A repairable high-strength medical polyurethane elastomer and preparation method thereof

Abstract

The present invention discloses a repairable high-strength medical polyurethane elastomer and a preparation method thereof, and belongs to the technical field of polyurethane materials. The raw materials of the repairable high-strength medical polyurethane elastomer include, by molar parts, 100 parts of prepolymer, 170-220 parts of diisocyanate and 87-142 parts of diamine chain extender; the prepolymer is a polyether diol containing terminal hydroxyl groups. The present invention prepares a series of mechanically strong, tough and repairable supramolecular polyurea (SPUU) elastomers by controlling the content of weak and strong intermolecular hydrogen bond interactions in the polymer network. Through this structural design, the interaction of hydrogen bonds at the internal level of the molecule is regulated, and the mechanical strength and repair ability of the polyurethane elastomer are regulated, taking into account both the mechanical strength and the repair ability of the material. The technical disadvantages of the contradiction between the repair efficiency of the material and the mechanical strength of the material at this stage are solved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane materials, and in particular to a repairable high-strength medical polyurethane elastomer and a preparation method thereof. Background Art

[0002] Polyurethane (PU) is a typical multi-block polymer with very flexible and variable structural designability. By adjusting the type, proportion and distribution of diisocyanates, chain extenders and oligomeric diols, the polyurethane material can not only obtain excellent mechanical properties, resilience and good processing properties, but also have excellent blood compatibility and tissue compatibility.

[0003] In recent years, medical polyurethane materials have played a very important role in medical biomaterials due to their excellent biocompatibility, adhesion and anti-thrombotic properties, as well as excellent mechanical properties. At present, medical polyurethane products are widely used in the fields of human urinary system, oral and digestive system, cardiovascular system, skeletal system and in vitro body surface. However, the existing polyurethane materials cannot fully meet the requirements of clinical applications, so the development of new multifunctional integrated and biostable medical non-toxic polyurethane will be one of the focuses of research in the field of applied materials. As people's quality requirements for medical products continue to increase, it is also a future development trend for medical polyurethane to replace PVC in medical infusion, blood transfusion, injection equipment, etc. However, in actual use, due to the existence of abrasions caused by operation and damage to the material caused by injection, the material function will be reduced, the liquid medicine will seep out or the body fluid will penetrate into the catheter, which will seriously shorten the service life of medical devices (such as built-in catheters). If replaced, it will cause secondary damage to the patient. At the same time, for expensive medical devices, material damage means that patients have to replace the device, which will result in a large amount of medical expenses and bring serious economic burden to patients. Therefore, designing and preparing medical polyurethane materials with self-healing properties can effectively extend their service life, improve their safety and reduce their use costs.

[0004] An important prerequisite for the healing ability of polymer materials is that the polymer segments can fully move and diffuse in the polymer network under certain stimuli. However, when the movement and diffusion of polymer segments in the polymer network are very easy, the mechanical strength of the polymer material will be limited. Adjusting the strength and arrangement of weak interactions in the polymer network is considered to be a feasible way to resolve this contradiction. The rationally designed hierarchical molecular structure in the polymer network can not only give the polymer material higher mechanical strength and toughness, but also enable it to heal quickly and effectively under certain stimuli.

[0005] Aida and colleagues used the design of a zigzag arrangement of high-density thiourea hydrogen bonds to report a room-temperature self-healing polymer with a mechanical strength of up to 36 MPa. Sun and colleagues developed a series of repairable and recyclable polymer composites with ultra-high mechanical strength and stiffness by introducing in situ prepared soft nanoparticles. Fu and colleagues prepared self-healing polyurethane elastomers with a mechanical strength of up to 33.4 MPa and a mechanical strength of about 503.3 MJ / m by systematically adjusting the strength and dynamic responsiveness of the hard phase at the molecular level. 3 All these results indicate that a balance between high mechanical strength and excellent healing efficiency can be achieved in synthetic polymer materials by tuning the structure and strength of supramolecular interactions between molecules.

[0006] However, in some cases, some special functional components are introduced into the polymer matrix, which will lead to unnecessary degradation of the mechanical properties of the polymer material. For example, the introduction of excessive rigid nanofillers, such as graphene or carbon nanotubes, will make the polymer matrix harder and also reduce the toughness of the polymer. Similarly, ionic liquids, due to their role as plasticizers in the polymer matrix, will transform strong and hard polymers into soft and tough polymers.

[0007] In general, the disadvantage of the existing technology is that it is impossible to have a good regulation on the repair efficiency and the mechanical strength of the material. Summary of the invention

[0008] The purpose of the present invention is to provide a repairable high-strength medical polyurethane elastomer and a preparation method thereof. By regulating the distribution and proportion of multi-level hydrogen bonds between molecules to adjust the mechanical strength and repair ability of the polymer, a supramolecular polyurethane elastomer (SPUU) integrating mechanical properties, repair and antibacterial ability is synthesized, wherein the SPUU elastomer with an R value (ratio of IPDI to PTMEG) of 1.8 exhibits excellent mechanical properties, with a mechanical strength of ~43MPa, an elongation at break of ~1150% and a toughness of ~154MJ / m 3 .

[0009] The hard phase of this supramolecular polyurethane elastomer is reasonably designed, and the multi-level hydrogen bonds are highly reversible, which makes the material have good repair ability, and the repair efficiency can reach 97% at 80°C for 12 hours. The defects and shortcomings of the existing technology that strength and repair ability cannot be achieved at the same time are solved. In addition, the present invention introduces natural polyphenol curcumin through physical blending to prepare a polyurethane / curcumin composite material, which can achieve a sterilization rate of 99% against Staphylococcus aureus, and has broad application prospects in the medical and health fields in the future.

[0010] To achieve the above object, the present invention provides the following technical solutions:

[0011] One of the technical solutions of the present invention is to provide a repairable high-strength medical polyurethane elastomer, the raw materials, measured by mole, comprising:

[0012] 100 parts of prepolymer, 170-220 parts of diisocyanate and 87-142 parts of diamine type chain extender;

[0013] The prepolymer is a polyether diol containing terminal hydroxyl groups.

[0014] Preferably, the polyether diol containing terminal hydroxyl groups is one or two of polytetrahydrofuran containing terminal hydroxyl groups, polypropylene glycol containing terminal hydroxyl groups, polysiloxane containing terminal hydroxyl groups, and polycaprolactone containing terminal hydroxyl groups.

[0015] Preferably, the diisocyanate is isophorone diisocyanate, dicyclohexyl diisocyanate, diphenyl diisocyanate or hexamethylene diisocyanate.

[0016] Preferably, the diamine type chain extender is one or two of 4,4-methylenebis(cyclohexylamine), isophoronediamine and hexamethylenediamine.

[0017] Preferably, the molar amount of isocyanate in the diisocyanate is 1.05 times the sum of the molar amounts of hydroxyl groups in the prepolymer and amino groups in the diamine-type chain extender.

[0018] The second technical solution of the present invention is to provide a method for preparing the above-mentioned repairable high-strength medical polyurethane elastomer, comprising the following steps:

[0019] (1) dissolving the prepolymer and the diisocyanate in a solvent, adding a catalyst, and reacting to obtain a prepolymer of supramolecular polyurethane;

[0020] (2) The diamine chain extender is dissolved and added to the prepolymer of the supramolecular polyurethane. After the reaction is completed, the obtained product is added to water and the precipitate is dried to obtain the repairable high-strength medical polyurethane elastomer.

[0021] Preferably, the prepolymer in step (1) is a dehydrated prepolymer; the solvent is N,N-dimethylacetamide (DMAC); the catalyst is an organic tin catalyst; the reaction temperature is 75° C. and the reaction time is 2 h.

[0022] Preferably, the organotin catalyst is dibutyltin dilaurate (DBTDL).

[0023] Preferably, the prepolymer is dehydrated by vacuum drying at 80° C. for 1 to 2 hours.

[0024] Preferably, the solvent for dissolving the diamine chain extender in step (2) is N,N-dimethylacetamide; the reaction temperature is 0° C. and the reaction time is 6 hours.

[0025] Preferably, the drying in step (2) is vacuum drying at 80°C.

[0026] The third technical solution of the present invention is to provide a supramolecular polyurethane composite material, the components of which include the above-mentioned repairable high-strength medical polyurethane elastomer and natural polyphenols.

[0027] Preferably, the natural polyphenols are one or more of curcumin, ginkgo biloba, aloin and berberine.

[0028] The supramolecular polyurethane composite material is prepared by dissolving the natural polyphenol, the natural polyphenol and the repairable high-strength medical polyurethane elastomer in a solvent, and removing the solvent after the dissolution is complete, thereby obtaining the supramolecular polyurethane composite material.

[0029] The beneficial technical effects of the present invention are as follows:

[0030] The present invention designs high mechanical strength and repairable antibacterial polymer materials by regulating the supramolecular interactions between molecules. To achieve this, a series of mechanically strong, tough and healable supramolecular polyurea (SPUU) elastomers were first prepared by controlling the content of weak and strong intermolecular hydrogen bonding interactions in the polymer network.

[0031] Through this structural design, the interaction of hydrogen bonds within the molecule is regulated, and the mechanical strength and repair ability of the polyurethane elastomer are adjusted, taking into account both the mechanical strength and repair ability of the material. This solves the technical shortcomings of the contradiction between the repair efficiency and mechanical strength of the material at this stage, and provides a solution for the promotion and application of repairable materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Schematic diagram of the hierarchical hydrogen bond structure of the repairable high-strength medical polyurethane elastomer prepared in Example 1.

[0033] Figure 2 This is the synthetic route for preparing the repairable high-strength medical polyurethane elastomer in Example 1.

[0034] Figure 3 The infrared spectra of the repairable high-strength medical polyurethane elastomer prepared in Examples 1 to 3, wherein a is Example 1, b is Example 2, and c is Example 3.

[0035] Figure 4The stress-strain curves and load-bearing diagrams of the repairable high-strength medical polyurethane elastomers prepared in Examples 1 to 3, wherein a is a stress-strain curve diagram, and b is a diagram of the SPUU prepared in Example 2. 1.8 Load-bearing diagram.

[0036] Figure 5 This is a graph showing the repair efficiency of the repairable high-strength medical polyurethane elastomer prepared in Examples 1 to 3 at 80°C for 9 hours.

[0037] Figure 6 SPUU prepared in Example 2 1.8 And SPUU prepared in Example 5 1.8 -Cur 1％ Tensile curves after repair under different conditions, where a is the SPUU prepared in Example 2 1.8 , b is SPUU prepared in Example 5 1.8 -Cur 1％ .

[0038] Figure 7 The stress-strain curves of the repairable high-strength medical polyurethane elastomer prepared in Example 2 and the curcumin supramolecular polyurethane composite materials prepared in Examples 4 to 9 are shown.

[0039] Figure 8 The antibacterial effect diagrams of the repairable high-strength medical polyurethane elastomer prepared in Example 2, the curcumin supramolecular polyurethane composite materials prepared in Examples 4 to 9, and the negative control on Staphylococcus aureus, wherein a is the antibacterial effect diagram of the negative control and Example 2, b is the antibacterial effect diagram of Examples 6 and 7, c is the antibacterial effect diagram of Examples 4 and 5, and d is the antibacterial effect diagram of Examples 8 and 9.

[0040] Fig. 9 SPUU prepared in Example 2 1.8 Schematic diagram of load-bearing after cutting and repair at room temperature for 30 seconds. DETAILED DESCRIPTION

[0041] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0042] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0043] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.

[0044] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0045] Example 1

[0046] Preparation of repairable high-strength medical polyurethane elastomer:

[0047] (1) 6 mmol of polytetrahydrofuran (PTMEG, molecular weight 1000) was placed in a three-necked flask and vacuum dried for 2 h in an oil bath at 80 °C;

[0048] (2) 15 mL of DMAC was added to the dried PTMEG in step (1) to dissolve it, 10.2 mmol of isophorone diisocyanate (IPDI) was added according to the R value of 1.7, and after mixing evenly, 15 μL of DBTDL was added to the reaction system as a catalyst, and condensed and refluxed in an oil bath at 75° C. for 2 h to obtain an isocyanate-terminated polyurethane prepolymer;

[0049] (3) After the reaction in step (2) is completed, the reaction system is moved to an ice water bath and cooled to 0°C; an appropriate amount of 4,4-methylenebis(cyclohexylamine) (HMDA) (the molar amount of isocyanate in IPDI is 1.05 times the total molar amount of hydroxyl in PTMEG and amino in HMDA) is placed in a small glass bottle, 20 mL of DMAC is added to dissolve, and the mixture is dripped into the cooled isocyanate-terminated polyurethane prepolymer at a rate of 1 mL / min, and the mixture is reacted in an ice water bath for 6 h to obtain a polyurethane elastomer solution;

[0050] (4) The polyurethane elastomer solution obtained in step (3) is precipitated in deionized water, and the precipitated product is placed in a vacuum oven at 80° C. and vacuum dried to constant weight to obtain a repairable high-strength medical polyurethane elastomer, denoted as SPUU 1.7 .

[0051] The schematic diagram of the hierarchical hydrogen bond structure of the repairable high-strength medical polyurethane elastomer prepared in Example 1 is shown in Figure 1 .

[0052] Example 1 The synthetic route for preparing a repairable high-strength medical polyurethane elastomer is shown in Figure 2 .

[0053] Example 2

[0054] Preparation of repairable high-strength medical polyurethane elastomer:

[0055] Compared with Example 1, the difference is that the designed R value is 1.8, the amount of IPDI added is 10.8 mmol, and the prepared repairable high-strength medical polyurethane elastomer is denoted as SPUU 1.8 .

[0056] Example 3

[0057] Preparation of repairable high-strength medical polyurethane elastomer:

[0058] Compared with Example 1, the difference is that the designed R value is 2.2, the amount of IPDI added is 13.2 mmol, and the prepared repairable high-strength medical polyurethane elastomer is denoted as SPUU 2.2 .

[0059] Example 4

[0060] Preparation of curcumin supramolecular polyurethane composites:

[0061] 5 mg of curcumin was weighed in a 100 ml round-bottom flask using an electronic balance, and 50 mL of anhydrous ethanol was added to the flask and stirred. After the curcumin was dissolved, 995 mg of SPUU prepared in Example 2 was added to the flask. 1.8 After the sample is completely dissolved, the mixture is poured into a silica gel mold to remove the solvent to obtain a curcumin supramolecular polyurethane composite material, denoted as SPUU 1.8 -Cur 0.5％ .

[0062] Example 5

[0063] Preparation of curcumin supramolecular polyurethane composites:

[0064] Compared with Example 4, the difference is that the amount of curcumin added is 10 mg, SPUU 1.8 The added amount was 990 mg, and the obtained curcumin supramolecular polyurethane composite material was denoted as SPUU 1.8 -Cur 1％ .

[0065] Example 6

[0066] Preparation of curcumin supramolecular polyurethane composites:

[0067] Compared with Example 4, the difference is that the amount of curcumin added is 30 mg, SPUU 1.8 The added amount was 970 mg, and the obtained curcumin supramolecular polyurethane composite material was denoted as SPUU 1.8 -Cur 3％ .

[0068] Example 7

[0069] Preparation of curcumin supramolecular polyurethane composites:

[0070] Compared with Example 4, the difference is that the amount of curcumin added is 50 mg, SPUU 1.8 The added amount was 950 mg, and the obtained curcumin supramolecular polyurethane composite material was denoted as SPUU 1.8 -Cur 5％ .

[0071] Example 8

[0072] Preparation of curcumin supramolecular polyurethane composites:

[0073] Compared with Example 4, the difference is that the amount of curcumin added is 100 mg, SPUU 1.8 The added amount was 900 mg, and the obtained curcumin supramolecular polyurethane composite material was denoted as SPUU 1.8 -Cur 10％ .

[0074] Example 9

[0075] Preparation of curcumin supramolecular polyurethane composites:

[0076] Compared with Example 4, the difference is that the amount of curcumin added is 150 mg, SPUU 1.8 The amount of curcumin added was 850 mg, and the obtained curcumin supramolecular polyurethane composite material was denoted as SPUU 1.8 -Cur 15％ .

[0077] The infrared spectra of the repairable high-strength medical polyurethane elastomer prepared in Examples 1 to 3 are shown in Figure 3 , wherein a is Example 1, b is Example 2, and c is Example 3.

[0078] Further, the mechanical properties of the composite materials prepared by each embodiment of the present invention are tested. During the test, each material is made into a dumbbell-shaped standard sample bar. The specific steps are as follows: 1) Before the experiment, the flat plate vulcanizer is turned on and the upper and lower plates are adjusted to 120°C for preheating; 2) A layer of polyimide film is laid on the upper and lower sides of the dumbbell-shaped sample bar mold to prevent polymer adhesion, and the dried polymer is cut into small pieces and evenly laid on the mold, and the mold is placed on the heating plate of the flat plate vulcanizer for preheating for 5 minutes; 3) After the preheating is completed, hot pressing is performed at 120°C and 10MPa for 15 minutes, and the bubbles are discharged twice in the middle to obtain a dumbbell-shaped standard sample bar for mechanical testing. The mechanical property tests are all carried out at room temperature (20°C). The gauge length of the dumbbell-shaped standard sample bar is 12.0mm, the width is 2.0mm, and the thickness is 0.4mm. In each experiment, different sample bars are stretched more than 3 times at the same stretching speed. The stretching speed used in the present invention is 50mm / min.

[0079] The stress-strain curve and load-bearing schematic diagram of the repairable high-strength medical polyurethane elastomer prepared in Examples 1 to 3 are shown in Figure 4 , where a is the stress-strain curve, and b is the SPUU prepared in Example 2 1.8 Load-bearing diagram.

[0080] Combination Figure 3 and Figure 4 It can be seen that the present invention achieves the control of the mechanical properties of the material by regulating the hydrogen bonds at the intermolecular level, which proves the feasibility of the present invention.

[0081] The repair of the repairable high-strength medical polyurethane elastomer prepared in Examples 1 to 3 at 80°C for 9 hours is performed as follows: the sample is cut in the middle with a scalpel, and then the two broken pieces of the sample are placed in contact with each other and placed in an oven at 80°C for 9 hours. Finally, the sample is cooled to room temperature and its mechanical properties are tested using a uniaxial tensile testing machine. The repair efficiency is calculated as the ratio of the stress of the repaired sample to the stress of the original sample. The repair efficiency is shown in Figure 5 .

[0082] from Figure 5 It can be seen that the polyurethane elastomers with different R values ​​all show good repair ability at 80°C. It is proved that the present invention takes into account both the mechanical properties and the repair ability of the material by adjusting the hierarchical hydrogen bonds.

[0083] SPUU prepared in Example 2 1.8 And SPUU prepared in Example 5 1.8 -Cur 1％ The tensile curves after repair under different conditions are shown in Figure 6 , wherein a is SPUU prepared in Example 2 1.8, b is SPUU prepared in Example 5 1.8 -Cur 1％ .

[0084] from Figure 6 It can be seen that the hard domain design of the supramolecular polyurethane elastomer of the present invention is reasonable, the hierarchical hydrogen bonds are highly reversible, and have good healing ability.

[0085] The stress-strain curves of the repairable high-strength medical polyurethane elastomer prepared in Example 2 and the curcumin supramolecular polyurethane composite material prepared in Examples 4 to 9 are shown in FIG. Figure 7 .

[0086] The antibacterial properties of the composite materials prepared in different embodiments of the present invention were tested:

[0087] 1. Preparation of agar medium: Calculate the amount of medium to be prepared according to 20 mL per culture plate. Prepare 33 g agar medium per 1000 mL deionized water according to the instructions. Sterilize with high-pressure steam at 121°C for 20 min. Pour the agar medium into the culture dish. After the medium solidifies, seal it and store it in a refrigerator at 4°C.

[0088] 2. Nutrient broth medium: According to the instructions, prepare 100 mL of culture medium with 18 g of nutrient broth medium per 1000 mL of deionized water, and sterilize with high-pressure steam at 121°C for 20 min (adjust the culture medium volume, inoculation concentration, constant temperature culture speed, and culture time according to the needs of bacterial enrichment).

[0089] 3. Bacterial enrichment culture: Pick up Staphylococcus aureus with the pipette tip and directly inject the tip into a 50 mL conical flask. Seal the flask with a breathable membrane and place it in a shaker for culture at 160 r / min and 37°C for 6-8 hours.

[0090] 4. Determination of bacterial liquid concentration:

[0091] 1) Take 1 mL of bacterial solution in a 2 mL centrifuge tube, centrifuge at 3000 r / min for 10 min, discard the upper culture medium and add 1 mL of sterile PBS solution to resuspend to form Staphylococcus aureus stock solution.

[0092] 2) The stock solution was diluted in multiples, and the absorbance of the solution was measured by an ELISA reader at 540 nm. Sterile PBS solution was used as a blank control to adjust the concentration to 106 CFU / mL using culture medium according to the concentration of the stock solution.

[0093] 5. Antibacterial test

[0094] 1) The repairable high-strength medical polyurethane elastomer prepared in Example 2, the curcumin supramolecular polyurethane composite material prepared in Examples 4 to 9, and the negative control (PE film material) were placed under ultraviolet light for sterilization;

[0095] 2) Cut each sterilized sample into 1.5×1.5 cm size and place it in a 6-well plate. Drop 25 μL of bacterial solution adjusted to a concentration of 106 CFU / mL onto the center of the sample to be tested and cover the bacterial solution with PE film material.

[0096] 3) Perform three replicate controls for each group, and add sterile PBS solution to the remaining wells to prevent evaporation of the bacterial solution;

[0097] 4) Place the 6-well plate in an incubator and culture for 6 hours;

[0098] 5) After the culture is completed, use tweezers to transfer all the membrane materials to a 2 mL centrifuge tube. No liquid remains at the bottom of the wells. Add 1000 μL of sterile PBS solution and sonicate for 5 minutes to completely wash off the bacteria on the membrane material to form a bacterial stock solution.

[0099] 6) Take 80 μL of bacterial stock solution, drop it onto the agar medium, spread it evenly with a spreader, and then culture the bacteria;

[0100] 7) Place the culture medium in an incubator and culture at 37°C. After 24 hours, record the total number of colonies in the negative control and the sample to be tested.

[0101] The antibacterial effect of the repairable high-strength medical polyurethane elastomer prepared in Example 2, the curcumin supramolecular polyurethane composite material prepared in Examples 4 to 9, and the negative control on Staphylococcus aureus is shown in FIG. Figure 8 , wherein a is the antibacterial effect diagram of the negative control and Example 2, b is the antibacterial effect diagram of Examples 6 and 7, c is the antibacterial effect diagram of Examples 4 and 5, and d is the antibacterial effect diagram of Examples 8 and 9.

[0102] Curcumin, a natural polyphenol extracted from turmeric rhizomes, has multiple biological activities such as antioxidant, anti-inflammatory, antiviral, antibacterial, antifungal, and even wound healing. Figure 7 and Figure 8 It can be seen that since curcumin can provide a large number of hydrogen bond acceptors and donors, the introduction of curcumin further increases the density of hydrogen bonds between molecules, which significantly improves the mechanical properties of the polymer. The tensile properties of the 1% curcumin composite material can reach 63MPa, with an improvement rate of 50%, and the toughness can reach 255MJ / m 3 , the improvement rate is 61%.

[0103] Moreover, since the polyurethane elastic molecules prepared by the present invention have a large amount of free active -NH2 at the end groups, these amino groups can be protonated under neutral conditions. The antibacterial experiment of the present invention is carried out under neutral conditions (pH=7). Therefore, the polymer molecules in the PBS buffer will carry a large amount of -NH3 + Since the cell wall of Gram-positive bacteria (Staphylococcus aureus) is thick, dense, and rich in phosphate, it is electronegative, and -NH3 + It can interact electrostatically with the electronegative cell wall, thereby hindering the normal physiological activities of bacteria to achieve an antibacterial effect. In addition, curcumin itself is a natural antibacterial molecule, and the composite material also exhibits good antibacterial ability.

[0104] The repairable high-strength medical polyurethane elastomer prepared by the invention can also be quickly repaired at room temperature.

[0105] SPUU prepared in Example 2 of the present invention 1.8 The load-bearing diagram of normal temperature repair for 30 seconds after cutting is shown in Fig. 9 .

[0106] from Fig. 9 It can be seen that the repairable high-strength medical polyurethane elastomer prepared by the present invention can lift heavy objects after being repaired for 30 seconds at room temperature.

[0107] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A curcumin supramolecular polyurethane composite material, characterized in that: The preparation steps of the curcumin supramolecular polyurethane composite material include: (1) Take 6 mmol of polytetrahydrofuran (PTMEG) with a molecular weight of 1000 and place it in a three-necked flask. Heat it in an oil bath at 80°C and vacuum dry it for 2 h. (2) Add 15 mL of N,N-dimethylacetamide to the polytetrahydrofuran (PTMEG) dried in step (1) to dissolve it, add 10.8 mmol of isophorone diisocyanate according to the R value of 1.8, mix well, add 15 μL of dibutyltin dilaurate as a catalyst to the reaction system, condense and reflux in an oil bath at 75°C for 2 h, and obtain an isocyanate-terminated polyurethane prepolymer; (3) After the reaction in step (2) is completed, the reaction system is moved to an ice water bath and cooled to 0°C. 4,4-methylenebis(cyclohexylamine) is weighed and placed in a small glass bottle so that the molar amount of isocyanate in isophorone diisocyanate is 1.05 times the total molar amount of hydroxyl groups in polytetrahydrofuran (PTMEG) and amino groups in 4,4-methylenebis(cyclohexylamine). 20 mL of N,N-dimethylacetamide is added to dissolve the mixture. The mixture is dripped into the cooled isocyanate-terminated polyurethane prepolymer at a rate of 1 mL / min and reacted in an ice water bath for 6 h to obtain a polyurethane elastomer solution. (4) The polyurethane elastomer solution obtained in step (3) is precipitated in deionized water, and the precipitated product is placed in a vacuum oven at 80° C. and vacuum dried to constant weight to obtain a repairable high-strength medical polyurethane elastomer, denoted as SPUU 1.8 ; (5) Weigh 10 mg of curcumin in a 100 mL round-bottom flask using an electronic balance and add 50 mL of anhydrous ethanol to the flask. Stir until the curcumin dissolves. Then add 990 mg of SPUU to the flask. 1.8 After the sample is completely dissolved, the mixture is poured into a silica gel mold to remove the solvent to obtain the curcumin supramolecular polyurethane composite material.

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