CN112877014A - 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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- CN112877014A CN112877014A CN202110068063.0A CN202110068063A CN112877014A CN 112877014 A CN112877014 A CN 112877014A CN 202110068063 A CN202110068063 A CN 202110068063A CN 112877014 A CN112877014 A CN 112877014A
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- 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
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- 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
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- 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
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- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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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 affectedThe yield is 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. 2-amino-4-hydroxy-6-methylpyrimidine used for the synthesis of polyetheramine UPy derivatives was purchased from Chi-Sei (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 ℃. At 80After 2 hours of reaction at room temperature, the reaction mixture 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 rapidly purified by column chromatography with gradient elution method, and the eluent components are anhydrous ether andand (3) mixing absolute ethyl alcohol. 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, 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 D400(45.0g,100.0mmol) of substance c (3.1g,10.0mmol) was dissolved and reacted for 12 hours, and then the reaction mixture was cooled to room temperatureDropwise adding into 0 deg.C n-hexane, separating, dissolving the mixture with 20ml dichloromethane, and dropwise adding into 0 deg.C n-hexane again. 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:
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, 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. Concentrating the organic phase, adding 30ml dichloromethane solution mixture dropwise into ice petroleum ether, and filtering to obtain 77g of Compound b. 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
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, cooling to room temperature after curing to obtain 9.80g of epoxy resin hot melt adhesive, wherein the yield is 93 percent. 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
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 9.41g of epoxy resin hot melt adhesive is obtained, and the yield is 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 surface dish, and curing at 70 ℃ for 6 hoursAt this time, after completion of curing, cooling was carried out to room temperature to obtain 8.76g of an epoxy resin hot melt adhesive with a 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
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 11.81g of epoxy resin hot melt adhesive is obtained, and the yield is 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 subjected to strip reaction at 60 DEG CStirring and mixing 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 10.10g of epoxy resin hot melt adhesive with the yield of 89 percent. 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. This example prepared heat in twenty-fiveThe nuclear magnetic map of the melt 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
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 9.98g of epoxy resin hot melt adhesive is obtained, and the yield is 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
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 into a polytetrafluoroethylene surface dishCuring at 60 ℃ for 12 hours, and cooling to room temperature after curing to obtain 9.76g of epoxy resin hot melt adhesive with the yield of 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
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 9.22g of the epoxy resin hot melt adhesive with the yield of 81%. 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
Derivatizing polyetheramines, polyetheramine UPyThe mixture and epoxy resin were stirred and mixed at 60 ℃ for 0.25 hour, poured into a teflon watch glass after sufficient stirring, cured at 60 ℃ for 12 hours, and cooled to room temperature after curing to obtain 11.93g of epoxy resin hot melt adhesive with a yield of 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 (7)
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;
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.
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.
6. The process according to claim 4, wherein the polyetheramine, the polyetheramine UPy derivative and the epoxy resin are stirred at a temperature of 50 ℃ to 70 ℃ for 0.1h to 0.5 h.
7. The process according to claim 4, wherein the epoxy resin hot melt adhesive prepolymer is cured at a temperature of 50 ℃ to 70 ℃ for a period of 6h to 24 h.
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