (ADEKAED506) 20
Mixture containing furan-Maleimide adduct: (FDB and FGE mol ratio 1:1) 55
The multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified: 1.5
Microspheres: (Japan Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 6
Firming agent: alicyclic firming agent (US Air chemistry ANCAMINE1618) 56
Formula three
Epoxy resin: ADEKAEP-4100HF30
Epoxide diluent: aliphatic diglycidylether (Shanghai Resin Factory 6350) 15
Mixture containing furan-Maleimide adduct: (FDB and FGE mol ratio 1:1) 70
The multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified: 2
Microspheres: (Japan Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 5
Firming agent: alicyclic firming agent (US Air chemistry ANCAMINE1618) 58
Formula four
Epoxy resin: carboxy terminated nitrile rubber cross-linked epoxy resin (ADEKAEPR-4023) 25
Flexible epoxy diluent: aliphatic diglycidylether (Shanghai Resin Factory 6350) 20
Mixture containing furan-Maleimide adduct: (FDB and FGE mol ratio 1:1) 75
The multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified: 1
Microspheres: (Japan Matsumoto Yushi-Seiyaku Co., Ltd. F-48) 4
Firming agent: alicyclic firming agent (US Air chemistry ANCAMINE1618) 54
Embodiment 4 can the rapid disassembling method of epoxy adhesive of rapid disassembling
Adhering part is toasted 30 minutes in 130 DEG C of baking ovens, stretch or peel off bonding adhering part and can realize disassembling, or adhering part is immersed in dimethyl sulfoxide and to toast 10～20 minutes in 120 DEG C of baking ovens, bonding epoxy adhesive can be completely dissolved or be partly dissolved。
The offer of comparative example
In order to contrast the effect embodying the present invention, it is provided that following two comparative example in addition comparative illustration。
Comparative example 1
Epoxy resin component includes following formula by weight:
Epoxy resin: Wuxi resin processing plant E-51100
Epoxide diluent: aliphatic diglycidylether (Shanghai Resin Factory 6350) 20
Firming agent: diethylenetriamine firming agent (DETA) 14
According to proportioning by all E-51 epoxy resin in above-mentioned comparative example 1 component and 6350 aliphatic diglycidylethers, stir 10 minutes with the speed of 1000 revs/min in the revolution rotation mixing deaeration machine of the RN-500 of THINKY company of Japan production, obtain pre-composition 1；Then weigh a certain amount of pre-composition 1 and all DETA epoxy hardeners by formula, with the speed of 1000 revs/min stirring 10 minutes in the revolution rotation mixing deaeration machine of Japan RN-500, obtaining can the epoxy adhesive pre-composition 2 of rapid disassembling；This pre-composition 2 is poured in vacuum stirring still and stir deaeration 30 minutes, vacuum-0.095MPa with the speed of 300 revs/min, obtain epoxy adhesive。
Comparative example 2
Epoxy resin component includes following formula by weight:
Epoxide diluent: aliphatic diglycidylether (ADEKAED506) 20
Mixture containing furan-Maleimide adduct: 100
Firming agent: alicyclic firming agent (US Air chemistry ANCAMINE1618) 48
The all of mixture containing furan-Maleimide adduct and 6350 aliphatic diglycidylethers in above-mentioned comparative example 2 component are weighed according to proportioning, it is slowly heated to 60 DEG C, the revolution rotation mixing deaeration machine of the RN-500 then produced in THINKY company of Japan stirs 10 minutes with the speed of 1000 revs/min, obtains epoxy pre-composition 1；Being subsequently adding all epoxy hardeners, in the revolution rotation mixing deaeration machine of RN-500, the speed with 1000 revs/min stirs 10 minutes, obtains the epoxy adhesive pre-composition for metal adhesive。This epoxy adhesive pre-composition is poured in vacuum stirring still and stir deaeration 30 minutes, vacuum-0.095MPa with the speed of 300 revs/min, obtain disassembled type epoxy adhesive。
Result and analysis
The epoxy adhesive that will obtain in embodiment 3 and comparative example, adopts the method for testing of above-mentioned physical and chemical performance to detect respectively, and its result is as shown in table 1。
His-and-hers watches 1 data are analyzed, we it is seen that before the heating of formula one～formula four tensile shear strength be above comparative example 1, illustrate to add the ethylenediamine end-blocking multi-walled carbon nano-tubes of polyethyleneimine-modified and microspheres contributes to the increase of tensile shear strength, this is because the multi-walled carbon nano-tubes of ethylenediamine end-blocking polyethyleneimine-modified and microspheres and epoxy adhesive matrix can form covalent bond, with epoxy matrix, there is good interface compatibility, when epoxy adhesive is subject to extraneous stress, stress energy is effectively passed in CNT and microspheres, dissipation energy, thus adding the tensile shear strength of epoxy adhesive。Additionally, along with in formula one～formula four containing the increase of the diglycidyl ether of furan-Maleimide adduct, before epoxy adhesive heating, tensile shear strength reduces seldom, but heating after-drawing shear strength reduces quickly, so that epoxy adhesive from heating before insoluble to heating rear section dissolve and be completely dissolved, the reversible covalent bond fission that furan in heating process-Maleimide adduct is formed is described, under the effect of microspheres expansive force, after the heating in fast cooling process, reversible covalent bonds has little time again to be formed, and then cause that the network cross-linked density of epoxy adhesive is substantially reduced, even resolve into lamellar segment, so that epoxy adhesive is partly dissolved or is completely dissolved after heating；And comparative example 1 is due to without reversible covalent bonds and microspheres, so mechanical property is in a slight decrease after heating, can not dissolving, this proves that the furan-reversible covalent bonds of Maleimide adduct formation and the expansive force of microspheres contribute to epoxy adhesive and realize disassembling further。And adopt the diglycidyl ether containing furan-Maleimide adduct to prepare epoxy adhesive (comparative example 2) completely, although disassembling of epoxy adhesive also can be realized, but tensile shear strength is relatively low before heating, the suitability under room temperature, metal adhesive required is poor。
Claims (10)
1. can the epoxy adhesive of rapid disassembling, each raw material including following weight portion forms:
Epoxy resin 20～50 parts；
Epoxide diluent 10～20 parts；
50～80 parts of mixture containing furan-Maleimide adduct；
40～70 parts of firming agent；
Amino modified CNT 0.5～2 part；
Microspheres 5～20 parts；
Wherein, the described mixture containing furan-Maleimide adduct is the mixture of the diglycidyl ether containing furan-Maleimide adduct and furan glycidyl ether。
2. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that described epoxy resin is the epoxy resin containing at least two epoxide group or rubber cross modified epoxy；The preferential EP-4100HF epoxy resin selecting ADEKA company of Japan or the cross-linking modified epoxy resin of EPR-4023 carboxy terminated nitrile rubber。
3. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that described epoxide diluent is the low-molecular-weight glycidyl ether containing two epoxide groups；Preferred strand contains the diglycidyl ether of aliphatic chain；More preferably select Shanghai Resin Factory 6350, Japan ADEKA company ED-506 glycidyl ether in any one。
4. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that the molar ratio of the diglycidyl ether containing furan-Maleimide adduct and furan glycidyl ether is 1:(0.5-1.5), it is preferred to 1:1；Wherein the diglycidyl ether structural formula containing furan-Maleimide adduct is as follows:
5. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that any one in aliphatic amine or alicyclic amine curing agent selected by described firming agent；Preferential selection US Air chemistry ANCAMINE1618 epoxy curing agent。
6. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that described amino modified CNT is the multi-walled carbon nano-tubes of end amido polyethyleneimine-modified。
7. according to claim 6 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that in described amino modified CNT, grafting polyethylene imine rate is 1-2wt%, it is preferred to (1.5 ± 0.2) wt%。
8. according to claim 6 a kind of can the epoxy adhesive of rapid disassembling, it is characterized in that, in described amino modified CNT, polymine is the polymine of ethylenediamine end-blocking, and number-average molecular weight is 600～2500, being preferably 600-800, structural formula is as follows:
9. according to claim 6 a kind of can the epoxy adhesive of rapid disassembling, it is characterised in that CNT mean outside diameter 8～15 nanometers, internal diameter 3～5 nanometers, length 30～50 microns；The JCMT-99-11-50 multi-walled carbon nano-tubes that preferred Nanjing Ji Cang nanosecond science and technology company limited produces。
10. according to claim 1 a kind of can the epoxy adhesive of rapid disassembling, it is characterized in that, described microspheres is shell is thermoplastic propene's acid ester polymer of being formed of butyl acrylate, methyl methacrylate and glycidyl methacrylate, and kernel is the globular powder granule of alkanes gas composition；Preferably, described microspheres particle diameter is 10～30 microns, and 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；More preferably the F-48 microspheres that Matsumoto Yushi-Seiyaku Co., Ltd. of Japan produces。
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