Modified intelligent wear tpu with improved self-repairing ability and preparation method thereof

Abstract

The present application belongs to the technical field of polyurethane elastomer, and particularly relates to a modified intelligent wearable TPU with improved self-repairing capability and a preparation method thereof. The preparation method of the modified intelligent wearable TPU with improved self-repairing capability comprises the following steps: mixing polyol, diisocyanate and solvent, adding a catalyst to perform end-capping pre-polymerization to obtain component A; mixing a mixed chain extender, solvent and a catalyst to obtain component B; and finally, mixing components A and B through a double-screw extrusion process, extruding and granulating to obtain the modified intelligent wearable TPU with improved self-repairing capability; the mixed chain extender is a mixture of BHEA and Upy-(OH)2 in a mass ratio of 3:1 to 5:1. The modified intelligent wearable TPU with improved self-repairing capability has good mechanical properties and strong self-repairing capability. The present application also provides a preparation method thereof.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyurethane elastomers, and specifically relates to a modified intelligent wearable TPU with improved self-repairing capability and a preparation method thereof. BACKGROUND

[0002] At present, thermoplastic polyurethane (TPU) is a linear block copolymer composed of hard segments (diisocyanate and chain extender) and soft segments (long-chain polyol), which combines the high elasticity of rubber and the processing performance of plastic. Due to its excellent mechanical strength, wear resistance, high elasticity and adjustable hardness range, it is widely used in intelligent wearable devices such as watch bands, fitness trackers, etc. However, intelligent wearable devices are in long-term contact with human skin and often in complex environments such as dynamic bending, sweat erosion, etc., which puts higher requirements on the comfort (such as coolness, dryness), weather resistance, stain resistance, durability and self-repairing capability of the material. The existing technology improves the performance of TPU through various chemical modifications and filler additions, but still has some limitations.

[0003] For example, CN117467112A discloses a cool TPU for intelligent wear and a preparation method thereof, which uses diisocyanate, silicone-modified polyether polyol and chain extender (such as 1,4-butanediol, ethylene glycol, etc. to enhance hardness) as the basic formula, and adds fillers such as cesium-doped tungsten oxide to increase coolness, such as CN113292842A which adds silicon carbide powder filler to improve wear resistance. The above intelligent wearable TPU is prepared by double screw reaction extrusion method. However, the above existing technology still has the problems of poor durability and stability, and it is difficult to balance the mechanical properties and comfort.

[0004] "Room-temperature self-healing supramolecular polyurethanes based on the synergistic strengthening of biomimetic hierarchical hydrogen-bonding interactions and coordination bonds, Chemical Engineering Journal (IF 13.2) Pub Date: 2022-08-18, DOI: 10.1016 / j.cej.2022.138673, Jing Xu et al." proposed to introduce 2-ureido-4[1H] imidazole (UPy) groups into the side chain of polyurethane, and cross-link with Zn 2+ Coordination to construct hierarchical hydrogen bond network, so that the material has room temperature self-repairing ability (24h repair efficiency reaches 95%), but the tensile strength (about 14MPa) of the material is still insufficient to meet the long-term requirements of intelligent wearable devices for high mechanical properties; and the metal ions (such as Zn 2+ ) introduced in the material may migrate or lose in long-term contact with sweat or wet environment, affecting the stability and biocompatibility of the repair network, limiting its practical application in wearable field. However, its research mainly focuses on the improvement of static mechanical properties, and does not involve the realization of self-repairing function; at the same time, the hard segment aggregation and high crystallinity caused by strong hydrogen bond in the material may reduce its flexibility and wearing comfort, and it is also difficult to realize self-repairing after damage at room temperature, which limits its application in intelligent wearable scenarios that require dynamic healing. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the above-mentioned defects existing in the prior art, and to provide a modified intelligent wearable TPU with improved self-repairing ability, good mechanical properties and strong self-repairing ability. The present application also provides a preparation method thereof.

[0006] The preparation method of the modified intelligent wearable TPU with improved self-repairing ability provided by the present application comprises the following steps: first, mixing polyol, diisocyanate and solvent, adding catalyst for end-capped pre-polymerization to obtain component A; then mixing chain extender, solvent and catalyst to obtain component B; finally, mixing components A and B by double screw extrusion process, and granulating to obtain the modified intelligent wearable TPU with improved self-repairing ability.

[0007] The mixed chain extender is N,N-bis(2-hydroxyethyl)oxamide (BHEA) and 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol (Upy(OH)2) mixed at a mass ratio of 3:1 to 5:1.

[0008] The polyol is a polyether polyol or a polyester polyol.

[0009] The polyether polyol is polytetrahydrofuran with a molecular weight of 1000-2000 g / mol, and the polyester polyol is polycaprolactone with a molecular weight of 2000 g / mol.

[0010] The diisocyanate is isophorone diisocyanate or 1,6-hexamethylene diisocyanate.

[0011] The catalyst is dibutyltin dilaurate (DBTDL) or stannous octoate.

[0012] The solvent is N,N-dimethylformamide or butanone.

[0013] After mixing the polyol, diisocyanate, and solvent, nitrogen is introduced and the temperature is raised to 70-80°C.

[0014] The temperature in the double-screw extrusion process is set to 180-200°C.

[0015] The preparation method of 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol is as follows: 2-amino-4-hydroxy-6-methylpyrimidine is placed in a hexamethylene diisocyanate solution, heated to reflux, hexane is added after the reaction is completed, the obtained precipitate is washed, and then vacuum dried to obtain 2-(6-isocyanate hexylurea)-6-methyl-4[1H]pyrimidinone. 2-(6-isocyanate hexylurea)-6-methyl-4[1H]pyrimidinone and 2-amino-1,3-propanediol are added to tetrahydrofuran, and an amidation reaction is carried out under a nitrogen atmosphere with stirring. After the reaction is completed, concentration, water precipitation, suction filtration, water washing, and vacuum drying are performed to obtain 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol.

[0016] The synthesis route is as follows:

[0017] .

[0018] The modified intelligent wearable TPU with improved self-repairing capability, wherein each material is proportioned according to the following weight parts: polyol, 43-56 parts; diisocyanate, 23-34 parts; mixed chain extender, 15-27 parts; catalyst, 1-2 parts; and solvent, 40-50 parts.

[0019] The application introduces BHEA containing oxamide structure into the polyurethane main chain structure by first end-capping and pre-polymerizing polyol and diisocyanate, and then reacting the prepared pre-polymer with BHEA and Upy(OH)2, the rich urethane and oxamide bonds in the main chain can form rich hydrogen bonds, and can form a certain hierarchical hydrogen bond structure; by introducing Upy(OH)2, the two form a gradient energy dissipation system (BHEA bond breaks first to buffer stress, and Upy(OH)2 bond maintains network integrity), finally realizing the synergistic optimization of high strength and rapid self-repairing, and the complementary hydrophobicity of Upy(OH)2 and the polarity of BHEA endow the material with excellent environmental stability.

[0020] Compared with the prior art, the application has the beneficial effects that:

[0021] (1) The application adopts BHEA and Upy(OH)2 as mixed chain extenders, and constructs a hierarchical hierarchical hydrogen bond network in the TPU molecular chain through the synergistic effect thereof. Among them, the high-density and high-bond-energy urea amide bond provided by BHEA serves as the main strength source, and the four hydrogen bonds introduced by Upy(OH)2 serve as dynamic reversible sacrificial bonds, which preferentially break under external force to dissipate energy, effectively preventing micro-crack propagation, thereby realizing high strength, high toughness and high-efficiency room-temperature self-repairing capability of the material at the same time.

[0022] (2) The application forms complementarity between the hydrophobic segment of Upy(OH)2 and the strong polar structure of BHEA through molecular design, significantly improves the hydrolysis resistance and environmental stability (such as resistance to sweat erosion) of the material, and enables the material to maintain stable performance and appearance integrity in the complex use environment of intelligent wearable products for a long time.

[0023] (3) The preparation process of the application adopts mature pre-polymer method and double-screw reaction extrusion technology, the reaction conditions are mild and controllable, the process flow is simple, no complex post-treatment is needed, and the selected raw materials are easy to obtain and low in cost, which is very suitable for large-scale industrial production, has significant economic efficiency and market competitiveness. DETAILED DESCRIPTION

[0024] The application will be further described below in combination with specific embodiments.

[0025] The preparation method of Upy(OH)2 used in the following examples and comparative examples is as follows: 2.5 g of 2-amino-4-hydroxy-6-methylpyrimidine is placed in a 17.5 mL (7 mol) solution of hexamethylene diisocyanate and refluxed at 100°C for 16 h, 50 mL of hexane is added, filtered, the obtained precipitate is washed with 100 mL of hexane, and the obtained product is dried at 50°C under vacuum for 72 h to obtain Upy-NCO (2-(6-isocyanate hexyl urea)-6-methyl-4[1H] pyrimidinone), Upy-NCO is added to 2-amino-1,3-propanediol according to a mass ratio of 100:60, added to tetrahydrofuran solvent, acylated at a temperature of 50°C under nitrogen atmosphere for 5 h, after completion, concentrated by rotary evaporation, precipitated by adding deionized water, suction filtered, washed with water, and vacuum dried to obtain Upy-(OH)2.

[0026] The following raw materials are commercially available:

[0027] Polytetrahydrofuran (PTMG-1000 or PTMG-2000): BASF SE;

[0028] Isophorone diisocyanate: Wanhua Chemical Group Co., Ltd.;

[0029] BHEA: Shanghai Aladdin Biochem Technology Co., Ltd.

[0030] The following parts are calculated according to the same mass unit, and no special instructions, other raw materials and auxiliaries are conventional commercially available products in the art.

[0031] Example 1

[0032] The modified intelligent wearable TPU with improved self-repairing ability is prepared according to the following weight ratio:

[0033] Isophorone diisocyanate, 28.5 parts;

[0034] PTMG-2000, 47 parts;

[0035] BHEA, 18 parts;

[0036] Upy-(OH)2, 4.5 parts;

[0037] DBTDL, 2 parts;

[0038] DMF, 40 parts.

[0039] The preparation method of the modified intelligent wear TPU with improved self-repairing capability is as follows: PTMG-2000, isophorone diisocyanate and 20 parts of DMF are mixed, nitrogen is introduced into the system and the temperature is raised to 80°C, 1 part of DBTDL is added for end-capping pre-polymerization for 3 hours to obtain a pre-polymer A component; BHEA and UPy-(OH)2 are mixed and dissolved in 20 parts of DMF, 1 part of DBTDL is added at the same time to obtain a B component, and finally, the A and B components are mixed and extruded at 200°C by using a double-screw extrusion process to obtain modified intelligent wear TPU particles with improved self-repairing capability, which is named as TPU-1.

[0040] Example 2

[0041] The modified intelligent wear TPU with improved self-repairing capability is prepared according to the following weight ratio:

[0042] isophorone diisocyanate, 33.2 parts;

[0043] PTMG-1000, 43.3 parts;

[0044] BHEA, 18 parts;

[0045] Upy-(OH)2, 4.5 parts;

[0046] DBTDL, 1 part;

[0047] butanone, 50 parts.

[0048] The preparation method of the modified intelligent wear TPU with improved self-repairing capability is as follows: PTMG-1000, isophorone diisocyanate and 25 parts of butanone are mixed, nitrogen is introduced into the system and the temperature is raised to 70°C, 0.5 parts of DBTDL is added for end-capping pre-polymerization for 2.5 hours to obtain a pre-polymer A component; BHEA and UPy-(OH)2 are mixed and dissolved in 25 parts of butanone, 0.5 parts of DBTDL is added at the same time to obtain a B component, and finally, the A and B components are mixed and extruded at 190°C by using a double-screw extrusion process to obtain modified intelligent wear TPU particles with improved self-repairing capability, which is named as TPU-2.

[0049] Example 3

[0050] The modified intelligent wear TPU with improved self-repairing capability is prepared according to the following weight ratio:

[0051] 1,6-hexamethylene diisocyanate, 29.1 parts;

[0052] polycaprolactone 2000 molecular weight, 55.9 parts;

[0053] BHEA, 12 parts;

[0054] Upy-(OH)2, 3 parts;

[0055] DBTDL, 2 copies;

[0056] DMF, 50 copies.

[0057] The preparation method of the modified smart wearable TPU with improved self-healing ability is as follows: First, polycaprolactone with a molecular weight of 2000, 1,6-hexamethylene diisocyanate, and 25 parts of DMF are mixed. Nitrogen gas is introduced into the system and the temperature is raised to 75°C. One part of DBTDL is added to carry out end-capping prepolymerization reaction for 2 hours to obtain prepolymer component A. Then, BHEA and UPy-(OH)2 are mixed and dissolved in 25 parts of DMF, and one part of DBTDL is added at the same time to obtain component B. Finally, the components A and B are mixed and extruded at 180°C using a twin-screw extrusion process to obtain modified smart wearable TPU particles with improved self-healing ability, named TPU-3.

[0058] Example 4

[0059] The modified smart wearable TPU with enhanced self-healing capabilities is formulated in the following weight proportions:

[0060] 1,6-Hexamethylene diisocyanate, 28 parts;

[0061] PTMG-2000, 25 copies;

[0062] Polycaprolactone, 25 parts;

[0063] BHEA, 16 servings;

[0064] Upy-(OH)2, 4 parts;

[0065] DBTDL, 2 copies;

[0066] Butanone, 50 parts.

[0067] The preparation method of the modified smart wearable TPU with improved self-healing ability is as follows: First, PTMG-2000, polycaprolactone, 1,6-hexamethylene diisocyanate, and 25 parts of methyl ethyl ketone are mixed. Nitrogen gas is introduced into the system and the temperature is raised to 80°C. One part of DBTDL is added to carry out end-capping prepolymerization reaction for 3 hours to obtain prepolymer component A. Then, BHEA and UPy-(OH)2 are mixed and dissolved in 25 parts of methyl ethyl ketone, and one part of DBTDL is added at the same time to obtain component B. Finally, the components A and B are mixed and extruded at 200°C using a twin-screw extrusion process to obtain modified smart wearable TPU particles with improved self-healing ability, named TPU-4.

[0068] Example 5

[0069] The modified intelligent wearable TPU with improved self-repairing capability is prepared according to the following weight ratio:

[0070] 1,6-hexamethylene diisocyanate, 28 parts;

[0071] PTMG-2000, 16.7 parts;

[0072] polycaprolactone, 33.3 parts;

[0073] BHEA, 16 parts;

[0074] Upy-(OH)2, 4 parts;

[0075] DBTDL, 2 parts;

[0076] DMF, 50 parts.

[0077] The preparation method of the modified intelligent wearable TPU with improved self-repairing capability is as follows: PTMG-2000, polycaprolactone, 1,6-hexamethylene diisocyanate, and 25 parts of DMF are mixed, nitrogen is introduced into the system, and the temperature is raised to 80°C; 1 part of DBTDL is added for end-capping pre-polymerization for 3 hours to obtain a pre-polymer A component; BHEA and UPy-(OH)2 are mixed and dissolved in 25 parts of DMF, and 1 part of DBTDL is added at the same time to obtain a B component; finally, the A and B components are mixed and extruded at 200°C by using a double-screw extrusion process, and granulation is performed to obtain modified intelligent wearable TPU particles with improved self-repairing capability, which are named as TPU-5.

[0078] Comparative Example 1

[0079] isophorone diisocyanate, 30.3 parts;

[0080] PTMG-2000, 45 parts;

[0081] BHEA, 22.7 parts;

[0082] DBTDL, 2 parts;

[0083] DMF, 40 parts.

[0084] The preparation method of the intelligent wearable TPU is as follows: PTMG-2000, isophorone diisocyanate, and 20 parts of DMF are mixed, nitrogen is introduced into the system, and the temperature is raised to 80°C; 1 part of DBTDL is added for reaction for 3 hours to obtain a pre-polymer, which is used as an A component; BHEA is dissolved in 20 parts of DMF, and 1 part of DBTDL is added at the same time to obtain a B component; finally, a double-screw extrusion process is used, and reaction is performed in a double-screw extruder at 200°C; granulation is performed to obtain TPU particles, which are named as TPU-6.

[0085] Comparative Example 2

[0086] Isonipecyl diisocyanate, 27 parts;

[0087] PTMG-2000, 48 parts;

[0088] BHEA, 17.2 parts;

[0089] UPy-(OH)2, 5.8 parts;

[0090] DBTDL, 2 parts;

[0091] DMF, 50 parts.

[0092] The preparation method of the smart wearable TPU is as follows: PTMG-2000, isophorone diisocyanate, and 25 parts of DMF are first added, nitrogen is introduced into the system, and the temperature is raised to 80°C; 1 part of DBTDL is added and reacted for 3 hours to obtain a prepolymer as component A; BHEA and UPy-(OH)2 are dissolved in 25 parts of DMF, and 1 part of DBTDL is added at the same time to obtain component B; finally, a double-screw extrusion process is adopted, reaction is carried out in a double-screw extruder at 200°C, and TPU particles are obtained by granulation, which are named as TPU-7.

[0093] Comparative Example 3

[0094] Isonipecyl diisocyanate, 27 parts;

[0095] PTMG-2000, 48 parts;

[0096] BHEA, 19.2 parts;

[0097] UPy-(OH)2, 3.8 parts;

[0098] DBTDL, 2 parts;

[0099] DMF, 50 parts.

[0100] The preparation method of the smart wearable TPU is as follows: PTMG-2000, isophorone diisocyanate, and 25 parts of DMF are first added, nitrogen is introduced into the system, and the temperature is raised to 80°C; 1 part of DBTDL is added and reacted for 3 hours to obtain a prepolymer as component A; BHEA and UPy-(OH)2 are dissolved in 25 parts of DMF, and 1 part of DBTDL is added at the same time to obtain component B; finally, a double-screw extrusion process is adopted, reaction is carried out in a double-screw extruder at 200°C, and TPU particles are obtained by granulation, which are named as TPU-7.

[0101] Comparative Example 4

[0102] Isonipecyl diisocyanate, 27 parts;

[0103] PTMG-2000, 48 parts;

[0104] UPy-(OH)2, 26.9 parts;

[0105] DBTDL, 2 parts;

[0106] DMF, 50 parts.

[0107] The preparation method of the smart wearable TPU is as follows: first, PTMG-2000, isophorone diisocyanate, and 25 parts of DMF are added, nitrogen is introduced into the system, and the temperature is raised to 80°C; 1 part of DBTDL is added and reacted for 3 hours to obtain a prepolymer as component A; UPy-(OH)2 is dissolved in 25 parts of DMF, and 1 part of DBTDL is added at the same time to obtain component B; finally, a double-screw extrusion process is adopted, and the reaction is carried out in a double-screw extruder at 200°C; the TPU particles are granulated, and named as TPU-9.

[0108] The TPU products obtained in Examples 1-5 and Comparative Examples 1-4 are tested for performance according to the following standards.

[0109] (1) Mechanical properties (tensile strength, elongation at break): according to GB / T528-2009 method, cut into dumbbell-shaped samples of type 2, respectively, and then test the data of the dumbbell-shaped samples cut according to the standard. The results are shown in Table 1.

[0110] (3) Hardness (A) test: according to ASTM-D2240, the hardness is tested. The results are shown in Table 1.

[0111] (4) Repair method test: the standard dumbbell-shaped sample is cut in the middle of the transverse direction with a sharp knife, and then the two broken surfaces are completely butted together. The sample is placed in a constant temperature oven at 25°C, and the tensile strength of the repaired sample is tested after 24 hours. The tensile strength of the sample before repair is denoted as σ1, and the tensile strength of the sample after repair is denoted as σ2. The self-repairing efficiency is denoted as η1, where η1=σ2 / σ1×100%.

[0112] (5) Chemical resistance test: according to GB / T528-2009 method, the dumbbell-shaped samples cut according to the standard are placed in 10% sodium hydroxide solution for testing, and the samples are taken out for mechanical property test at certain intervals (d / day). The results are shown in Table 2.

[0113] Table 1 Mechanical property test results

[0114]

[0115] Table 2 Chemical resistance test results of the products of Examples and Comparative Examples

[0116]

[0117] As can be seen from the data in Table 1, the present application can realize the synthesis of quadruple hydrogen bond self-repairing TPU, and by adjusting the ratio of two chain extenders, the repair efficiency of the examples is higher than 90%, and the repeated repair still maintains a high tensile strength, while the repair efficiency of other ratios and only one chain extender is significantly reduced. Examples 4 and 5 are mixed systems of polyether and polyester, which have high strength, high repair efficiency and excellent hydrolysis resistance, and exhibit a synergistic effect of "1+1>2" in self-repairing applications, and the performance can be adjusted for wide applicability. By comparing Example 1 and Comparative Examples 1, 2, 3 and 4, with the increase of the proportion of UPy(OH)2 in the chain extender in the polyurethane elastomer, the strength and toughness first increase and then significantly decrease, and the elongation at break slightly decreases, which is because when the side chain UPy(OH)2 in the elastomer further increases, more UPy(OH)2 dimers are formed, which reduces the interaction force between the main chains and reduces the degree of microphase separation in the elastomer, thereby greatly reducing the mechanical properties of the elastomer. By comparing the chemical resistance of Example 1 and Comparative Examples 1 and 2, the higher the content of BHEA, the higher the tensile strength retention rate, and the formation of regular hard segment network by BHEA significantly improves the chemical resistance of TPU.

Claims

1. A method for preparing a modified smart wearable TPU with improved self-healing capabilities, characterized in that: The polyol, diisocyanate and solvent are mixed, nitrogen is introduced and the temperature is raised to 70-80 DEG C. The temperature in the double screw extrusion process is set to 180-200 DEG C.

2. The method for preparing modified smart wear TPU with improved self-repairing ability according to claim 1, characterized in that: The mixing chain extender is N,N-bis(2-hydroxyethyl)oxamide, 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol mixed in a mass ratio of 3:1-5:

1.

3. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 2, characterized in that: The polyol is polyether polyol or polyester polyol.

4. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: The polyether polyol is polytetrahydrofuran and the polyester polyol is polycaprolactone.

5. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: The diisocyanate is one of isophorone diisocyanate and 1,6-hexamethylene diisocyanate.

6. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: The catalyst is one of dibutyltin dilaurate and stannous octoate.

7. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: The solvent is one of N,N-dimethylformamide and butanone.

8. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: After the polyol, diisocyanate and solvent are mixed, nitrogen is introduced and the temperature is raised to 70-80 DEG C.

9. The method for preparing the modified smart wearable TPU with improved self-healing ability according to claim 1, characterized in that: The temperature in the double screw extrusion process is set to 180-200 DEG C.

10. A modified smart wear TPU with improved self-repairing capability, characterized in that: The preparation method of 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol is as follows: 2-amino-4-hydroxy-6-methylpyrimidine is placed in a hexamethylene diisocyanate solution, heated to reflux, hexane is added after the reaction is completed, the obtained precipitate is washed, and then vacuum dried to obtain 2-(6-isocyanate hexyl urea)-6-methyl-4[1H]pyrimidinone; 2-(6-isocyanate hexyl urea)-6-methyl-4[1H]pyrimidinone and 2-amino-1,3-propanediol are added to tetrahydrofuran, and an amidation reaction is carried out under a nitrogen atmosphere while stirring; after the reaction is completed, concentration, water precipitation, suction filtration, water washing and vacuum drying are carried out to obtain 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylureido}-1,3-propanediol. The modified intelligent wearable TPU with improved self-repairing capability is prepared by the preparation method of the modified intelligent wearable TPU with improved self-repairing capability according to any one of claims 1-9, wherein the materials are proportioned in the following weight parts: polyol, 43-56 parts; diisocyanate, 23-34 parts; mixing chain extender, 15-27 parts; catalyst, 1-2 parts; and solvent, 40-50 parts.

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