CN106010416A - Polyurethane adhesive system based on D-A reaction and preparation method of polyurethane adhesive system - Google Patents
Polyurethane adhesive system based on D-A reaction and preparation method of polyurethane adhesive system Download PDFInfo
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a polyurethane adhesive system based on the D-A reaction and a preparation method of the polyurethane adhesive system. The structural formula of an adhesive is shown in the description, wherein R is -CH2CH2-; according to the invention, the D-A reaction and the polyurethane adhesive system are innovatively combined. Although the D-A reaction is widely applied to self-healing thermosetting materials due to the temperature response and the high efficiency, almost no report shows that the self-healing performance is introduced into the adhesive system. In fact, introduction of the self-healing performance into the adhesive system has huge scientific research and practical application significances. Moreover, the adhesion strength of the system is better than the conventional polyacrylate adhesive.
Description
Technical field
The present invention relates to a kind of gluing system of polyurethane constructed based on diels Alder reaction and preparation method thereof.
Background technology
Along with social production and the lifting day by day of living standard, people have had higher requirement to the performance of bonding system,
There is the bonding system of intelligent response in recent years cause people and pay close attention to the most widely.So-called intelligent response, refers to
Enough sense the change of certain environmental stimuli, and itself some physical property, chemical constitution or other performance can respond these
Stimulate and corresponding change occurs, there is the plurality of advantages such as environment-adapting ability is strong, controllability is strong, application is wide.Give adhesive
With stimulating responsive, there is great scientific research and real world applications meaning, as adhesion strength can carry out intelligent control by environmental stimuli
Adhesive can apply in adhesive bandage: high intensity can be realized when pasting, and certain by applying after wound healing
Condition is induced, and adhesive bandage can easily peel, thus is effectively prevented from the injury to skin.In order to give bonding system with
Intelligent response, needs to introduce the chemical group with stimulating responsive in system.Yet with traditional chemical bond system
Not there is reversibility, it is difficult to realize the reversible regulation and control of adhesion strength；Although and non-covalent supramolecular system have excellence can
Inverse property, but little because of active force, it is impossible to realize high adhesion strength, applicable it is limited in scope.And quickly grew in recent years dynamic
Covalent systems has that the two intensity is high concurrently and the advantage such as good reversibility because of it, for intelligence bonding realize provide one most suitable
System platform.
Major part dynamically covalent systems is pH value response, is only applicable to proton environments.It has been reported that many dynamic
In state covalent systems, Diels-Alder reaction (D-A reaction) provides the dynamic reversible system of a temperature-responsive: in temperature
When spending relatively low, conjugated diene and the reaction of the generation six-membered cyclic compound of the compound generation annulation containing double-strand, and
Back reaction can occur again under high temperature.Since self-discovery, D-A reaction is easy and simple to handle with it, and efficiency is high, and selectivity is good and the external world does
Disturb the advantages such as little, be widely used at numerous areas such as organic synthesis, self-healing material, medicine controlled releasing, active interfaces.
The research of forefathers shows, at ambient temperature, this reaction is little to carry out；When 80 ° of C, this reaction can be complete in 3 h
Becoming, reaction efficiency has reached more than 95%；And when temperature is higher than 120 ° of C, the back reaction of scission of link occupies leading position.Such as Chen
Prepare a kind of heat cured epoxy resin Deng based on D-A reaction, utilize high efficiency and reversibility, this resin material that D-A reacts
The self-healing on pattern and performance can be realized by simple heat treatment after fracture.
Polyurethane be by the compound containing NCO (-NCO) with containing active hydrogen compound (as-OH ,-NH-,-
NH2Deng) reaction and the macromolecule that generates.Polyurethane itself has special soft section and hard segment structure, molten between soft section and hard section
Solve property difference, cause flexible polyurethane section and the incompatible phenomenon therefore producing microphase-separated of hard section thermodynamics, hard section molecule it
Between be dispersed in soft section of phase substrate due to the effect strong associations of hydrogen bond together, its machinery and adhesive property can be at the biggest models
Regulate and control in enclosing.What is more important, due to containing a large amount of the most very extensive chemical activities and highly polar in polyurethane adhesives
NCO (-NCO) and carbamate groups (-NHCOO-), therefore with the material containing active hydrogen, as foam plastics,
The material of any surface finish such as the porous materials such as leather, pottery, timber, paper, fabric and metal, rubber, resin glass suffers from
Excellent bond strength.Meanwhile, polyurethane can improve molecular separating force phase interaction with the hydrogen bond action produced between base material
Firmly, bonding strength therebetween is strengthened.Therefore compared to polyacrylate base adhesive, polyurethane-based adhesive has more
Strong adhesion strength, and its adhesion strength can regulate and control in the larger context.
Summary of the invention
An object of the present invention is to provide a kind of gluing system of polyurethane constructed based on diels Alder reaction.
The two of the purpose of the present invention are to provide the preparation method of this polyurethane adhesive.
First the present invention with ethylenediamine and maleic anhydride synthesis maleimide crossing linking reagent, is denoted as product 1, its structural formula
For:Specifically；Again with isophorone diisocyanate (IPDI) and polytetrahydrofuran diol
(PTMG, mean molecule quantity 2000) synthesis low molecular weight polyurethane, is denoted as product 2, and its structural formula is:
Then with dihydromethyl propionic acid (DMPA), 2,2-dimethoxypropane (DMP) and the furfuryl alcohol synthesis poly-ammonia containing furan group
Ester chain extender, is denoted as product 3, and its structural formula is:；Product 3 adds synthesis produce
In the reaction system of thing 2, synthesizing uncrosslinked polyurethane adhesive, be denoted as product 4, its structural formula is:；Finally product 1 and product 4 are mixed with end-product new polyurethane adhesive, are denoted as
Product 5, its structural formula is:。
R represents CH2CH2—；The polymer chain structure that above-mentioned wave represents is:
A kind of gluing system of polyurethane constructed based on diels Alder reaction, it is characterised in that the structural formula of this adhesive
For:
Wherein said R is: CH2CH2—；The polymer chain structure that above-mentioned wave represents is:
Wherein m is in the range of 50～200, and n is in the range of 25～35；The end of the chain is isocyanate groups end-blocking, by polyurethane
Chain extension mechanism carry out reacting with maleimide crossing linking reagent again after introducing furan group on polyurethane side chain i.e. can get above-mentioned
The gluing system of polyurethane；In above-mentioned polyurethane, the mol ratio containing furan group and cross-linking agent is 2: 1.
A kind of prepare the above-mentioned gluing system of polyurethane constructed based on diels Alder reaction, it is characterised in that should
Concretely comprising the following steps of method:
A., under ice bath, the dichloromethane solution of maleic anhydride is slowly added dropwise the dichloromethane solution of ethylenediamine, after dropping
Continuing at room temperature to react 4 ~ 5 hours, rotation is evaporated off DCM, adds acetone solution, adds triethylamine, sodium acetate and acetic anhydride,
50 ~ 60 ° of C react overnight, and after reaction terminates, separating-purifying obtains maleimide crossing linking reagent, i.e. product 1；Described maleic acid
The mol ratio of acid anhydride, ethylenediamine, triethylamine, sodium acetate and acetic anhydride be 10: 5: 2: 2: 20(this ratio control at aforementioned proportion and
Between 10.2: 5.2: 2.1: 2.1: 20.2, effectiveness comparison is good, and reactant slightly excess subsequent step can remove with remove impurity)；
B. by dihydromethyl propionic acid and 2,2-dimethoxy propane in molar ratio 10: 3 ratio (this ratio controls at aforementioned proportion
And between 10.2: 3) disperse in acetone, add the p-methyl benzenesulfonic acid of catalytic amount, then proceed to react 4 ~ 5 h at 40 ~ 45 ° of C；
After reaction terminates, it is cooled to room temperature, adds NaHCO3To neutralize the acid of excess；Filtering, rotation adds dichloromethane after acetone is evaporated off
Alkane dissolves, and respectively with saturated aqueous common salt and deionized water wash, is dried, and finally rotation is evaporated off dichloromethane, obtains intermediate product,
Structural formula is:；
C. under ice bath, by step b products therefrom, furfuryl alcohol, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and
DMAP(4-dimethylamino naphthyridine) in molar ratio 1: 1.2: 1.21: 0.1 ratio (this ratio controls at aforementioned proportion and 1: 1.21
: between 1.22: 0.11, EDC HCl slightly excess) it is dissolved in dichloromethane, it is stirred overnight, reaction adds dichloromethane after terminating
Alkane dilutes, and uses 0.1mol/l dilute hydrochloric acid, saturated sodium carbonate solution and deionized water wash respectively, collects oil phase and is dried；Warp again
Cross separating-purifying and obtain colourless liquid；By this colourless liquid and trifluoroacetic acid, in the mol ratio of 2:5, (this ratio controls at aforementioned proportion
And between 2: 5.2) be dissolved in methanol, react under room temperature overnight, after having reacted, remove impurity is dried, and obtains gathering containing furan group
Urethane chain extender, i.e. product 3；
D. polytetrahydrofuran diol and isophorone diisocyanate are pressed 1:2.1 (isophorone diisocyanate slightly excess)
Mixed in molar ratio, add catalytic amount dibutyl tin laurate, 90 ~ 95 ° of C nitrogen atmospheres in react 5 ~ 5.5 h, must
Base polyurethane prepolymer for use as, is then dissolved in the polyurethane chain extender of step c gainedN’N-dimethylformamide also adds reaction system
In, continuing to react 5 ~ 5.5 h at 90 ~ 95 ° of C, reaction obtains the polyurethane of furan functionalization, i.e. product 4 after terminating；Described
The mol ratio of polyurethane chain extender and polytetrahydrofuran diol is that 1: 1(this ratio controls between 1: 1 to 1.1: 1 effect relatively
Good)；
A. the polyurethane of step a gained maleimide crossing linking reagent with step d gained furan functionalization is dissolved inN’ N-two
In methylformamide, the furan group contained in described polyurethane and the mol ratio of cross-linking agent are that 2: 1(this ratio controls 2:
Between 1 to 2: 1.1, effect is preferable, i.e. cross-linking agent can be slightly excessive), after being then coated with making solvent volatilization completely on a pet film,
Another PET film sheet is covered on it, is incubated 12 ~ 14h at 75 ~ 80 ° of C, so that D-A reaction carries out completely, being subsequently cooled to room
Wen Hou, i.e. obtains the gluing system of polyurethane.
The polyurethane gluing system feature of the present invention is:
1.D-A reaction is a kind of typical thermal response-type dynamic chemical reaction, has fine reversibility.When the temperature is low, flat
Weighing apparatus is carried out to cyclization direction, and when temperature is higher, reaction then can be carried out to back reaction direction.D-A reacts a advantage the biggest
It is that its reaction is only the most relevant with the factor such as temperature and light, and all little with the other factors impact such as reaction medium, the most extensively should
Solution reaction in solid state reaction and various different solvents, the particularly preparation of thermosetting self-healing material.
2. will change the difficulty pasted in military and civil upper water, and the stickup realizing intelligence conciliates paste functionality, more
Add the requirement meeting Green Chemistry and environmental conservation.And the adhesive strength of this system to be better than traditional polyacrylate gluing
Agent.
The present invention has following outstanding feature and a remarkable advantage: this innovation by D-A reaction and polyurethane gluing
System combines.Although the temperature-responsive of D-A reaction and its high efficiency make it obtain in self-healing thermosets
It is widely applied, but self-healing performance is introduced that adhesive system is nearly no crosses report.In fact by self-healing performance
Introduce bonding system and have huge scientific research and actual application value.
Accompanying drawing explanation
The synthetic route of the Fig. 1 polyurethane chain extender containing furan group.
The synthetic route of the Fig. 2 polyurethane containing furan group.
Cross-linking process is conciliate in the crosslinking of Fig. 3 polyurethane adhesive.
Fig. 4 changes variable temperature control new polyurethane adhesive adhesive strength.
The cyclically-varying of Fig. 5 new polyurethane adhesive adhesive strength.
Tri-kinds of cross-linking agent of Fig. 6 are to polyurethane adhesive intensity effect (No. 1 is used cross-linking agent by this invention).
Fig. 7 maleimide crossing linking reagent (product 1) hydrogen nuclear magnetic resonance spectrogram.
Fig. 8 polyurethane chain extender (product 3) the hydrogen nuclear magnetic resonance spectrogram containing furan group.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment one:
A. maleic anhydride (9.8 g, 100 mmol) is dissolved in 60 g DCM, is cooled to 0 ° of C, is slowly added dropwise ethylenediamine (3.0
G, 50 mmol) DCM(25 g) solution.Drip complete follow-up continuous at room temperature reaction 5 hours.Rotation is evaporated off DCM, adds 60
G acetone solution, adds triethylamine (2.76 mL, 20 mmol), sodium acetate (1.64 g, 20 mmol) and acetic anhydride (20
G, 200 mmol), 60 ° of C react overnight.After reaction terminates, cooling, and precipitate 2 times in frozen water.Finally with normal hexane and
Ethyl acetate (volume ratio 3:1) is flowing phase, obtains maleimide crossing linking reagent (product after carrying out separating-purifying with silicagel column
1).
B. DMPA (13.4 g, 0.1 mmol) and DMP (13.5 g, 0.13 mmol) is disperseed in acetone, add catalytic amount
TsOH, stir 1 h under room temperature and be allowed to dissolve, then proceed to react 4 h at 40 ° of C.After reaction terminates, it is cooled to room temperature, adds
Enter 5 g NaHCO3Stir 10 min to neutralize the acid of excess.Filtering, rotation adds 120 g DCM and dissolves after acetone is evaporated off, point
Yong saturated aqueous common salt and washing 2 times, MgSO4Being dried, finally rotation is evaporated off DCM；By the product of above-mentioned preparation (8.7 g, 50
Mmol), furfuryl alcohol (5.88 g, 60 mmol), EDC HCl (12.46 g, 65 mmol), DMAP (0.61 g, 5
Mmol) it is dissolved in the DCM of 100 0 ° of C of g, is stirred overnight.Reaction adds 100 g DCM dilutions after terminating, the most respectively with 40
ML 0.1 M HCl, saturated Na2CO3Solution and deionized water wash, collect oil phase and use MgSO4It is dried.By this liquid by steaming
Send out and concentrate, and develop the color with normal hexane and ethyl acetate (volume ratio 5:1) for flowing phase, molybdic acid, carry out separating-purifying with silicagel column,
Obtain colourless liquid；The said goods (5.5 g, 20 mmol) is dissolved in 100 g methanol, and addition trifluoroacetic acid (5.7 g, 50
Mmol), react under room temperature overnight, determine that reaction is complete by silica gel plate.Rotation is evaporated off methanol and trifluoroacetic acid, and uses
DCM cleans 5 times, and lyophilization obtains the polyurethane chain extender (product 3) containing furan group.
Before c.PTMG use, first in vacuum drying oven, 120 ° of C are dried overnight except water.By PTMG (0.6 g, 0.3 mmol)
Mix with IPDI (0.139 g, 0.63 mmol), add the dibutyl tin laurate of catalytic amount, at 90 ° of C nitrogen atmospheres
Interior reaction 5 h.Then the polyurethane chain extender (0.064 g, 0.3 mmol) above-mentioned synthesis synthesized is dissolved in 0.3 mL DMF
And add in reaction system, continue to react 5 h at 90 ° of C.Reaction is cooled to Room-temperature seal after terminating and obtains uncrosslinked poly-ammonia
Ester gum stick (product 4) is stand-by.
D. the maleimide crossing linking reagent (product 1) of above-mentioned synthesis is abundant with the polyurethane (product 4) of furan functionalization
It is dissolved in DMF, after being then coated with making solvent volatilization completely on a pet film, another PET film sheet is covered on it.Again by PET film
Sheet is placed in 80 ° of C baking ovens and is incubated 12 h, so that D-A reaction carries out completely, after being then cooled to room temperature.
Embodiment two:
With the polyurethane adhesive of novel crosslinking of invention as object of study, have studied the viscous of polyurethane adhesive under different temperatures
Knotting strength regulation and control behavior.See Fig. 4, the adhesive through 140-80 ° of C cross-linking reaction is carried out inverse by 140 ° of C-RT processes
After D-A reaction solves crosslinking, hot strength is reduced to 2.73 MPa(black dotted lines).Same, for initial through 140 ° of C-
The system (red dotted line) that RT process is uncrosslinked, after 140-80 ° of C cross-linking reaction, its hot strength brings up to 2.83
MPa.This process has certain reversibility, repeats crosslinking-solution crosslinking and instead just can realize reply and the decline of hot strength.
But it is pointed out that the increase along with cycle-index, the hot strength after treatment of different temperature tends to close.
Embodiment three:
Intrinsically, adhesive system and self-healing solid system are unified, and therefore we are new with invent further
The cross-linked polyurethane adhesive of type is object of study, tests the self-healing performance of this adhesive.As previously described prepared by method
After the PET film of bonding, by mechanical force by two panels PET film separately, with hands by two diaphragms again by together, then it is placed on
140 ° of C baking ovens are incubated 3 h, then are cooled to 80 ° of C and are incubated 12 h, after being cooled to room temperature, carry out tensile property test.Such as Fig. 5
Shown in, after once fracture-tack range, hot strength almost without decline, show sample have the most excellent once
Self-healing capability.After twice fracture-tack range, hot strength the most only have dropped 12%.But from the 3rd fracture-bonding
In the cycle, hot strength decrease speed drastically accelerates, and after 5 fracture-tack ranges, hot strength have dropped 85%, only
It is 0.56 MPa.This is because be required for through 140 ° of C high-temperature process in each adhesion process, high temperature significantly can accelerate to gather
Polymer segments aging, thus causes the decline of the performance of adhesive, and the heat stability deficiency in this polyurethane system is then led
Cause declining to a great extent of the most several cycle adhesive property.The most preliminary trial result shows that D-A reaction can introduce poly-completely
Urethane adhesive system realizes its self-healing effect, is expected to improve further by the heat resistant performance improving polyurethane
Its self-healing capability.
Embodiment four:
As additionally we are also prepared for other two kinds, maleimide crossing linking reagent is as the contrast of this invention, and test finds should
The adhesive strength using cross-linking agent in invention is the highest.
By the most molten with the polyurethane of furan functionalization (product 4) for the maleimide crossing linking reagent (product 1) of above-mentioned synthesis
Another PET film sheet, in DMF, after being then coated with making solvent volatilization completely on a pet film, is covered on it by solution.Again by PET film sheet
It is placed in 80 ° of C baking ovens and is incubated 12 h, so that D-A reaction carries out completely, to carry out hot strength after being then cooled to room temperature
Performance test.The ultimate tensile strength of contrast four systems, as shown in Figure 6, after adding cross-linking agent, the hot strength of system all has
Raising by a relatively large margin, is respectively increased 3.96,3.45 and 3.84 MPa by 2.17 MPa, adds 82% respectively, 59% He
77%.The cross linked polymer that original linear polymers crosslinking is body phase can the most only produced by the addition of cross-linking agent with hydrogen bond
Raw cohesion system adds more strong chemical bond, thus significantly increases the cohesiveness of molecule, increase stretching strong
Degree.On the other hand crosslinking also reduces system toughness so that stretchable displacement reduces.Additionally it is noted that and acrylic acid
Ester adhesive system hot strength is compared less than 1.5 MPa, and in polyurethane system, the adhesion strength of all adhesive is super
Crossing 2 MPa, the hot strength (cross-linking agent used by this invention) that wherein intensity is the highest is 3 times of acrylate adhesive.
Claims (2)
1. the gluing system of polyurethane constructed based on diels Alder reaction, it is characterised in that the structure of this adhesive
Formula is:
Wherein said R is: CH2CH2—；The polymer chain structure that above-mentioned wave represents is:
Wherein m is in the range of 50～200, and n is in the range of 25～35；The end of the chain is isocyanate groups end-blocking, by polyurethane
Chain extension mechanism carry out reacting with maleimide crossing linking reagent again after introducing furan group on polyurethane side chain i.e. can get above-mentioned
The gluing system of polyurethane；In above-mentioned polyurethane, the mol ratio containing furan group and cross-linking agent is 2: 1.
2. prepare the gluing system of polyurethane constructed based on diels Alder reaction according to claim 1,
It is characterized in that concretely comprising the following steps of the method:
A., under ice bath, the dichloromethane solution of maleic anhydride is slowly added dropwise the dichloromethane solution of ethylenediamine, after dropping
Continuing at room temperature to react 4 ~ 5 hours, rotation is evaporated off DCM, adds acetone solution, adds triethylamine, sodium acetate and acetic anhydride,
50 ~ 60 ° of C react overnight, and after reaction terminates, separating-purifying obtains maleimide crossing linking reagent, i.e. product 1；Described maleic acid
The mol ratio of acid anhydride, ethylenediamine, triethylamine, sodium acetate and acetic anhydride be 10: 5: 2: 2: 20(this ratio control at aforementioned proportion and
Between 10.2: 5.2: 2.1: 2.1: 20.2, effectiveness comparison is good, and reactant slightly excess subsequent step can remove with remove impurity)；
B. by dihydromethyl propionic acid and 2,2-dimethoxy propane in molar ratio 10: 3 ratio (this ratio controls at above-mentioned ratio
Between example and 10.2: 3) disperse in acetone, add the p-methyl benzenesulfonic acid of catalytic amount, then proceed to react 4 ~ 5 at 40 ~ 45 ° of C
h；After reaction terminates, it is cooled to room temperature, adds NaHCO3To neutralize the acid of excess；Filtering, rotation adds dichloro after acetone is evaporated off
Methane dissolves, and respectively with saturated aqueous common salt and deionized water wash, is dried, and finally rotation is evaporated off dichloromethane, obtains middle product
Thing, structural formula is:；
C. under ice bath, by step b products therefrom, furfuryl alcohol, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and
DMAP(4-dimethylamino naphthyridine) in molar ratio 1: 1.2: 1.21: 0.1 ratio (this ratio controls at aforementioned proportion and 1: 1.21
: between 1.22: 0.11, EDC HCl slightly excess) it is dissolved in dichloromethane, it is stirred overnight, reaction adds dichloromethane after terminating
Alkane dilutes, and uses 0.1mol/l dilute hydrochloric acid, saturated sodium carbonate solution and deionized water wash respectively, collects oil phase and is dried；Warp again
Cross separating-purifying and obtain colourless liquid；By this colourless liquid and trifluoroacetic acid, in the mol ratio of 2:5, (this ratio controls at aforementioned proportion
And between 2: 5.2) be dissolved in methanol, react under room temperature overnight, after having reacted, remove impurity is dried, and obtains gathering containing furan group
Urethane chain extender, i.e. product 3；
D. polytetrahydrofuran diol and isophorone diisocyanate are pressed 1:2.1 (isophorone diisocyanate slightly mistake
Amount) mixed in molar ratio, add catalytic amount dibutyl tin laurate, 90 ~ 95 ° of C nitrogen atmospheres in reaction 5 ~ 5.5 h,
Obtain base polyurethane prepolymer for use as, then the polyurethane chain extender of step c gained is dissolved inN’ N-dimethylformamide also adds reactant
In system, continuing to react 5 ~ 5.5 h at 90 ~ 95 ° of C, reaction obtains the polyurethane of furan functionalization, i.e. product 4 after terminating；Described
Polyurethane chain extender and the mol ratio of polytetrahydrofuran diol be that 1: 1(this ratio controls between 1: 1 to 1.1: 1 effect relatively
Good)；
E. the polyurethane of step a gained maleimide crossing linking reagent with step d gained furan functionalization is dissolved inN’ N-two
In methylformamide, the furan group contained in described polyurethane and the mol ratio of cross-linking agent are that 2: 1(this ratio controls 2:
Between 1 to 2: 1.1, effect is preferable, i.e. cross-linking agent can be slightly excessive), after being then coated with making solvent volatilization completely on a pet film,
Another PET film sheet is covered on it, is incubated 12 ~ 14h at 75 ~ 80 ° of C, so that D-A reaction carries out completely, being subsequently cooled to room
Wen Hou, i.e. obtains the gluing system of polyurethane.
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