CN107201211A - 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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- CN107201211A CN107201211A CN201710457117.6A CN201710457117A CN107201211A CN 107201211 A CN107201211 A CN 107201211A CN 201710457117 A CN201710457117 A CN 201710457117A CN 107201211 A CN107201211 A CN 107201211A
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- polytriazoles
- adhesive
- nitrine
- reversible
- double
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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
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of reversible polytriazoles adhesive of high-strength hot and its preparation and application, the adhesive is prepared from by polytriazoles polymer, and the chemical structure of general formula 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 technology
Adhesive as a major class high polymer material, with it is easy to use, have a wide range of application, high financial profit the features such as,
Highly important effect is played in modern economy, modern national defense, modern science and technology.
In order to obtain excellent adhesive property and the in use characteristic such as solvent resistant, creep resistant, adhesive is general
For crosslinking polymer.These crosslinkings are generally irreversible covalent cross-linking, for adhesive high-adhesive-strength etc. can be brought excellent
Performance, this be also adhesive can extensively using the reason for one of.But these irreversible crosslinkings also cause adhesive not have
Actively separating capacity again, brings inconvenience, for example, can not realize adjustable bonding in actual use.In addition, adhesive
It can not be reused after failure or using end, it is necessary to remove residual resin or throw aside whole 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, it can gradually occur polymerization even crosslinking curing with the time in storage process, lose cementability so that the storage of adhesive
The phase of depositing is restricted, and influences it to use.
Application publication number discloses a kind of Thermal reversible adhesive, preparation method for CN103374318A patent and its answered
With the adhesive including following parts by weight of component by being 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 a penylene
One or more in maleimide.
Application publication number discloses a kind of reversible adhesive-debinding epobond epoxyn for CN103184024A patent
And preparation method thereof, the adhesive is by following raw material components：5-70 parts by weight epoxy resin, epoxide equivalent is less than 550g/mol,
3-50 parts by weight organic amine curing agents, molecular weight be less than 900g/mol, 0-50 weight parts thermoplastic resins, molecular weight is in 1000-
Between 100000g/mol, and 0-70 parts by weight solvent is made；And epoxy resin is further disclosed selected from the shrink of bisphenol-A two
One or more in glycerin ether, Bisphenol F diglycidyl ether, epoxidization phenolic resin or cycloaliphatic epoxy resin, organic amine
Selected from diethylenetriamine, triethylene tetramine, TEPA, diaminobenzene sulfone, benzidine, aminoethyl piperazine, polytrimethylene ether two
One or more in amine or polytrimethylene ether triamine, thermoplastic resin be selected from thermoplastic acrylic resin, thermoplastic polyester or
One or more in polyvinyl alcohol.
Although adhesive disclosed in above-mentioned two patented technology has the characteristic of heated reversible adhesion, it is gluing as liquid
Agent, still containing a large amount of crosslinkable groups, its storage period is also limited.
Application No. 201110350612.X Chinese invention patent discloses a kind of polytriazoles tree of high temperature resistant wet-heat resisting
Fat adhesive and preparation method and application, the molecular structure of the polytriazoles resin adhesive are as follows：
, and the preparation of hot-melt adhesive is further disclosed：Massaged by azido compound and many alkynyl compounds of aliphatic
You feed intake than [azido]/[alkynyl]=1.0: 0.6~1.5, are mixed directly at room temperature, are melted at 30~80 DEG C anti-
Should, obtain polytriazoles resin adhesive；The preparation of solution maintaining equilibrium：Pressed by many alkynyl compounds of azido compound and aliphatic
Mol ratio [azido]/[alkynyl]=1.0: 0.6~1.5 feed intake, and add solvent, and solvent is selected from acetone, butanone, tetrahydrochysene furan
Mutter, one kind in 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, either there are a large amount of crosslinkable groups in heat molten type or solution-type, its storage period by
To limitation, and the crosslinking of adhesive disclosed in above-mentioned patent is irreversible covalent cross-linking, and it does not possess the characteristic of reversible adhesion.
In summary, in existing patented technology, some adhesive do not have the characteristic of reversible adhesion, some adhesive
Though with certain reversible adhesion, itself also having a large amount of crosslinkable groups, its banking system and period of storage are by tight
Limit again, this also constrains its commercial Application significantly.Different from existing patented technology, the present invention is by polytriazoles adhesive
Middle introducing reversible crosslink key, and adhesive is made to the glued membrane of completion of cure, make wherein to be free of crosslinkable groups, storage period is significantly
Extension, and can realize heat bonding, then thermal reversion bonding can also be carried out after being bonded.As can be seen here, invention adhesive is
The convenient green reversible adhesion adhesive of one kind application.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of adhesive strength is high, can
Repeat to be bonded, easy construction, the reversible polytriazoles adhesive of the high high-strength hot of bin 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 is prepared from by polytriazoles polymer, described polytriazoles
The chemical structure of general formula 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, and value is 2-60.
Described adhesive is the polytriazoles glued membrane being prepared from using such as logical formula (I) polymer, the polytriazoles glued membrane
Thickness is 50-300 μm.
As preferred technical scheme, the thickness of described polytriazoles glued membrane is 80-150 μm.
The preparation method of the reversible polytriazoles adhesive of high-strength hot, this method specifically includes following steps：
Step (1)：Diine monomer, two nitrine monomers and dihalo- crosslinking agent are added in organic solvent together, stirred
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, 1-5h is incubated in 50-100 DEG C, then
120-180 DEG C of insulation 1-8h is warming up to, room temperature is cooled to, then 6-48h will be soaked in substrate immersion deionized water, makes glued membrane from base
Automatically strip, dry on plate, you can.
Described diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- double (2- (2- propargyl alcoholates) ethyoxyl) benzene, 1,4-
In double (2- propargyl alcoholates) benzene of diacetylene-benzene, 1,3- diacetylene-benzenes, 1,4- or double (2- propargyl alcoholates) benzene of 1,3- at least
It is a kind of；
Two described nitrine monomers are selected from double (azido-methyl) benzene of 1,4-, double (azido-methyl) benzene of 1,3-, the double (nitrine of 4,4-
Methyl) at least one of biphenyl or the nitrine diphenyl-methanes of 4,4- bis-；
Described dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexanes, 1,6- dibromos oneself
Alkane, the iodohexanes of 1,6- bis-, 1,10- dibromo-decanes, at least one of two benzyl chlorides or two benzyl chloride；
Described organic solvent is selected from acetone, tetrahydrofuran, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, N, N-
At least one of dimethyl acetamide or dimethyl sulfoxide (DMSO).
The mol ratio of diine monomer and two nitrine monomers described in step (1) is 100:67-100, described dihalo- is handed over
The mol ratio for joining agent and two nitrine monomers is 10-80:100, quality and diine monomer, the two nitrine monomers of described organic solvent
And the ratio between dihalo- crosslinking agent gross mass is 100:20-150.
As preferred technical scheme, the mol ratio of diine monomer and two nitrine monomers described in step (1) is 100:
80-100, described dihalo- crosslinking agent and the mol ratio of two nitrine monomers are 20-70:100, the quality of described 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) groove
Kind.
Described adhesive is the polytriazoles liquid adhesive being prepared from using 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
Dihalo- crosslinking agent is mixed, and is warming up to 50-100 DEG C, is thoroughly mixed uniform, you can.
Described diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- double (2- (2- propargyl alcoholates) ethyoxyl) benzene, 1,4-
In double (2- propargyl alcoholates) benzene of diacetylene-benzene, 1,3- diacetylene-benzenes, 1,4- or double (2- propargyl alcoholates) benzene of 1,3- at least
It is a kind of；
Two described nitrine monomers are selected from double (azido-methyl) benzene of 1,4-, double (azido-methyl) benzene of 1,3-, the double (nitrine of 4,4-
Methyl) at least one of biphenyl or the nitrine diphenyl-methanes of 4,4- bis-；
Described dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexanes, 1,6- dibromos oneself
Alkane, the iodohexanes of 1,6- bis-, 1,10- dibromo-decanes, at least one of two benzyl chlorides or two benzyl chloride.
Described diine monomer and the mol ratio of two nitrine monomers are 100:67-100, described dihalo- crosslinking agent and two is folded
The mol ratio of nitrogen monomer is 10-80:100.
As preferred technical scheme, described diine monomer and the mol ratio of two nitrine monomers are 100:80-100, institute
The dihalo- crosslinking agent and the mol ratio of two nitrine monomers stated are 20-70:100.
The application of the reversible polytriazoles adhesive of high-strength hot, described adhesive is to be prepared using such as logical formula (I) polymer
Polytriazoles glued membrane when, the polytriazoles glued membrane is clipped in two and treated in the middle of adhesives, under 0.5-1.5MPa pressure,
In 150-200 DEG C of environmental treatment 0.5-4h, two are treated that adhesives is bonded together, by bonding gluded joint in 100-
200 DEG C of processing 5-60min, it is micro- firmly to treat that adhesives is separated by two, then separated treat that adhesives is assembled into by this two
Together, 1-48h is handled in 80-200 DEG C, this two separated to treat that adhesives is bonded together again, is repeated with this viscous
Connect-unsticking process；
When described adhesive is the polytriazoles liquid adhesive being prepared from using such as logical formula (I) polymer, this is gathered
Triazole liquid adhesive is evenly coated in two and treats adhesives surface, and thickness is 0.2-2mm, and treatment temperature is 80-200 DEG C, place
The reason time is 1-48h, and two are treated that adhesives is bonded together, and bonding gluded joint is handled into 5- in 100-200 DEG C
60min, it is micro- firmly to treat that adhesives is separated by two, then by this two it is separated treat that adhesives is assemblied together, in 80-
200 DEG C of processing 1-48h, this two separated to treat that adhesives is bonded together again, and bonding-unsticking mistake is repeated with this
Journey.
Described treats adhesives including a kind of several in glass, ceramics, metal or polymer matrix composites.
Described metal includes the one or more in aluminium, stainless steel or copper.
Described polymer matrix composites include polytriazoles polymer matrix composites, polyimide resin based composites or
One or more in epoxy resin-base composite material.
Polytriazoles adhesive bonding form of the present invention is versatile and flexible, can be bonded with two kinds of forms of glued membrane and glue.
Wherein polytriazoles glued membrane has that preparation method is simple, construction technology is easy, storage convenient transport, thickness are uniform, resin added is accurate
And storage period it is long the advantages of.The difference of the polytriazoles glued membrane and traditional adhesive is that polytriazoles glued membrane is cured friendship
Linked polymer, is not susceptible to the change of physics and chemistry in storage process, and bin 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 technology is simple, repeatable to make
With；
2) polytriazoles adhesive of the present invention have well can hot unsticking performance, heating can peel off easily, again can after being combined
Recover high bonding strength, realize 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 recycle, the conservation rate of adhesive strength still may be up to
81%, service life cycle is long；
5) polytriazoles glued membrane of the present invention is cured cross-linked polymer, and physics and chemistry are not susceptible in storage process
Change, bin stability is high；
6) polytriazoles adhesive of the present invention can be applied to Aeronautics and Astronautics, precision optical machinery, petrochemical industry as sqtructural adhesive
Deng the metal and the bonding of composite that recycling is needed in field, with good application prospect.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, 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-decanes are added to 254
In parts by weight DMA (DMAC), mechanical agitation, mixing speed 100rpm, reaction temperature is 120 DEG C, during 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 soaks 36h, glued membrane is automatically stripped from glass plate, drying is gathered
Triazole glued membrane, the glued membrane is in light yellow, transparent, and thickness is 150 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two blocks of aluminium sheets, under 0.5-1.5MPa pressure, in 180 DEG C of environmental treatments
2h, two blocks of aluminium sheets can be adhered well to together, and its room temperature tensile shear strength is 20.3MPa.Bonding splicing is connect
Head handles 15min in 180 DEG C, and its tensile shear strength is 0.1MPa, micro- firmly can be separated two blocks of aluminium sheets.Two pieces are separated again
Aluminium sheet be assemblied together, handle 1h in 180 DEG C, two blocks of aluminium sheets can adhere well to together again, its tensile strength can be extensive
19.9MPa is arrived again, and strength retention is 98%.The process of this bonding-unsticking can be repeated, and after the 20th circulation, it draws
Shear strength is stretched for 18.9MPa, strength retention is 93.1%, after the 50th circulation, its tensile shear strength still has
15.2MPa, strength retention is 75%.
Gluded joint made from above-mentioned polytriazoles glued membrane bonding aluminium sheet is placed into 12d in the environment of 50 DEG C/100%RH,
Its tensile shear strength can keep more than 60%.Gluded joint made from the glued membrane is protected under 10MPa and 15MPa stress
More than 2h is held, does not have creep.Therefore show good durability and creep resistance after glued membrane bonding.In addition, should
Polytriazoles glued membrane has excellent solvent resistance, and its gluded joint soaks 60 in water, ethanol, DMF respectively
Remain to keep preferable adhesive effect more than it.
Above-mentioned polytriazoles glued membrane has very excellent shelf characteric, and it is placed 6 months under atmosphere at room temperature environment, and it glues
97% or so can be kept by connecing intensity, be placed 1 year, adhesive strength can keep the polytriazoles glued membrane of this in 95% or so, and storage process
Technique for sticking performance there is no significant change.
Embodiment 2：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, by 82 weight
Part Isosorbide-5-Nitrae-bis- (2- (2- propargyl alcoholates) ethyoxyls) benzene, 65 parts by weight 4, the nitrine diphenyl-methanes of 4- bis- and 13 parts by weight 1,2- dichloros
Ethane is added in 107 parts by weight N-N-methyl 2-pyrrolidone N (NMP), mechanical agitation, and mixing speed 100rpm, reaction temperature is 140
DEG C, the reaction time is 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, through 100 DEG C/2h, 170 DEG C/2h processing
Afterwards, it is down to room temperature.The stainless steel plate is immersed in deionized water and soaks 24h, glued membrane is automatically stripped from stainless steel plate, is dried
Polytriazoles glued membrane is obtained, the glued membrane is in light yellow, transparent, and thickness is 200 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two pieces of ceramic wafers, under 0.5-1.5MPa pressure, at 200 DEG C of environment
1h is managed, two pieces of ceramic wafers can be adhered well to together.Bonding gluded joint is handled into 5min in 200 DEG C, micro- can be used
Power separates two pieces of ceramic wafers.Two pieces of separated ceramic wafers are assemblied together again, 0.5h, two pieces of ceramic wafers are handled in 200 DEG C
It can adhere well to again together.The process of this bonding-unsticking can be repeated.
Embodiment 3：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, by 38 weight
Part Isosorbide-5-Nitrae-diacetylene-benzene, 45 parts by weight 1, double (azido-methyl) benzene of 3- and 23 parts by weight 1,2- Bromofumes are added to 105 weights
Measure in part DMF, mechanical agitation, 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, room temperature is down to.The polyfluortetraethylene plate is immersed in deionized water and soaks 24h, makes glued membrane from polyfluortetraethylene plate
Automatically strip, drying obtains polytriazoles glued membrane, the glued membrane is in light yellow, transparent, and thickness is 100 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two pieces of glass plates, under 0.5-1.5MPa pressure, at 160 DEG C of environment
4h is managed, two pieces of glass plates can be adhered well to together.Bonding gluded joint is handled into 20min in 160 DEG C, micro- can be used
Power separates two pieces of glass plates.Two pieces of separated glass plates are assemblied together again, 3h are handled in 160 DEG C, two pieces of glass plates can
Adhere well to again together.The process of this bonding-unsticking can be repeated.
Embodiment 4：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, by 56 weight
Part Isosorbide-5-Nitrae-bis- (2- propargyl alcoholates) benzene, 66 parts by weight 4, double (azido-methyl) biphenyl of 4- and 85 parts by weight 1, the iodohexanes of 6- bis- are added
Into 326 pbw acetones, mechanical agitation, mixing speed 100rpm is heated to backflow, the reaction time is 8h, obtains light brown
Homogeneous polytriazoles pre-polymerization liquid.
Above-mentioned polytriazoles pre-polymerization liquid is poured into the smooth polytetrafluoroethylene (PTFE) groove in surface, through 50 DEG C/5h, 120 DEG C/8h processing
Afterwards, it is down to room temperature.The polytetrafluoroethylene (PTFE) drill traverse is entered to soak 48h in deionized water, makes glued membrane automatic from polytetrafluoroethylene (PTFE) groove
Peel off, drying obtains polytriazoles glued membrane, the glued membrane is in light yellow, transparent, and thickness is 80 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two pieces of stainless steel plates, under 0.5-1.5MPa pressure, in 120 DEG C of environment
12h is handled, two pieces of stainless steel plates can be adhered well to together.Bonding gluded joint is handled into 60min in 120 DEG C,
Micro- firmly two pieces of stainless steel plates can be separated.Two pieces of separated stainless steel plates are assemblied together again, 8h, two are handled in 120 DEG C
Block stainless steel plate can be adhered well to together again.The process of this bonding-unsticking can be repeated.
Embodiment 5：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, 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-hexanes are added to 307 weights
Measure in part tetrahydrofuran, mechanical agitation, mixing speed 100rpm, be heated to backflow, the reaction time is 6h, obtains light brown homogeneous
Polytriazoles pre-polymerization liquid.
Above-mentioned polytriazoles pre-polymerization liquid is poured into the smooth polytetrafluoroethylene (PTFE) groove in surface, through 60 DEG C/5h, 130 DEG C/7h processing
Afterwards, it is down to room temperature.The polytetrafluoroethylene (PTFE) drill traverse is entered to soak 48h in deionized water, makes glued membrane automatic from polytetrafluoroethylene (PTFE) groove
Peel off, drying obtains polytriazoles glued membrane, the glued membrane is in light yellow, transparent, and thickness is 80 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two pieces of copper coins, under 0.5-1.5MPa pressure, in 150 DEG C of environmental treatments
6h, two pieces of copper coins can be adhered well to together.Bonding gluded joint is handled into 30min in 150 DEG C, micro- firmly can will
Two pieces of copper coins are separated.Two pieces of separated copper coins are assemblied together again, 4h are handled in 150 DEG C, two pieces of copper coins can again well
It is bonded together.The process of this bonding-unsticking can be repeated.
Embodiment 6：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, by 56 weight
Double two benzyl chlorides between (azido-methyl) biphenyl and 42 parts by weight of double (2- propargyl alcoholates) benzene of part 1,3-, 79 parts by weight 4,4- are added to
In 216 parts by weight dimethyl sulfoxide (DMSO)s, mechanical agitation, mixing speed 100rpm, reaction temperature is 80 DEG C, and the reaction time is 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 soaks 12h, glued membrane is automatically stripped from glass plate, drying is gathered
Triazole glued membrane, the glued membrane is in light yellow, transparent, and thickness is 150 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two blocks of polytriazoles polymer matrix composites plates, in 0.5-1.5MPa pressure
Under, in 130 DEG C of environmental treatment 10h, two blocks of polytriazoles polymer matrix composites plates can be adhered well to together.Will be bonding
Gluded joint in 130 DEG C handle 50min, can it is micro- firmly two blocks of polytriazoles polymer matrix composites plates are separated.Again by two pieces
Separated polytriazoles polymer matrix composites plate is assemblied together, and 6h, two pieces of polytriazoles polymer matrix composites are handled in 130 DEG C
Plate can be adhered well to together again.The process of this bonding-unsticking can be repeated.
Embodiment 7：
The preparation of polytriazoles glued membrane is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, 91 weights are added
Part bisphenol-A dipropargyl ether, 73 parts by weight 4 are measured, the nitrine diphenyl-methanes of 4- bis- and 41 parts by weight are to two benzyl chlorides, and mechanical agitation is stirred
Speed 100rpm is mixed, reaction temperature is 80 DEG C, and the reaction time is 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, through 80 DEG C/2h, 120 DEG C/8h processing
Afterwards, it is down to room temperature.The stainless steel plate is immersed in deionized water and soaks 36h, glued membrane is automatically stripped from stainless steel plate, is dried
Polytriazoles glued membrane is obtained, the glued membrane is in light yellow, transparent, and thickness is 200 μm.
Above-mentioned polytriazoles glued membrane is clipped in the middle of two blocks of aluminium sheets, under 0.5-1.5MPa pressure, in 170 DEG C of environmental treatments
3h, two blocks of aluminium sheets can be adhered well to together.Bonding gluded joint is handled into 15min in 170 DEG C, micro- firmly can will
Two blocks of aluminium sheets are separated.Two blocks of separated aluminium sheets are assemblied together again, 2h are handled in 170 DEG C, two blocks of aluminium sheets can again well
It is bonded together.The process of this bonding-unsticking can be repeated.
Embodiment 8：
The preparation of polytriazoles liquid adhesive is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, 56 weights are added
Measure part Isosorbide-5-Nitrae-bis- (2- propargyl alcoholates) benzene, 55 parts by weight 1, double (azido-methyl) benzene of 3- and 36 parts by weight 1,6- dichloro hexanes, machine
Tool is stirred, mixing speed 100rpm, and reaction temperature is 80 DEG C, and the reaction time is 10min, obtains light yellow homogeneous polytriazoles liquid
Adhesive.
Above-mentioned polytriazoles liquid adhesive is evenly coated in two pieces of surface of aluminum plate, thickness is 200 μm, through 100 DEG C/2h, 160
DEG C/4h processing after, two blocks of aluminium sheets can be adhered well to together.Bonding gluded joint is handled into 4h in 160 DEG C, can be micro-
Firmly two blocks of aluminium sheets are separated.Two blocks of separated aluminium sheets are assemblied together again, 3h are handled in 160 DEG C, two blocks of aluminium sheets can be again
Adhere well to together.The process of this bonding-unsticking can be repeated.
Embodiment 9：
The preparation of polytriazoles liquid adhesive is with using
In a four round flask equipped with mechanical agitation, nitrogen inlet, condenser pipe and thermometer, 56 weights are added
Measure part 1,3- double (2- propargyl alcoholates) benzene, 68 parts by weight 4, the nitrine diphenyl-methanes of 4- bis- and 57 parts by weight 1,10- dibromo-decanes, machine
Tool is stirred, mixing speed 100rpm, and reaction temperature is 70 DEG C, and the reaction time is 15min, obtains the homogeneous polytriazoles liquid of light brown
Adhesive.
Above-mentioned polytriazoles liquid adhesive is evenly coated in two pieces of stainless steel surfaces, thickness is 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.By bonding gluded joint in 140 DEG C of processing
40min, micro- firmly can separate two pieces of stainless steel plates.Two pieces of separated stainless steel plates are assemblied together again, in 140 DEG C of processing
5h, two pieces of stainless steel plates can be adhered well to together again.The process of this bonding-unsticking can be repeated.
Embodiment 1-9 prepares the initial bond strenght of gained adhesive with recycling performance, the experiment of bin stability
As a result it is as shown in table 1.
Table 1
Claims (10)
1. the reversible polytriazoles adhesive of high-strength hot, it is characterised in that the adhesive is prepared from by polytriazoles polymer, described
Polytriazoles polymer chemical structure of general formula 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, and value is 2-60.
2. the reversible polytriazoles adhesive of high-strength hot according to claim 1, it is characterised in that described adhesive is to adopt
With the polytriazoles glued membrane that formula (I) polymer is prepared from such as is led to, the thickness of the polytriazoles glued membrane is 50-300 μm.
3. the preparation method of the reversible polytriazoles adhesive of high-strength hot as claimed in claim 1 or 2, it is characterised in that the party
Method specifically includes 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, 1-5h is incubated in 50-100 DEG C, then heat up
To 120-180 DEG C of insulation 1-8h, room temperature is cooled to, then 6-48h will be soaked in substrate immersion deionized water, makes glued membrane from substrate
Automatically strip, dry, you can.
4. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 3, it is characterised in that described
Diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- double (2- (2- propargyl alcoholates) ethyoxyl) benzene, 1,4- diacetylene-benzenes, 1,
At least one of double (2- propargyl alcoholates) benzene of 3- diacetylene-benzenes, 1,4- or double (2- propargyl alcoholates) benzene of 1,3-；
Two described nitrine monomers are selected from double (azido-methyl) benzene of 1,4-, double (azido-methyl) benzene of 1,3-, double (the nitrine first of 4,4-
Base) at least one of biphenyl or the nitrine diphenyl-methanes of 4,4- bis-；
Described dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexanes, 1,6- dibromo-hexanes,
The iodohexanes of 1,6- bis-, 1,10- dibromo-decanes, at least one of two benzyl chlorides or two benzyl chloride；
Described organic solvent is selected from acetone, tetrahydrofuran, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, N, N- diformazans
At least one of yl acetamide or dimethyl sulfoxide (DMSO).
5. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 3, it is characterised in that step
(1) mol ratio of diine monomer and two nitrine monomers described in is 100:67-100, described dihalo- crosslinking agent and two nitrine
The mol ratio of monomer is 10-80:100, quality and diine monomer, two nitrine monomers and the dihalo- crosslinking agent of described organic solvent
The ratio between gross mass is 100:20-150.
6. the reversible polytriazoles adhesive of high-strength hot according to claim 1, it is characterised in that described adhesive is to adopt
The polytriazoles liquid adhesive being prepared from such as logical formula (I) polymer.
7. the preparation method of the reversible polytriazoles adhesive of high-strength hot as described in claim 1 or 6, it is characterised in that the party
Method is to mix diine monomer, two nitrine monomers and dihalo- crosslinking agent, is 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, it is characterised in that described
Diine monomer is selected from bisphenol-A dipropargyl ether, 1,4- double (2- (2- propargyl alcoholates) ethyoxyl) benzene, 1,4- diacetylene-benzenes, 1,
At least one of double (2- propargyl alcoholates) benzene of 3- diacetylene-benzenes, 1,4- or double (2- propargyl alcoholates) benzene of 1,3-；
Two described nitrine monomers are selected from double (azido-methyl) benzene of 1,4-, double (azido-methyl) benzene of 1,3-, double (the nitrine first of 4,4-
Base) at least one of biphenyl or the nitrine diphenyl-methanes of 4,4- bis-；
Described dihalo- crosslinking agent be selected from 1,2- dichloroethanes, glycol dibromide, 1,6- dichloro hexanes, 1,6- dibromo-hexanes,
The iodohexanes of 1,6- bis-, 1,10- dibromo-decanes, at least one of two benzyl chlorides or two benzyl chloride.
9. the preparation method of the reversible polytriazoles adhesive of high-strength hot according to claim 7, it is characterised in that described
The mol ratio of diine monomer and two nitrine monomers is 100:67-100, described dihalo- crosslinking agent and the mol ratio of two nitrine monomers
For 10-80:100.
10. the application of the reversible polytriazoles adhesive of high-strength hot as claimed in claim 1, it is characterised in that described is gluing
When agent is the polytriazoles glued membrane being prepared from using such as logical formula (I) polymer, the polytriazoles glued membrane is clipped in two materials to be bonded
In the middle of material, under 0.5-1.5MPa pressure, in 150-200 DEG C of environmental treatment 0.5-4h, two are treated that adhesives is adhered to one
Rise, bonding gluded joint is handled into 5-60min in 100-200 DEG C, it is micro- firmly to treat that adhesives is separated by two, then should
Two separated to treat that adhesives is assemblied together, and handles 1-48h in 80-200 DEG C, and this two separated to treat adhesives again
It is bonded together, bonding-unsticking process is repeated with this；
When described adhesive is the polytriazoles liquid adhesive being prepared from using such as logical formula (I) polymer, by the polytriazoles
Liquid adhesive is evenly coated in two and treats adhesives surface, and thickness is 0.2-2mm, and treatment temperature is 80-200 DEG C, during processing
Between be 1-48h, two are treated that adhesives is bonded together, by bonding gluded joint in 100-200 DEG C handle 5-60min,
It is micro- firmly to treat that adhesives is separated by two, then by this two it is separated treat that adhesives is assemblied together, at 80-200 DEG C
Manage 1-48h, this two separated to treat that adhesives is bonded together again, and bonding-unsticking process is repeated with this.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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