Room-temperature self-repairing polyurethane with quadruple hydrogen bonds / disulfide bonds and preparation method of room-temperature self-repairing polyurethane

Abstract

The invention relates to room-temperature self-repairing polyurethane with quadruple hydrogen bonds / disulfide bonds and a preparation method of the room-temperature self-repairing polyurethane, and the prepared polyurethane is a thermoplastic polymer and shows a dynamic cross-linked structure. The polyurethane is prepared by adopting a step-by-step polymerization method in the presence of two chain extenders containing different dynamic bonds, the prepared polyurethane has good mechanical properties, self-repairing of cracks can be realized in a room temperature environment, and the method is simple and easy to industrialize. The polyurethane has important application value in the industries of flexible electronics, medical instruments, long-acting protection and the like.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials and relates to a room temperature self-healing polyurethane with four hydrogen bonds / disulfide bonds and its preparation method. Background Technology

[0002] Polyurethane is favored by scholars and engineers in sealing, protection, and bonding fields due to its good viscoelasticity and rich processing versatility. However, its relatively weak mechanical strength inevitably leads to defects and damage during molding and use. To improve its application reliability and extend its service life, developing polyurethane with self-healing capabilities has become an important goal for both academia and industry.

[0003] Self-healing polymers are a class of smart materials that can actively or under external stimuli repair damage and restore their performance. They can be divided into exogenous self-healing polymers containing repair agents and intrinsic self-healing polymers containing dynamic bonds. Compared to exogenous self-healing polymers, intrinsic self-healing polymers have the advantages of repeatable repair and simple preparation processes, and have received more widespread attention. However, the repair efficiency of intrinsic self-healing polymers is closely related to the recovery ability of dynamic bonds and the mobility of polymer chains, making it a technical challenge to balance the self-healing ability and mechanical properties. In addition, most self-healing polymers currently still require high temperature, high pressure, or catalyst assistance to complete the repair process, which limits their application in practical engineering. Summary of the Invention

[0004] To overcome the shortcomings of existing technologies, this invention proposes a room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds and its preparation method. First, a -NCO-terminated prepolymer is synthesized. Then, chain extenders containing quadruple hydrogen bonds and disulfide bonds are introduced respectively, and a chain extension reaction is performed to obtain a polyurethane with room-temperature self-healing function and good mechanical properties. The self-healing function and mechanical properties of this polyurethane are mainly adjusted by controlling the content of quadruple hydrogen bonds and disulfide bonds, as well as the ratio of soft to hard segments. Furthermore, this method is easily industrialized and has significant application prospects.

[0005] To achieve the above objectives, the technical solution adopted by the present invention includes: A method for preparing a room-temperature self-healing polyurethane with four hydrogen bonds / disulfide bonds, comprising the following steps: Step 1: 2-Amino-4-hydroxy-6-methylpyrimidine and 1,6-hexanediisocyanate in a molar ratio of 1:6 are reacted at 100°C in a N2 atmosphere to obtain powder UPy-NCO. Step 2: UPy-NCO and amino-2-methyl-1,3-propanediol in a molar ratio of 1:1.3 are added to chloroform and reacted at 60°C. The reaction product is washed with chloroform and then dissolved in N,N-dimethylformamide. The supernatant is collected by centrifugation. The supernatant is poured into diethyl ether to obtain solution A. Solution A is washed with acetone to obtain the precipitate DiOH-UPy. Step 3: PTMG-1000, isophorone diisocyanate and dibutyltin dilaurate are reacted at 80-83℃, then PTMG-250 is added, and the reaction is continued at 80-83℃ to obtain a -NCO-terminated prepolymer. The molar ratio of PTMG-1000, isophorone diisocyanate, dibutyltin dilaurate and PTMG-250 is 1:4:10:0.04. Step 4: Raise the temperature to 84-86℃, add DiOH-UPy and 3,3-dihydroxydiphenyl disulfide, two chain extenders, to the -NCO-terminated prepolymer and react them. The resulting viscous product is then dried to obtain the final product.

[0006] Optionally, in step four, the amount of DiOH-UPy accounts for 40% to 80% of the total amount of the two chain extenders, DiOH-UPy and 3,3-dihydroxydiphenyl disulfide.

[0007] Optionally, in step four, the total amount of the two chain extenders is in a ratio of 4:1 to the amount of PTMG-1000.

[0008] Optionally, in step four, the two chain extenders react for 3 hours, and the resulting viscous product is first vacuum dried at 60°C for 12 hours, and then vacuum dried at 80°C for 12 hours to obtain the final product.

[0009] Optionally, in step three, the molecular weight of PTMG-1000 is 1000; the molecular weight of PTMG-250 is 250.

[0010] Optionally, in step three, PTMG-1000, isophorone diisocyanate, and dibutyltin dilaurate are reacted at 80–83°C for 1 hour, and then PTMG-250 is added, and the reaction is continued at 80–83°C for another hour.

[0011] Optionally, in step one, the reaction is carried out at 100°C for 20–25 h in a N2 atmosphere.

[0012] Optionally, in step two, the mixture is stirred at 60°C for 10 hours.

[0013] Optionally, the chloroform, PTMG-1000, PTMG-250 and isophorone diisocyanate are pre-dried for 24-36 hours.

[0014] A room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds is prepared by any of the preparation methods of room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds described in this invention.

[0015] The beneficial effects of this invention are as follows: The room-temperature self-healing polyurethane and its preparation method of this invention are innovative in that they possess a quadruple hydrogen bond and disulfide bond structure. Compared with existing technologies, the polyurethane material of this invention exhibits significant performance advantages: by controlling the molecular weight of the soft segment monomers and the ratio of two dynamic chain extenders, the synergistic regulation of molecular chain mobility and dynamic cross-linking network is achieved, thereby endowing the material with excellent self-healing properties. Experimental results show that the polyurethane can achieve a repair efficiency of over 90% within 24 hours at room temperature, and rapid repair can be achieved by heating at 60°C for 2 hours. This self-healing characteristic without external intervention significantly reduces the labor costs of material maintenance. In addition, by introducing a long molecular chain dynamic chain extender containing quadruple hydrogen bonds, the cross-linking network density of the polyurethane is significantly enhanced, thereby greatly improving its mechanical properties and laying a solid foundation for practical applications. Attached Figure Description

[0016] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings: Figure 1 The polyurethane Raman spectrum curve in Example 5 of this invention; Figure 2 These are photos of the polyurethane pre-applied scratches in Example 5 of the present invention, and photos taken 24 hours after the scratches self-heal at room temperature. Figure 3 The stress-strain curves are shown for the initial state of polyurethane and for 24 hours of self-healing at room temperature in Example 5 of this invention. Detailed Implementation

[0017] The present invention will be described in further detail below with reference to specific embodiments, but the implementation of the present invention includes, but is not limited to, the scope represented by the following embodiments.

[0018] The preparation method of the room temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds of the present invention comprises the following steps: Step 1: 2-Amino-4-hydroxy-6-methylpyrimidine and 1,6-hexanediisocyanate in a molar ratio of 1:6 are reacted at 100°C in a N2 atmosphere to obtain powder UPy-NCO. Step 2: UPy-NCO and amino-2-methyl-1,3-propanediol in a molar ratio of 1:1.3 are added to chloroform and reacted at 60°C. The reaction product is washed with chloroform and then dissolved in N,N-dimethylformamide. The supernatant is collected by centrifugation. The supernatant is poured into diethyl ether to obtain solution A. Solution A is washed with acetone to obtain the precipitate DiOH-UPy. Step 3: PTMG-1000, isophorone diisocyanate and dibutyltin dilaurate are reacted at 80-83℃, then PTMG-250 is added, and the reaction is continued at 80-83℃ to obtain a -NCO-terminated prepolymer. The molar ratio of PTMG-1000, isophorone diisocyanate, dibutyltin dilaurate and PTMG-250 is 1:4:10:0.04. Step 4: Raise the temperature to 84-86℃, add DiOH-UPy and 3,3-dihydroxydiphenyl disulfide, two chain extenders, to the -NCO-terminated prepolymer and react them. The resulting viscous product is then dried to obtain the final product.

[0019] In the embodiments of this disclosure, the amount of DiOH-UPy in step four accounts for 40% to 80% of the total amount of the two chain extenders, DiOH-UPy and 3,3-dihydroxydiphenyl disulfide.

[0020] In the embodiments of this disclosure, the total amount of the two chain extenders in step four is in a ratio of 4:1 to the amount of PTMG-1000.

[0021] In the embodiments of this disclosure, the two chain extenders in step four react for 3 hours, and the resulting viscous product is first vacuum dried at 60°C for 12 hours, and then vacuum dried at 80°C for 12 hours to obtain the final product.

[0022] In the embodiments of this disclosure, the molecular weight of PTMG-1000 in step three is 1000; the molecular weight of PTMG-250 is 250.

[0023] In the embodiments disclosed herein, in step three, PTMG-1000, isophorone diisocyanate and dibutyltin dilaurate are reacted at 80-83°C for 1 hour, and then PTMG-250 is added, and the reaction is continued at 80-83°C for another hour.

[0024] In the embodiments of this disclosure, step one involves reacting at 100°C in a N2 atmosphere for 20–25 h.

[0025] In the embodiments of this disclosure, step two involves stirring at 60°C for 10 hours.

[0026] In the embodiments of this disclosure, chloroform, PTMG-1000, PTMG-250 and isophorone diisocyanate were pre-dried for 24 to 36 hours.

[0027] The more specific steps are as follows: Step 1: 2-Amino-4-hydroxy-6-methylpyrimidine and 1,6-hexanediisocyanate were reacted at 100℃ for 20-25 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and washed to remove impurities, yielding powder UPy-NCO (synthetic route diagram as shown below). The molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 1,6-hexanediisocyanate was 1:6, and the amount of 2-amino-4-hydroxy-6-methylpyrimidine was 25-30 mmol.

[0028] ; Step 2: UPy-NCO and amino-2-methyl-1,3-propanediol were added to chloroform and stirred at 60°C for 10 h. The reaction product was washed with chloroform, dissolved in N,N-dimethylformamide, and the supernatant was collected by centrifugation. Next, the supernatant was poured into diethyl ether to obtain solution A. Finally, solution A was washed with acetone to obtain the dynamic chain extender DiOH-UPy containing four hydrogen bonds (synthetic route diagram below). The molar ratio of UPy-NCO to amino-2-methyl-1,3-propanediol was 1:1.3, and the amount of UPy-NCO was 10–15 mmol.

[0029] ; Step 3: Add polytetrahydrofuran diol (PTMG-1000) with a molecular weight of 1000, isophorone diisocyanate, and dibutyltin dilaurate to a flask and react at 80-83°C for 1 h. Then add polytetrahydrofuran diol (PTMG-250) with a molecular weight of 250 and continue reacting at 80-83°C for 1 h to obtain a -NCO-terminated prepolymer. The molar ratio of PTMG-1000, PTMG-250, isophorone diisocyanate, and dibutyltin dilaurate is 1:4:10:0.04, and the amount of PTMG-1000 is 5-10 mmol.

[0030] Step 4: Then raise the temperature to 84-86℃, add DiOH-UPy and 3,3-dihydroxydiphenyl disulfide, two chain extenders, to the -NCO-terminated prepolymer and react for 3 hours. Then pour the resulting viscous product into a mold and vacuum dry it at 60℃ for 12 hours, and then vacuum dry it at 80℃ for 12 hours. Finally, room temperature self-healing polyurethane is obtained. The amount of DiOH-UPy accounts for 40%-80% of the total amount of the two chain extenders, and the ratio of the total amount of the two chain extenders to the amount of PTMG-1000 is 4:1.

[0031] The room-temperature self-healing polyurethane with four hydrogen bonds / disulfide bonds was prepared by the method described above.

[0032] Example 1: ① 3.13 g of 2-amino-4-hydroxy-6-methylpyrimidine and 25.23 g of 1,6-hexanediisocyanate were reacted at 100 °C for 20 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and washed to remove impurities, and UPy-NCO powder was obtained.

[0033] ② Add 2.79 g of UPy-NCO and 1.37 g of amino-2-methyl-1,3-propanediol to chloroform and stir at 60 °C for 10 h. Wash the reaction product with chloroform, dissolve it in N,N-dimethylformamide, and then collect the supernatant by centrifugation. Next, pour the supernatant into diethyl ether to obtain solution A. Finally, wash solution A with acetone to obtain the precipitate DiOH-UPy.

[0034] ③ Add 5.00g of polytetrahydrofuran diol (PTMG-1000) with a molecular weight of 1000, 11.12g of isophorone diisocyanate and 0.13g of dibutyltin dilaurate to a flask, react at 80℃ for 1 h, then add 5.00g of polytetrahydrofuran diol (PTMG-250) with a molecular weight of 250, and continue to react at 83℃ for 1 h to obtain the -NCO-terminated prepolymer.

[0035] ④Then the temperature is raised to 84℃, and 3.18g of DiOH-UPy and 3.00g of 3,3-dihydroxydiphenyl disulfide are added to the -NCO-terminated prepolymer and reacted for 3h. The resulting viscous product is then poured into a mold and vacuum dried at 60℃ for 12h, and then vacuum dried at 80℃ for 12h to obtain room temperature self-healing polyurethane.

[0036] Example 2: ① 3.50 g of 2-amino-4-hydroxy-6-methylpyrimidine and 28.26 g of 1,6-hexanediisocyanate were reacted at 100 °C for 22 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and the impurities were removed by rinsing to obtain powder UPy-NCO.

[0037] ② Add 3.63 g of UPy-NCO and 1.78 g of amino-2-methyl-1,3-propanediol to chloroform and stir at 60 °C for 10 h. Wash the reaction product with chloroform, dissolve it in N,N-dimethylformamide, and then centrifuge to collect the supernatant. Next, pour the supernatant into diethyl ether to obtain solution A. Finally, wash solution A with acetone to obtain the precipitate DiOH-UPy.

[0038] ③ Add 8.00g of PTMG-1000, 17.79g of isophorone diisocyanate and 0.20g of dibutyltin dilaurate to a flask, react at 81℃ for 1h, then add 8.00g of PTMG-250, and continue to react at 83℃ for 1h to obtain the -NCO-terminated prepolymer.

[0039] ④Then the temperature is raised to 85℃, and 5.10g of DiOH-UPy and 4.81g of 3,3-dihydroxydiphenyl disulfide are added to the -NCO-terminated prepolymer and reacted for 3 h. The resulting viscous product is then poured into a mold and vacuum dried at 60℃ for 12 h, and then vacuum dried at 80℃ for 12 h to obtain room temperature self-healing polyurethane.

[0040] Example 3: ① 3.75 g of 2-amino-4-hydroxy-6-methylpyrimidine and 30.28 g of 1,6-hexanediisocyanate were reacted at 100 °C for 25 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and washed to remove impurities, and UPy-NCO powder was obtained.

[0041] ② Add 4.19 g of UPy-NCO and 2.05 g of amino-2-methyl-1,3-propanediol to chloroform and stir at 60 °C for 10 h. Wash the reaction product with chloroform, dissolve it in N,N-dimethylformamide, and then centrifuge to collect the supernatant. Next, pour the supernatant into diethyl ether to obtain solution A. Finally, wash solution A with acetone to obtain the precipitate DiOH-UPy.

[0042] ③ Add 10.00g of PTMG-1000, 22.23g of isophorone diisocyanate and 0.25g of dibutyltin dilaurate to a flask, react at 82℃ for 1h, then add 10.00g of PTMG-250, and continue to react at 83℃ for 1h to obtain the -NCO-terminated prepolymer.

[0043] ④Then the temperature is raised to 86℃, and 6.37g of DiOH-UPy and 6.00g of 3,3-dihydroxydiphenyl disulfide are added to the -NCO-terminated prepolymer and reacted for 3 h. The resulting viscous product is then poured into a mold and vacuum dried at 60℃ for 12 h, and then vacuum dried at 80℃ for 12 h to obtain room temperature self-healing polyurethane.

[0044] Example 4: ① 3.13 g of 2-amino-4-hydroxy-6-methylpyrimidine and 25.23 g of 1,6-hexanediisocyanate were reacted at 100 °C for 20 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and washed to remove impurities, and UPy-NCO powder was obtained.

[0045] ② Add 2.79 g of UPy-NCO and 1.37 g of amino-2-methyl-1,3-propanediol to chloroform and stir at 60 °C for 10 h. Wash the reaction product with chloroform, dissolve it in N,N-dimethylformamide, and then collect the supernatant by centrifugation. Next, pour the supernatant into diethyl ether to obtain solution A. Finally, wash solution A with acetone to obtain the precipitate DiOH-UPy.

[0046] ③ Add 5.00g of polytetrahydrofuran diol (PTMG-1000) with a molecular weight of 1000, 11.12g of isophorone diisocyanate and 0.13g of dibutyltin dilaurate to a flask, react at 80℃ for 1 h, then add 5.00g of polytetrahydrofuran diol (PTMG-250) with a molecular weight of 250, and continue to react at 83℃ for 1 h to obtain the -NCO-terminated prepolymer.

[0047] ④Then the temperature is raised to 84℃, and 4.78g of DiOH-UPy and 2.00g of 3,3-dihydroxydiphenyl disulfide are added to the -NCO-terminated prepolymer and reacted for 3h. The resulting viscous product is then poured into a mold and vacuum dried at 60℃ for 12h, and then vacuum dried at 80℃ for 12h to obtain room temperature self-healing polyurethane.

[0048] Example 5: ① 3.13 g of 2-amino-4-hydroxy-6-methylpyrimidine and 25.23 g of 1,6-hexanediisocyanate were reacted at 100 °C for 20 h in a N2 atmosphere. After the reaction was completed, the product was precipitated with n-hexane and washed to remove impurities, and UPy-NCO powder was obtained.

[0049] ② Add 2.79 g of UPy-NCO and 1.37 g of amino-2-methyl-1,3-propanediol to chloroform and stir at 60 °C for 10 h. Wash the reaction product with chloroform, dissolve it in N,N-dimethylformamide, and then collect the supernatant by centrifugation. Next, pour the supernatant into diethyl ether to obtain solution A. Finally, wash solution A with acetone to obtain the precipitate DiOH-UPy.

[0050] ③ Add 5.00g of polytetrahydrofuran diol (PTMG-1000) with a molecular weight of 1000, 11.12g of isophorone diisocyanate and 0.13g of dibutyltin dilaurate to a flask, react at 80℃ for 1 h, then add 5.00g of polytetrahydrofuran diol (PTMG-250) with a molecular weight of 250, and continue to react at 83℃ for 1 h to obtain the -NCO-terminated prepolymer.

[0051] ④Then the temperature is raised to 84℃, and 6.37g of DiOH-UPy and 1.60g of 3,3-dihydroxydiphenyl disulfide are added to the -NCO-terminated prepolymer and reacted for 3h. The resulting viscous product is then poured into a mold and vacuum dried at 60℃ for 12h, and then vacuum dried at 80℃ for 12h. Finally, room temperature self-healing polyurethane is obtained.

[0052] The material obtained in Example 5 was subjected to relevant tests to obtain... Figure 1-3 As a result, Figure 1 The polyurethane Raman spectrum curve in Example 5 of this invention; Figure 2 These are photos of the polyurethane pre-applied scratches in Example 5 of the present invention, and photos taken 24 hours after the scratches self-heal at room temperature. Figure 3 The stress-strain curves are shown for the initial state of polyurethane and for 24 hours of self-healing at room temperature in Example 5 of this invention.

[0053] Raman spectroscopy ( Figure 1 ) 510 cm -1 and 640 cm -1 The peaks belong to v(SS) and v(CS), respectively, indicating that the SS bond was successfully introduced into the polyurethane system. From Figure 2 It can be seen that the pre-made scratches on the polyurethane were deep and wide, and after 24 hours of self-healing at room temperature, the scratches became significantly shallower and fainter, indicating that the scratches healed quickly and efficiently. To further characterize the self-healing ability of polyurethane, the scratches before pre-made scratches ( Figure 3 Original), after pre-cut scratches and 24 hours of room temperature healing ( Figure 3 Tensile tests were conducted on the polyurethane sample in the Healed rt 24h sample. Because the pre-marked sample was almost completely severed, it lost all mechanical properties and did not meet the requirements for the tensile test. Figure 3 The stress-strain curves of the samples immediately after pre-scratching are not available. By comparing the stress-strain curves of the samples after 24 hours of room temperature healing and before pre-scratching, it is clear that after 24 hours of room temperature healing, polyurethane achieved efficient healing, with both strain repair rate and stress repair rate exceeding 90%.

[0054] 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 within the protection scope of the present invention.

Claims

1. A method for preparing a room-temperature self-healing polyurethane with four hydrogen bonds / disulfide bonds, characterized in that, The steps are as follows: Step 1: 2-Amino-4-hydroxy-6-methylpyrimidine and 1,6-hexanediisocyanate in a molar ratio of 1:6 are reacted at 100°C in a N2 atmosphere to obtain powder UPy-NCO. Step 2: UPy-NCO and amino-2-methyl-1,3-propanediol in a molar ratio of 1:1.3 are added to chloroform and reacted at 60°C. The reaction product is washed with chloroform and then dissolved in N,N-dimethylformamide. The supernatant is collected by centrifugation. The supernatant is poured into diethyl ether to obtain solution A. Solution A is washed with acetone to obtain the precipitate DiOH-UPy. Step 3: PTMG-1000, isophorone diisocyanate and dibutyltin dilaurate are reacted at 80-83℃, then PTMG-250 is added, and the reaction is continued at 80-83℃ to obtain a -NCO-terminated prepolymer. The molar ratio of PTMG-1000, isophorone diisocyanate, dibutyltin dilaurate and PTMG-250 is 1:4:10:0.

04. Step 4: Raise the temperature to 84-86℃, add DiOH-UPy and 3,3-dihydroxydiphenyl disulfide, two chain extenders, to the -NCO-terminated prepolymer and react them. The resulting viscous product is then dried to obtain the final product.

2. The method for preparing room temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1, characterized in that, In step four, the amount of DiOH-UPy accounts for 40% to 80% of the total amount of the two chain extenders, DiOH-UPy and 3,3-dihydroxydiphenyl disulfide.

3. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step four, the total amount of the two chain extenders is in a ratio of 4:1 to the amount of PTMG-1000.

4. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step four, the two chain extenders react for 3 hours, and the resulting viscous product is first vacuum dried at 60°C for 12 hours, and then vacuum dried at 80°C for 12 hours to obtain the final product.

5. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step three, the molecular weight of PTMG-1000 is 1000; the molecular weight of PTMG-250 is 250.

6. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step three, PTMG-1000, isophorone diisocyanate, and dibutyltin dilaurate are reacted at 80–83°C for 1 hour, and then PTMG-250 is added, and the reaction continues at 80–83°C for another hour.

7. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step one, the reaction is carried out at 100°C for 20–25 h in a N2 atmosphere.

8. The method for preparing room-temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, In step two, the mixture is stirred at 60°C for 10 hours.

9. The method for preparing room temperature self-healing polyurethane with quadruple hydrogen bonds / disulfide bonds according to claim 1 or 2, characterized in that, The chloroform, PTMG-1000, PTMG-250 and isophorone diisocyanate were pre-dried for 24-36 hours.

10. A room-temperature self-healing polyurethane with four hydrogen bonds / disulfide bonds, characterized in that, The self-healing polyurethane with four hydrogen bonds / disulfide bonds at room temperature was prepared using the preparation method described in any one of claims 1-9.

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