CN112877014B - Epoxy resin hot melt adhesive and preparation method thereof - Google Patents
Epoxy resin hot melt adhesive and preparation method thereof Download PDFInfo
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- CN112877014B CN112877014B CN202110068063.0A CN202110068063A CN112877014B CN 112877014 B CN112877014 B CN 112877014B CN 202110068063 A CN202110068063 A CN 202110068063A CN 112877014 B CN112877014 B CN 112877014B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 196
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 196
- 239000004831 Hot glue Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 120
- 150000001412 amines Chemical class 0.000 claims abstract description 120
- 229920000570 polyether Polymers 0.000 claims abstract description 120
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- -1 amine ureido pyrimidinone derivatives Chemical class 0.000 abstract description 41
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 90
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 238000005160 1H NMR spectroscopy Methods 0.000 description 45
- 238000005303 weighing Methods 0.000 description 42
- 238000005259 measurement Methods 0.000 description 40
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 40
- 239000004810 polytetrafluoroethylene Substances 0.000 description 40
- 239000011521 glass Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- 238000007711 solidification Methods 0.000 description 27
- 230000008023 solidification Effects 0.000 description 27
- 239000012074 organic phase Substances 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 238000001816 cooling Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 230000003993 interaction Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- PFKFTWBEEFSNDU-UHFFFAOYSA-N 1,1'-Carbonyldiimidazole Substances C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 description 3
- HGINADPHJQTSKN-UHFFFAOYSA-M 3-ethoxy-3-oxopropanoate Chemical compound CCOC(=O)CC([O-])=O HGINADPHJQTSKN-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- WVUCPRGADMCTBN-UHFFFAOYSA-M potassium;3-ethoxy-3-oxopropanoate Chemical compound [K+].CCOC(=O)CC([O-])=O WVUCPRGADMCTBN-UHFFFAOYSA-M 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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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)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, supramolecular materials and adhesives, and particularly relates to an epoxy resin hot melt adhesive and a preparation method thereof. The epoxy resin hot melt adhesive material is prepared by using epoxy resin, polyether amine and polyether amine ureido pyrimidinone derivatives. Under the high-temperature condition, UPy is dissociated, hot melt adhesive flows, and the surface of an adherend is soaked; under low temperature conditions, the UPy associates and the hot melt adhesive cures, bonding the adherends together. The UPy-based epoxy resin hot melt adhesive has the advantages of repeatable bonding, high bonding strength, wide bonding range, high bonding speed, low bonding temperature, adjustable bonding strength, environmental friendliness and the like. The epoxy resin hot melt adhesive prepared by the invention has a simple structure and wide raw material sources. In the process of preparing the epoxy resin hot melt adhesive, no solvent is used, the solid content of the hot melt adhesive is 100 percent, and the adhesive is an environment-friendly adhesive. Meanwhile, the method has the advantages of simple process, no byproduct generation, no waste discharge and 100% atom utilization rate.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, supramolecular materials and adhesives, and particularly relates to an epoxy resin hot melt adhesive and a preparation method thereof.
Background
The hot melt adhesive is an adhesive which is solid at room temperature, is melted into liquid after being heated, and is bonded through physical solidification or chemical solidification after being coated and cooled. Hot melt adhesives can be divided into thermoplastic hot melt adhesives and thermosetting hot melt adhesives. The thermoplastic hot melt adhesive has no covalent bond connection among the high polymer chains, has a linear molecular chain structure, and has the advantages of high initial bonding strength, repeatable bonding and the like. The thermosetting hot melt adhesive has a chemically crosslinked three-dimensional network structure, and has the advantages of high bonding strength, heat resistance, corrosion resistance and the like (Ind.
In order to combine the advantages of thermoplastic hot melt adhesives and thermosetting hot melt adhesives, researchers design cross-linking agents containing dynamic bonds to prepare hot melt adhesive materials with high bonding strength and repeatable bonding. Dynamic bonds refer to chemical bonds that can be reversibly broken and formed under certain conditions, and are classified into dynamic covalent bonds and non-covalent interactions. Dynamic covalent bond based hot melt adhesive systems have been reported in the literature (mater. chem. front.2019,3,1833.; int.j. adhes. adhes.2020,100,102597.). Although such hot melt adhesives have advantages such as high initial adhesive strength and repairability, they have disadvantages such as low adhesive strength. Common non-covalent interactions include hydrogen bonding, coordination bonding, van der waals forces, ionic bonding, and the like. The bond energy of the non-covalent interaction is lower than that of the covalent bond, the non-covalent interaction is sensitive to external stimulation, and the repeated bonding of the hot melt adhesive can be realized through the reversible dissociation and association of the non-covalent interaction. Supramolecular hot melt adhesive systems based on non-covalent interactions have been reported in the literature (Macromolecules2016,49,7877.; adv Funct. Mater.2020, 2006944.). Although the supermolecule hot melt adhesive has the advantages of low viscosity in a viscous flow state and the like, the supermolecule hot melt adhesive cannot meet the actual use requirement due to low bonding strength and poor corrosion resistance, and has low application value. Accordingly, there is a need to develop a class of hot melt adhesive materials that have high bond strength and are capable of repeated bonding.
Disclosure of Invention
Aiming at the defects in the literature reports and commercial hot melt adhesives, the invention introduces a covalent chain extender (polyetheramine) and a non-covalent cross-linking agent (polyetheramine UPy derivative) into an epoxy resin adhesive, and endows the epoxy resin adhesive with the characteristic of repeatable adhesion on the basis of keeping the excellent adhesion performance of the epoxy resin adhesive so as to obtain the epoxy resin hot melt adhesive with high adhesion strength and repeatable adhesion.
The invention provides an epoxy resin-based hot melt adhesive, which has the molecular formula:
wherein: a is 1 to 7, b is 2 to 7, z is 0 to 0.5, m is 3 to 9, and n is 1 to 19.
In the epoxy resin-based hot melt adhesive, the percentage alpha of the molar amount of the polyether amine UPy derivative in the total molar amount of the polyether amine and the polyether amine UPy derivative is 0.5-1.0.
The preparation method of the epoxy resin-based hot melt adhesive comprises the following steps:
polyetheramines containing one amine group:
polyetheramine UPy derivatives containing one amine group:
and epoxy resins containing two epoxy groups:
the epoxy resin-based hot melt adhesive is obtained by adopting a melting method to carry out reaction, and the molecular formula of the obtained epoxy resin-based hot melt adhesive is as follows:
the preparation method comprises the following specific processes:
preparing raw materials according to molar parts;
under the condition of high temperature, fully stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin to obtain an epoxy resin hot melt adhesive prepolymer;
and curing the epoxy resin hot melt adhesive prepolymer for a period of time under the high-temperature condition to obtain the epoxy resin hot melt adhesive.
In the preparation method, the following raw materials are prepared according to the following molar parts:
polyether amine containing amine group: 0 to 0.5 part
The polyetheramine UPy derivatives are: 0.5 to 1 portion
Epoxy group-containing epoxy resin: 1 part of
Wherein the mole amount of the polyether amine UPy derivative accounts for 0.5-1.0 percent of the total mole amount of the polyether amine and the polyether amine UPy derivative;
calculating the weight according to the molar parts, and weighing the raw materials according to the weight;
in the preparation method, the temperature for stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin is 50-70 ℃, and the stirring and mixing time is 0.1-0.5 h
In the preparation method, the curing temperature of the epoxy resin hot melt adhesive prepolymer is 50-70 ℃, and the curing time is 6-24 hours.
The epoxy resin hot melt adhesive and the preparation method thereof provided by the invention have the following advantages:
(1) compared with the literature report and the commercial hot melt adhesive, the method of the invention adopts the non-covalent cross-linking agent (UPy-OPG-NH)2) The epoxy resin hot melt adhesive is introduced into an epoxy resin adhesive to replace a traditional covalent cross-linking agent to prepare the epoxy resin hot melt adhesive. Under the condition of room temperature, the associated non-covalent cross-linking agent can cross-link the main chain of the epoxy resin, so that the epoxy resin hot melt adhesive has excellent bonding performance. Under the high temperature condition, the non-covalent cross-linking agent is dissociated, the polymer chains are relatively slipped, and the hot melt adhesive is subjected to viscous flow, so that the epoxy resin hot melt adhesive can be repeatedly bonded. After the prepared epoxy resin hot melt adhesive is repeatedly bonded for 6 times, the bonding performance is not obviously reduced.
(2) In the preparation method, under the condition of room temperature, because UPy has a very high binding constant and the interaction between epoxy resin molecular chains is strong, the epoxy resin hot melt adhesive has high colloid strength (Young modulus is 184MPa), and the bonding strength of the hot melt adhesive is favorably improved.
(3) In the method, the used UPy can form hydrogen bond interaction with different substrates (such as metal materials, inorganic non-metal materials, high polymer materials and the like), so that the epoxy resin hot melt adhesive can be used for bonding various materials, and the bonding strength of the hot melt adhesive is improved. For stainless steel substrates, the lap shear strength of the epoxy hot melt adhesive is as high as 10 MPa.
(4) In the method, the performance of the epoxy resin hot melt adhesive can be regulated and controlled by changing the percentage alpha of the molar weight of the polyether amine UPy derivative in the total molar weight of the polyether amine and the polyether amine UPy derivative. When the alpha value is lower, the interaction between the epoxy resin high molecular chains is strong, and the hot melt adhesive has high bonding strength. When the alpha value is higher, the interaction between epoxy resin high molecular chains is weak, and the hot melt adhesive has low melt viscosity. The invention can regulate and control the performance of the epoxy resin hot melt adhesive in a wide range, and broadens the application range of the epoxy resin hot melt adhesive.
(5) In the preparation method, due to the excellent thermal responsiveness of the used UPy, the epoxy resin hot melt adhesive has low bonding temperature (80 ℃) and short bonding time (5 minutes), so that thermolabile materials can be bonded, and the application range of the hot melt adhesive is greatly expanded. Moderate bonding temperature does not cause harm to operators, and meets the requirements of safety and health. The traditional hot melt adhesive has the bonding temperature of more than 150 ℃ and the bonding time of more than 30 minutes. The long-time high-temperature environment can bring aging and other problems to the materials, and brings health and safety problems to operators.
(6) The epoxy resin hot melt adhesive prepared by the invention has a simple structure and wide raw material sources. In the process of preparing the epoxy resin hot melt adhesive, no solvent is used, and the solid content of the hot melt adhesive is 100 percent, so the epoxy resin hot melt adhesive is an environment-friendly adhesive. Meanwhile, the method has the advantages of simple process, no byproduct generation, no waste discharge and 100% atom utilization rate.
Drawings
FIG. 1 is a nuclear magnetic image of a hot melt adhesive prepared according to example two of the process of the present invention.
FIG. 2 is a nuclear magnetic image of a hot melt adhesive prepared in example five of the process of the present invention.
FIG. 3 is a nuclear magnetic image of a hot melt adhesive prepared according to example seven of the process of the present invention.
FIG. 4 is a nuclear magnetic diagram of a hot melt adhesive prepared by example ten of the method of the present invention.
FIG. 5 is a nuclear magnetic image of a hot melt adhesive prepared according to twenty-two examples of the method of the present invention.
FIG. 6 is a nuclear magnetic image of a hot melt adhesive prepared according to twenty-five examples of the method of the present invention.
FIG. 7 is a nuclear magnetic image of a hot melt adhesive prepared according to twenty-seventh example of the method of the present invention.
FIG. 8 is a nuclear magnetic map of a hot melt adhesive prepared thirty embodiments of the method of the present invention.
FIG. 9 is an infrared spectrum of a hot melt adhesive prepared according to example two of the method of the present invention.
Detailed Description
The invention provides an epoxy resin-based hot melt adhesive, which has the molecular formula:
wherein: a is 1 to 7, b is 2 to 7, z is 0 to 0.5, m is 3 to 9, and n is 1 to 19.
In the epoxy resin-based hot melt adhesive, the percentage alpha of the molar amount of the polyether amine UPy derivative in the total molar amount of the polyether amine and the polyether amine UPy derivative is 0.5-1.0.
The preparation method of the epoxy resin-based hot melt adhesive comprises the following steps:
polyetheramines containing one amine group:
polyetheramine UPy derivatives containing one amine group:
and epoxy resins containing two epoxy groups:
the epoxy resin-based hot melt adhesive is obtained by adopting a melting method to carry out reaction, and the molecular formula of the obtained epoxy resin-based hot melt adhesive is as follows:
the preparation method comprises the following specific processes:
preparing raw materials according to molar parts;
under the condition of high temperature, fully stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin to obtain an epoxy resin hot melt adhesive prepolymer;
and curing the epoxy resin hot melt adhesive prepolymer for a period of time under the high-temperature condition to obtain the epoxy resin hot melt adhesive.
In the preparation method, the following raw materials are prepared according to the following molar parts:
polyether amine containing amine group: 0 to 0.5 part
The polyetheramine UPy derivatives are: 0.5 to 1 portion
Epoxy group-containing epoxy resin: 1 part of
Wherein the mole amount of the polyether amine UPy derivative accounts for 0.5-1.0 percent of the total mole amount of the polyether amine and the polyether amine UPy derivative;
calculating the weight according to the molar parts, and weighing the raw materials according to the weight;
in the preparation method, the temperature for stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin is 50-70 ℃, and the stirring and mixing time is 0.1-0.5 h
In the preparation method, the curing temperature of the epoxy resin hot melt adhesive prepolymer is 50-70 ℃, and the curing time is 6-24 hours.
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
In the following examples, epoxy resins (epoxy resin E) were used51And epoxy resin E44) Polyetheramine (polyetheramine M) purchased from Nantong star Synthesis materials Ltd600And polyetheramine M1000) Polyetheramine UPy derivatives (MeUPy-OPG) from Hensman, USA6.4-NH2、MeUPy-OPG2.5-NH2、[4+2]UPy-OPG6.4-NH2、[4+2]UPy-OPG2.5-NH2) Synthesized by the following procedure, reference Macromolecules2015,48,8128. Synthetic polyethers2-amino-4-hydroxy-6-methylpyrimidine used for amine UPy derivatives was purchased from Chi-Seai (Shanghai) chemical industry development Co., Ltd., polyetheramine D230And polyetheramine D400N, N' -carbonyldiimidazole, potassium monoethylmalonate, 2-ethylhexanoyl chloride, guanidine carbonate, triethylamine were purchased from Bailingwei Tech Co., Ltd, and acetone, dimethyl sulfoxide, N-hexane, methylene chloride, dehydrated ether, dehydrated alcohol, hydrochloric acid, sodium chloride, sodium hydrogen carbonate, sodium sulfate and magnesium chloride were purchased from Guanghong chemical industries, Beijing.
MeUPy-OPG for use in the invention6.4-NH2The synthesis steps are as follows:
2-amino-4-hydroxy-6-methylpyrimidine (10.1g,80.0mmol) and N, N' -carbonyldiimidazole (18.1g,112.0mmol) were dissolved in 400ml of dimethyl sulfoxide at 80 ℃. After reacting at 80 ℃ for 2 hours, the reaction solution was cooled to room temperature, filtered, and the filter cake was washed with acetone 3 times to give 13.0g of substance a. At 40 ℃ using D400(267.0g,594.0mmol) dissolved substance a (13.0g,59.3 mmol). After reacting at 40 ℃ for 12 hours, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 0 ℃ n-hexane, after liquid separation, the mixture was dissolved with 50ml dichloromethane, and again added dropwise to 0 ℃ n-hexane. After repeating the reaction for 5 times, the mixture was dissolved in 300ml of dichloromethane, the organic phase was extracted successively with saturated brine and water, the organic phase was dried over anhydrous sodium sulfate, the sodium sulfate was removed by suction filtration, and the mixture was concentrated. The mixture is quickly purified by passing through a column by adopting a gradient leaching method, and the leaching agent component is a mixed solution of anhydrous ether and anhydrous ethanol. Concentrating the eluate to obtain 18.0g MeUPy-OPG6.4-NH2。1H-NMR(CDCl3),δ(ppm):5.77(s,1H),3.56(m,23.2H),2.18(s,3H),1.10(m,22.8H).
MeUPy-OPG for use in the invention2.5-NH2The synthesis steps are as follows:
2-amino-4-hydroxy-6-methylpyrimidine (10.1g,80.0mmol) and N, N' -carbonyldiimidazole (18.1g,112.0mmol) were dissolved in 400ml of dimethyl sulfoxide at 80 ℃. After reacting at 80 ℃ for 2 hours, the reaction solution was cooled to room temperature, filtered, and the filter cake was washed with acetone 3 times to give 13.0g of substance a. At 40 ℃ using D230(136.6g,594.0mmol) dissolved substance a (13.0g,59.3 mmol). After reacting at 40 ℃ for 12 hours, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 0 ℃ n-hexane, after liquid separation, the mixture was dissolved with 50ml dichloromethane, and again added dropwise to 0 ℃ n-hexane. After repeating the reaction for 5 times, the mixture was dissolved in 300ml of dichloromethane, the organic phase was extracted successively with saturated brine and water, the organic phase was dried over anhydrous sodium sulfate, the sodium sulfate was removed by suction filtration, and the mixture was concentrated. The mixture is quickly purified by passing through a column by adopting a gradient leaching method, and the leaching agent component is a mixed solution of anhydrous ether and anhydrous ethanol. Concentrating the eluate to obtain 11.1g MeUPy-OPG2.5-NH2。1H-NMR(CDCl3),δ(ppm):5.77(s,1H),3.56(m,11.6H),2.18(s,3H),1.10(m,11.3H).
[4+2 ] for use in the invention]UPy-OPG6.4-NH2The synthesis steps are as follows:
after 150ml of methylene chloride was used to dissolve the potassium salt of monoethyl malonate (18.7g,110mmol), triethylamine (36ml,258mmol) and magnesium chloride (12.6g,131mmol) were added to the solution, and the mixture was stirred at room temperature for 10 hours. The solution was cooled to 0 ℃ and 2-ethylhexanoyl chloride (13.0g,80mmol) was added dropwise. After the solution was returned to room temperature, it was stirred for 12 hours. The solution was cooled to 0 ℃, 250ml of 13% hydrochloric acid was added dropwise, the layers were separated, and the aqueous phase was extracted with 100ml of dichloromethane. The combined organic phases were extracted twice with 250ml of 13% hydrochloric acid and the organic phase was extracted four times with 250ml of saturated sodium bicarbonate solutionThe organic phase was extracted with 250ml of a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered to remove sodium sulfate, and concentrated to obtain 15.4g of compound a. Compound a (15.4g,71.9mmol) and guanidine carbonate (6.5g,35.9mmol) were dissolved in 130ml of ethanol. The solution was refluxed at 120 ℃ for 24 hours, cooled to room temperature, concentrated to remove ethanol, and 120ml of a dichloromethane mixture was added. The organic phase was extracted three times with 150ml of saturated aqueous sodium bicarbonate solution and 150ml of saturated brine. The organic phase was concentrated, 30ml of a dichloromethane solution mixture was used, the dichloromethane solution was added dropwise to ice petroleum ether, and 7.7g of compound b was obtained by suction filtration. Compound b (2.2g,10mmol) and N, N' -carbonyldiimidazole (2.43g,15.0mmol) were dissolved in 50ml of dichloromethane and reacted at room temperature for 3 hours. The organic phase was extracted twice with 50ml of saturated brine, dried over anhydrous sodium sulfate, filtered off with suction to remove sodium sulfate and concentrated to give 3.1g of compound c. At 40 ℃ using D400(45.0g,100.0mmol) of substance c (3.1g,10.0mmol) was dissolved, and after 12 hours of reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropwise added to n-hexane at 0 ℃ and after liquid separation, the mixture was dissolved with 20ml of dichloromethane and again dropwise added to n-hexane at 0 ℃. After repeating the reaction for 5 times, the mixture was dissolved in 100ml of dichloromethane, the organic phase was extracted successively with saturated brine and water, the organic phase was dried over anhydrous sodium sulfate, the sodium sulfate was removed by suction filtration, and the mixture was concentrated. The mixture is quickly purified by passing through a column by adopting a gradient leaching method, and the leaching agent component is a mixed solution of anhydrous ether and anhydrous ethanol. The eluate was concentrated to give 3.42g of [4+2 ]]UPy-OPG6.4-NH2。1H-NMR(CDCl3),δ(ppm):5.78(s,0.84H),5.52(s,0.09H),3.44(m,20.76H),2.27(s,1H),1.25(m,4H),0.99(m,23.68H),0.87(m,6H).
[4+2 ] for use in the invention]UPy-OPG2.5-NH2The synthesis steps are as follows:
the potassium salt of monoethyl malonate (1) was dissolved in 150ml of dichloromethane8.7g,110mmol), triethylamine (36ml,258mmol) and magnesium chloride (12.6g,131mmol) were added to the solution, and the mixture was stirred at room temperature for 10 hours. The solution was cooled to 0 ℃ and 2-ethylhexanoyl chloride (13.0g,80mmol) was added dropwise. After the solution was returned to room temperature, it was stirred for 12 hours. The solution was cooled to 0 ℃, 250ml of 13% hydrochloric acid was added dropwise, the layers were separated, and the aqueous phase was extracted with 100ml of dichloromethane. The combined organic phases were extracted twice with 250ml of 13% hydrochloric acid, the organic phase was extracted four times with 250ml of saturated sodium bicarbonate solution, the organic phase was extracted with 250ml of saturated aqueous sodium chloride solution, the organic phase was dried over anhydrous sodium sulfate, the sodium sulfate was removed by suction filtration and concentrated to give 15.4g of compound a. Compound a (15.4g,71.9mmol) and guanidine carbonate (6.5g,35.9mmol) were dissolved in 130ml of ethanol. The solution was refluxed at 120 ℃ for 24 hours, cooled to room temperature, concentrated to remove ethanol, and 120ml of a dichloromethane mixture was added. The organic phase was extracted three times with 150ml of saturated aqueous sodium bicarbonate solution and 150ml of saturated brine. The organic phase was concentrated, 30ml of a dichloromethane solution mixture was used, the dichloromethane solution was added dropwise to ice petroleum ether, and 7.7g of compound b was obtained by suction filtration. Compound b (2.2g,10mmol) and N, N' -carbonyldiimidazole (2.43g,15.0mmol) were dissolved in 50ml of dichloromethane and reacted at room temperature for 3 hours. The organic phase was extracted twice with 50ml of saturated brine, dried over anhydrous sodium sulfate, filtered off with suction to remove sodium sulfate and concentrated to give 3.1g of compound c. At 40 ℃ using D230(23.0g,100.0mmol) of substance c (3.1g,10.0mmol) was dissolved, and after 12 hours of reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropwise added to n-hexane at 0 ℃ and after liquid separation, the mixture was dissolved with 20ml of dichloromethane and again dropwise added to n-hexane at 0 ℃. After repeating the reaction for 5 times, the mixture was dissolved in 100ml of dichloromethane, the organic phase was extracted successively with saturated brine and water, the organic phase was dried over anhydrous sodium sulfate, the sodium sulfate was removed by suction filtration, and the mixture was concentrated. The mixture is quickly purified by passing through a column by adopting a gradient leaching method, and the leaching agent component is a mixed solution of anhydrous ether and anhydrous ethanol. The eluate was concentrated to give 2.27g of [4+2 ]]UPy-OPG6.4-NH2。1H-NMR(CDCl3),δ(ppm):5.78(s,0.84H),5.52(s,0.09H),3.44(m,9.26H),2.27(s,1H),1.25(m,4H),0.99(m,12.68H),0.87(m,6H).
The detection of the samples obtained in the following examples of the invention, in which hydrogen nuclear magnetic resonance spectroscopy (NMR)1H-NMR) was performed using a JNM-ECA400 nuclear magnetic resonance apparatus, japan electronics corporation, using deuterated chloroform as a solvent and a residual chloroform solvent peak as an internal standard. The lap shear strength is detected by using an INSTRON 3365 type universal electronic tensile machine, and the test method refers to the determination of the tensile shear strength of GBT7124-2008 adhesive (rigid material to rigid material). The detection of Fourier transform infrared spectroscopy (FT-IR) is measured by a PerkinElmer Spectrum Two type instrument of PerkinElmer company, and the detection adopts an attenuated total reflection mode and has a bandwidth of 400-4000 cm-1And measuring at room temperature.
The invention provides a preparation method of an epoxy resin hot melt adhesive, wherein amino groups in polyetheramine and polyetheramine UPy derivatives and epoxy groups in epoxy resin are subjected to nucleophilic reaction under a melting condition.
The first embodiment is as follows:
a is 1, b is 6.4, z is 0.18, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 3.01g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.5 hour at the temperature of 50 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 24 hours at the temperature of 50 ℃, and are cooled to room temperature after the solidification is finished, so that 9.43g of epoxy resin hot melt adhesive is obtained, and the yield is 95%. The lap shear strength measurement was 2.72 MPa.1H-NMR(CDCl3),δ(ppm):12.95(s,0.50H),11.71(s,0.71H),9.87(s,0.75H),6.97(d,10.21H),6.65(d,10.13H),5.65(s,1H),3.40(m,89.14H),2.05(s,3.31H),1.47(s,16.1H),0.98(m,54.15H).
Example two:
a is 1, b is 6.4, z is 0.18, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 1.20g
Polyetheramine UPy derivatives: 4.80g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.1 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 8.93g of epoxy resin hot melt adhesive is obtained, and the yield is 90%. The lap shear strength measurement was 10.04 MPa. The nuclear magnetic diagram of the hot melt adhesive prepared in the second example is shown in fig. 1, and the infrared spectrum of the hot melt adhesive is shown in fig. 9.1H-NMR(CDCl3),δ(ppm):12.95(s,0.51H),11.71(s,0.71H),9.87(s,0.75H),6.97(d,6.78H),6.65(d,6.80H),5.65(s,1H),3.40(m,57.16H),2.05(s,3H),1.47(s,10.59H),0.98(m,34.44H).
Example three:
a is 1, b is 6.4, z is 0.18, and α is 1.0.
Weighing:
epoxy resin: 3.92g
Polyetheramine UPy derivatives: 6.01g
And stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 8.43g of epoxy resin hot melt adhesive, wherein the yield is 85%. The lap shear strength measurement was 2.07 MPa.1H-NMR(CDCl3),δ(ppm):12.95(s,0.51H),11.71(s,0.72H),9.87(s,0.77H),6.97(d,5.86H),6.65(d,5.84H),5.65(s,1H),3.40(m,47.06H),2.05(s,3.35H)1.47(s,9.17H),0.98(m, 28.08H.) example four:
a is 1, b is 6.4, z is 0.18, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 3.01g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 11.22g of epoxy resin hot melt adhesive is obtained, and the yield is 94%. The lap shear strength measurement was 0.47 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.24H),11.86(s,0.45H),10.0(s,0.60H),7.11(d,11.06H),6.79(d,10.97H),5.80(s,1H),3.64(m,158.98H),2.20(s,4.19H),1.61(s,17.73H),1.12(m,38.77H)。
Example five:
a is 1, b is 6.4, z is 0.18, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 4.80g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 9.55g of epoxy resin hot melt adhesive is obtained, and the yield is 89%. The lap shear strength measurement was 1.15 MPa. The nuclear magnetic diagram of the hot melt adhesive prepared in the fifth example is shown in figure 2,1H-NMR(CDCl3),δ(ppm):13.10(s,0.24H),11.86(s,0.45H),10.0(s,0.60H),7.11(d,7.74H),6.79(d,7.70H),5.80(s,1H),3.64(m,82.17H),2.20(s,3.96H),1.61(s,12.13H),1.12(m,32.63H)。
example six:
a is 1, b is 6.4, z is 0.4, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 3.01g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.5 hour at the temperature of 50 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 24 hours at the temperature of 50 ℃, and are cooled to room temperature after solidification, so that 9.80g of epoxy resin hot melt adhesive is obtained, and the yield is 93%. The lap shear strength measurement was 1.58 MPa.1H-NMR(CDCl3),δ(ppm):13.09(s,0.54H),11.85(s,0.63H),10.00(s,0.68H),7.11(d,13.19H),6.79(d,13.09H),5.80(s,1H),3.54(m,99.27H),2.19(s,3.97H),1.61(s,20.89H),1.12(m,59.18).
Example seven:
a is 1, b is 6.4, z is 0.4, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 4.82g
Stirring and mixing the polyether amine, the polyether amine UPy derivative and the epoxy resin for 0.25 hour at the temperature of 60 ℃, pouring the mixture into a polytetrafluoroethylene surface dish after fully stirring, curing the mixture for 12 hours at the temperature of 60 ℃, cooling the mixture to room temperature after curing,9.41g of epoxy resin hot melt adhesive were obtained with a yield of 89%. The lap shear strength measurement was 4.65 MPa. The nuclear magnetic diagram of the hot melt adhesive prepared in the seventh embodiment is shown in figure 3,1H-NMR(CDCl3),δ(ppm):13.09(s,0.50H),11.85(s,0.65H),10.00(s,0.72H),7.11(d,9.01H),6.79(d,8.92H),5.80(s,1H),3.54(m,64.56H),2.19(s,3.96H),1.61(s,14.17H),1.12(m,38.59)。
example eight:
a is 1, b is 6.4, z is 0.4, and α is 1.0.
Weighing:
epoxy resin: 4.54g
Polyetheramine UPy derivatives: 6.01g
Stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 8.76g of epoxy resin hot melt adhesive with the yield of 83%. The lap shear strength measurement was 1.56 MPa.1H-NMR(CDCl3),δ(ppm):13.09(s,0.53H),11.85(s,0.70H),10.00(s,0.66H),7.11(d,7.74H),6.79(d,7.63H),5.80(s,1H),3.54(m,54.08H),2.19(s,3.96H),1.61(s,12.15H),1.12(m,31.92).
Example nine:
a is 1, b is 6.4, z is 0.4, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 3.01g
Stirring and mixing the polyether amine, the polyether amine UPy derivative and the epoxy resin for 0.25 hour at the temperature of 60 ℃, fully stirring and pouring polytetrafluoroethylene into the mixtureIn a petri dish, curing was carried out at 60 ℃ for 12 hours, and after completion of curing, cooling was carried out to room temperature to obtain 11.81g of an epoxy resin hot melt adhesive with a yield of 94%. The lap shear strength measurement was 1.68 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.26H),11.85(s,0.60H),10.00(s,0.58H),7.11(d,13.10H),6.79(d,13.03H),5.80(s,1H),3.54(m,162.67H),2.19(s,3.92H),1.61(s,18.78H),1.12(m,38.27).
Example ten:
a is 1, b is 6.4, z is 0.4, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 4.80g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.10g of epoxy resin hot melt adhesive is obtained, and the yield is 89%. The lap shear strength measurement was 3.61 MPa. The nuclear magnetic diagram of the hot melt adhesive prepared in this example is shown in figure 4,1H-NMR(CDCl3),δ(ppm):13.10(s,0.26H),11.85(s,0.60H),10.00(s,0.58H),7.11(d,9.05H),6.79(d,8.98H),5.80(s,1H),3.54(m,83.64H),2.19(s,3.92H),1.61(s,14.29H),1.12(m,31.95)。
example eleven:
a is 1, b is 2.5, z is 0.18, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 1.85g
And stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at 50 ℃ for 0.5 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 50 ℃ for 24 hours, and cooling to room temperature after curing to obtain 8.60g of epoxy resin hot melt adhesive, wherein the yield is 98%. The lap shear strength measurement was 1.08 MPa.1H-NMR(CDCl3),δ(ppm):12.95(s,0.53H),11.71(s,0.72H),9.87(s,0.80H),6.97(d,10.44H),6.65(d,10.72H),5.65(s,1H),3.40(m,77.85H),2.05(s,3.37H),1.47(s,16.15H),0.98(m,42.57H).
Example twelve:
a is 1, b is 2.5, z is 0.18, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 2.96g
And stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at 60 ℃ for 0.25 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 60 ℃ for 12 hours, and cooling to room temperature after curing to obtain 7.44g of epoxy resin hot melt adhesive with the yield of 92 percent. The lap shear strength measurement was 4.56 MPa.1H-NMR(CDCl3),δ(ppm):12.95(s,0.55H),11.71(s,0.74H),9.87(s,0.78H),6.97(d,6.92H),6.65(d,6.75H),5.65(s,1H),3.40(m,45.63H),2.05(s,3.80H),1.47(s,10.44H),0.98(m,23.05H).
Example thirteen:
a is 1, b is 2.5, z is 0.18, and α is 1.0.
Weighing:
epoxy resin: 3.92g
Polyetheramine UPy derivatives: 3.71g
Stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 6.71g of epoxy resin hot melt adhesive with the yield of 88%. The lap shear strength measurement was 0.98 MPa.1H-NMR(CDCl3) δ (ppm) 12.95(s,0.59H),11.71(s,0.74H),9.87(s,0.78H),6.97(d,5.77H),6.65(d,5.65H),5.65(s,1H),3.40(m,35.26H),2.05(s,3.42H),1.47(s,9.25H),0.98(m, 16.47H.) example fourteen:
a is 1, b is 2.5, z is 0.18, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 1.85g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.35g of epoxy resin hot melt adhesive is obtained, and the yield is 96%. The lap shear strength measurement was 0.36 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.18H),11.86(s,0.49H),10.0(s,0.52H),7.11(d,11.43H),6.79(d,10.57H),5.80(s,1H),3.64(m,144.53H),2.20(s,3.90H),1.61(s,17.53H),1.12(m,25.86H).
Example fifteen:
a is 1, b is 2.5, z is 0.18, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 2.96g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification is finished, so that 8.09g of epoxy resin hot melt adhesive is obtained, and the yield is 91%. The lap shear strength measurement was 0.56 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.29H),11.86(s,0.51H),10.0(s,0.57H),7.11(d,7.16H),6.79(d,7.14H),5.80(s,1H),3.64(m,61.52H),2.20(s,3.49H),1.61(s,10.79H),1.12(m,27.47H).
Example sixteen:
a is 1, b is 2.5, z is 0.4, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 1.85g
And stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at 50 ℃ for 0.5 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 50 ℃ for 24 hours, and cooling to room temperature after curing to obtain 9.12g of epoxy resin hot melt adhesive, wherein the yield is 97%. The lap shear strength measurement was 0.98 MPa.1H-NMR(CDCl3),δ(ppm):13.09(s,0.51H),11.85(s,0.65H),10.00(s,0.65H),7.11(d,13.29H),6.79(d,13.79H),5.80(s,1H),3.54(m,88.15H),2.19(s,3.45H),1.61(s,20.75H),1.12(m,47.32).
Example seventeen:
a is 1, b is 2.5, z is 0.4, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 2.96g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 7.93g of epoxy resin hot melt adhesive is obtained, and the yield is 92%. The lap shear strength measurement was 2.31 MPa.1H-NMR(CDCl3),δ(ppm):13.09(s,0.55H),11.85(s,0.62H),10.00(s,0.71H),7.11(d,9.21H),6.79(d,8.85H),5.80(s,1H),3.54(m,52.77H),2.19(s,3.75H),1.61(s,14.37H),1.12(m,26.76).
Example eighteen:
a is 1, b is 2.5, z is 0.4, and α is 1.0.
Weighing:
epoxy resin: 4.54g
Polyetheramine UPy derivatives: 3.71g
And stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 7.09g of the epoxy resin hot melt adhesive with the yield of 86%. The lap shear strength measurement was 0.66 MPa.1H-NMR(CDCl3),δ(ppm):13.09(s,0.57H),11.85(s,0.72H),10.00(s,0.53H),7.11(d,7.69H),6.79(d,7.57H),5.80(s,1H),3.54(m,42.58H),2.19(s,3.46H),1.61(s,12.35H),1.12(m,20.19).
Example nineteenth:
a is 1, b is 2.5, z is 0.4, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 1.85g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.60g of epoxy resin hot melt adhesive is obtained, and the yield is 93 percent. The lap shear strength measurement was 0.68 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.36H),11.85(s,0.65H),10.00(s,0.62H),7.11(d,13.07H),6.79(d,13.05H),5.80(s,1H),3.54(m,152.88H),2.19(s,3.85H),1.61(s,18.58H),1.12(m,26.77).
Example twenty:
a is 1, b is 2.5, z is 0.4, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 2.96g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 8.46g of epoxy resin hot melt adhesive is obtained, and the yield is 89%. The lap shear strength measurement was 1.68 MPa.1H-NMR(CDCl3),δ(ppm):13.10(s,0.17H),11.85(s,0.49H),10.00(s,0.51H),7.11(d,8.59H),6.79(d,8.77H),5.80(s,1H),3.54(m,71.75H),2.19(s,4.01H),1.61(s,14.36H),1.12(m,20.85).
Example twenty one:
a is 7, b is 6.4, z is 0.18, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 3.42g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.5 hour at the temperature of 50 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 24 hours at the temperature of 50 ℃, and are cooled to room temperature after the solidification is finished, so that 9.73g of epoxy resin hot melt adhesive is obtained, and the yield is 94%. The lap shear strength measurement was 1.06 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.28H),11.90(s,0.36H),10.07(s,0.17H),7.11(d,11.34H),6.79(d,11.36H),5.80(s,0.88H),5.57(s,0.12H),3.53(m,96.21H),1.61(s,23.19H),1.12(m,70.70H).
Example twenty two:
a is 7, b is 6.4, z is 0.18, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 5.47g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 9.54g of epoxy resin hot melt adhesive is obtained, and the yield is 90%. The lap shear strength measurement was 4.56 MPa. A nuclear magnetic diagram of the hot melt adhesive prepared in twenty-two of the examples is shown in figure 5,1H-NMR(CDCl3),δ(ppm):13.25(s,0.32H),11.90(s,0.38H),10.07(s,0.34H),7.11(d,7.98H),6.79(d,8.00H),5.80(s,0.88H),5.57(s,0.12H),3.53(m,64.12H),1.61(s,17.86H),1.12(m,50.59H)。
example twenty three:
a is 7, b is 6.4, z is 0.18, and α is 1.0.
Weighing:
epoxy resin: 3.92g
Polyetheramine UPy derivatives: 6.84g
And stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 9.04g of epoxy resin hot melt adhesive with the yield of 84%. The lap shear strength measurement was 1.28 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.38H),11.90(s,0.36H),10.07(s,0.36H),7.11(d,6.83H),6.79(d,6.84H),5.80(s,0.87H),5.57(s,0.13H),3.53(m,52.71H),1.61(s,16.06H),1.12(m,43.33H)。
Example twenty-four:
a is 7, b is 6.4, z is 0.18, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 3.42g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 11.61g of epoxy resin hot melt adhesive is obtained, and the yield is 94%. The lap shear strength measurement was 0.16 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.32H),11.90(s,0.35H),10.06(s,0.42H),7.11(d,7.88H),6.79(d,7.86H),5.80(s,0.87H),5.55(s,0.13H),3.53(m,131.54H),1.61(s,17.16H),1.12(m,42.42H).
Example twenty-five:
a is 7, b is 6.4, z is 0.18, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 5.47g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.03g of epoxy resin hot melt adhesive is obtained, and the yield is 88%. The lap shear strength measurement was 0.38 MPa. A nuclear magnetic diagram of the hot melt adhesive prepared in twenty-five of the example is shown in figure 6,1H-NMR(CDCl3),δ(ppm):13.25(s,0.32H),11.90(s,0.37H),10.06(s,0.47H),7.11(d,4.51H),6.79(d,4.51H),5.80(s,0.86H),5.55(s,0.14H),3.53(m,53.69H),1.61(s,11.79H),1.12(m,35.87H)。
example twenty-six:
a is 7, b is 6.4, z is 0.4, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 3.42g
Stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at 50 ℃ for 0.5 hour, fully stirring, pouring into a polytetrafluoroethylene surface dish, curing at 50 ℃ for 24 hours, and cooling to the temperature of 50 DEG after curingAt room temperature, 9.98g of epoxy resin hot melt adhesive was obtained, with a yield of 91%. The lap shear strength measurement was 1.06 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.35H),11.91(s,0.42H),10.07(s,0.32H),7.11(d,14.36H),6.79(d,14.37H),5.80(s,0.92H),5.57(s,0.08H),3.70(m,104.38H),1.61(s,28.51H),1.12(m,75.44H).
Example twenty-seven:
a is 7, b is 6.4, z is 0.4, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 5.47g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 9.76g of epoxy resin hot melt adhesive is obtained, and the yield is 87%. The lap shear strength measurement was 2.72 MPa. A nuclear magnetic diagram of the hot melt adhesive prepared in twenty-seven of this example is shown in figure 7,1H-NMR(CDCl3),δ(ppm):13.25(s,0.29H),11.91(s,0.37H),10.07(s,0.35H),7.11(d,9.88H),6.79(d,9.84H),5.80(s,0.88H),5.57(s,0.12H),3.70(m,68.01H),1.61(s,21.01H),1.12(m,52.91H)。
example twenty-eight:
a is 7, b is 6.4, z is 0.4, and α is 1.0.
Weighing:
epoxy resin: 4.54g
Polyetheramine UPy derivatives: 6.84g
The polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.1 hour at the temperature of 70 DEG CAnd pouring the mixture into a polytetrafluoroethylene watch glass after fully stirring, curing the mixture for 6 hours at 70 ℃, and cooling the mixture to room temperature after the curing is finished to obtain 9.22g of epoxy resin hot melt adhesive with the yield of 81 percent. The lap shear strength measurement was 0.86 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.36H),11.91(s,0.34H),10.07(s,0.38H),7.11(d,8.60H),6.79(d,8.61H),5.80(s,0.90H),5.57(s,0.10H),3.70(m,57.34H),1.61(s,19.07H),1.12(m,46.84H).
Example twenty-nine:
a is 7, b is 6.4, z is 0.4, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 3.42g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 11.93g of epoxy resin hot melt adhesive is obtained, and the yield is 92%. The lap shear strength measurement was 0.12 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.39H),11.91(s,0.41H),10.07(s,0.40H),7.11(d,17.77H),6.79(d,17.70H),5.80(s,0.87H),5.57(s,0.13H),3.70(m,189.72H),1.61(s,33.54H),1.12(m,53.50H).
Example thirty:
a is 7, b is 6.4, z is 0.4, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 5.47g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.58g of epoxy resin hot melt adhesive is obtained, and the yield is 88%. The lap shear strength measurement was 0.23 MPa. The nuclear magnetic diagram of the hot melt adhesive prepared thirty times in this example is shown in figure 8,1H-NMR(CDCl3),δ(ppm):13.25(s,0.18H),11.90(s,0.24H),10.06(s,0.23H),7.11(d,13.79H),6.79(d,13.69H),5.80(s,0.87H),5.57(s,0.13H),3.70(m,111.06H),1.61(s,26.99H),1.12(m,47.20H)。
example thirty one:
a is 7, b is 2.5, z is 0.18, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 2.27g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.5 hour at the temperature of 50 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 24 hours at the temperature of 50 ℃, and are cooled to room temperature after the solidification is finished, so that 8.92g of epoxy resin hot melt adhesive is obtained, and the yield is 97%. The lap shear strength measurement was 0.86 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.38H),11.90(s,0.39H),10.07(s,0.27H),7.11(d,11.44H),6.79(d,11.54H),5.80(s,0.86H),5.57(s,0.14H),3.53(m,83.73H),1.61(s,23.69H),1.12(m,58.25H).
Example thirty-two:
a is 7, b is 2.5, z is 0.18, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 3.63g
And stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at 60 ℃ for 0.25 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 60 ℃ for 12 hours, and cooling to room temperature after curing to obtain 8.15g of epoxy resin hot melt adhesive, wherein the yield is 92%. The lap shear strength measurement was 2.08 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.35H),11.90(s,0.41H),10.07(s,0.41H),7.11(d,7.56H),6.79(d,7.56H),5.80(s,0.91H),5.57(s,0.09H),3.53(m,52.09H),1.61(s,17.46H),1.12(m,37.88H).
Example thirty-three:
a is 7, b is 2.5, z is 0.18, and α is 1.0.
Weighing:
epoxy resin: 3.92g
Polyetheramine UPy derivatives: 4.54g
Stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 7.36g of epoxy resin hot melt adhesive with the yield of 87%. The lap shear strength measurement was 0.60 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.41H),11.90(s,0.45H),10.07(s,0.44H),7.11(d,6.79H),6.79(d,6.81H),5.80(s,0.89H),5.57(s,0.11H),3.53(m,41.79H),1.61(s,15.99H),1.12(m,31.83H).
Example thirty-four:
a is 7, b is 2.5, z is 0.18, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 3.92g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 2.27g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.64g of epoxy resin hot melt adhesive is obtained, and the yield is 95%. The lap shear strength measurement was 0.15 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.36H),11.90(s,0.41H),10.06(s,0.45H),7.11(d,8.03H),6.79(d,7.96H),5.80(s,0.90H),5.55(s,0.10H),3.53(m,118.19H),1.61(s,17.06H),1.12(m,29.60H).
Example thirty-five:
a is 7, b is 2.5, z is 0.18, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 3.92g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 3.63g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 8.80g of epoxy resin hot melt adhesive is obtained, and the yield is 92%. The lap shear strength measurement was 0.18 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.41H),11.90(s,0.50H),10.06(s,0.52H),7.11(d,4.39H),6.79(d,4.35H),5.80(s,0.90H),5.55(s,0.10H),3.53(m,41.19H),1.61(s,11.29H),1.12(m,22.95H).
Example thirty-six:
a is 7, b is 2.5, z is 0.4, m is 9, n is 1, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 3.01g
Polyetheramine UPy derivatives: 2.27g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.5 hour at the temperature of 50 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 24 hours at the temperature of 50 ℃, and are cooled to room temperature after solidification, so that 9.33g of epoxy resin hot melt adhesive is obtained, and the yield is 95%. The lap shear strength measurement was 0.26 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.39H),11.91(s,0.45H),10.07(s,0.49H),7.11(d,14.59H),6.79(d,14.69H),5.80(s,0.91H),5.57(s,0.09H),3.70(m,91.50H),1.61(s,27.99H),1.12(m,61.81H).
Example thirty-seven:
a is 7, b is 2.5, z is 0.4, m is 9, n is 1, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 1.21g
Polyetheramine UPy derivatives: 3.63g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 8.72g of epoxy resin hot melt adhesive is obtained, and the yield is 93 percent. The lap shear strength measurement was 1.26 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.41H),11.91(s,0.45H),10.07(s,0.49H),7.11(d,10.21H),6.79(d,10.22H),5.80(s,0.91H),5.57(s,0.01H),3.70(m,56.42H),1.61(s,22.10H),1.12(m,42.95H).
Example thirty-eight:
a is 7, b is 2.5, z is 0.4, and α is 1.0.
Weighing:
epoxy resin: 4.54g
Polyetheramine UPy derivatives: 4.54g
And stirring and mixing the polyether amine UPy derivative and the epoxy resin at 70 ℃ for 0.1 hour, fully stirring, pouring into a polytetrafluoroethylene watch glass, curing at 70 ℃ for 6 hours, and cooling to room temperature after curing to obtain 8.17g of epoxy resin hot melt adhesive, wherein the yield is 90%. The lap shear strength measurement was 0.12 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.41H),11.91(s,0.51H),10.07(s,0.49H),7.11(d,8.73H),6.79(d,8.74H),5.80(s,0.91H),5.57(s,0.09H),3.70(m,44.89H),1.61(s,18.89H),1.12(m,33.84H).
Example thirty-nine:
a is 7, b is 2.5, z is 0.4, m is 3, n is 19, α is 0.5.
Weighing:
epoxy resin: 4.54g
Polyether amine: 5.01g
Polyetheramine UPy derivatives: 2.27g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 10.87g of epoxy resin hot melt adhesive is obtained, and the yield is 92%. The lap shear strength measurement was 0.12 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.41H),11.91(s,0.49H),10.07(s,0.51H),7.11(d,8.43H),6.79(d,8.44H),5.80(s,0.89H),5.57(s,0.11H),3.70(m,45.25H),1.61(s,18.96H),1.12(m,33.65H).。
Example forty:
a is 7, b is 2.5, z is 0.4, m is 3, n is 19, α is 0.8.
Weighing:
epoxy resin: 4.54g
Polyether amine: 2.01g
Polyetheramine UPy derivatives: 3.63g
The polyether amine, the polyether amine UPy derivative and the epoxy resin are stirred and mixed for 0.25 hour at the temperature of 60 ℃, are poured into a polytetrafluoroethylene watch glass after being fully stirred, are solidified for 12 hours at the temperature of 60 ℃, and are cooled to room temperature after solidification, so that 9.16g of epoxy resin hot melt adhesive is obtained, and the yield is 90%. The lap shear strength measurement was 0.21 MPa.1H-NMR(CDCl3),δ(ppm):13.25(s,0.42H),11.90(s,0.51H),10.06(s,0.53H),7.11(d,13.65H),6.79(d,13.53H),5.80(s,0.90H),5.57(s,0.10H),3.70(m,96.88H),1.61(s,26.87H),1.12(m,35.28H)。
The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It will be apparent to those skilled in the art that variations and modifications can be made without departing from the principles of the invention, and these variations and modifications are to be considered within the scope of the invention.
Claims (5)
1. The utility model provides a hot melt adhesive based on epoxy which characterized in that: the molecular formula of the hot melt adhesive based on the epoxy resin is as follows:
wherein: a is 1 to 7, b is 2 to 7, z is 0 to 0.5, m is 3 to 9, and n is 1 to 19.
2. The epoxy-based hot melt adhesive of claim 1, wherein: the percentage alpha of the molar weight of the polyether amine UPy derivative in the epoxy resin-based hot melt adhesive in the total molar weight of the polyether amine and the polyether amine UPy derivative is 0.5-1.0.
3. A method for preparing a hot melt adhesive based on epoxy resin according to claim 1, characterized in that: the hot melt adhesive based on the epoxy resin is prepared from the following components in parts by weight: polyetheramines containing one amine group:
polyetheramine UPy derivatives containing one amine group:
and epoxy resins containing two epoxy groups:
the epoxy resin-based hot melt adhesive is obtained by adopting a melting method to carry out reaction, and the molecular formula of the obtained epoxy resin-based hot melt adhesive is as follows:
4. the process according to claim 3, characterized in that:
preparing raw materials according to molar parts;
fully stirring and mixing the polyetheramine, the polyetheramine UPy derivative and the epoxy resin at the temperature of 50-70 ℃, wherein the stirring and mixing time is 0.1-0.5 h, so as to obtain an epoxy resin hot melt adhesive prepolymer;
curing the epoxy resin hot melt adhesive prepolymer for 6 to 24 hours at the temperature of between 50 and 70 ℃ to obtain the epoxy resin hot melt adhesive.
5. The process according to claim 4, characterized in that:
the following raw materials are prepared according to the following molar parts:
polyether amine containing amine group: 0 to 0.5 part
The polyetheramine UPy derivatives are: 0.5 to 1 portion
Epoxy group-containing epoxy resin: 1 part of
Wherein the mole amount of the polyether amine UPy derivative accounts for 0.5-1.0 percent of the total mole amount of the polyether amine and the polyether amine UPy derivative;
the raw materials are weighed according to the weight by the conversion of molar parts.
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| CN104231157A (en) * | 2014-09-23 | 2014-12-24 | 厦门大学 | Epoxy resin with self-repair function and preparation method thereof |
| CN110423337A (en) * | 2019-07-08 | 2019-11-08 | 浙江大学衢州研究院 | A kind of Thermo-sensitive supermolecule polymer and preparation method thereof of multiple hydrogen bonding regulation |
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