CN106010416B - The polyurethane gluing system and preparation method thereof constructed based on diels-Alder reaction - Google Patents
The polyurethane gluing system and preparation method thereof constructed based on diels-Alder reaction 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 Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of polyurethane gluing systems and preparation method thereof constructed based on diels-Alder reaction.The structural formula of the adhesive are as follows:, wherein the R are as follows:-CH2CH2-, which combines D-A reaction and polyurethane gluing system.Although the temperature-responsive of D-A reaction and its high efficiency are widely used it in self-healing thermosetting material, self-healing performance is introduced into hardly seen cross of adhesive system and is reported.In fact self-healing performance introducing bonding system there are into huge scientific research and practical application meaning.And the adhesive strength of the system is better than traditional acrylate resin.
Description
Technical field
The present invention relates to a kind of polyurethane gluing systems and preparation method thereof constructed based on diels-Alder reaction.
Background technique
With the increasingly promotion of social production and living standard, people have higher requirement to the performance of bonding system,
The bonding system with intelligent response causes people and more widely pays close attention in recent years.So-called intelligent response, refers to energy
Enough incude the variation of certain environmental stimuli, and itself certain physical properties, chemical structure or other performance can respond these
Corresponding variation occurs for stimulation, has many advantages, such as environment-adapting ability is strong, controllability is strong, application field is wide.Assign adhesive
There is great scientific research and practical application meaning with stimulating responsive, as adhesion strength can carry out intelligent control by environmental stimuli
Adhesive can be applied in adhesive bandage: high intensity may be implemented when pasting, and certain by applying after wound healing
Condition induction, adhesive bandage can be peeled easily, to be effectively prevented from the injury to skin.In order to assign bonding system with
Intelligent response needs to introduce the chemical group with stimulating responsive in system.However due to traditional chemical bond system
Without invertibity, it is difficult to realize the reversible regulation of adhesion strength；Although and non-covalent supramolecular system can with excellent
Inverse property can not achieve high adhesion strength but because active force is small, applicable to be limited in scope.And the dynamic quickly grown in recent years
The advantages that covalent systems both have both intensity height and good reversibility because of it, the realization intelligently to bond provide one it is most suitable
System platform.
Most of dynamic covalent systems are pH value responsiveness, are only applicable to proton environments.It has been reported that it is many dynamic
In state covalent systems, Diels-Alder reaction (D-A reaction) provides the dynamic reversible system an of temperature-responsive: in temperature
When spending lower, conjugated diene is reacted with the compound generation annulation generation six-membered cyclic compound containing double-strand, and
Back reaction can occur under high temperature again.Since self-discovery, D-A reaction is easy to operate with its, high-efficient, and selectivity is good and the external world is dry
The advantages such as small are disturbed, are widely used in numerous areas such as organic synthesis, self-healing material, medicine controlled releasing, active interfaces.
Forefathers' studies have shown that at room temperature, which can hardly carry out；At 80 °C, which can be complete in 3 h
At reaction efficiency has reached 95% or more；And when temperature is higher than 120 °C, the back reaction of scission of link occupies leading position.Such as Chen
A kind of heat cured epoxy resin is prepared Deng based on D-A reaction, the high efficiency and invertibity reacted using D-A, the resin material
It can be by being simply heat-treated the self-healing that can be realized on pattern and performance after fracture.
Polyurethane be by containing isocyanate group (- NCO) compound with containing active hydrogen compound (as-OH ,-NH- ,-
NH2Deng) reaction and generate macromolecule.Polyurethane itself has special soft segment and hard segment structure, molten between soft segment and hard section
Solution property difference, cause polyurethane soft segment and hard section thermodynamics it is incompatible therefore generate microphase-separated the phenomenon that, hard section molecule it
Between be dispersed in soft segment phase matrix together due to the effect strong associations of hydrogen bond, mechanical and adhesive property can be in very big model
Enclose it is interior regulated and controled.More importantly due to containing a large amount of very extensive chemical activities and highly polar in polyurethane adhesives
Isocyanate group (- NCO) and carbamate groups (- NHCOO-), thus with the material containing active hydrogen, as foamed plastics,
The material of any surface finish such as the porous materials such as leather, ceramics, timber, paper, fabric and metal, rubber, resin glass suffers from
Excellent bond strength.At the same time, polyurethane can improve molecular separating force phase interaction with the hydrogen bond action generated between substrate
Firmly, enhance bonding strength between the two.Therefore compared to polyacrylate base adhesive, polyurethane-based adhesive has more
Strong adhesion strength, and its adhesion strength can be regulated and controled in the larger context.
Summary of the invention
An object of the present invention is to provide a kind of polyurethane gluing system constructed based on diels-Alder reaction.
The second object of the present invention is to provide the preparation method of the polyurethane adhesive.
The present invention uses ethylenediamine and maleic anhydride to synthesize maleimide crossing linking reagent first, is denoted as product 1, structural formula
Are as follows:Specifically；Isophorone diisocyanate (IPDI) and polytetrahydrofuran diol are used again
(PTMG, average molecular weight 2000) synthesizes low molecular weight polyurethane, is denoted as product 2, structural formula are as follows:
Then dihydromethyl propionic acid (DMPA) is used, 2,2-dimethoxypropane (DMP) and furfuryl alcohol synthesis are containing furan group
Polyurethane chain extender is denoted as product 3, structural formula are as follows:；Product 3 is added and is closed
In reaction system at product 2, uncrosslinked polyurethane adhesive is synthesized, is denoted as product 4, structural formula are as follows:；Product 1 and product 4 are finally mixed with final product --- new polyurethane adhesive is denoted as
Product 5, structural formula are as follows:。
- R-representative-CH2CH2—；The polymer chain structure that above-mentioned wave indicates are as follows:
The polyurethane gluing system that one kind is constructed based on diels-Alder reaction, it is characterised in that the knot of the adhesive
Structure formula are as follows:
The wherein R are as follows:-CH2CH2—；The polymer chain structure that above-mentioned wave indicates are as follows:
The range that wherein range of m is 50~200, n is 25~35；The end of the chain is isocyanate groups sealing end, passes through poly- ammonia
The chain extension mechanism of ester is introduced to carry out reacting with maleimide crossing linking reagent again after furan group on polyurethane side chain and be can be obtained
Above-mentioned polyurethane gluing system；Molar ratio containing furan group and crosslinking agent in above-mentioned polyurethane is 2: 1.
It is a kind of to prepare the above-mentioned polyurethane gluing system constructed based on diels-Alder reaction, it is characterised in that should
The specific steps of method are as follows:
A. under ice bath, the dichloromethane solution of maleic anhydride is slowly added dropwise to the dichloromethane solution of ethylenediamine, is dripped
Continue to react at room temperature 4 ~ 5 hours after finishing, revolving removes DCM, and acetone solution is added, adds triethylamine, sodium acetate and second
Acid anhydrides, overnight, after reaction, separating-purifying obtains maleimide crossing linking reagent, i.e. product 1 for 50 ~ 60 °C of reactions；Described
Maleic anhydride, ethylenediamine, triethylamine, sodium acetate and acetic anhydride molar ratio be that 10: 5: 2: 2: the 20(ratio is controlled in above-mentioned ratio
Effect is relatively good between example and 10.2: 5.2: 2.1: 2.1: 20.2, and reactant slightly excess subsequent step can clean removing)；
B. by dihydromethyl propionic acid and 2,2- dimethoxy propane in molar ratio 10: 3 ratio (ratio control above-mentioned
Between ratio and 10.2: 3) dispersion in acetone, the p-methyl benzenesulfonic acid of catalytic amount is added, then proceed to 40 ~ 45 °C react 4 ~
5 h；After reaction, it is cooled to room temperature, NaHCO is added3To neutralize excessive acid；Filtering, revolving are added two after removing acetone
Chloromethanes dissolution, is washed with saturated salt solution and deionized water respectively, dry, and finally revolving removes methylene chloride, obtains centre
Product, structural formula are as follows:；
C. under ice bath, by step b products therefrom, furfuryl alcohol, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
With DMAP(4- dimethylamino naphthyridine) in molar ratio 1: 1.2: 1.21: 0.1 ratio (ratio control in aforementioned proportion and 1:
Between 1.21: 1.22: 0.11, EDCHCl is slightly excessive) it is dissolved in methylene chloride, it is stirred overnight, two is added after reaction
Chloromethanes dilution uses 0.1mol/l dilute hydrochloric acid, saturated sodium carbonate solution and deionized water washing respectively, it is mutually and dry to collect oil；
Colourless liquid is obtained using separating-purifying；By the colourless liquid and trifluoroacetic acid, in the molar ratio of 2:5, (ratio is controlled above-mentioned
Between ratio and 2: 5.2) it is dissolved in methanol, overnight, after the reaction was completed, clean drying for reaction at room temperature, obtains containing furan group
Polyurethane chain extender, i.e. product 3；
D. by polytetrahydrofuran diol and isophorone diisocyanate, by 1:2.1, (isophorone diisocyanate is slightly
Molar ratio mixing excessively), is added the dibutyl tin dilaurate of catalytic amount, the reaction 5 ~ 5.5 in 90 ~ 95 °C of nitrogen atmospheres
H obtains base polyurethane prepolymer for use as, is then dissolved in the resulting polyurethane chain extender of step cN’ NSimultaneously reaction is added in dimethylformamide
In system, continue to obtain the functionalized polyurethane of furans, i.e. product 4 after reaction in 90 ~ 95 °C of 5 ~ 5.5 h of reaction；Institute
The molar ratio of the polyurethane chain extender and polytetrahydrofuran diol stated is that 1: the 1(ratio controls the effect between 1: 1 to 1.1: 1
Preferably)；
A. maleimide crossing linking reagent obtained by step a and the functionalized polyurethane of furans obtained by step d are dissolved inN’ N-
In dimethylformamide, the molar ratio of the furan group and crosslinking agent that contain in the polyurethane is that 2: the 1(ratio controls
Effect is preferable between 2: 1 to 2: 1.1, i.e., crosslinking agent can be slightly excessive), be then coated with makes solvent volatilization complete on a pet film
Afterwards, thereon by the covering of another PET film piece, in 75 ~ 80 °C of 12 ~ 14h of heat preservation, so that D-A reaction completely, be subsequently cooled to
After room temperature to get arrive polyurethane gluing system.
Polyurethane gluing system feature of the invention is:
1.D-A reaction is a kind of typical thermal response-type dynamic chemical reaction, has fine invertibity.When temperature is lower
When, it balances and is carried out to cyclic direction, when temperature is higher, reaction can then be carried out to back reaction direction.D-A reaction is one very big
Advantage is that the factors such as its reaction and temperature and light are related, and influences with other factors such as reaction mediums little therefore wide
The general solution reaction applied in solid phase reaction and various different solvents, the especially preparation of thermosetting property self-healing material.
2. by the difficulty pasted in military and civil upper water is changed, and realizing intelligent stickup reconciliation paste functionality, more
Add the requirement for meeting Green Chemistry and environmental protection.And the adhesive strength of the system is better than traditional polyacrylate gluing
Agent.
The present invention has following outstanding feature and remarkable advantage: the innovation reacts D-A and polyurethane gluing
System combines.Although the temperature-responsive of D-A reaction and its high efficiency obtain it in self-healing thermosetting material
It is widely applied, but self-healing performance is introduced into hardly seen cross of adhesive system and is reported.In fact by self-healing performance
Introducing bonding system has huge scientific research and practical application meaning.
Detailed description of the invention
The synthetic route of polyurethane chain extender of the Fig. 1 containing furan group.
The synthetic route of polyurethane of the Fig. 2 containing furan group.
Fig. 3 polyurethane adhesive crosslinking reconciliation cross-linking process.
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 crosslinking agents of Fig. 6 are to polyurethane adhesive intensity effect (No. 1 is used crosslinking agent by the invention).
Fig. 7 maleimide crossing linking reagent (product 1) hydrogen nuclear magnetic resonance spectrogram.
Polyurethane chain extender (product 3) hydrogen nuclear magnetic resonance spectrogram of Fig. 8 containing furan group.
Specific embodiment
Details are as follows for the preferred embodiment of the present invention:
Embodiment one:
A. maleic anhydride (9.8 g, 100 mmol) is dissolved in 60 g DCM, is cooled to 0 °C, ethylenediamine is slowly added dropwise
DCM(25 g of (3.0 g, 50 mmol)) solution.Continue to react at room temperature 5 hours after being added dropwise.Revolving removes DCM,
60 g acetone solutions are added, add triethylamine (2.76 mL, 20 mmol), sodium acetate (1.64 g, 20 mmol) and acetic acid
Acid anhydride (20 g, 200 mmol), 60 °C of reactions are overnight.After reaction, cooling, and precipitated 2 times in ice water.Finally with just
Hexane and ethyl acetate (volume ratio 3:1) are mobile phase, obtain maleimide crossing linking reagent after carrying out separating-purifying with silicagel column
(product 1).
B. in acetone by DMPA (13.4 g, 0.1 mmol) and DMP (13.5 g, 0.13 mmol) dispersion, addition is urged
The TsOH of change amount stirs 1 h at room temperature and is allowed to dissolve, and then proceedes in 40 °C of 4 h of reaction.After reaction, it is cooled to room
5 g NaHCO are added in temperature310 min are stirred to neutralize excessive acid.It filters, it is molten that 120 g DCM are added after revolving removing acetone
Solution, respectively with saturated salt solution and washing 2 times, MgSO4Dry, finally revolving removes DCM；By the product (8.7 of above-mentioned preparation
G, 50 mmol), furfuryl alcohol (5.88 g, 60 mmol), EDCHCl (12.46 g, 65 mmol), DMAP (0.61 g,
5 mmol) it is dissolved in the DCM of 0 °C of 100 g, it is stirred overnight.100 g DCM dilution is added after reaction, then uses respectively
40 mL, 0.1 M HCl is saturated Na2CO3Solution and deionized water washing, collect oil mutually and use MgSO4It is dry.This liquid is led to
Pervaporation concentration, and with n-hexane and ethyl acetate (volume ratio 5:1) for mobile phase, molybdic acid colour developing is separated with silicagel column
Purification, obtains colourless liquid；The said goods (5.5 g, 20 mmol) are dissolved in 100 g methanol, addition trifluoroacetic acid (5.7 g,
50 mmol), reaction overnight, determines that reaction has been completed by silica gel plate at room temperature.Revolving removes methanol and trifluoroacetic acid, and
It is cleaned 5 times with DCM, is freeze-dried, obtains the polyurethane chain extender (product 3) containing furan group.
C.PTMG is dried overnight water removal for 120 °C in vacuum drying oven using preceding elder generation.By PTMG (0.6 g, 0.3 mmol)
It is mixed with IPDI (0.139 g, 0.63 mmol), the dibutyl tin dilaurate of catalytic amount is added, in 90 °C of nitrogen atmospheres
5 h of interior reaction.Then the polyurethane chain extender (0.064 g, 0.3 mmol) above-mentioned synthesis synthesized is dissolved in 0.3 mL DMF
And be added in reaction system, continue in 90 °C of 5 h of reaction.It is cooled to room temperature sealing after reaction 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 and the functionalized polyurethane of furans (product 4) is abundant
It is dissolved in DMF, is then coated with after making solvent volatilization completely on a pet film, thereon by the covering of another PET film piece.Again by PET film
Piece is placed in 80 °C of baking ovens and keeps the temperature 12 h, so that D-A reaction carries out completely, after then cooling to room temperature.
Embodiment two:
Using the polyurethane adhesive of the novel crosslinking of invention as research object, polyurethane adhesive under different temperatures is had studied
Adhesion strength regulate and control behavior.Referring to fig. 4, by the adhesive Jing Guo 140-80 °C of cross-linking reaction by 140 °C of-RT processes into
After the reverse D-A reaction solution crosslinking of row, tensile strength is reduced to 2.73 MPa(black dotted lines).Likewise, for initially passing through 140
°C uncrosslinked system of-RT process (red dotted line), after 140-80 °C of cross-linking reaction, tensile strength is increased to 2.83
MPa.This process has certain invertibity, and repeating crosslinking-solution crosslinking instead just can be realized the reply and decline of tensile strength.
However it is pointed out that the increase with cycle-index, the tensile strength after treatment of different temperature tends to be close.
Embodiment three:
Intrinsically, adhesive system and self-healing solid system are unified, thus we further with invention
Novel cross-linked polyurethane adhesive be research object, test the self-healing performance of the adhesive.Method as previously described
After the PET film for preparing bonding, two panels PET film is separated with mechanical force, two diaphragms are pressed together again with hand, are then set
3 h are kept the temperature in 140 °C of baking ovens, then are cooled to 80 °C of 12 h of heat preservation, tensile property test is carried out after being cooled to room temperature.Such as figure
Shown in 5, by be once broken-tack range after, it is very excellent primary to show that sample has almost without decline for tensile strength
Self-healing capability.By be broken twice-tack range after, tensile strength also only has dropped 12%.However from the 3rd fracture-bonding
Period, tensile strength decrease speed are sharply accelerated, and after 5 fracture-tack ranges, tensile strength has dropped 85%, only
For 0.56 MPa.This is because being required in each adhesion process by 140 °C of high-temperature process, high temperature can significantly accelerate to gather
Thus the aging of polymer segments leads to the decline of the performance of adhesive, and the thermal stability deficiency in the polyurethane system is then led
Cause below several period adhesive properties decline to a great extent.The above preliminary trial the result shows that D-A fully reacting can introduce it is poly-
Its self-healing effect is realized in urethane adhesive system, the heat resistant performance by improving polyurethane is expected to further increase
Its self-healing capability.
Example IV:
In addition comparison of the maleimide crossing linking reagent as the invention as we are also prepared for other two type, test hair
The adhesive strength highest of crosslinking agent is now used in the invention.
The maleimide crossing linking reagent (product 1) of above-mentioned synthesis is sufficiently molten with the functionalized polyurethane of furans (product 4)
Solution is then coated with after making solvent volatilization completely on a pet film in DMF, thereon by the covering of another PET film piece.Again by PET film piece
It is placed in 80 °C of baking ovens and keeps the temperature 12 h, so that D-A reaction carries out completely, tensile strength being carried out after then cooling to room temperature
Performance test.The ultimate tensile strength of four systems is compared, as shown in fig. 6, the tensile strength of system after crosslinking agent, which is added, to be had
Raising by a relatively large margin, is respectively increased to 3.96,3.45 and 3.84 MPa by 2.17 MPa, has increased separately 82%, 59% He
77%.Original linear polymers crosslinking can be the cross-linked polymer of body phase by the addition of crosslinking agent, only be produced originally with hydrogen bond
More strong chemical bond is increased in the system of raw cohesion, to significantly increase the cohesive force of molecule, it is strong to increase stretching
Degree.On the other hand crosslinking also reduces system toughness, so that stretchable displacement reduces.In addition it is noted that and acrylic acid
Ester adhesive system tensile strength is no more than 1.5 MPa and compares, and in polyurethane system, the adhesion strength of all adhesive is super
2 MPa are crossed, wherein the highest tensile strength of intensity (crosslinking agent used in the invention) is 3 times of acrylate adhesive.
Claims (2)
1. the polyurethane gluing system that one kind is constructed based on diels-Alder reaction, it is characterised in that the structure of the adhesive
Formula are as follows:
The wherein R are as follows:-CH2CH2—；The polymer chain structure that above-mentioned wave indicates are as follows:
The range that wherein range of m is 50~200, n is 25~35；The end of the chain is isocyanate groups sealing end, passes through polyurethane
Chain extension mechanism introduced on polyurethane side chain after furan group carried out again with maleimide crossing linking reagent reaction can be obtained it is above-mentioned
Polyurethane gluing system；Molar ratio containing furan group and crosslinking agent in above-mentioned polyurethane is 2: 1.
2. a kind of prepare the polyurethane gluing system according to claim 1 constructed based on diels-Alder reaction,
It is characterized in that the specific steps of this method are as follows:
A. under ice bath, the dichloromethane solution of maleic anhydride is slowly added dropwise to the dichloromethane solution of ethylenediamine, after being added dropwise
Continue to react 4~5 hours at room temperature, revolving removes DCM, and acetone solution is added, adds triethylamine, sodium acetate and acetic acid
Acid anhydride, overnight, after reaction, separating-purifying obtains maleimide crossing linking reagent, i.e. product 1 for 50~60 DEG C of reactions；The Malaysia
Acid anhydrides, ethylenediamine, triethylamine, sodium acetate and acetic anhydride molar ratio be 10: 5: 2: 2: 20 or 10.2: 5.2: 2.1: 2.1:
20.2, reactant is slightly excessively cleaned by subsequent step and is removed；
B. by dihydromethyl propionic acid and 2,2-dimethoxypropane in molar ratio 10: 3 or 10.2: 3 ratio dispersion in acetone,
The p-methyl benzenesulfonic acid of catalytic amount is added, then proceedes in 40~45 DEG C of 4~5h of reaction；After reaction, it is cooled to room temperature, is added
NaHCO3To neutralize excessive acid；Methylene chloride dissolution is added after removing acetone in filtering, revolving, respectively with saturated salt solution and going
Ion water washing, dry, finally revolving removes methylene chloride, obtains intermediate product, structural formula are as follows:
C. under ice bath, by step b products therefrom, furfuryl alcohol, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and
DMAP (4-dimethylaminopyridine) in molar ratio 1: 1.2: 1.21: 0.1 or 1: 1.21: 1.22: 0.11 ratio, make EDCHCl
It is slightly excessive, and be dissolved in methylene chloride, it is stirred overnight, methylene chloride dilution is added after reaction, uses 0.1mol/l respectively
Dilute hydrochloric acid, saturated sodium carbonate solution and deionized water washing, it is mutually and dry to collect oil；Colourless liquid is obtained using separating-purifying；
The colourless liquid and trifluoroacetic acid are dissolved in methanol by the molar ratio of 2:5 or 2: 5.2, overnight, reaction is completed for reaction at room temperature
Afterwards, clean drying, obtains the polyurethane chain extender containing furan group, i.e. product 3；
D. polytetrahydrofuran diol and isophorone diisocyanate are mixed by the molar ratio of 1:2.1, keeps isophorone two different
Cyanate is slightly excessive, and the dibutyl tin dilaurate of catalytic amount is added, and 5~5.5h is reacted in 90~95 DEG C of nitrogen atmospheres,
Base polyurethane prepolymer for use as is obtained, the resulting polyurethane chain extender of step c is then dissolved in N ' dinethylformamide and reactant is added
In system, continue to obtain the functionalized polyurethane of furans, i.e. product 4 after reaction in 90~95 DEG C of 5~5.5h of reaction；It is described
The molar ratio of polyurethane chain extender and polytetrahydrofuran diol is (1-1.1): 1；
E. the functionalized polyurethane of furans obtained by maleimide crossing linking reagent obtained by step a and step d is dissolved in N ' N- diformazan
In base formamide, the molar ratio of the furan group and crosslinking agent that contain in the polyurethane is 2: (1-1.1) makes crosslinking agent slightly
It is excessive, it is then coated with after making solvent volatilization completely on a pet film, thereon by the covering of another PET film piece, keeps the temperature 12 at 75~80 DEG C
~14h arrives polyurethane gluing system after then cooling to room temperature so that D-A reaction carries out completely.
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| US20210062056A1 (en) * | 2017-10-27 | 2021-03-04 | Taiyo Seiki Co., Ltd. | Thermally reversible cross-linked hot-melt adhesive |
| CN108329184B (en) * | 2018-02-06 | 2020-07-07 | 中国工程物理研究院化工材料研究所 | High polymer bonded explosive with self-repairing function and preparation method thereof |
| CN108586700A (en) * | 2018-05-15 | 2018-09-28 | 浙江华峰热塑性聚氨酯有限公司 | non yellowing can self-healing thermoplastic polyurethane elastomer and preparation method thereof |
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| CN110028648A (en) * | 2019-04-29 | 2019-07-19 | 中国科学院长春应用化学研究所 | A kind of selfreparing water-base polyurethane material and preparation method thereof |
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| CN111944474A (en) * | 2020-09-01 | 2020-11-17 | 重庆韩拓科技有限公司 | Thermally reversible polyurethane hot melt adhesive and preparation method thereof |
| CN113897165B (en) * | 2021-11-26 | 2023-05-26 | 韦尔通科技股份有限公司 | Detachable polyurethane hot melt adhesive, preparation raw materials, preparation method and bonding method thereof |
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| CN116120877A (en) * | 2022-12-24 | 2023-05-16 | 烟台德邦科技股份有限公司 | Polyurethane hot melt adhesive based on DIELS-ALDERS reaction and preparation method thereof |
| CN115819159A (en) * | 2023-02-10 | 2023-03-21 | 中北大学 | Self-healing high polymer bonded explosive and preparation method thereof |
| CN117363298B (en) * | 2023-10-09 | 2024-05-07 | 江西欣美新材料科技有限公司 | Halogen-free flame-retardant functional polyurethane sealant and preparation process thereof |
| CN117757053B (en) * | 2024-01-29 | 2024-10-15 | 湖南聚仁新材料股份公司 | Multi-branched polycaprolactone and preparation method thereof |
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