CN113105608B - Self-healing hyperbranched polyurethane with high mechanical strength and preparation method and application thereof - Google Patents

Self-healing hyperbranched polyurethane with high mechanical strength and preparation method and application thereof Download PDF

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CN113105608B
CN113105608B CN202110362914.2A CN202110362914A CN113105608B CN 113105608 B CN113105608 B CN 113105608B CN 202110362914 A CN202110362914 A CN 202110362914A CN 113105608 B CN113105608 B CN 113105608B
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CN113105608A (en
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高传慧
王思凯
赵景明
王日璇
王彦庆
刘月涛
武玉民
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Qingdao University of Science and Technology
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Abstract

The invention belongs to the field of polymer preparation, and relates to self-healing hyperbranched polyurethane with high mechanical strength, and a preparation method and application thereof, wherein the self-healing hyperbranched polyurethane comprises the following steps: reacting polytetrahydrofuran, N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline (VA) and isophorone diisocyanate to obtain prepolymer of isocyanate-terminated polyurethane, heating the prepolymer with hyperbranched polyester, triaminopyridine and tannic acid to 80 ℃ under the protection of nitrogen, and reacting to obtain the self-healing crosslinked polyurethane based on hydrogen bonds. The preparation method of the self-repairing polyurethane is novel, the hyperbranched polyester is used for reacting with the isocyanate-terminated prepolymer to prepare the polyurethane with stronger self-repairing capability and higher mechanical strength, and the polyurethane has wide market prospect. Simple steps, convenient operation and strong practicability.

Description

Self-healing hyperbranched polyurethane with high mechanical strength and preparation method and application thereof
Technical Field
The invention relates to a preparation method of polyurethane, in particular to a hyperbranched polyurethane network rich in a large number of hydrogen bonds prepared by reacting hyperbranched polyester, triaminopyridine, tannic acid and polyurethane with isocyanate groups, belonging to the field of polymer preparation.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyester polyol is a polymer prepared by polycondensation of polycarboxylic acid and polyol, and is the most common and important synthetic raw material for polyurethane, because it can provide flexible soft segment for polyurethane during polyurethane synthesis, thereby endowing polyurethane with excellent properties. As a source of the flexible soft segment structure of polyurethane, the characteristics such as the molecular chain structure, the relative molecular mass and the like of polyester polyol have a significant influence on the final properties of polyurethane.
The polyurethane is named polyurethane as a general name of macromolecular compounds with a main chain having urethane groups (-NHCOO-). Most of polyurethane is a segmented copolymer and consists of a hard chain segment and a soft chain segment, and a polyester flexible chain segment or a polyether flexible chain segment in a polyurethane molecular chain can endow the polyurethane with higher mechanical property, high flexibility and high resilience, and excellent oil resistance, water resistance, solvent resistance and fire resistance.
Hyperbranched polyester is a polyol with a large number of hydroxyl groups on the surface, and mainly consists of a central core molecule and branched molecules. Due to the unique molecular structure, the hyperbranched polyester has a compact molecular structure and a spherical three-dimensional spatial structure, can show Newtonian fluid behavior and has good fluidity. Meanwhile, the hyperbranched polyester has a molecular structure similar to a sphere, intermolecular chain entanglement is less, and the interaction between molecules mainly comes from the interaction between terminal functional groups. The hyperbranched polyesters thus have a lower melt viscosity compared to linear polyesters, in particular with nonpolar end groups. Meanwhile, because the surface of the material contains a large number of terminal hydroxyl groups, a large number of hydrogen bonds can be formed in a certain space, so that the material is endowed with self-healing capability and has high mechanical properties.
The hydrogen bonding is a widely studied supramolecular chemical interaction, and is widely concerned by people because of the characteristics of reversibility, directionality, high speed, high sensitivity, good environmental responsiveness under certain conditions and the like. The self-healing material based on the hydrogen bond interaction is a novel self-healing material developed in recent years, does not need to be implanted with a repairing agent, can realize self-healing of the material by means of the breakage and recombination of hydrogen bonds in molecules or between molecules, and has the advantages of low repairing temperature, good repeatability and the like, so that the self-healing material is widely applied to the preparation of the self-healing material.
Polyurethane is a hot spot in the near-term research and is called as a universal material. The material has the characteristics of microphase separation structure and excellent mechanical property, and can be used as an excellent self-repairing material carrier. Therefore, the hyperbranched polyester is introduced into the polyurethane, so that the polyurethane contains a large number of hydrogen bonds, and the polyurethane material is endowed with excellent self-healing capability. The research uses isocyanate-terminated polyurethane prepolymer, hyperbranched polyester, dopamine hydrochloride and Fe3+The hyperbranched polyurethane can be self-healed in seawater by coordinating with catechol in dopamine, has a repair efficiency of 87% in seawater, and has repeated adhesion performance in seawater. However, the inventor finds that the mechanical property of the existing self-healing hyperbranched polyurethane is low, and the field of preparing the hyperbranched polyurethane with high mechanical property and self-healing property is still a blank.
Disclosure of Invention
In order to overcome the defects, the invention provides novel cross-linked polyurethane with self-healing performance and a preparation method thereof, and the cross-linked polyurethane has excellent self-healing efficiency and ultrahigh mechanical strength based on hydrogen bond interaction.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, a method for preparing a self-healing hyperbranched polyurethane having high mechanical strength is provided, comprising:
in the presence of N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline VA, polyester dihydric alcohol and isocyanate are used as raw materials to synthesize the isocyanate group-containing blocked VA-containing linear polyurethane PU-VA-NCO;
the isocyanate group-containing blocked VA-containing linear polyurethane PU-VA-NCO is crosslinked with a crosslinking agent to form a high-strength crosslinking self-healing polyurethane network.
The invention ensures that physical damage has high self-healing efficiency at a certain temperature based on a large number of hydrogen bonds, introduces a prepolymer containing isocyanate groups and N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline (VA) on the terminal hydroxyl groups of hyperbranched polyester and tannic acid by grafting, adjusts the self-healing performance and the mechanical property of polyurethane by controlling reaction conditions and a material ratio, can generate hydrogen bond action among polyurethane functional groups generated by reaction, and can generate hydrogen bond action when the tannic acid is rich in a large number of phenolic hydroxyl groups, thereby jointly enhancing the self-healing performance and the mechanical property of the polyurethane. Meanwhile, the introduced VA contains benzene rings and imine bonds, the benzene rings enable the material to form a structure with soft and hard segments uniformly distributed, the mechanical property of the material is improved, the self-healing property of the material is further improved through the imine bonds, and the reports that the hyperbranched polyurethane has high mechanical property and self-healing capability are few by using tannic acid and VA to modify the hyperbranched polyurethane at present.
In a second aspect of the present invention, there is provided a self-healing hyperbranched polyurethane having high mechanical strength prepared by any of the above-mentioned methods.
The self-healing hyperbranched polyurethane prepared by the invention has higher mechanical strength and self-healing capability.
In a third aspect of the invention, the application of the self-healing hyperbranched polyurethane with high mechanical strength in the fields of load bearing, aerospace, military, electronic equipment and intelligent wearable equipment is provided.
The self-healing hyperbranched polyurethane prepared by the invention has high mechanical strength, so the self-healing hyperbranched polyurethane is expected to be widely applied to the fields of load bearing, aerospace, military, electronic equipment, intelligent wearable equipment and the like.
In a fourth aspect of the invention, an isocyanate group-containing blocked linear polyurethane PU-VA-NCO containing VA is provided, the reaction equation is as follows:
Figure BDA0003006306300000041
wherein x and y are natural numbers equal to zero.
In the fifth aspect of the present invention, the sample strip is attached to a finger, and connected to an electrochemical workstation by a wire to perform a bending motion of the finger, and a generated current signal can be detected by the electrochemical workstation, and the detection result is shown in fig. 4.
The invention has the beneficial effects that:
(1) the preparation method of the hyperbranched polyurethane with the self-healing capability is novel, and the hyperbranched polyurethane with the self-healing capability has higher mechanical strength and self-healing capability.
(2) The invention ensures that physical damage has high self-healing efficiency at a certain temperature based on a large number of hydrogen bonds, introduces a prepolymer containing isocyanate groups and N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline (VA) on the terminal hydroxyl groups of hyperbranched polyester and tannic acid by grafting, adjusts the self-healing performance and the mechanical property of polyurethane by controlling reaction conditions and a material ratio, can generate hydrogen bond action among polyurethane functional groups generated by reaction, and can generate hydrogen bond action when the tannic acid is rich in a large number of phenolic hydroxyl groups, thereby jointly enhancing the self-healing performance and the mechanical property of the polyurethane. Meanwhile, the introduced VA contains benzene rings and imine bonds, the benzene rings enable the material to form a structure with soft and hard segments uniformly distributed, the mechanical property of the material is improved, the self-healing property of the material is further improved through the imine bonds, and the reports that the hyperbranched polyurethane has high mechanical property and self-healing capability are few by using tannic acid and VA to modify the hyperbranched polyurethane at present.
(3) The invention uses the carbon nano tube to modify the hyperbranched polyurethane with the self-healing capability to prepare the conductive nano elastomer composite material with the capability of sensing the micro-movement of the muscle, and the current response of the muscle movement can be still detected after the conductive nano elastomer composite material is cut and repaired.
(4) The preparation method is simple, has strong practicability and can be widely applied to the bearing field.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an infrared chart of VA and PNHT in example 1 of the present invention;
fig. 2 is a cyclic stretch diagram of PNTH in example 1 of the present invention.
FIG. 3 is a stress-strain graph of comparative examples 1-3 and examples 1-3 according to the present invention.
FIG. 4 is a current response graph of finger bending motion before (a) and after (b) self-repair of the hyperbranched polyurethane conductive nanocomposite.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
A novel cross-linking type polyurethane with self-healing performance and a preparation method thereof are disclosed, wherein based on the interaction of hydrogen bonds, the material has excellent self-healing efficiency and ultrahigh mechanical strength.
Firstly, polyester dihydric alcohol and isocyanate react to synthesize a prepolymer with an isocyanate group, wherein the polyester dihydric alcohol comprises polyethylene glycol, polytetrahydrofuran, polycaprolactone and the like, and the polytetrahydrofuran is preferred.
Adding polytetrahydrofuran and isophorone diisocyanate in a certain proportion into a four-neck flask provided with a mechanical stirring paddle, a water separator and a nitrogen circulating system, taking N, N-dimethylformamide as a solvent and dibutyltin dilaurate as a catalyst, raising the temperature to 50 ℃ for dissolving, raising the temperature to 60-90 ℃ for reacting for 1-4 hours under the protection of nitrogen after the polytetrahydrofuran in the flask is completely dissolved, and obtaining the isocyanate-terminated polyurethane prepolymer PU-NCO.
Dissolving vanillin and p-aminophenol in a certain proportion in 170mL deionized water and 70mL ethanol respectively. Then, the two solutions were mixed and stirred at 50 ℃ for 2 hours. Then, it was filtered with a Buchner funnel to give N- (4-hydroxy-3-methylphenylmethylene) -p-hydroxyphenylamine (VA) (compositions Communications, DOI:10.1016/j.coco.2020.100445) as a pale yellow solid, which was washed with deionized water and then dried to constant weight. Adding VA into PU-NCO, and reacting at 60-90 deg.C for 1-3 hr to obtain PU-VA-NCO.
The isocyanate group-containing blocked VA-containing linear polyurethane (PU-VA-NCO) has the following reaction equation:
Figure BDA0003006306300000061
wherein x and y are natural numbers larger than zero.
In some embodiments, the isocyanate group-containing terminated VA-containing linear polyurethane (PU-VA-NCO) has a number average molecular weight of 2000 to 5000 and a molecular weight distribution of 1.01 to 1.85.
Adding triaminopyridine, hyperbranched polyester, tannic acid and the like in a certain proportion into a four-neck flask filled with PU-VA-NCO, reacting at normal temperature, raising the temperature to 70-100 ℃ for 1-4 hours after white powder completely disappears, continuing reacting at normal temperature for 48 hours to obtain brownish red viscous liquid, pouring the viscous liquid into a tetrafluoro mold, and putting the tetrafluoro mold into a vacuum drying oven for 48 hours to obtain a Product (PNHT).
The hyperbranched polyester is not particularly limited, and in some embodiments, the preparation method of the hyperbranched polyester comprises:
mixing the components in a molar ratio of 1: putting the glycerol and the bishydroxymethylpropanoic acid of 3 into a 250ml four-neck flask, adding dibutyltin dilaurate as a catalyst, connecting a water separator, a thermometer and a stirrer, heating to 140 ℃ under the protection of nitrogen, stirring, reacting for 3 hours, keeping the temperature at 140 ℃, reducing the pressure to-0.1 MPa, carrying out polycondensation, and continuing to react for 3 hours. Obtaining the hyperbranched polyester.
The invention also provides application of the self-healing hyperbranched polyurethane with high mechanical strength prepared by any one of the methods.
A preparation method of a high-strength self-healing hyperbranched polyurethane cross-linked network based on hydrogen bonds is characterized by taking N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline (VA), polytetrahydrofuran and isophorone diisocyanate as raw materials to prepare VA-containing linear polyurethane with an isocyanate group-terminated end, and adding a cross-linking agent to perform a cross-linking reaction to obtain the high-strength cross-linked self-healing polyurethane network.
In some embodiments, the molar ratio of the total content of the VA-based linear polyurethane is: 0 to 40 percent.
In some embodiments, the crosslinking agent is triaminopyridine, hyperbranched polyester, tannic acid, and the three crosslinking agents are added simultaneously in different proportions.
In some embodiments, the molar ratio of triaminopyridine to total crosslinker is: 0 to 30 percent.
In some embodiments, the hyperbranched polyester is present in a molar ratio to the total amount of crosslinker of: 30 to 70 percent.
In some embodiments, the molar ratio of tannic acid to total crosslinker is: 0 to 30 percent.
In the following examples, the following test methods were employed:
the tensile test is carried out according to the national standard GB/T1024.2-2006, the testing speed is 50mm/min, and the tensile test is carried out at room temperature.
The preparation method of the hyperbranched polyester comprises the following steps:
mixing the components in a molar ratio of 1: putting the glycerol and the bishydroxymethylpropanoic acid of 3 into a 250ml four-neck flask, adding dibutyltin dilaurate as a catalyst, connecting a water separator, a thermometer and a stirrer, heating to 140 ℃ under the protection of nitrogen, stirring, reacting for 3 hours, keeping the temperature at 140 ℃, reducing the pressure to-0.1 MPa, carrying out polycondensation, and continuing to react for 3 hours. Obtaining the hyperbranched polyester.
The features of the present invention and other related features are further described in detail below by way of examples to facilitate understanding by those skilled in the art:
example 1
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.15:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 75 ℃ for reaction for 3 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 15% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 65% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 20% by mole of isophorone diisocyanate, and the reaction was continued for 2 hours at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
The cyclic tensile properties of the polyurethane film of example 1 were tested and the results are shown in figure 1.
Example 2
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.4:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 70 ℃ for reaction for 2 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 20% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 50% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 30% by mole of isophorone diisocyanate, and the reaction was continued for 2 hours at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Example 3
Placing polytetrahydrofuran, VA and isophorone diisocyanate with a molar ratio of 1:0.1:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, then heating to 60 ℃ and reacting for 1 hour to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 0% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 70% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 30% by mole of isophorone diisocyanate, and the reaction was continued for 2 hours at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Example 4
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 85 ℃ for reaction for 3 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 5% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 70% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 25% by mole of isophorone diisocyanate, and the reaction was continued at 80 ℃ for 3 hours under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Example 5
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.05:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 90 ℃ to react for 4 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 15% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 70% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 15% by mole of isophorone diisocyanate, and the reaction was continued for 1 hour at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Example 6
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.2:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 90 ℃ to react for 4 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 15% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 55% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 30% by mole of isophorone diisocyanate, and the reaction was continued for 1 hour at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Example 7
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.35:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 65 ℃ for reaction for 1 hour to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 25% by mole of isophorone diisocyanate, and a catalyst dibutyltin dilaurate in an amount of 0.05% by mass of PBIS was added, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, then the hyperbranched polyester was added thereto in an amount of 45% by mole of isophorone diisocyanate, and then tannic acid was added thereto in an amount of 30% by mole of isophorone diisocyanate, and the reaction was continued for 2 hours at 80 ℃ under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Comparative example 1
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.15:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 75 ℃ for reaction for 3 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, a catalyst dibutyltin dilaurate was added in an amount of 0.05% by mass of the PBIS, followed by addition of a hyperbranched polyester in an amount of 65% by mole of isophorone diisocyanate, followed by addition of tannic acid in an amount of 20% by mole of isophorone diisocyanate, and the reaction was continued at 80 ℃ for 2 hours under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Comparative example 2
Placing polytetrahydrofuran, VA and isophorone diisocyanate in a molar ratio of 1:0.4:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, and then heating to 70 ℃ for reaction for 2 hours to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine was slowly added into the flask in an amount of 20% by mole based on the isophorone diisocyanate, and a catalyst dibutyltin dilaurate was added in an amount of 0.05% by mass based on the PBIS, and after the raw materials were completely dissolved, the reaction was carried out for 1 hour, followed by adding tannic acid thereto in an amount of 30% by mole based on the isophorone diisocyanate, and the reaction was continued at 80 ℃ for 2 hours under nitrogen protection. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
Comparative example 3
Placing polytetrahydrofuran, VA and isophorone diisocyanate with a molar ratio of 1:0.1:2 into a 250ml four-neck flask, taking N, N-dimethylformamide as a solvent, connecting a spherical condenser tube, a thermometer and a stirrer, heating to 50 ℃ under the protection of nitrogen, dissolving and stirring the raw materials, then heating to 60 ℃ and reacting for 1 hour to obtain the prepolymer of isocyanate-terminated polyurethane. Then, 2,4, 6-triaminopyridine is slowly added into the flask, the adding amount is 0 percent of the molar amount of isophorone diisocyanate, a catalyst dibutyltin dilaurate is added, the adding amount is 0.05 percent of the mass of PBIS, after the raw materials are completely dissolved, the reaction is carried out for 1 hour, then hyperbranched polyester is added, the adding amount is 70 percent of the molar amount of isophorone diisocyanate, and the reaction is continued for 2 hours at 80 ℃ under the protection of nitrogen. And finally, cooling to normal temperature, stirring and continuously reacting for 24 hours, and placing the mixture in a vacuum drying oven to remove redundant solvent to obtain the product polyurethane film.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (8)

1. A preparation method of self-healing hyperbranched polyurethane with high mechanical strength is characterized by comprising the following steps:
in the presence of N- (4-hydroxy-3-methylphenyl methylene) -p-hydroxyaniline VA, polyester dihydric alcohol and isocyanate are used as raw materials to synthesize the isocyanate group-containing blocked VA-containing linear polyurethane PU-VA-NCO;
the isocyanate group-containing blocked VA-containing linear polyurethane PU-VA-NCO is crosslinked with a crosslinking agent to form a high-strength crosslinking self-healing polyurethane network;
the cross-linking agent is triaminopyridine, hyperbranched polyester and tannic acid;
the molar ratio of the triaminopyridine to the hyperbranched polyester to the tannic acid is 0-3: 3-7: 0-3, and the using amount of each raw material is more than zero.
2. The method according to claim 1, wherein the molar ratio of the polyester diol, VA and isocyanate is: 1: 0-0.4.15, wherein the dosage of VA is more than zero.
3. The method for preparing self-healing hyperbranched polyurethane having high mechanical strength as claimed in claim 1, wherein the molar amount of VA is 0% to 40% of the total content of the isocyanate group-containing terminated VA-containing linear polyurethane PU-VA-NCO, and the molar amount of VA is greater than zero.
4. The method for preparing self-healing hyperbranched polyurethane having high mechanical strength according to claim 1, wherein the synthesis conditions are as follows: reacting at 60-90 deg.c for 1-4 hr.
5. The method according to claim 1, wherein the polyester diol is at least one of polyethylene glycol, polytetrahydrofuran or polycaprolactone.
6. The method for preparing self-healing hyperbranched polyurethane having high mechanical strength according to claim 1, wherein the isocyanate group-containing terminated VA-containing linear polyurethane PU-VA-NCO has the following structural formula:
Figure 591808DEST_PATH_IMAGE001
formula I
Wherein x and y are natural numbers larger than zero;
the isocyanate group-containing blocked VA-containing linear polyurethane PU-VA-NCO has the number average molecular weight of 2000-5000 and the molecular weight distribution of 1.01-1.85.
7. Self-healing hyperbranched polyurethanes having high mechanical strength prepared by the process according to any one of claims 1 to 6.
8. The self-healing hyperbranched polyurethane with high mechanical strength as claimed in claim 7, which is used in the fields of aerospace, military, electronic equipment and intelligent wearable equipment.
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