Multi-hydrogen bond hyperbranched polyurethane, preparation method and application

Abstract

The present invention relates to the field of polymer chemistry technology, and in particular to a multi-hydrogen bond hyperbranched polyurethane, a preparation method and an application. The multi-hydrogen bond hyperbranched polyurethane is prepared by reacting a diisocyanate, a ternary thiol compound and a multi-hydrogen bond monomer. The multi-hydrogen bond hyperbranched polyurethane can be applied to carbon fiber composites, artificial muscles, electronic skin and wearable electronic devices. The multi-hydrogen bond hyperbranched polyurethane has the characteristics of high strength, high toughness, room temperature self-repairing and recyclability. The room temperature self-repairing polyurethane elastomer prepared therefrom can be chemically recycled under mild conditions, and the performance retention rate after recycling is high. The process of the present invention is simple and the cost is low, and it can be applied to the fields of carbon fiber composites, artificial muscles, electronic skin and conductive stretching devices.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer chemistry, in particular to a multi-hydrogen bond hyperbranched polyurethane, a preparation method and an application thereof. Background Art

[0002] Polyurethane elastomers have excellent physical and mechanical properties, such as high mechanical strength, a wide range of adjustable hardness, excellent low-temperature performance, good physical durability and heat resistance, and high pH stability. In recent years, they have been widely used in carbon fiber composite materials, soft protective equipment, electronic skin, wearable devices and other fields. Polyurethane elastomers with self-repairing functions can prevent structural damage caused by light, electricity, heat and force during use, thereby increasing the service life of devices and the functional reliability of equipment. Achieving self-repairing capabilities and improving mechanical properties are the difficulties and challenges of current research in this field. However, traditional polyurethane elastomers usually have stable covalent cross-links. Once damaged, it is difficult to restore their original strength through repair, and they are difficult to recycle, resulting in limited application scenarios and causing serious environmental pollution.

[0003] Currently, the introduction of reversible forces between polyurethane segments to act as sacrificial bonds and driving forces for repair has enabled polyurethane elastomers to exhibit excellent repair and recyclability, as well as high toughness. The highly branched topology of hyperbranched polymers could open up a new avenue for the design and preparation of high-performance self-healing polyurethane elastomers.

[0004] Although self-healing polyurethanes based on dynamic chemical bonds and the synergistic action of multiple dynamic bonds have developed rapidly, achieving high repair efficiency of self-healing polyurethanes and imparting other functionalities remain difficult and challenging. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a multi-hydrogen bond hyperbranched polyurethane, a preparation method and an application.

[0006] The technical solution of the present invention to solve the above technical problems is as follows:

[0007] The present invention provides a multi-hydrogen bond hyperbranched polyurethane, the structural formula of which is shown in general formula (1):

[0008]

[0009] R', R'', and R''' are the same or different and are independently represented by the structure of general formula (2), general formula (3), or general formula (4):

[0010]

[0011] wherein at least one X is represented by R3, and the remaining Xs are represented by H;

[0012] R1 is represented by one of the general formula (5), general formula (6) or general formula (7); wherein, when R1 is connected to -NHCO and R2 respectively, * indicates the position connected to -NHCO, and ** indicates the position connected to R2; when R1 is connected to two R2s, * and ** respectively indicate the position connected to one R2;

[0013]

[0014] R2 is represented by the general formula (8) or the general formula (9); wherein, when R2 is connected to -NHCO, *** indicates the position of connection to -NHCO; when R2 is connected to R1 and -SX, *** indicates the position of connection to R1 or -SX:

[0015]

[0016] R3 is represented by the general formula (10), where **** indicates the position where it is connected to -S-:

[0017]

[0018] On the basis of the above technical solution, the present invention can also be improved as follows.

[0019] Furthermore, R`, R``, and R``` are the same and represent the structure of the general formula (2); wherein the number of -SR3 is m, the number of -SX is 6-m, and the value of m is 1 to 5;

[0020] Or, R`, R``, and R``` are the same and represent the structure of the general formula (3); wherein the number of -SR3 is n, the number of -SX is 12-n, and the value of n is 1 to 11;

[0021] Or, R`, R``, and R``` are the same and represent the structure of the general formula (4); wherein the number of -SR3 is q, the number of -SX is 24-q, and the value of q is 1 to 23.

[0022] The present invention also provides applications of the multi-hydrogen bond hyperbranched polyurethane described above in carbon fiber composite materials, artificial muscles, electronic skin, and wearable electronic devices.

[0023] The present invention also provides a method for preparing the above-mentioned multi-hydrogen bond hyperbranched polyurethane, comprising the following steps:

[0024] S1. Mixing a diisocyanate, a ternary thiol compound, and a first catalyst uniformly and reacting them at 40-80° C. for 1-4 hours to obtain a thiol-terminated hyperbranched polyurethane, wherein the mass ratio of the diisocyanate to the ternary thiol compound is (0.4-0.6):1, and the mass of the first catalyst is 0.5-1 wt% of the diisocyanate and the ternary thiol compound;

[0025] S2. Evenly mix the thiol-terminated hyperbranched polyurethane with a multiple hydrogen-bonding monomer HDI-UPy, an organic solvent, and the second catalyst, and react at 60-80° C. for 4-6 hours to obtain a multiple hydrogen-bonded hyperbranched polyurethane; the molar ratio of the multiple hydrogen-bonding monomer to the thiol-terminated hyperbranched polyurethane is 1:(0.1-1), the mass of the second catalyst in this step is 0.5-1wt% of the thiol-terminated hyperbranched polyurethane, and the mass ratio of the organic solvent to the thiol-terminated hyperbranched polyurethane is (1-3):1.

[0026] Furthermore, in step S1, the diisocyanate is one of isophorone diisocyanate, toluene-2,4-diisocyanate or 4-4'-dicyclohexylmethane diisocyanate; the ternary mercapto compound is one of trimethylolpropane tris(3-mercaptopropionate) or 2,2,2-(1,3,5)-triphenylmercaptan-s-triazine; the first catalyst and the second catalyst are the same or different, and the first catalyst and the second catalyst are one of triethanolamine, dibutyltin dilaurate, dibutyltin dichloride or 1,5-diazabicyclo[4.3.0]-5-nonene.

[0027] Furthermore, in step S2, the structural formula of the multiple hydrogen bond monomer HDI-UPy is shown in formula (14);

[0028]

[0029] The organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane.

[0030] The present invention also provides a room temperature self-repairing polyurethane elastomer, which is prepared by using the above-mentioned multiple hydrogen bond hyperbranched polyurethane.

[0031] The present invention also provides a method for preparing a room temperature self-repairing polyurethane elastomer, comprising the following steps:

[0032] The multi-hydrogen bond hyperbranched polyurethane is evenly mixed with a polyurethane prepolymer and an organic solvent, and reacted at 60-80° C. for 1-2 hours; and then cured at 80-100° C. for 2-4 hours to obtain the room temperature self-healing polyurethane elastomer.

[0033] Furthermore, the molar ratio of the number of -SX groups in the multiple hydrogen bond hyperbranched polyurethane to the isocyanate groups in the polyurethane prepolymer is (0.9-1.1):1; and the mass ratio of the organic solvent to the multiple hydrogen bond hyperbranched polyurethane is (2-4):1.

[0034] Furthermore, the organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane; and the polyurethane prepolymer is a PTMG type polyurethane prepolymer.

[0035] The beneficial effects of the present invention are:

[0036] (1) The multi-hydrogen bond hyperbranched polyurethane of the present invention has a hyperbranched structure that can effectively provide the material with strength, toughness and room temperature self-repairing ability;

[0037] (2) The multi-hydrogen bond hyperbranched polyurethane of the present invention can be applied to carbon fiber composite materials, artificial muscles, electronic skin, and conductive stretchable devices. It not only has good performance, but also has the advantages of being recyclable and reusable, which is beneficial to environmental protection and reduces the cost of use.

[0038] (3) The method for preparing the multi-hydrogen bond hyperbranched polyurethane of the present invention has a simple process and is suitable for industrial production;

[0039] (4) The polyurethane elastomer prepared based on the multi-hydrogen bond hyperbranched polyurethane of the present invention can be chemically recycled under mild conditions, and the performance retention rate after chemical recycling is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 These are shape pictures of the room temperature self-healing hyperbranched polyurethane elastomer of Example 5 of the present invention at 0 min, 1 min, 2 min, 3 min, 4 min and 5 min during the process of stretching and then shrinking. DETAILED DESCRIPTION

[0041] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0042] The multi-hydrogen bond hyperbranched polyurethane of the present invention has a structural formula as shown in general formula (1):

[0043]

[0044] R', R'', and R''' are the same or different and are independently represented by the structure of general formula (2), general formula (3), or general formula (4):

[0045]

[0046]

[0047] wherein at least one X is represented by R3, and the remaining Xs are represented by H;

[0048] R1 is represented by one of the general formula (5), general formula (6) or general formula (7); wherein, when R1 is connected to -NHCO and R2 respectively, * indicates the position connected to -NHCO, and ** indicates the position connected to R2; when R1 is connected to two R2s, * and ** respectively indicate the position connected to one R2;

[0049]

[0050] R2 is represented by the general formula (8) or the general formula (9); wherein, when R2 is connected to -NHCO, *** indicates the position of connection to -NHCO; when R2 is connected to R1 and -SX, *** indicates the position of connection to R1 or -SX:

[0051]

[0052] R3 is represented by the general formula (10), where **** indicates the position where it is connected to -S:

[0053]

[0054] Preferably, R', R'', and R''' are the same and represent the structure of general formula (2); wherein the number of -SR3 is m, the number of -SX is 6-m, and the value of m is 1 to 5; in this case, the branched structure of the multi-hydrogen bond hyperbranched polyurethane is shown in general formula (11):

[0055]

[0056] Preferably, R', R'', and R''' are the same and represent the structure of general formula (3); wherein the number of -SR3 is n, the number of -SX is 12-n, and the value of n is 1 to 11; in this case, the branched structure of the multi-hydrogen bonded hyperbranched polyurethane is shown in general formula (12):

[0057]

[0058] Preferably, R', R'', and R''' are the same and represent the structure of general formula (4); wherein the number of -SR3 is q, the number of -SX is 24-q, and the value of q is 1 to 23; in this case, the branched structure of the multi-hydrogen bond hyperbranched polyurethane is shown in general formula (13):

[0059]

[0060] The multi-hydrogen bond hyperbranched polyurethane of the present invention can be applied to carbon fiber composite materials, artificial muscles, electronic skin and wearable electronic devices.

[0061] The preparation method of the multi-hydrogen bond hyperbranched polyurethane of the present invention comprises the following steps:

[0062] S1. Evenly mix a diisocyanate, a ternary thiol compound, and a first catalyst, and react them at 40-80° C. for 1-4 hours to obtain a thiol-terminated hyperbranched polyurethane, wherein the mass ratio of the diisocyanate to the ternary thiol compound is (0.4-0.6):1, and the mass of the first catalyst is 0.5-1wt% of the diisocyanate and the ternary thiol compound.

[0063] S2. Evenly mixing the thiol-terminated hyperbranched polyurethane with a multiple hydrogen-bonding monomer HDI-UPy, an organic solvent, and a second catalyst, and reacting them at 60-80° C. for 4-6 hours to obtain a multiple hydrogen-bonded hyperbranched polyurethane; the molar ratio of the multiple hydrogen-bonding monomer to the thiol-terminated hyperbranched polyurethane is 1:(0.1-1), the mass of the second catalyst in this step is 0.5-1wt% of the thiol-terminated hyperbranched polyurethane, and the mass ratio of the organic solvent to the thiol-terminated hyperbranched polyurethane is (1-3):1.

[0064] Preferably, in step S1, the diisocyanate is one of isophorone diisocyanate, toluene-2,4-diisocyanate or 4-4'-dicyclohexylmethane diisocyanate; the ternary thiol compound is one of trimethylolpropane tris(3-mercaptopropionate) or 2,2,2-(1,3,5)-triphenylmercaptan-s-triazine; the first catalyst and the second catalyst are the same or different, and the first catalyst and the second catalyst are one of triethanolamine, dibutyltin dilaurate, dibutyltin dichloride or 1,5-diazabicyclo[4.3.0]-5-nonene.

[0065] Preferably, in step S2, the structural formula of the multi-hydrogen bond monomer HDI-UPy is as shown in formula (14):

[0066]

[0067] The organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane.

[0068] The preparation method of the room temperature self-repairing polyurethane elastomer of the present invention is prepared using the multi-hydrogen bond hyperbranched polyurethane of the present invention, and the preparation method comprises the following steps:

[0069] The multi-hydrogen bond hyperbranched polyurethane is evenly mixed with a polyurethane prepolymer and an organic solvent, and reacted at 60-80°C for 1-2 hours; then cured at 80-100°C for 2-4 hours to obtain a room temperature self-healing polyurethane elastomer.

[0070] Preferably, the molar ratio of the number of -SX groups in the multi-hydrogen bond hyperbranched polyurethane to the isocyanate groups in the polyurethane prepolymer is (0.9-1.1):1; and the mass ratio of the organic solvent to the multi-hydrogen bond hyperbranched polyurethane is (2-4):1.

[0071] Preferably, the organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane; and the polyurethane prepolymer is a PTMG type polyurethane prepolymer.

[0072] The present invention is illustrated below by means of specific examples.

[0073] Example 1

[0074] 55.8 g of isophorone diisocyanate, 132.8 g of trimethylolpropane tris(3-mercaptopropionate), and 1.1 g of dibutyltin dilaurate were mixed and reacted at 80° C. for 1 h to obtain a mercapto-terminated hyperbranched polyurethane HBI-1 with a GPC molecular weight of 2261 g / mol.

[0075] Then, 95.6 g of HBI-1, 24.8 g of multiple hydrogen bond monomer HDI-UPy, 190 ml of N,N-dimethylformamide and 0.8 g of dibutyltin dilaurate were mixed evenly and reacted at 80°C for 4 h to obtain multiple hydrogen bond hyperbranched polyurethane HUBP-1, with a GPC test molecular weight of 2848 g / mol.

[0076] 28.5 g HUBP-1, 28.9 g polyurethane prepolymer and 110 ml N, N-dimethylformamide were mixed evenly, reacted at 80 ° C for 1 hour, and then cured at 90 ° C for 3 hours to obtain a room temperature self-healing polyurethane elastomer.

[0077] The obtained room temperature self-healing hyperbranched polyurethane elastomer was subjected to mechanical property and self-healing property tests, and the results are shown in Table 1.

[0078] Example 2

[0079] 87.1 g of toluene-2,4-diisocyanate, 228.3 g of 2,2,2-(1,3,5)-triphenylthiol-s-triazine and 1.8 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed evenly and reacted at 60° C. for 3 h to obtain a thiol-terminated hyperbranched polyurethane HBM-2 with a GPC-tested molecular weight of 5677 g / mol.

[0080] Then, 154.2 g of HBM-2, 28.4 g of the multiple hydrogen-bonding monomer HDI-UPy, 300 ml of chloroform, and 1.2 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed evenly and reacted at 60°C for 6 h to obtain the multiple hydrogen-bonded hyperbranched polyurethane HUBP-2, with a GPC-tested molecular weight of 6850 g / mol.

[0081] After 46.6 g HUBP-2, 39.7 g polyurethane prepolymer and 130 ml chloroform were mixed evenly, reacted at 60 ° C for 2 hours, and then cured at 80 ° C for 4 hours to obtain a room temperature self-healing polyurethane elastomer.

[0082] The obtained room temperature self-healing hyperbranched polyurethane elastomer was subjected to mechanical property and self-healing property tests, and the results are shown in Table 1.

[0083] Example 3

[0084] 131.2 g of 4-4'-dicyclohexylmethane diisocyanate, 209.8 g of trimethylolpropane tris(3-mercaptopropionate) and 2.4 g of triethanolamine were mixed uniformly and reacted at 40°C for 4 h to obtain thiol-terminated hyperbranched polyurethane HBH-3, with a GPC molecular weight of 14277 g / mol.

[0085] Then, 307.4 g of HBH-3, 37.9 g of the multiple hydrogen-bonding monomer HDI-UPy, 700 ml of N,N-dimethylacetamide, and 1.5 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed evenly and reacted at 60°C for 6 h to obtain the multiple hydrogen-bonding hyperbranched polyurethane HUBP-3, with a GPC-tested molecular weight of 16036 g / mol.

[0086] After 72.9 g HUBP-3, 57.8 g polyurethane prepolymer and 250 ml N, N-dimethylacetamide were mixed evenly, reacted at 60 ° C for 3 hours, and then cured at 80 ° C for 4 hours to obtain a room temperature self-healing polyurethane elastomer.

[0087] The obtained room temperature self-healing hyperbranched polyurethane elastomer was subjected to mechanical property and self-healing property tests, and the results are shown in Table 1.

[0088] Example 4

[0089] 55.8 g of isophorone diisocyanate, 132.8 g of trimethylolpropane tris(3-mercaptopropionate), and 1.1 g of dibutyltin dilaurate were mixed and reacted at 80° C. for 1 h to obtain a mercapto-terminated hyperbranched polyurethane HBI-1 with a GPC molecular weight of 2261 g / mol.

[0090] Then, 95.6 g of HBI-1, 24.8 g of multiple hydrogen bond monomer HDI-UPy, 190 ml of N,N-dimethylformamide and 0.8 g of dibutyltin dilaurate were mixed evenly and reacted at 80°C for 4 h to obtain multiple hydrogen bond hyperbranched polyurethane HUBP-1, with a GPC test molecular weight of 2848 g / mol.

[0091] 28.5 g HUBP-1, 28.9 g polyurethane prepolymer and 110 ml N, N-dimethylformamide were mixed evenly, reacted at 80 ° C for 1 hour, and then cured at 90 ° C for 3 hours to obtain a room temperature self-healing polyurethane elastomer.

[0092] Example 5

[0093] 87.1 g of toluene-2,4-diisocyanate, 228.3 g of 2,2,2-(1,3,5)-triphenylthiol-s-triazine, and 1.8 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed uniformly and reacted at 60° C. for 3 h to obtain a thiol-terminated hyperbranched polyurethane HBM-2 with a GPC molecular weight of 5677 g / mol.

[0094] Then, 154.2 g of HBM-2, 28.4 g of the multiple hydrogen-bonding monomer HDI-UPy, 300 ml of chloroform, and 1.2 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed evenly and reacted at 60°C for 6 h to obtain the multiple hydrogen-bonded hyperbranched polyurethane HUBP-2, with a GPC-tested molecular weight of 6850 g / mol.

[0095] After 46.6 g HUBP-2, 39.7 g polyurethane prepolymer and 130 ml chloroform were mixed evenly, reacted at 60 ° C for 2 hours, and then cured at 80 ° C for 4 hours to obtain a room temperature self-healing polyurethane elastomer.

[0096] Example 6

[0097] 131.2 g of 4-4'-dicyclohexylmethane diisocyanate, 209.8 g of trimethylolpropane tris(3-mercaptopropionate) and 2.4 g of triethanolamine were mixed uniformly and reacted at 40°C for 4 h to obtain thiol-terminated hyperbranched polyurethane HBH-3, with a GPC molecular weight of 14277 g / mol.

[0098] Then, 307.4 g of HBH-3, 37.9 g of the multiple hydrogen-bonding monomer HDI-UPy, 700 ml of N,N-dimethylacetamide, and 1.5 g of 1,5-diazabicyclo[4.3.0]-5-nonene were mixed evenly and reacted at 60°C for 6 h to obtain the multiple hydrogen-bonding hyperbranched polyurethane HUBP-3, with a GPC-tested molecular weight of 16036 g / mol.

[0099] 72.9 g HUBP-3, 57.8 g polyurethane prepolymer and 250 ml N, N-dimethylacetamide were mixed evenly, reacted at 60 ° C for 2 hours, and then cured at 80 ° C for 4 hours to obtain a room temperature self-healing polyurethane elastomer.

[0100] 2g of room-temperature self-healing polyurethane elastomer was immersed in 30ml of methanol solution at 90°C for 1 hour to obtain a transparent, colorless solution. This solution was then mixed with a certain amount of polyurethane prepolymer, reacted at 40°C for 2 hours, and then cured at 60°C for 4 hours to obtain the room-temperature self-healing polyurethane elastomer that can be chemically recycled.

[0101] Example 7

[0102] 11.0 g of 2,2,2-(1,3,5)-triphenylthiol-s-triazine, 57.8 g of polyurethane prepolymer and 30 ml of N,N-dimethylformamide were mixed evenly, reacted at 60° C. for 4 h, and then cured at 100° C. for 4 h to obtain a room temperature self-healing polyurethane elastomer.

[0103] In the above embodiment, the specific process of the mechanical properties and self-repairing performance tests is as follows:

[0104] Standard tensile test: Tensile test was performed using INSTRON universal testing machine 5966. The sample was cut into rectangular strips with a length of 4 cm and a width of 1 cm. The sample was stretched at a speed of 100 mm / min using the universal testing machine. The tensile strength and elongation at break were recorded. The toughness was defined as the area under the stress-strain curve (unit: MJ / m 3 ).

[0105] Mechanical self-healing test: The specimens were cut horizontally in the middle with a scalpel, the sections were spliced ​​together, and left at room temperature for 24 hours. The mechanical properties were tested using an INSTRON 5966 universal material testing machine.

[0106] The test results of each embodiment are shown in Table 1:

[0107] Table 1 Mechanical properties and self-repairing performance test results of each embodiment

[0108]

[0109] The results in Table 1 show that the room temperature self-repairing hyperbranched polyurethane elastomers of Examples 1 to 6 of the present invention have significantly higher tensile strength, tensile modulus, elongation at break, and toughness than general polyurethane elastomers. This indicates that the room temperature self-repairing hyperbranched polyurethane elastomers of Examples 1 to 6 have excellent mechanical properties, especially tensile strength, ductility, and toughness, and their room temperature self-repairing efficiency can reach over 98%. The room temperature self-repairing hyperbranched polyurethane not only has high strength and toughness, but also can achieve room temperature self-repair and chemical recycling, with a high performance retention rate after self-repair and recycling.

[0110] The room temperature self-repairing polyurethane elastomers of Examples 4 and 5 were subjected to application tests. The specific experimental process is as follows:

[0111] (1) Nanosilver / polyurethane elastomer conductive composite materials

[0112] A 2mg / ml ethanol dispersion of silver nanowires (AgNWs, 50nm in length) was applied to the room-temperature self-healing polyurethane elastomer of Example 4. The mixture was heated at 80°C for 5 minutes and then naturally cooled to room temperature to produce a room-temperature self-healing nanosilver / polyurethane elastomer conductive composite material. The nanosilver / polyurethane elastomer conductive composite coating was cut with a scalpel to test its self-healing properties. The nanosilver / polyurethane elastomer conductive composite coating could rapidly heal from a non-conductive state to a conductive state at 80°C. After ultrasonication in water for 1 hour, the nanosilver / polyurethane elastomer conductive composite material was tested, and its resistance retention was 90%, indicating its potential for electronic skin and conductive stretchable devices.

[0113] (2) Artificial muscles based on shape memory

[0114] The room temperature self-repairing hyperbranched polyurethane elastomer has shape editability. The room temperature self-repairing hyperbranched polyurethane elastomer of Example 5 was first stretched by more than 80% and then fixed in the stretched state. After heating to 80°C, it shrunk and recovered to its original length within 300s. The shapes at 0min, 1min, 2min, 3min, 4min and 5min are as follows Figure 1 shown.

[0115] According to the above tests, it can be seen that the room temperature self-repairing hyperbranched polyurethane elastic material of Example 5 can lift objects six times its own weight and can be applied to artificial muscles and other aspects.

[0116] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A multi-hydrogen bond hyperbranched polyurethane, characterized in that: Its structural formula is shown in general formula (1): R', R'', and R''' are the same or different and are independently represented by general formula (2) or general formula (3): wherein at least one X is represented by R3, and the remaining Xs are represented by H; R1 is represented by one of the general formula (5), general formula (6) or general formula (7); Wherein, when R1 is connected to -NHCO and R2 respectively, * indicates the position connected to -NHCO, and ** indicates the position connected to R2; When R1 is connected to two R2, * indicates the position of connection with -NHCO, -NHCO is connected to one R2, and ** indicates the position of connection with one R2; R2 is represented by the general formula (8) or the general formula (9); When R2 is connected to -NHCO, *** indicates the position of connection to -NHCO. When R2 is connected to R1 and -X, one *** indicates the position of connection to -NHCO, -NHCO is connected to R1, and the other two *** indicate the positions of connection to -X: R3 is represented by the general formula (10), where **** indicates the position where it is connected to -S:

2. A multi-hydrogen bond hyperbranched polyurethane according to claim 1, characterized in that R`, R``, and R``` are the same and represent the structure of the general formula (2); wherein the number of -SR3 is m, the number of -SH is 6-m, and the value of m is 1 to 5; Or, R`, R``, and R``` are the same and represent the structure of the general formula (3); wherein the number of -SR3 is n, the number of -SH is 12-n, and the value of n is 1 to 11; Or, R`, R``, and R``` are the same and represent the structure of the general formula (4); wherein the number of -SR3 is q, the number of -SH is 24-q, and the value of q is 1 to 23.

3. An application of the multi-hydrogen bond hyperbranched polyurethane according to claim 1 or 2, characterized in that: Used to make carbon fiber composites, artificial muscles, electronic skin or wearable electronic devices.

4. A method for preparing a multi-hydrogen bond hyperbranched polyurethane according to claim 1 or 2, characterized in that: The following steps are involved: S1. Mixing a diisocyanate, a ternary thiol compound, and a first catalyst uniformly and reacting them at 40-80° C. for 1-4 hours to obtain a thiol-terminated hyperbranched polyurethane, wherein the mass ratio of the diisocyanate to the ternary thiol compound is (0.4-0.6):1, and the mass of the first catalyst is 0.5-1 wt% of the diisocyanate and the ternary thiol compound; S2, mixing the thiol-terminated hyperbranched polyurethane with a multiple hydrogen-bonding monomer HDI-UPy, an organic solvent, and a second catalyst, and reacting them at 60-80° C. for 4-6 hours to obtain a multiple hydrogen-bonded hyperbranched polyurethane; the molar ratio of the multiple hydrogen-bonding monomer HDI-UPy to the thiol-terminated hyperbranched polyurethane is 1:(0.1-1), the mass of the second catalyst is 0.5-1wt% of the thiol-terminated hyperbranched polyurethane, and the mass ratio of the organic solvent to the thiol-terminated hyperbranched polyurethane is (1-3):1; The diisocyanate is one of isophorone diisocyanate, toluene-2,4-diisocyanate or 4-4'-dicyclohexylmethane diisocyanate; The ternary mercapto compound is one of trimethylolpropane tris(3-mercaptopropionate) or 2,2,2-(1,3,5)-triphenylthiol-s-triazine; The structural formula of the multiple hydrogen bond monomer HDI-UPy is shown in formula (14):

5. The method for preparing a multi-hydrogen bond hyperbranched polyurethane according to claim 4, wherein: In step S1, the diisocyanate is one of isophorone diisocyanate, toluene-2,4-diisocyanate or 4-4'-dicyclohexylmethane diisocyanate; the ternary mercapto compound is one of trimethylolpropane tris(3-mercaptopropionate) or 2,2,2-(1,3,5)-triphenylthiol-s-triazine; The first catalyst and the second catalyst are the same or different, and the first catalyst and the second catalyst are respectively one of triethanolamine, dibutyltin dilaurate, dibutyltin dichloride or 1,5-diazabicyclo[4.3.0]-5-nonene.

6. The method for preparing a multi-hydrogen bond hyperbranched polyurethane according to claim 5, characterized in that: In step S2, the structural formula of the multiple hydrogen bond monomer HDI-UPy is shown in formula (14): The organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane.

7. A room temperature self-repairing polyurethane elastomer, characterized in that: The polyurethane is prepared by using the multi-hydrogen bond hyperbranched polyurethane according to claim 1 or 2.

8. A method for preparing a room temperature self-repairing polyurethane elastomer according to claim 7, characterized in that: The following steps are involved: The multi-hydrogen bond hyperbranched polyurethane, polyurethane prepolymer and organic solvent are mixed evenly and reacted at 60-80° C. for 1-2 hours; and then cured at 80-100° C. for 2-4 hours to obtain the room temperature self-healing polyurethane elastomer.

9. The method for preparing a room temperature self-repairing polyurethane elastomer according to claim 8, characterized in that: The molar ratio of the number of -SX groups in the multiple hydrogen bond hyperbranched polyurethane to the isocyanate groups in the polyurethane prepolymer is (0.9-1.1):1; the mass ratio of the organic solvent to the multiple hydrogen bond hyperbranched polyurethane is (2-4):

1.

10. The method for preparing a room temperature self-repairing polyurethane elastomer according to claim 9, characterized in that: The organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, chloroform or dichloromethane; and the polyurethane prepolymer is a PTMG type polyurethane prepolymer.

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