CN113072910B - Single-component polyurethane adhesive and preparation method thereof - Google Patents
Single-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN113072910B CN113072910B CN202110396076.0A CN202110396076A CN113072910B CN 113072910 B CN113072910 B CN 113072910B CN 202110396076 A CN202110396076 A CN 202110396076A CN 113072910 B CN113072910 B CN 113072910B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention provides a preparation method of a single-component polyurethane adhesive, which comprises the following steps: heating the anhydrous polyalcohol mixture to 60-80 ℃ under the conditions of nitrogen atmosphere and stirring, and adding polyisocyanate for reaction; after cooling, adding a chain extender to continue the reaction to obtain a polyurethane prepolymer; dispersing the ethyl orthosilicate oligomer into a silane coupling agent, and adding the silane coupling agent into the obtained polyurethane prepolymer for reaction to obtain organic-inorganic hybrid polyurethane; and uniformly mixing the organic-inorganic hybrid polyurethane, epoxy resin, curing agent and accelerator, and placing the mixture into a vacuum defoaming machine for vacuum defoaming to obtain the single-component polyurethane adhesive. According to the preparation method of the single-component polyurethane adhesive, provided by the invention, the inorganic phase is introduced into a polyurethane system, and then the epoxy resin is adopted to modify organic-inorganic hybrid polyurethane, so that the single-component high-strength polyurethane adhesive is prepared, and the mechanical property is further improved.
Description
Technical Field
The invention relates to the technical field of polyurethane preparation, in particular to a single-component polyurethane adhesive and a preparation method thereof.
Background
The single-component polyurethane adhesive has the advantages of convenience in construction, high impact strength, high peel strength, high flexibility, vibration fatigue resistance, high low-temperature performance and the like, but the existing single-component polyurethane adhesive has poor mechanical strength, so that the application of the single-component polyurethane adhesive as a structural adhesive is limited.
Disclosure of Invention
The invention solves the problem that the existing single-component polyurethane adhesive has poor mechanical strength.
In order to solve the above problems, the present invention provides a method for preparing a single-component polyurethane adhesive, comprising the steps of:
s1: preparing tetraethoxysilane oligomer;
s2: carrying out reduced pressure distillation on polyether polyol and polyester polyol to obtain an anhydrous polyol mixture;
s3: heating the anhydrous polyalcohol mixture to 60-80 ℃ under the conditions of nitrogen atmosphere and stirring, and adding polyisocyanate for reaction;
s4: cooling the product obtained after the reaction in the step S3, adding a chain extender to continue the reaction to obtain a polyurethane prepolymer;
s5: dispersing the ethyl orthosilicate oligomer into a silane coupling agent, and adding the silane coupling agent into the polyurethane prepolymer obtained in the step S4 to react at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: and uniformly mixing the organic-inorganic hybrid polyurethane, epoxy resin, a curing agent and an accelerant at room temperature, and placing the mixture in a vacuum defoaming machine for vacuum defoaming to obtain the single-component polyurethane adhesive.
In the present application, it is preferable that the polyether polyol in step S2 is polytetrahydrofuran diol, and the polyester polyol is polyethylene glycol adipate diol; and the rotating speed of the vacuum defoaming machine in the step S6 is preferably 1200-3000 r/min, and the defoaming time is preferably 1-3 min.
An inorganic phase is introduced into the polyurethane system through the tetraethoxysilane oligomer to obtain an organic-inorganic hybrid polyurethane system, which is favorable for improving the mechanical strength and the heat resistance of the polyurethane; the epoxy resin is endowed with excellent adhesive force to polar base materials such as metal, ceramic, glass, wood and the like by combining polar groups such as epoxy group, hydroxyl group, ether bond, amino group, ester group and the like with extremely high activity in an epoxy resin system, the internal polymerization force is strong, the molecular structure is compact, the mechanical property is higher than that of common general-purpose resin, and the epoxy resin is adopted to modify organic-inorganic hybrid polyurethane, so that the one-component high-strength polyurethane adhesive can be prepared; in addition, by adding the silane coupling agent, the silane coupling agent is preferentially reacted with the residual isocyanic acid radical in the polyurethane system, so that the phenomenon that the isocyanic acid radical reacts with water vapor to generate carbon dioxide in the later curing process is avoided, and the single-component polyurethane adhesive generates bubbles after being cured to influence the comprehensive performance of the single-component polyurethane adhesive.
Optionally, in step S3, the anhydrous polyol mixture is added in an amount of 100 to 200 parts by weight, and the polyisocyanate is added in an amount of 20 to 60 parts by weight; the reaction time ranges from 2 to 3 hours.
Optionally, the polyisocyanate is selected from at least one of polymeric diphenylmethane diisocyanate and hexamethylene diisocyanate trimer.
Optionally, in step S4, the addition amount of the chain extender is 1 to 5 parts by weight; the chain extender is 1,4-butanediol. And the reaction is preferably continued for 5 to 10 minutes after the addition of the chain extender.
Optionally, in step S5, the amount of the tetraethoxysilane oligomer added is 6 to 20 parts by weight; the adding amount of the silane coupling agent is 20-60 parts by weight; the silane coupling agent is 3-aminopropyltriethoxysilane. The reaction time in step S5 is preferably in the range of 30 to 60 minutes.
By adding the silane coupling agent containing amino and alkoxy, the alkoxy can react with silicon hydroxyl on the surface of an inorganic phase, and the amino can react with residual isocyanic acid radical in polyurethane, so that the phenomenon that the isocyanic acid radical reacts with water vapor to generate carbon dioxide in the subsequent curing process to influence the comprehensive performance of the adhesive is prevented.
Optionally, in step S6, the organic-inorganic hybrid polyurethane is added in an amount of 50 to 90 parts by weight, the epoxy resin is added in an amount of 20 to 50 parts by weight, the curing agent is added in an amount of 15 to 30 parts by weight, and the accelerator is added in an amount of 0.1 to 0.5 part by weight.
Optionally, the epoxy resin is bisphenol a epoxy resin E51; the curing agent is selected from at least one of methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride; the accelerant is 2,4,6-tris (dimethylaminomethyl) phenol.
Optionally, step S1 comprises: according to the weight portion, stirring 40 to 60 portions of ethyl orthosilicate, 30 to 60 portions of absolute ethyl alcohol and 1 to 5 portions of water under the conditions that the pH value is 5 to 6 and the temperature is room temperature for reaction; and after the reaction is finished, drying the reaction product to obtain the tetraethoxysilane oligomer.
The pH is preferably adjusted by adding dilute hydrochloric acid, the reaction time in step S1 is 48 hours, and drying is preferably carried out in a vacuum oven at 50 ℃ for 48 hours until the solvent is completely volatilized to obtain the tetraethoxysilane oligomer.
Optionally, step S2 includes: according to the weight portion, 50-100 portions of the polyether polyol and 50-100 portions of the polyester polyol are distilled under reduced pressure at 150 ℃ and-0.1 MPa to obtain the anhydrous polyol mixture. The time for distillation under reduced pressure is preferably 2 hours.
Preferred polyether polyols herein are polytetrahydrofuran diols and polyester polyols are polyethylene adipate diols.
Another object of the present invention is to provide a one-component polyurethane adhesive, which is prepared by the method for preparing the one-component polyurethane adhesive as described above.
The single-component polyurethane adhesive provided by the invention can be completely cured after being heated for 2 hours at 100 ℃, is convenient to use, does not generate bubbles in the curing process, and has excellent mechanical property, bonding strength and comprehensive performance.
Compared with the prior art, the preparation method of the single-component polyurethane adhesive provided by the invention has the following advantages:
according to the preparation method of the single-component polyurethane adhesive, the organic-inorganic hybrid polyurethane system is prepared by introducing the inorganic phase into the polyurethane system, so that the mechanical strength and the heat resistance of the polyurethane can be improved; then, epoxy resin is adopted to modify organic-inorganic hybrid polyurethane to prepare a single-component high-strength polyurethane adhesive, and the mechanical property is further improved; in addition, the silane coupling agent is added to react with the isocyanic acid radical in the polyurethane, so that the phenomenon that the isocyanic acid radical generates carbon dioxide through a steam reaction in a subsequent curing process, and the adhesive generates bubbles after being cured to influence the appearance and comprehensive performance of the adhesive is avoided.
Drawings
FIG. 1 is a SEM photograph of a one-component polyurethane adhesive in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a third comparative sample of comparative example 3.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below are exemplary and are intended to be illustrative of the present invention and should not be construed as limiting the present invention, and all other embodiments that can be obtained by one of ordinary skill in the art based on the embodiments of the present invention without inventive step fall within the scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
S1: pouring 40 parts by weight of ethyl orthosilicate, 30 parts by weight of absolute ethyl alcohol and 1 part by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain an ethyl orthosilicate oligomer;
s2: according to the weight portion, 50 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa to obtain an anhydrous polyalcohol mixture;
s3: heating 100 parts by weight of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 20 parts by weight of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 1 part by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s5: taking 6 parts by weight of ethyl orthosilicate oligomer, dispersing the ethyl orthosilicate oligomer into 20 parts by weight of 3-aminopropyltriethoxysilane in advance, adding the 3-aminopropyltriethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting for 30 minutes at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: weighing 50 parts by weight of organic-inorganic hybrid polyurethane, 20 parts by weight of bisphenol A epoxy resin E51, 15 parts by weight of methyl tetrahydrophthalic anhydride and 0.1 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming for 180 seconds in vacuum at the rotating speed of 1200 r/min to obtain the single-component polyurethane adhesive.
Example 2
S1: pouring 45 parts by weight of ethyl orthosilicate, 35 parts by weight of absolute ethyl alcohol and 2 parts by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain an ethyl orthosilicate oligomer;
s2: according to the weight portion, 70 portions of polytetrahydrofuran diol and 50 portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at 150 ℃ and-0.1 MPa to obtain an anhydrous polyalcohol mixture;
s3: heating 120 parts by weight of anhydrous polyol mixture to 60 ℃ under the conditions of nitrogen atmosphere and stirring, adding 30 parts by weight of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 2 parts by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s5: taking 8 parts by weight of ethyl orthosilicate oligomer, dispersing the ethyl orthosilicate oligomer into 25 parts by weight of 3-aminopropyltriethoxysilane in advance, adding the 3-aminopropyltriethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting at 60 ℃ for 35 minutes to obtain organic-inorganic hybrid polyurethane;
s6: weighing 70 parts by weight of organic-inorganic hybrid polyurethane, 25 parts by weight of bisphenol A epoxy resin E51, 18 parts by weight of methyl tetrahydrophthalic anhydride and 0.2 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming the mixture for 120 seconds in vacuum at the rotating speed of 1500 r/min to obtain the single-component polyurethane adhesive.
Example 3
S1: pouring 50 parts by weight of ethyl orthosilicate, 40 parts by weight of absolute ethyl alcohol and 3 parts by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain tetraethoxysilane oligomer;
s2: according to the weight portion, 80 weight portions of polytetrahydrofuran diol and 85 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa, and an anhydrous polyol mixture is obtained;
s3: heating 150 parts by weight of anhydrous polyol mixture to 80 ℃ under the conditions of nitrogen atmosphere and stirring, adding 45 parts by weight of polymeric diphenylmethane diisocyanate, and reacting for 2.5 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 3 parts by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s5: taking 10 parts by weight of ethyl orthosilicate oligomer, dispersing the ethyl orthosilicate oligomer into 30 parts by weight of 3-aminopropyltriethoxysilane in advance, adding the 3-aminopropyltriethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting for 40 minutes at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: weighing 80 parts by weight of organic-inorganic hybrid polyurethane, 30 parts by weight of bisphenol A epoxy resin E51, 20 parts by weight of methyl hexahydrophthalic anhydride and 0.3 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming for 180 seconds in vacuum at the rotating speed of 1800 rpm to obtain the single-component polyurethane adhesive.
Example 4
S1: pouring 55 parts by weight of tetraethoxysilane, 50 parts by weight of absolute ethyl alcohol and 4 parts by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain an ethyl orthosilicate oligomer;
s2: according to the weight portion, 90 portions of polytetrahydrofuran diol and 100 portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at 150 ℃ and-0.1 MPa to obtain an anhydrous polyalcohol mixture;
s3: heating 170 parts by weight of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 50 parts by weight of hexamethylene diisocyanate trimer, and reacting for 3 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 4 parts by weight of 1,4-butanediol, and continuing to react for 10 minutes to obtain a polyurethane prepolymer;
s5: taking 15 parts by weight of ethyl orthosilicate oligomer, dispersing the ethyl orthosilicate oligomer into 45 parts by weight of 3-aminopropyltriethoxysilane in advance, adding the 3-aminopropyltriethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting for 50 minutes at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: weighing 80 parts by weight of organic-inorganic hybrid polyurethane, 40 parts by weight of bisphenol A epoxy resin E51, 25 parts by weight of methylhexahydrophthalic anhydride and 0.4 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming for 180 seconds at the rotating speed of 1800 rpm to obtain the single-component polyurethane adhesive.
Example 5
S1: pouring 60 parts by weight of ethyl orthosilicate, 60 parts by weight of absolute ethyl alcohol and 5 parts by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain an ethyl orthosilicate oligomer;
s2: according to the weight portion, 100 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa to obtain an anhydrous polyalcohol mixture;
s3: heating 200 weight parts of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 60 weight parts of hexamethylene diisocyanate trimer, and reacting for 3 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 5 parts by weight of 1,4-butanediol, and continuing to react for 10 minutes to obtain a polyurethane prepolymer;
s5: taking 20 parts by weight of ethyl orthosilicate oligomer, dispersing the ethyl orthosilicate oligomer into 60 parts by weight of 3-aminopropyltriethoxysilane in advance, adding the 3-aminopropyltriethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting for 60 minutes at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: weighing 90 parts by weight of organic-inorganic hybrid polyurethane, 50 parts by weight of bisphenol A epoxy resin E51, 30 parts by weight of methyl hexahydrophthalic anhydride and 0.5 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming in vacuum for 60 seconds at the rotating speed of 3000 r/min to obtain the single-component polyurethane adhesive.
Comparative example 1
S1: according to the weight portion, 50 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa to obtain an anhydrous polyalcohol mixture;
s2: heating 100 weight parts of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 20 weight parts of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s3: cooling the product obtained in the step S2 to 60 ℃, adding 1 part by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s4: weighing 50 parts by weight of polyurethane prepolymer, 20 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of methyltetrahydrophthalic anhydride and 0.1 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol in a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture in a vacuum defoaming machine, and defoaming in vacuum for 180 seconds at the rotating speed of 1200 revolutions per minute to obtain a first comparison sample.
Comparative example 2
S1: pouring 40 parts by weight of ethyl orthosilicate, 30 parts by weight of absolute ethyl alcohol and 1 part by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain an ethyl orthosilicate oligomer;
s2: according to the weight portion, 50 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa, and an anhydrous polyol mixture is obtained;
s3: heating 100 parts by weight of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 20 parts by weight of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 1 part by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s5: taking 6 parts by weight of tetraethoxysilane oligomer, dispersing into 20 parts by weight of 3-aminopropyltriethoxysilane in advance, adding into the polyurethane prepolymer obtained in the step S4, and reacting at 60 ℃ for 30 minutes to obtain organic-inorganic hybrid polyurethane;
s6: weighing 50 parts by weight of organic-inorganic hybrid polyurethane, 15 parts by weight of methyl tetrahydrophthalic anhydride and 0.1 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture into a vacuum defoaming machine, and defoaming for 120 seconds at the rotating speed of 1200 revolutions per minute to obtain a second comparison sample.
Comparative example 3
S1: pouring 40 parts by weight of ethyl orthosilicate, 30 parts by weight of absolute ethyl alcohol and 1 part by weight of water into a single-neck flask, adjusting the pH value to 5-6 by using dilute hydrochloric acid, and magnetically stirring for 48 hours at room temperature; after the reaction is finished, transferring the reaction mixture in the single-neck flask into a vacuum oven, and drying for 48 hours at 50 ℃ until the solvent is completely volatilized to obtain tetraethoxysilane oligomer;
s2: according to the weight portion, 50 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa, and an anhydrous polyol mixture is obtained;
s3: heating 100 weight parts of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 20 weight parts of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s4: cooling the product obtained in the step S3 to 60 ℃, adding 1 part by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s5: adding 6 parts by weight of tetraethoxysilane oligomer into the polyurethane prepolymer obtained in the step S4, and reacting at 60 ℃ for 30 minutes to obtain organic-inorganic hybrid polyurethane;
s6: weighing 50 parts by weight of organic-inorganic hybrid polyurethane, 20 parts by weight of bisphenol A epoxy resin E51, 15 parts by weight of methyl tetrahydrophthalic anhydride and 0.1 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol into a beaker in sequence, stirring and mixing uniformly at room temperature, placing the beaker in a vacuum defoaming machine, and defoaming for 120 seconds in vacuum at the rotating speed of 1200 r/min to obtain a third comparative sample.
Comparative example 4
S1: according to the weight portion, 50 weight portions of polytetrahydrofuran diol and 70 weight portions of polyethylene glycol adipate diol are distilled under reduced pressure for 2 hours at the temperature of 150 ℃ and the pressure of-0.1 MPa, and an anhydrous polyol mixture is obtained;
s2: heating 100 weight parts of anhydrous polyol mixture to 70 ℃ under the conditions of nitrogen atmosphere and stirring, adding 20 weight parts of polymeric diphenylmethane diisocyanate, and reacting for 2 hours;
s3: cooling the product obtained in the step S2 to 60 ℃, adding 1 part by weight of 1,4-butanediol, and continuing to react for 5 minutes to obtain a polyurethane prepolymer;
s4: weighing 50 parts by weight of polyurethane prepolymer, 20 parts by weight of 3-aminopropyltriethoxysilane, 20 parts by weight of bisphenol A epoxy resin E51, 15 parts by weight of methyl tetrahydrophthalic anhydride and 0.1 part by weight of 2,4,6-tris (dimethylaminomethyl) phenol in a beaker in sequence, stirring and mixing uniformly at room temperature, placing the mixture in a vacuum defoaming machine, and defoaming for 180 seconds at the rotating speed of 1200 rpm to obtain a fourth comparative sample.
To verify the performance of the one-component polyurethane adhesives provided by the present invention, the following tests were performed on the products obtained in the above examples 1 to 5 and comparative examples 1 to 3:
1. tensile shear Strength test
A universal material tester is used, and the ASTM-D1002-01 standard is adopted, wherein the coating area is 12.5mm multiplied by 25mm, and the glue line thickness is 0.2mm. After curing was complete, tensile shear tests were carried out at a rate of 2mm/min, adjusted for 24h at standard laboratory temperature (humidity not required) in accordance with GB/T2981. Each set of bars was measured for 5 sets of data and the results averaged and are shown in table 1.
TABLE 1
From the above test results, it can be seen that the tensile shear strength of the single-component polyurethane adhesives prepared in examples 1 to 5 of the present application is about 25 times that of the first comparative sample prepared in comparative example 1, and meanwhile, the tensile shear strength of the single-component polyurethane adhesives prepared in examples 1 to 5 of the present application is much greater than that of the comparative samples prepared in comparative examples 1 to 4, which indicates that the tensile shear strength of the single-component polyurethane adhesives is greatly improved and the mechanical strength of the single-component polyurethane adhesives is improved by the synergistic effect of the inorganic phase of the tetraethoxysilane oligomer, the epoxy resin and the silane coupling agent in the present application; in addition, it is known from the analysis of the tensile shear strength of each of the above samples that although ethyl orthosilicate and epoxy resin are added in comparative example 3, a large amount of bubbles are generated in the curing process of the third comparative example due to no addition of a silane coupling agent, and the tensile shear strength is greatly reduced by the bubbles, which greatly affects the mechanical properties of the product, thereby also proving that the mechanical strength of the one-component polyurethane adhesive is improved by the synergistic action of the inorganic phase of the ethyl orthosilicate oligomer, the epoxy resin and the silane coupling agent in the present invention.
2. Topography analysis
The cured sample cross-sectional morphology was observed using a zeiss SIGMA HD type field emission scanning electron microscope, germany. The sample is quenched and cracked in liquid nitrogen, and the section morphology of the sample is observed after the sample is subjected to gold spraying treatment, and the result is shown in figures 1 and 2.
FIG. 1 is a SEM of a single-component polyurethane adhesive prepared after adding a silane coupling agent in example 1 of the present invention, and FIG. 2 is a SEM of a first sample prepared without adding a silane coupling agent in comparative example 3 of the present invention; as can be seen from fig. 2, the third sample prepared in comparative example 3 had more bubbles; the single-component polyurethane adhesive prepared in the embodiment 1 of the application has no bubbles, so that the addition of the silane coupling agent can effectively eliminate the bubbles generated in the curing process of the single-component polyurethane adhesive, and the appearance and the comprehensive performance of a product are improved.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (9)
1. The preparation method of the single-component polyurethane adhesive is characterized by comprising the following steps:
s1: preparing tetraethoxysilane oligomer;
s2: carrying out reduced pressure distillation on polyether polyol and polyester polyol to obtain an anhydrous polyol mixture;
s3: heating the anhydrous polyalcohol mixture to 60-80 ℃ under the conditions of nitrogen atmosphere and stirring, and adding polyisocyanate for reaction;
s4: cooling the product obtained after the reaction in the step S3, adding a chain extender, and continuing the reaction to obtain a polyurethane prepolymer;
s5: dispersing the ethyl orthosilicate oligomer into a silane coupling agent, and adding the silane coupling agent into the polyurethane prepolymer obtained in the step S4 to react at 60 ℃ to obtain organic-inorganic hybrid polyurethane;
s6: uniformly mixing the organic-inorganic hybrid polyurethane with epoxy resin, a curing agent and an accelerant at room temperature, and placing the mixture in a vacuum defoaming machine for vacuum defoaming to obtain a single-component polyurethane adhesive;
the step S1 comprises the following steps: stirring and reacting 40-60 parts by weight of ethyl orthosilicate, 30-60 parts by weight of absolute ethyl alcohol and 3238 parts by weight of water at the pH value of 5~6 and the temperature of room temperature; after the reaction is finished, drying the reaction product to obtain the tetraethoxysilane oligomer;
in the step S5, the silane coupling agent is 3-aminopropyltriethoxysilane;
the adding amount of the organic-inorganic hybrid polyurethane in the step S6 is 50 to 90 parts by weight, and the adding amount of the epoxy resin is 20 to 50 parts by weight.
2. The method for preparing the one-component polyurethane adhesive according to claim 1, wherein in step S3, the anhydrous polyol mixture is added in an amount of 100 to 200 parts by weight, and the polyisocyanate is added in an amount of 20 to 60 parts by weight; the reaction time range is 2~3 hours.
3. The method of claim 2, wherein the polyisocyanate is at least one selected from the group consisting of polymeric diphenylmethane diisocyanate and hexamethylene diisocyanate trimer.
4. The method for preparing the one-component polyurethane adhesive according to claim 1, wherein in the step S4, the amount of the chain extender is 1~5 parts by weight; the chain extender is 1,4-butanediol.
5. The method for preparing the one-component polyurethane adhesive according to claim 1, wherein in step S5, the ethyl orthosilicate oligomer is added in an amount of 6 to 20 parts by weight; the addition amount of the silane coupling agent is 20 to 60 parts by weight.
6. The method for preparing the one-component polyurethane adhesive according to claim 1, wherein in step S6, the curing agent is added in an amount of 15 to 30 parts by weight, and the accelerator is added in an amount of 0.1 to 0.5 part by weight.
7. The method of preparing the one-component polyurethane adhesive of claim 6, wherein the epoxy resin is bisphenol a type epoxy resin E51; the curing agent is at least one of methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride; the accelerant is 2,4, 6-tris (dimethylaminomethyl) phenol.
8. The method of preparing the one-component polyurethane adhesive of claim 1, wherein the step S2 comprises: taking 50-100 parts by weight of the polyether polyol and 50-100 parts by weight of the polyester polyol, and distilling under reduced pressure at 150 ℃ and-0.1 MPa to obtain the anhydrous polyol mixture.
9. A one-component polyurethane adhesive prepared by the method of claim 1~8.
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| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| CN102816289A (en) * | 2012-08-14 | 2012-12-12 | 北方涂料工业研究设计院 | Preparation method for epoxy pouring sealant with characteristics of low viscosity, high elongation rate, and high strength |
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| JP5177252B2 (en) * | 2011-04-12 | 2013-04-03 | 横浜ゴム株式会社 | Epoxy resin composition |
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| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| CN102816289A (en) * | 2012-08-14 | 2012-12-12 | 北方涂料工业研究设计院 | Preparation method for epoxy pouring sealant with characteristics of low viscosity, high elongation rate, and high strength |
| CN105524584A (en) * | 2014-10-21 | 2016-04-27 | 中国科学院兰州化学物理研究所 | Polyethylene pipe reparation adhesive |
| CN108342181A (en) * | 2018-02-28 | 2018-07-31 | 佛山市三水日邦化工有限公司 | A kind of single-component water-based polyurethane adhesive of water resistant, high temperature resistant and preparation method thereof |
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