CN107201211B - The reversible polytriazoles adhesive of high-strength hot and its preparation and application - Google Patents
The reversible polytriazoles adhesive of high-strength hot and its preparation and application Download PDFInfo
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- CN107201211B CN107201211B CN201710457117.6A CN201710457117A CN107201211B CN 107201211 B CN107201211 B CN 107201211B CN 201710457117 A CN201710457117 A CN 201710457117A CN 107201211 B CN107201211 B CN 107201211B
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- polytriazoles
- adhesive
- bis
- nitrine
- benzene
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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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
Abstract
The present invention relates to a kind of reversible polytriazoles adhesive of high-strength hot and its preparation and application, the adhesive to be prepared by polytriazoles polymer, and the general formula of the chemical structure of polytriazoles polymer is such as shown in (I)；
Description
Technical field
The invention belongs to novel adhesive field of material technology, be related to a kind of reversible polytriazoles adhesive of high-strength hot and its
Preparation and application.
Background technique
Adhesive as a major class high molecular material, have the characteristics that it is easy to use, have a wide range of application, high financial profit,
Highly important effect is played in modern economy, modern national defense, modern science and technology.
In order to obtain excellent adhesive property and the characteristics such as solvent resistant, creep resistant, adhesive are general in use
For crosslinking polymer.These crosslinkings are generally irreversible covalent cross-linking, high-adhesive-strength etc. can be brought excellent for adhesive
Performance, this is also one of the reason of adhesive can be widely applied.But these irreversible crosslinkings are not but also adhesive has
Actively separating capacity again, brings inconvenience, such as cannot achieve adjustable bonding in actual use.In addition, adhesive
It can not be reused after failure or use, it is necessary to remove residual resin or throw aside entire gluded joint.This undoubtedly can band
Come a large amount of human and material resources and waste of time.In addition, due to there are a large amount of crosslinkable bases in traditional Cross-linkable adhesive
Group can gradually occur polymerization even crosslinking curing at any time during storage, cementability be lost, so that the storage of adhesive
The phase of depositing is restricted, and influences its use.
The patent that application publication number is CN103374318A discloses a kind of Thermal reversible adhesive, preparation method and its answers
With the adhesive is by including that following parts by weight of component is made: 40~90 parts of furane resins, 10~60 parts of maleimide, solvent 0
~30 parts and 0~10 part of auxiliary agent；And furane resins are further disclosed in furfural acetone resin, furfural resin or furfuryl alcohol resin
One or more, it is double that maleimide is selected from N-phenylmaleimide, diphenyl methane dimaleimide or penylene
One of maleimide or more than one.
Application publication number is that the patent of CN103184024A discloses a kind of reversible adhesive-debinding epobond epoxyn
And preparation method thereof, the adhesive is by following raw material components: 5-70 parts by weight epoxy resin, and epoxide equivalent is less than 550g/mol,
3-50 parts by weight organic amine curing agent, molecular weight are less than 900g/mol, and 0-50 weight parts thermoplastic resin, molecular weight is in 1000-
Between 100000g/mol and 0-70 parts by weight solvent is made；And it further discloses epoxy resin and shrinks selected from bisphenol-A two
One or more of glycerin ether, Bisphenol F diglycidyl ether, epoxidization phenolic resin or cycloaliphatic epoxy resin, organic amine
Selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, diaminobenzene sulfone, benzidine, aminoethyl piperazine, polytrimethylene ether two
One or more of amine or polytrimethylene ether triamine, thermoplastic resin be selected from thermoplastic acrylic resin, thermoplastic polyester or
One or more of polyvinyl alcohol.
Although adhesive disclosed in above-mentioned two patented technology has the characteristic of heated reversible adhesion, it is as liquid gluing
Agent still contains a large amount of crosslinkable groups, and storage period is also limited.
Application No. is the Chinese invention patents of 201110350612.X to disclose a kind of polytriazoles tree of high temperature resistant wet-heat resisting
The molecular structure of rouge adhesive and preparation method and application, the polytriazoles resin adhesive is as follows:
, and the preparation of hot-melt adhesive is further disclosed: it is massaged by azido compound and aliphatic polyyne based compound
You feed intake than [azido]/[alkynyl]=1.0: 0.6~1.5, are mixed directly at room temperature, melt at 30~80 DEG C anti-
It answers, obtains polytriazoles resin adhesive；The preparation of solution maintaining equilibrium: it is pressed by azido compound and aliphatic polyyne based compound
Molar ratio [azido]/[alkynyl]=1.0: 0.6~1.5 feed intake, and solvent is added, and solvent is selected from acetone, butanone, tetrahydro furan
It mutters, one of dichloroethanes, chloroform；Reactant concentration is 30~85wt%；Reaction temperature is 30~80 DEG C；Reaction time is
0.5~10h.In above-mentioned patented technology, there are a large amount of crosslinkable groups in either heat molten type or solution-type, storage period by
To limitation, and the crosslinking of the adhesive of above-mentioned patent disclosure is irreversible covalent cross-linking, does not have the characteristic of reversible adhesion.
In conclusion some adhesive do not have the characteristic of reversible adhesion, some adhesive in existing patented technology
Though having certain reversible adhesion, there are also a large amount of crosslinkable groups for itself, and banking system and period of storage are by tight
It limits again, this also constrains its industrial application significantly.Different from existing patented technology, the present invention passes through in polytriazoles adhesive
Middle introducing reversible crosslink key, and adhesive is made to the glue film of completion of cure, make wherein without crosslinkable groups, storage period is significantly
Extend, and heat bonding may be implemented, then thermal reversion bonding can also be carried out after being bonded.It can be seen that invention adhesive is
A kind of convenient green reversible adhesion adhesive of application.
Summary of the invention
That it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of adhesive strengths is high, can
It repeats to be bonded, easy for construction, the reversible polytriazoles adhesive of the high high-strength hot of storage stability.
Another object of the present invention is just to provide the preparation method of the reversible polytriazoles adhesive of the high-strength hot.
Another object of the present invention is just to provide the application of the reversible polytriazoles adhesive of the high-strength hot.
The purpose of the present invention can be achieved through the following technical solutions:
The reversible polytriazoles adhesive of high-strength hot, the adhesive are prepared by polytriazoles polymer, the polytriazoles
The general formula of the chemical structure of polymer is such as shown in (I)；
Wherein, Ar1Selected from least one of following radicals:
Ar2Selected from least one of following radicals:
Any one of M in following radicals is several:
X is selected from least one of following halogens: Cl, Br or I；
In formula, n is integer, value 2-60.
The adhesive is the polytriazoles glue film being prepared using such as logical formula (I) polymer, the polytriazoles glue film
With a thickness of 50-300 μm.
As a preferred technical solution, the polytriazoles glue film with a thickness of 80-150 μm.
The preparation method of the reversible polytriazoles adhesive of high-strength hot, this method specifically includes the following steps:
Step (1): diine monomer, two nitrine monomers and dihalo- crosslinking agent are added in organic solvent together, stirring
Mixing, and it is warming up to 60-140 DEG C, 1-24h is persistently stirred, polytriazoles pre-polymerization liquid is made；
Step (2): polytriazoles pre-polymerization liquid made from step (1) is coated on substrate, in 50-100 DEG C of heat preservation 1-5h, then
It is warming up to 120-180 DEG C of heat preservation 1-8h, is cooled to room temperature, then substrate is immersed in deionized water and impregnates 6-48h, makes glue film from base
It automatically strips, dries on plate.
The diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- bis- (2- (2- propargyl alcoholate) ethyoxyl) benzene, 1,4-
In bis- (2- propargyl alcoholate) benzene of diacetylenic benzene, 1,3- diacetylenic benzene, 1,4- or bis- (2- propargyl alcoholate) benzene of 1,3- at least
It is a kind of；
The two nitrine monomers are selected from bis- (azido-methyl) benzene of 1,4-, bis- (azido-methyl) benzene of 1,3-, the bis- (nitrine of 4,4-
At least one of methyl) bis- nitrine diphenyl-methane of biphenyl or 4,4-；
The dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexane, 1,6- dibromo oneself
Alkane, bis- iodohexane of 1,6-, 1,10- dibromo-decane, at least one of two benzyl chlorides or two benzyl chlorides；
The organic solvent is selected from acetone, tetrahydrofuran, N-Methyl pyrrolidone, N,N-dimethylformamide, N, N-
At least one of dimethyl acetamide or dimethyl sulfoxide.
The molar ratio of diine monomer described in step (1) and two nitrine monomers is 100:67-100, and the dihalo- is handed over
The molar ratio for joining agent and two nitrine monomers is 10-80:100, the quality and diine monomer, two nitrine monomers of the organic solvent
And the ratio between dihalo- crosslinking agent gross mass is 100:20-150.
The molar ratio of diine monomer described in step (1) and two nitrine monomers is 100 as a preferred technical solution:
The molar ratio of 80-100, the dihalo- crosslinking agent and two nitrine monomers be 20-70:100, the quality of the organic solvent with
The ratio between diine monomer, two nitrine monomers and dihalo- crosslinking agent gross mass are 100:40-100.
Substrate described in step (2) includes one in glass plate, stainless steel plate, polyfluortetraethylene plate or polytetrafluoroethylene (PTFE) slot
Kind.
The adhesive is using the polytriazoles liquid adhesive being prepared such as logical formula (I) polymer.
The preparation method of the reversible polytriazoles adhesive of high-strength hot, this method be by diine monomer, two nitrine monomers and
The mixing of dihalo- crosslinking agent, is warming up to 50-100 DEG C, is thoroughly mixed uniformly.
The diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- bis- (2- (2- propargyl alcoholate) ethyoxyl) benzene, 1,4-
In bis- (2- propargyl alcoholate) benzene of diacetylenic benzene, 1,3- diacetylenic benzene, 1,4- or bis- (2- propargyl alcoholate) benzene of 1,3- at least
It is a kind of；
The two nitrine monomers are selected from bis- (azido-methyl) benzene of 1,4-, bis- (azido-methyl) benzene of 1,3-, the bis- (nitrine of 4,4-
At least one of methyl) bis- nitrine diphenyl-methane of biphenyl or 4,4-；
The dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexane, 1,6- dibromo oneself
Alkane, bis- iodohexane of 1,6-, 1,10- dibromo-decane, at least one of two benzyl chlorides or two benzyl chlorides.
The molar ratio of the diine monomer and two nitrine monomers is 100:67-100, and the dihalo- crosslinking agent and two fold
The molar ratio of nitrogen monomer is 10-80:100.
The molar ratio of the diine monomer and two nitrine monomers is 100:80-100, institute as a preferred technical solution,
The molar ratio of the dihalo- crosslinking agent and two nitrine monomers stated is 20-70:100.
The application of the reversible polytriazoles adhesive of high-strength hot, the adhesive are using such as logical formula (I) polymer preparation
Made of polytriazoles glue film when, by the polytriazoles glue film be clipped in two to adhesives among, under the pressure of 0.5-1.5MPa,
In 150-200 DEG C of environmental treatment 0.5-4h, two are bonded together to adhesives, by bonding gluded joint in 100-
200 DEG C of processing 5-60min, it is micro- firmly to separate two to adhesives, then this two sseparated is assembled into adhesives
Together, in 80-200 DEG C of processing 1-48h, this is two sseparated to be bonded together again to adhesives, is repeated with this viscous
Connect-unsticking process；
When the adhesive is using the polytriazoles liquid adhesive being prepared such as logical formula (I) polymer, this is gathered
Triazole liquid adhesive is evenly coated in two to adhesives surface, and with a thickness of 0.2-2mm, treatment temperature is 80-200 DEG C, place
The reason time is 1-48h, and two are bonded together to adhesives, by bonding gluded joint in 100-200 DEG C of processing 5-
60min, it is micro- firmly two are separated to adhesives, then by this it is two sseparated be assemblied together to adhesives, in 80-
200 DEG C of processing 1-48h, this is two sseparated to be bonded together again to adhesives, and bonding-unsticking mistake is repeated with this
Journey.
Described includes that one of glass, ceramics, metal or polymer matrix composites are several to adhesives.
The metal includes one or more of aluminium, stainless steel or copper.
The polymer matrix composites include polytriazoles polymer matrix composites, polyimide resin based composites or
One or more of epoxy resin-base composite material.
Polytriazoles adhesive bonding form of the present invention is versatile and flexible, can be bonded in the form of glue film and two kinds of glue.
Wherein polytriazoles glue film is with preparation method is simple, construction technology is easy, storage convenient transport, thickness is uniform, resin added is accurate
And storage period it is long the advantages that.The difference of the polytriazoles glue film and traditional adhesive is that polytriazoles glue film is cured friendship
Linked polymer, is not susceptible to the variation of physics and chemistry during storage, and storage stability is high.
Compared with prior art, the invention has the characteristics that:
1) polytriazoles adhesive bonding form of the present invention is versatile and flexible, and raw material is simple, and preparation process is simple, repeatable to make
With；
2) polytriazoles adhesive of the present invention have well can hot unsticking performance, heating can remove easily, again can after compound
Restore high adhesive strength, realizes reversible adhesive-unsticking ability；
3) initial bond strenght of polytriazoles adhesive of the present invention is high, and reversible adhesion is good, by 20 recyclings
Afterwards, the conservation rate of adhesive strength may be up to 96%, and after 50 times are recycled, the conservation rate of adhesive strength still be may be up to
81%, service life cycle is long；
5) polytriazoles glue film of the present invention is cured cross-linked polymer, is not susceptible to physics and chemistry during storage
Variation, storage stability is high；
6) polytriazoles adhesive of the present invention can be used as sqtructural adhesive applied to Aeronautics and Astronautics, precision machinery, petrochemical industry
The bonding of the metal and composite material that need to reuse in equal fields, has a good application prospect.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 91 weight
Part bisphenol-A dipropargyl ether, 53 parts by weight Isosorbide-5-Nitraes-bis- (azido-methyl) benzene and 25 parts by weight 1,10- dibromo-decane are added to 254
In parts by weight n,N-dimethylacetamide (DMAC), mechanical stirring, mixing speed 100rpm, reaction temperature is 120 DEG C, when reaction
Between be 1h, obtain the homogeneous polytriazoles pre-polymerization liquid of light brown.
Above-mentioned polytriazoles pre-polymerization liquid is coated on the smooth glass plate in surface, through 70 DEG C/3h, after 160 DEG C/3h processing,
It is down to room temperature.The glass plate is immersed in deionized water and impregnates 36h, automatically strips glue film from glass plate, drying is gathered
Triazole glue film, the glue film is in light yellow, transparent, with a thickness of 150 μm.
Above-mentioned polytriazoles glue film is clipped among two blocks of aluminium sheets, under the pressure of 0.5-1.5MPa, in 180 DEG C of environmental treatments
2h, two blocks of aluminium sheets can adhere well to together, and room temperature tensile shear strength is 20.3MPa.Bonding splicing is connect
Head micro- firmly can separate two blocks of aluminium sheets in 180 DEG C of processing 15min, tensile shear strength 0.1MPa.Two pieces are separated again
Aluminium sheet be assemblied together, in 180 DEG C of processing 1h, two blocks of aluminium sheets can be adhered well to again together, and tensile strength can be extensive
19.9MPa, strength retention 98% are arrived again.This bonding-unsticking process can be repeated, and after the 20th circulation, draw
Stretching shear strength is 18.9MPa, and strength retention 93.1%, after the 50th time recycles, tensile shear strength still has
15.2MPa, strength retention 75%.
Above-mentioned polytriazoles glue film is bonded gluded joint made from aluminium sheet and places 12d in the environment of 50 DEG C/100%RH,
Its tensile shear strength can keep 60% or more.Gluded joint made from the glue film is protected under the stress of 10MPa and 15MPa
2h or more is held, does not have creep.Therefore good durability and creep resistance are shown after glue film bonding.In addition, should
Polytriazoles glue film has excellent solvent resistance, and gluded joint impregnates 60 in water, ethyl alcohol, n,N-Dimethylformamide respectively
Preferable adhesive effect is still able to maintain more than it.
Above-mentioned polytriazoles glue film has very excellent shelf characteric, places 6 months under atmosphere at room temperature environment, glues
97% or so can be kept by connecing intensity, be placed 1 year, adhesive strength can keep 95% or so, and the polytriazoles glue film in storage process
Technique for sticking performance there is no significant change.
Embodiment 2:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 82 weight
Part Isosorbide-5-Nitrae-bis- (2- (2- propargyl alcoholate) ethyoxyl) benzene, 65 parts by weight 4, bis- nitrine diphenyl-methane of 4- and 13 parts by weight 1,2- dichloro
Ethane is added in 107 parts by weight N-N-methyl 2-pyrrolidone N (NMP), mechanical stirring, mixing speed 100rpm, reaction temperature 140
DEG C, reaction time 20min obtains the homogeneous polytriazoles pre-polymerization liquid of light brown.
Above-mentioned polytriazoles pre-polymerization liquid is coated on the smooth stainless steel plate in surface, is handled through 100 DEG C/2h, 170 DEG C/2h
Afterwards, it is down to room temperature.The stainless steel plate is immersed in deionized water and is impregnated for 24 hours, automatically strips glue film from stainless steel plate, is dried
Polytriazoles glue film is obtained, the glue film is in light yellow, transparent, with a thickness of 200 μm.
Above-mentioned polytriazoles glue film is clipped among two pieces of ceramic wafers, under the pressure of 0.5-1.5MPa, at 200 DEG C of environment
1h is managed, two pieces of ceramic wafers can adhere well to together.By bonding gluded joint in 200 DEG C of processing 5min, micro- can use
Power separates two pieces of ceramic wafers.Two pieces of separated ceramic wafers are assemblied together again, in 200 DEG C of processing 0.5h, two pieces of ceramic wafers
It can adhere well to again together.This bonding-unsticking process can be repeated.
Embodiment 3:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 38 weight
Part Isosorbide-5-Nitrae-diacetylenic benzene, 45 parts by weight 1, bis- (azido-methyl) benzene of 3- and 23 parts by weight 1,2- Bromofume are added to 105 weights
It measures in part n,N-Dimethylformamide, mechanical stirring, mixing speed 100rpm, reaction temperature is 130 DEG C, and the reaction time is
40min obtains the homogeneous polytriazoles pre-polymerization liquid of light brown.
Above-mentioned polytriazoles pre-polymerization liquid is coated on the smooth polyfluortetraethylene plate in surface, through 90 DEG C/2.5h, 150 DEG C/4h
After processing, it is down to room temperature.The polyfluortetraethylene plate is immersed in deionized water and is impregnated for 24 hours, makes glue film from polyfluortetraethylene plate
It automatically strips, drying obtains polytriazoles glue film, and the glue film is in light yellow, transparent, with a thickness of 100 μm.
Above-mentioned polytriazoles glue film is clipped among two pieces of glass plates, under the pressure of 0.5-1.5MPa, at 160 DEG C of environment
4h is managed, two pieces of glass plates can adhere well to together.By bonding gluded joint in 160 DEG C of processing 20min, micro- can use
Power separates two pieces of glass plates.Two pieces of separated glass plates are assemblied together again, in 160 DEG C of processing 3h, two pieces of glass plates can
It adheres well to again together.This bonding-unsticking process can be repeated.
Embodiment 4:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 56 weight
Bis- (2- propargyl alcoholate) benzene of part Isosorbide-5-Nitrae-, 66 parts by weight 4, bis- (azido-methyl) biphenyl of 4- and 85 parts by weight 1, bis- iodohexane of 6- are added
Into 326 pbw acetones, mechanical stirring, mixing speed 100rpm is heated to flowing back, and reaction time 8h obtains light brown
Homogeneous polytriazoles pre-polymerization liquid.
Above-mentioned polytriazoles pre-polymerization liquid is poured into the smooth polytetrafluoroethylene (PTFE) slot in surface, is handled through 50 DEG C/5h, 120 DEG C/8h
Afterwards, it is down to room temperature.Enter the polytetrafluoroethylene (PTFE) drill traverse to impregnate 48h in deionized water, keeps glue film automatic from polytetrafluoroethylene (PTFE) slot
Removing, drying obtain polytriazoles glue film, and the glue film is in light yellow, transparent, with a thickness of 80 μm.
Above-mentioned polytriazoles glue film is clipped among two pieces of stainless steel plates, under the pressure of 0.5-1.5MPa, in 120 DEG C of environment
12h is handled, two pieces of stainless steel plates can adhere well to together.By bonding gluded joint in 120 DEG C of processing 60min,
Micro- firmly two pieces of stainless steel plates can be separated.Two pieces of separated stainless steel plates are assemblied together again, in 120 DEG C of processing 8h, two
Block stainless steel plate can adhere well to again together.This bonding-unsticking process can be repeated.
Embodiment 5:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 91 weight
Part bisphenol-A dipropargyl ether, 49 parts by weight Isosorbide-5-Nitraes-bis- (azido-methyl) benzene and 13 parts by weight 1,6- dibromo-hexane are added to 307 weights
It measures in part tetrahydrofuran, mechanical stirring, mixing speed 100rpm is heated to flowing back, and it is homogeneous to obtain light brown by reaction time 6h
Polytriazoles pre-polymerization liquid.
Above-mentioned polytriazoles pre-polymerization liquid is poured into the smooth polytetrafluoroethylene (PTFE) slot in surface, is handled through 60 DEG C/5h, 130 DEG C/7h
Afterwards, it is down to room temperature.Enter the polytetrafluoroethylene (PTFE) drill traverse to impregnate 48h in deionized water, keeps glue film automatic from polytetrafluoroethylene (PTFE) slot
Removing, drying obtain polytriazoles glue film, and the glue film is in light yellow, transparent, with a thickness of 80 μm.
Above-mentioned polytriazoles glue film is clipped among two pieces of copper sheets, under the pressure of 0.5-1.5MPa, in 150 DEG C of environmental treatments
6h, two pieces of copper sheets can adhere well to together.By bonding gluded joint in 150 DEG C of processing 30min, micro- firmly can will
Two pieces of copper sheets separate.Two pieces of separated copper sheets are assemblied together again, in 150 DEG C of processing 4h, two pieces of copper sheets can again well
It is bonded together.This bonding-unsticking process can be repeated.
Embodiment 6:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, by 56 weight
Two benzyl chlorides are added between bis- (2- propargyl alcoholate) benzene of part 1,3-, bis- (azido-methyl) biphenyl of 79 parts by weight 4,4- and 42 parts by weight
In 216 parts by weight dimethyl sulfoxides, mechanical stirring, mixing speed 100rpm, reaction temperature is 80 DEG C, and reaction time 5h is obtained
To the homogeneous polytriazoles pre-polymerization liquid of light brown.
Above-mentioned polytriazoles pre-polymerization liquid is coated on the smooth glass plate in surface, through 80 DEG C/5h, after 140 DEG C/5h processing,
It is down to room temperature.The glass plate is immersed in deionized water and impregnates 12h, automatically strips glue film from glass plate, drying is gathered
Triazole glue film, the glue film is in light yellow, transparent, with a thickness of 150 μm.
Above-mentioned polytriazoles glue film is clipped among two blocks of polytriazoles polymer matrix composites plates, in the pressure of 0.5-1.5MPa
Under, in 130 DEG C of environmental treatment 10h, two blocks of polytriazoles polymer matrix composites plates can be adhered well to together.It will be bonding
Gluded joint in 130 DEG C of processing 50min, micro- firmly two blocks of polytriazoles polymer matrix composites plates can be separated.Again by two pieces
Separated polytriazoles polymer matrix composites plate is assemblied together, in 130 DEG C of processing 6h, two pieces of polytriazoles polymer matrix composites
Plate can adhere well to again together.This bonding-unsticking process can be repeated.
Embodiment 7:
The preparation and use of polytriazoles glue film
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, 91 weights are added
Part bisphenol-A dipropargyl ether, 73 parts by weight 4 are measured, to two benzyl chlorides, mechanical stirring is stirred for bis- nitrine diphenyl-methane of 4- and 41 parts by weight
Speed 100rpm is mixed, reaction temperature is 80 DEG C, reaction time 10min, obtains light yellow homogeneous polytriazoles pre-polymerization liquid.
Above-mentioned polytriazoles pre-polymerization liquid is coated on the smooth stainless steel plate in surface, is handled through 80 DEG C/2h, 120 DEG C/8h
Afterwards, it is down to room temperature.The stainless steel plate is immersed in deionized water and impregnates 36h, automatically strips glue film from stainless steel plate, is dried
Polytriazoles glue film is obtained, the glue film is in light yellow, transparent, with a thickness of 200 μm.
Above-mentioned polytriazoles glue film is clipped among two blocks of aluminium sheets, under the pressure of 0.5-1.5MPa, in 170 DEG C of environmental treatments
3h, two blocks of aluminium sheets can adhere well to together.By bonding gluded joint in 170 DEG C of processing 15min, micro- firmly can will
Two blocks of aluminium sheets separate.Two blocks of separated aluminium sheets are assemblied together again, in 170 DEG C of processing 2h, two blocks of aluminium sheets can again well
It is bonded together.This bonding-unsticking process can be repeated.
Embodiment 8:
The preparation and use of polytriazoles liquid adhesive
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, 56 weights are added
Measure bis- (2- propargyl alcoholate) benzene of part Isosorbide-5-Nitrae-, 55 parts by weight 1, bis- (azido-methyl) benzene of 3- and 36 parts by weight 1,6- dichloro hexane, machine
Tool stirring, mixing speed 100rpm, reaction temperature are 80 DEG C, reaction time 10min, obtain light yellow homogeneous polytriazoles liquid
Adhesive.
Above-mentioned polytriazoles liquid adhesive is evenly coated in two pieces of surface of aluminum plate, with a thickness of 200 μm, through 100 DEG C/2h, 160
DEG C/4h processing after, two blocks of aluminium sheets can adhere well to together.It, can be micro- by bonding gluded joint in 160 DEG C of processing 4h
Firmly two blocks of aluminium sheets are separated.Two blocks of separated aluminium sheets are assemblied together again, in 160 DEG C of processing 3h, two blocks of aluminium sheets can be again
It adheres well to together.This bonding-unsticking process can be repeated.
Embodiment 9:
The preparation and use of polytriazoles liquid adhesive
In a four round flask equipped with mechanical stirring, nitrogen inlet, condenser pipe and thermometer, 56 weights are added
Measure part 1, bis- (2- propargyl alcoholate) benzene of 3-, 68 parts by weight 4, bis- nitrine diphenyl-methane of 4- and 57 parts by weight 1,10- dibromo-decane, machine
Tool stirring, mixing speed 100rpm, reaction temperature are 70 DEG C, reaction time 15min, obtain the homogeneous polytriazoles liquid of light brown
Adhesive.
Above-mentioned polytriazoles liquid adhesive is evenly coated in two pieces of stainless steel surfaces, with a thickness of 200 μm, through 90 DEG C/2h,
After 140 DEG C/8h processing, two pieces of stainless steel plates can be adhered well to together.Bonding gluded joint is handled in 140 DEG C
40min micro- firmly can separate two pieces of stainless steel plates.Two pieces of separated stainless steel plates are assemblied together again, are handled in 140 DEG C
5h, two pieces of stainless steel plates can adhere well to again together.This bonding-unsticking process can be repeated.
The initial bond strenght of embodiment 1-9 preparation gained adhesive and the test that performance, storage stability is recycled
The results are shown in Table 1.
Table 1
Claims (10)
1. the reversible polytriazoles adhesive of high-strength hot, which is characterized in that the adhesive is prepared by polytriazoles polymer, described
Polytriazoles polymer general formula of the chemical structure it is shown in formula I；
Wherein, Ar1Selected from least one of following radicals:
Ar2Selected from least one of following radicals:
Any one of M in following radicals is several:
X is selected from least one of following halogens: Cl, Br or I；
In formula, n is integer, value 2-60.
2. the reversible polytriazoles adhesive of high-strength hot according to claim 1, which is characterized in that the adhesive is to adopt
The polytriazoles glue film being prepared with such as Formulas I polymer, the polytriazoles glue film with a thickness of 50-300 μm.
3. the reversible polytriazoles adhesive of high-strength hot according to claim 1, which is characterized in that the adhesive is to adopt
The polytriazoles liquid adhesive being prepared with such as Formulas I polymer.
4. the preparation method of the reversible polytriazoles adhesive of high-strength hot as claimed in claim 1 or 2, which is characterized in that the party
Method specifically includes the following steps:
Step (1): diine monomer, two nitrine monomers and dihalo- crosslinking agent being added in organic solvent together, are stirred,
And it is warming up to 60-140 DEG C, 1-24h is persistently stirred, polytriazoles pre-polymerization liquid is made；
Step (2): polytriazoles pre-polymerization liquid made from step (1) is coated on substrate, in 50-100 DEG C of heat preservation 1-5h, then is heated up
It to 120-180 DEG C of heat preservation 1-8h, is cooled to room temperature, then substrate is immersed in deionized water and impregnates 6-48h, make glue film from substrate
It automatically strips, dries.
5. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 4, which is characterized in that described
Diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- bis- (2- (2- propargyl alcoholate) ethyoxyl) benzene, 1,4- diacetylenic benzene, 1,
At least one of bis- (2- propargyl alcoholate) benzene of 3- diacetylenic benzene, 1,4- or bis- (2- propargyl alcoholate) benzene of 1,3-；
The two nitrine monomers are selected from bis- (azido-methyl) benzene of 1,4-, bis- (azido-methyl) benzene of 1,3-, bis- (the nitrine first of 4,4-
At least one of base) bis- nitrine diphenyl-methane of biphenyl or 4,4-；
The dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexane, 1,6- dibromo-hexane,
Bis- iodohexane of 1,6-, 1,10- dibromo-decane, at least one of two benzyl chlorides or two benzyl chlorides；
The organic solvent is selected from acetone, tetrahydrofuran, N-Methyl pyrrolidone, N,N-dimethylformamide, N, N- diformazan
At least one of yl acetamide or dimethyl sulfoxide.
6. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 4, which is characterized in that step
(1) molar ratio of diine monomer and two nitrine monomers described in is 100:67-100, the dihalo- crosslinking agent and two nitrine
The molar ratio of monomer is 10-80:100, the quality and diine monomer, two nitrine monomers and dihalo- crosslinking agent of the organic solvent
The ratio between gross mass is 100:20-150.
7. the preparation method of the reversible polytriazoles adhesive of high-strength hot as described in claim 1, which is characterized in that this method is
Diine monomer, two nitrine monomers and dihalo- crosslinking agent are mixed, are warming up to 50-100 DEG C, is thoroughly mixed uniformly.
8. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 7, which is characterized in that described
Diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- bis- (2- (2- propargyl alcoholate) ethyoxyl) benzene, 1,4- diacetylenic benzene, 1,
At least one of bis- (2- propargyl alcoholate) benzene of 3- diacetylenic benzene, 1,4- or bis- (2- propargyl alcoholate) benzene of 1,3-；
The two nitrine monomers are selected from bis- (azido-methyl) benzene of 1,4-, bis- (azido-methyl) benzene of 1,3-, bis- (the nitrine first of 4,4-
At least one of base) bis- nitrine diphenyl-methane of biphenyl or 4,4-；
The dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexane, 1,6- dibromo-hexane,
Bis- iodohexane of 1,6-, 1,10- dibromo-decane, at least one of two benzyl chlorides or two benzyl chlorides.
9. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 7, which is characterized in that described
The molar ratio of diine monomer and two nitrine monomers is 100:67-100, the molar ratio of the dihalo- crosslinking agent and two nitrine monomers
For 10-80:100.
10. the application of the reversible polytriazoles adhesive of high-strength hot as described in claim 1, which is characterized in that the gluing
When agent is the polytriazoles glue film being prepared using such as Formulas I polymer, which is clipped in two in adhesives
Between, under the pressure of 0.5-1.5MPa, in 150-200 DEG C of environmental treatment 0.5-4h, two are bonded together to adhesives, will
Bonding gluded joint is micro- firmly to separate two to adhesives in 100-200 DEG C of processing 5-60min, then by this two
Separated is assemblied together to adhesives, and in 80-200 DEG C of processing 1-48h, this is two sseparated to be bonded again to adhesives
To together, bonding-unsticking process is repeated with this；
When the adhesive is the polytriazoles liquid adhesive being prepared using such as Formulas I polymer, by the polytriazoles liquid
Adhesive is evenly coated in two to adhesives surface, and with a thickness of 0.2-2mm, treatment temperature is 80-200 DEG C, and the processing time is
1-48h, two are bonded together to adhesives, by bonding gluded joint in 100-200 DEG C of processing 5-60min, micro- use
Power separates two to adhesives, then by this it is two sseparated be assemblied together to adhesives, in 80-200 DEG C of processing 1-
48h, this is two sseparated to be bonded together again to adhesives, and bonding-unsticking process is repeated with this.
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| CN101022895A (en) * | 2004-07-22 | 2007-08-22 | 斯克里普斯研究学院 | Polymeric materials via click chemistry |
| CN103087671A (en) * | 2011-11-08 | 2013-05-08 | 华东理工大学 | High temperature-resistant damp heat-resistant polytriazole resin adhesive and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101022895A (en) * | 2004-07-22 | 2007-08-22 | 斯克里普斯研究学院 | Polymeric materials via click chemistry |
| CN103087671A (en) * | 2011-11-08 | 2013-05-08 | 华东理工大学 | High temperature-resistant damp heat-resistant polytriazole resin adhesive and preparation method and application |
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