Curcumin-based polyurethane material, and preparation method and application thereof

Abstract

This invention belongs to the field of polymer materials technology and discloses a curcumin-based polyurethane material, its preparation method, and its application. The raw materials for preparing the curcumin-based polyurethane material include: a curcumin chain extender and polyetheramine-modified curcumin. Both the curcumin chain extender and the polyetheramine-modified curcumin used in this invention contain the natural antibacterial and anti-inflammatory component curcumin. Using curcumin as the main component in the synthesis of the polyurethane material can significantly increase the content of antibacterial and anti-inflammatory components in the polyurethane material. The curcumin content in the polyurethane material of this invention can reach approximately 30% without affecting the transparency and mechanical properties of the material. Simultaneously, the imine bonds in the polyetheramine-modified curcumin are reversible dynamic covalent bonds. Through the penetration of water molecules, the dynamic imine bonds slowly hydrolyze, effectively controlling the slow release of curcumin.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and specifically relates to a curcumin-based polyurethane material, its preparation method, and its application. Background Technology

[0002] Thermoplastic polyurethane (TPU) is a polymer material synthesized by the reaction of diisocyanate, macromolecular polyol, and chain extender. It consists of soft and hard segments linked by covalent bonds along a linear macromolecular backbone and can be made from different original molecular components. TPU possesses excellent stability, chemical resistance, resilience, and mechanical properties, exhibiting lower compression set. It is widely used in construction, automotive, aerospace, footwear, adhesives, coatings, synthetic leather, and the medical industry. In recent years, bio-based TPUs made from renewable molecular building blocks have been used in the biomedical field due to their high tunability, responsive mechanical properties, controlled biodegradation, and low-toxicity residue formation. However, applications in the medical field, particularly in in vivo tissue engineering scaffolds, place high demands on the biocompatibility and antibacterial properties of the materials.

[0003] Currently, most antibacterial polyurethane materials are produced by blending antibacterial agents into polyurethane materials. These added antibacterial agents include nano-silver particles, nano-zinc oxide, nano-titanium oxide, quaternary ammonium salts, quaternary phosphate salts, pyridine compounds, biguanides, alcohols, phenols, aldehydes, organic acids, and halogen-containing compounds. However, antibacterial polyurethane materials prepared by physically blending antibacterial agents have the following drawbacks: the antibacterial agents themselves have a certain degree of toxicity; the physical blending method not only results in a low loading capacity for antibacterial agents but also makes it difficult to control the release of antibacterial agents, thus failing to achieve long-lasting antibacterial effects. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention provides a curcumin-based polyurethane material, its preparation method and application. The curcumin-based polyurethane material contains a high content of the natural antibacterial and anti-inflammatory component curcumin, and can effectively control the sustained release of curcumin, thus possessing long-lasting antibacterial and anti-inflammatory effects.

[0005] The first aspect of this invention provides a curcumin-based polyurethane material, wherein the raw materials for preparing the curcumin-based polyurethane material include: a curcumin chain extender and polyetheramine-modified curcumin;

[0006] The general structural formula of the curcumin chain extender is shown in formula (1) below:

[0007]

[0008] Where R is a compound with one or more hydroxyl groups at the end or in the side chain;

[0009] The general structural formula of the polyetheramine-modified curcumin is shown in formula (2) below:

[0010]

[0011] Where n1 is an integer from 1 to 50, and R0 is an H or -CH3 group.

[0012] Preferably, the general structural formula of the curcumin-based polyurethane material is shown in formula (3) below:

[0013]

[0014] Where R1 is diisocyanate, R2 is diol, m2 is an integer from 10 to 50, m3 is an integer from 10 to 50, m4 is an integer from 1 to 50, E is polyurethane repeating unit segment, and F is polyetheramine modified curcumin.

[0015] Preferably, the curcumin chain extender is selected from one or more of the following compounds:

[0016]

[0017]

[0018] Preferably, the polyetheramine-modified curcumin is selected from one or more of the following compounds:

[0019]

[0020] The second aspect of the present invention provides a method for preparing the curcumin-based polyurethane material of the present invention, comprising the following steps: dissolving the curcumin chain extender in a polar solvent, then mixing it with a diol, a diisocyanate, and an HDI trimer, and reacting to obtain a curcumin polyurethane prepolymer;

[0021] The polyetheramine-modified curcumin and curcumin polyurethane prepolymer are mixed and reacted to obtain the curcumin-based polyurethane material.

[0022] Preferably, the preparation method of the curcumin-based polyurethane material includes the following steps:

[0023] The curcumin chain extender is dissolved in a polar solvent, then a diol and a diisocyanate are added, and the mixture is stirred and reacted at 30-70°C for 1-24 hours. Then, HDI trimer is added, and the mixture is stirred and reacted at 40-60°C for 3-24 hours to obtain curcumin polyurethane prepolymer.

[0024] The polyetheramine-modified curcumin and curcumin polyurethane prepolymer were mixed and reacted to obtain the curcumin-based polyurethane material.

[0025] Preferably, the curcumin chain extender accounts for 0.5%-40% of the mass of the curcumin polyurethane prepolymer. More preferably, the curcumin chain extender accounts for 10%-20% of the mass of the curcumin polyurethane prepolymer.

[0026] Preferably, the preparation method of the curcumin chain extender includes the following steps:

[0027] Curcumin is dissolved in a polar solvent and then mixed with a compound containing one or more hydroxyl groups at the end or on the side chain and an alkaline catalyst to obtain the curcumin chain extender.

[0028] Preferably, the preparation method of the curcumin chain extender includes the following steps:

[0029] Curcumin is dissolved in a polar solvent, and then a compound with one or more hydroxyl groups at the end or side chain and an alkaline catalyst are added. The mixture is stirred at room temperature for 8-60 hours, and then the mixed solution is poured into water. The resulting precipitate is washed with water and dried to obtain the curcumin chain extender.

[0030] Preferably, the compound having one or more hydroxyl groups at the end or on the side chain includes one or more mixtures of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, vinyl glycol ether, vinyl propylene glycol ether, and dihydroxypropyl methacrylate.

[0031] Preferably, the alkaline catalyst comprises potassium hydroxide and / or sodium hydroxide.

[0032] Preferably, the polar solvent includes tetrahydrofuran and / or acetone.

[0033] Preferably, the diol comprises polytetrahydrofuran diol and / or polycaprolactone diol.

[0034] Preferably, the diisocyanate includes one or more mixtures of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI).

[0035] Preferably, the general structural formula of the curcumin polyurethane prepolymer is shown in formula (4) below:

[0036]

[0037] Where R1 is one or more diisocyanates of TDI, HDI, MDI, and IPDI, R2 is a diol, m2 is an integer from 10 to 50, m3 is an integer from 10 to 50, m4 is an integer from 1 to 50, and E is a polyurethane repeating unit segment.

[0038] Preferably, the mass ratio of the curcumin polyurethane prepolymer to the polyetheramine-modified curcumin is 1-99.5. Further, the mass ratio of the curcumin polyurethane prepolymer to the polyetheramine-modified curcumin is 1-50. Even further, the mass ratio of the curcumin polyurethane prepolymer to the polyetheramine-modified curcumin is 1-17.

[0039] Preferably, the preparation method of the polyetheramine-modified curcumin includes the following steps:

[0040] Curcumin and polyetheramine are mixed in a polar solvent and reacted to obtain the polyetheramine-modified curcumin.

[0041] Preferably, the preparation method of the polyetheramine-modified curcumin includes the following steps:

[0042] Curcumin was dissolved in a polar solvent to obtain solution A;

[0043] Polyetheramine is dissolved in a polar solvent to obtain solution B;

[0044] The solution A is slowly added dropwise to the solution B, and the mixture is stirred at room temperature for 0.2-2 hours to obtain the polyetheramine-modified curcumin.

[0045] Preferably, the molar ratio of the polyetheramine to curcumin is 1.1-2. More preferably, the molar ratio of the polyetheramine to curcumin is 1.5-2.

[0046] Preferably, the polyetheramine includes one or a mixture of polypropoxyetheramine (PPA-400), polypropoxyetheramine (PPA-1000), polypropoxyetheramine (PPA-2000), polyethoxyetheramine (PEA-400), and polyethoxyetheramine (PEA-2000).

[0047] A third aspect of this invention provides the application of the curcumin-based polyurethane material described herein in medical devices or food packaging.

[0048] Specifically, the curcumin-based polyurethane material described in this invention can be used to prepare antibacterial and anti-inflammatory functional implantable prostheses, such as hernia patches and surgical sutures; it can be used as a coating material for medical devices, such as a coating material for implantable prosthesis stents, including coating materials for bone repair stents and vascular stents; and it can be used as a coating material for food packaging, etc.

[0049] Based on the above applications, the present invention also provides a prosthesis comprising the curcumin-based polyurethane material described in the present invention.

[0050] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0051] (1) The curcumin chain extender and polyetheramine-modified curcumin used in this invention both contain natural antibacterial and anti-inflammatory components, curcumin. Using curcumin as the main component in the synthesis of polyurethane materials can significantly increase the content of antibacterial and anti-inflammatory components in polyurethane materials. The curcumin content in the polyurethane materials of this invention can reach about 30%, without affecting the transparency and mechanical properties of the materials. At the same time, the imine bond in polyetheramine-modified curcumin is a reversible dynamic covalent bond. Through the penetration of water molecules, the imine dynamic bond is slowly hydrolyzed, which can effectively control the slow release of curcumin and ensure the maximum efficacy of curcumin in the local microenvironment.

[0052] (2) The polyurethane material of the present invention is loaded with a high content of curcumin and can effectively control the release of curcumin, thereby having long-lasting antibacterial and anti-inflammatory effects. The curcumin in the polyurethane material of the present invention can be released slowly for more than half a year in the ethanol / water accelerated simulated release system. Attached Figure Description

[0053] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0054] Figure 1 This is the infrared spectrum of product 1 of the present invention;

[0055] Figure 2 This is the NMR spectrum of product 1 of the present invention;

[0056] Figure 3 This is the infrared spectrum of product 8 of the present invention;

[0057] Figure 4 This is the infrared spectrum of product 17 of the present invention;

[0058] Figure 5 This is the infrared spectrum of product 18 of the present invention;

[0059] Figure 6 This is the tensile stress spectrum of product 18 of the present invention;

[0060] Figure 7 This is a physical image of product 18 of the present invention;

[0061] Figure 8 This is a physical image of product 29 of the present invention;

[0062] Figure 9 This is the tensile stress spectrum of product 29 of the present invention;

[0063] Figure 10 This is a curve of curcumin release from product 29 of the present invention in a mixture of ethanol and PBS;

[0064] Figure 11This is a graph showing the anti-Staphylococcus aureus effect of the soaking solution obtained by soaking the product 29 of this invention in PBS solution for different times. Detailed Implementation

[0065] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0066] Unless otherwise specified, the raw materials, reagents, and apparatus used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0067] The following are explanations of some terms used in this invention:

[0068] Room temperature: refers to 25±5℃.

[0069] Antibacterial: The process of killing bacteria or inhibiting their growth, reproduction and activity using chemical or physical methods.

[0070] Anti-inflammatory: Tissues defend against stimuli from various damaging factors. The pathological process that occurs during this defense is the inflammatory response. Drugs can resist the inflammation caused by these factors, and this process is called anti-inflammatory.

[0071] The following specific examples illustrate the preparation of curcumin chain extenders:

[0072] Example 1

[0073] The preparation method of curcumin chain extender includes the following steps:

[0074] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 1.8g of 2-hydroxyethyl methacrylate was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 1. The structural formula of the product is as follows:

[0075]

[0076] The infrared spectrum of product 1 is as follows: Figure 1 As shown, Figure 1 In this context, HEMA-Cur represents a curcumin chain extender modified with 2-hydroxyethyl methacrylate, and Wavenumber indicates the absorption wavelength. The wavelength range is 3400-3600 cm⁻¹. 1 The absorption peak at 1710 is the absorption peak of the hydroxyl group in curcumin phenol and the hydroxyl group in 2-hydroxyethyl methacrylate (HEMA); the absorption peak at 1710 is the absorption peak of the ester bond in HEMA.

[0077] The NMR spectrum of product 1 is as follows: Figure 2 As shown, the peak at 9.5-9.7 ppm is the absorption peak of the hydroxyl group in curcuminol; the peak at 4.4-4.5 ppm is the absorption peak of the hydroxyl group on HEMA. The disappearance of the characteristic peak on the HEMA double bond at around 5.5-5.8 ppm proves that the synthesis reaction was relatively successful.

[0078] Example 2

[0079] The preparation method of curcumin chain extender includes the following steps:

[0080] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 1.7g of hydroxyethyl acrylate and 10mg of potassium hydroxide were added. After stirring at room temperature for 40 hours, the mixture was poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 2. The structural formula of the product is as follows:

[0081]

[0082] Example 3

[0083] The preparation method of curcumin chain extender includes the following steps:

[0084] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 2g of hydroxypropyl acrylate was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 3. The structural formula of the product is as follows:

[0085]

[0086] Example 4

[0087] The preparation method of curcumin chain extender includes the following steps:

[0088] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 2.3g of hydroxypropyl methacrylate was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 4. The structural formula of the product is as follows:

[0089]

[0090] Example 5

[0091] The preparation method of curcumin chain extender includes the following steps:

[0092] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 2g of vinyl propylene glycol ether was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 5. The structural formula of the product is as follows:

[0093]

[0094] Example 6

[0095] The preparation method of curcumin chain extender includes the following steps:

[0096] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 2g of vinyl glycol ether was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 6. The structural formula of the product is as follows:

[0097]

[0098] Example 7

[0099] The preparation method of curcumin chain extender includes the following steps:

[0100] 5g of curcumin was dissolved in 30g of tetrahydrofuran solution, then 2g of dihydroxypropyl methacrylate was added, followed by 10mg of potassium hydroxide. The mixture was stirred at room temperature for 40 hours, then poured into 500g of water to settle. The precipitate was centrifuged, washed five times with water, and vacuum dried to obtain product 7. The structural formula of the product is as follows:

[0101]

[0102] The following specific examples illustrate the preparation of polyetheramine-modified curcumin:

[0103] Example 8

[0104] The preparation method of polyetheramine modified curcumin includes the following steps:

[0105] Solution A was prepared by dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution. Solution B was prepared by adding 0.6g of poly(propylene ether amine) PPA-400 to 20g of tetrahydrofuran solution. Solution A was slowly added dropwise to solution B, and the mixture was stirred at room temperature for 30 minutes to obtain product 8 solution, with a solid content of 2.676 wt%. The structural formula of the product is as follows:

[0106]

[0107] The infrared spectrum of product 8 is as follows: Figure 3 As shown. 3400-3500cm-1 The amino absorption peak on the polyetheramine at 3500-3600 cm⁻¹ -1 The broad absorption peak is the absorption peak of the phenolic hydroxyl groups on curcumin; 1420-1470 cm⁻¹ -1 The absorption peak at that point is a characteristic absorption peak of the generated imine bond.

[0108] Example 9

[0109] The preparation method of polyetheramine modified curcumin includes the following steps:

[0110] Solution A was prepared by dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution. Solution B was prepared by adding 3g of poly(propylene ether amine) PPA-2000 to 20g of tetrahydrofuran solution. Solution A was slowly added dropwise to solution B, and the mixture was stirred at room temperature for 30 minutes to obtain product 9 solution, with a solid content of 8.046 wt%. The structural formula of the product is as follows:

[0111]

[0112] Example 10

[0113] The preparation method of polyetheramine modified curcumin includes the following steps:

[0114] Solution A was prepared by dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution. Solution B was prepared by adding 3g of poly(propylene ether amine) PPA-1000 to 20g of tetrahydrofuran solution. Solution A was slowly added dropwise to solution B, and the mixture was stirred at room temperature for 30 minutes to obtain product 10 solution with a solid content of 8.046 wt%. The structural formula of the product is as follows:

[0115]

[0116] Example 11

[0117] The preparation method of polyetheramine modified curcumin includes the following steps:

[0118] Solution A was prepared by dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution. Solution B was prepared by adding 0.6g of polyethoxyetheramine PEA-400 to 20g of tetrahydrofuran solution. Solution A was slowly added dropwise to solution B, and the mixture was stirred at room temperature for 30 minutes to obtain product 11 solution with a solid content of 2.676wt%. The structural formula of the product is as follows:

[0119]

[0120] Example 12

[0121] The preparation method of polyetheramine modified curcumin includes the following steps:

[0122] Solution A was prepared by dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution. Solution B was prepared by adding 3g of polyethoxyetheramine PEA-2000 to 20g of tetrahydrofuran solution. Solution A was slowly added dropwise to solution B, and the mixture was stirred at room temperature for 30 minutes to obtain solution 12. The solid content was 8.046wt%. The structural formula of the product is as follows:

[0123]

[0124] The solid component in Examples 8-12 above refers to polyetheramine-modified curcumin.

[0125] The following specific examples illustrate the preparation of curcumin polyurethane prepolymer:

[0126] Example 13

[0127] The preparation method of curcumin polyurethane prepolymer includes the following steps:

[0128] First, 0.5g of curcumin chain extender was added to 20mL of tetrahydrofuran solution and stirred until dissolved. Then, 5g of polytetrahydrofuran diol (Mn=1000) was added, followed by 0.6g of IPDI. After stirring and reacting at 60℃ for 6 hours, 1.2g of HDI trimer was added. Then, after stirring and reacting at 50℃ for 12 hours, a curcumin polyurethane prepolymer solution was obtained. Product 13 had a solid content of 26.74wt%. According to the feed ratio, the polymer contained 6.85wt% curcumin chain extender.

[0129] Example 14

[0130] The preparation method of curcumin polyurethane prepolymer includes the following steps:

[0131] First, 1g of curcumin chain extender was added to 20mL of acetone solution and stirred until dissolved. Then, 5g of polytetrahydrofuran diol (Mn=1000) was added, followed by 0.6g of IPDI. After stirring and reacting at 60℃ for 6 hours, 1.2g of HDI trimer was added. Then, the mixture was stirred and reacted at 50℃ for 12 hours to obtain curcumin polyurethane prepolymer solution, product 14, with a solid content of 26.74wt%. According to the feed ratio, the polymer contains 12.82wt% curcumin chain extender.

[0132] Example 15

[0133] The preparation method of curcumin polyurethane prepolymer includes the following steps:

[0134] First, 2g of curcumin chain extender was added to 40mL of tetrahydrofuran solvent and stirred until dissolved. Then, 5g of polytetrahydrofuran diol (Mn=1000) was added, followed by 1g of IPDI. After stirring and reacting at 60℃ for 6 hours, 1.5g of HDI trimer was added. Then, after stirring and reacting at 50℃ for 12 hours, a curcumin polyurethane prepolymer solution was obtained. Product 15 had a solid content of 19.19wt%. According to the feed ratio, the polymer contained 21.wt% curcumin chain extender.

[0135] Example 16

[0136] The preparation method of curcumin polyurethane prepolymer includes the following steps:

[0137] First, 1g of curcumin chain extender was added to 20mL of tetrahydrofuran solvent and stirred until dissolved. Then, 5g of polycaprolactone diol (Mn=1000) was added, followed by 0.6g of IPDI. After stirring and reacting at 60℃ for 6 hours, 1.2g of HDI trimer was added. Then, the mixture was stirred and reacted at 50℃ for 12 hours to obtain a curcumin polyurethane prepolymer solution, product 16, with a solid content of 28.06wt%. Based on the feed ratio, the polymer contained 12.82wt% curcumin chain extender.

[0138] The solid component in Examples 13-16 above refers to curcumin polyurethane prepolymer.

[0139] Curcumin polyurethane prepolymer was prepared into a thin film, and the following specific examples are provided:

[0140] Example 17

[0141] The curcumin polyurethane prepolymer solution obtained in Example 13 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 17.

[0142] The infrared spectrum of product 17 is as follows: Figure 4 As shown. 1735cm -1 The absorption peak at 1540 cm⁻¹ is the carbonyl absorption peak on polyurethane; -1 The peak at this location corresponds to the NH absorption peak of polyurethane.

[0143] Example 18

[0144] The curcumin polyurethane prepolymer solution obtained in Example 14 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 18.

[0145] The infrared spectrum of product 18 is as follows: Figure 5 As shown. 1420-1470cm -1The absorption peak at 1730 cm⁻¹ is a characteristic absorption peak of the generated imine bond; -1 The absorption peak at 1540 cm⁻¹ is the carbonyl absorption peak on polyurethane; -1 The absorption peak for polyurethane is NH at 1080 cm⁻¹. -1 The peak at this point is the absorption peak of polyether.

[0146] The tensile stress spectrum of product 18 is as follows: Figure 6 As shown in the figure, the vertical axis "Stress" represents tensile stress, and the horizontal axis "Strain" represents tensile deformation. The curcumin-based polyurethane film has an elongation at break of 245% and a tensile strength of 23 MPa.

[0147] The actual product image of product 18 is as follows: Figure 7 As shown, the content of curcumin chain extender in product 18 is 12.82%, and its transparency remains very high.

[0148] Example 19

[0149] The curcumin polyurethane prepolymer solution obtained in Example 15 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 19.

[0150] Example 20

[0151] The curcumin polyurethane prepolymer solution obtained in Example 16 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 20.

[0152] The following specific examples illustrate the preparation of curcumin-based polyurethane materials:

[0153] Example 21

[0154] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0155] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 14 was added to a mixing tank, and stirring was started. Then, 6g of the polyetheramine-modified curcumin solution prepared in Example 8 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 21. Based on the feed ratio, the total mass of curcumin accounted for 14.6% of the total polymer mass.

[0156] Example 22

[0157] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0158] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 14 was added to a mixing tank, and stirring was started. Then, 20g of the polyetheramine-modified curcumin solution prepared in Example 8 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 22. Based on the feed ratio, the total mass of curcumin accounted for 18% of the total polymer mass.

[0159] Example 23

[0160] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0161] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 14 was added to a mixing tank, and stirring was started. Then, 30g of the polyetheramine-modified curcumin solution prepared in Example 8 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 23. Based on the feed ratio, the total mass of curcumin accounted for 21.83% of the total polymer mass.

[0162] Example 24

[0163] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0164] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 14 was added to a mixing tank, and stirring was started. Then, 50g of the polyetheramine-modified curcumin solution prepared in Example 8 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 24. Based on the feed ratio, the total mass of curcumin accounted for 23.3% of the total polymer mass.

[0165] Example 25

[0166] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0167] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 15 was added to a mixing tank, and stirring was started. Then, 60g of the polyetheramine-modified curcumin solution prepared in Example 8 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 25. Based on the feed ratio, the total mass of curcumin accounted for 30.4% of the total polymer mass.

[0168] Example 26

[0169] The preparation method of curcumin-based polyurethane materials includes the following steps:

[0170] First, 10g of the curcumin polyurethane prepolymer solution prepared in Example 14 was added to a mixing tank, and stirring was started. Then, 30g of the polyetheramine-modified curcumin solution prepared in Example 11 was slowly added dropwise to the mixing tank. After the addition was complete, the mixture was stirred at room temperature for 30 minutes to obtain a curcumin-based polyurethane material solution, product 26. Based on the feed ratio, the total mass of curcumin accounted for 21.83% of the total polymer mass.

[0171] The curcumin-based polyurethane material was prepared into a thin film, and the following specific examples are provided:

[0172] Example 27

[0173] The curcumin-based polyurethane material solution obtained in Example 21 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 27.

[0174] Example 28

[0175] The curcumin-based polyurethane material solution obtained in Example 22 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 28.

[0176] Example 29

[0177] The curcumin-based polyurethane material solution obtained in Example 23 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 29.

[0178] The actual product image of product 29 is as follows: Figure 8 As shown, product 29 contains approximately 21.8% curcumin, and its transparency remains very high.

[0179] The tensile stress spectrum of product 29 is as follows: Figure 9 As shown, the curcumin-based polyurethane film has an elongation at break of 1450% and a tensile strength of 34 MPa.

[0180] The release curve of product 29 in a mixture of ethanol and PBS (mass ratio = 1 / 3) is shown in the figure below. Figure 10 As shown in the figure, curcumin release is approximately 62% after 6 months in the ethanol / PBS mixed solution.

[0181] The anti-Staphylococcus aureus effect of the soaking solutions obtained by immersing product 29 in PBS solution for different times is shown in the figure below. Figure 11 As shown in the figure, the solution after soaking product 29 for 6 hours has a significant antibacterial effect, and the antibacterial effect of the film soaking solution becomes more obvious with the extension of soaking time.

[0182] Example 30

[0183] The curcumin-based polyurethane material solution obtained in Example 24 was coated into a film, and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 30.

[0184] Example 31

[0185] The curcumin-based polyurethane material solution obtained in Example 25 was coated into a film and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 31.

[0186] Example 32

[0187] The curcumin-based polyurethane material solution obtained in Example 26 was coated into a film, and then baked at 80°C for 24 hours to obtain a curcumin-based polyurethane film, product 32.

[0188] The proportions of curcumin in products 17-20 and 27-32 are shown in Table 1 below.

[0189] Table 1. Proportion of curcumin in the product

[0190] compound Curcumin as a percentage of the total polymer mass (%) Product 17 6.85 Product 18 12.82 Product 19 21.1 Product 20 12.82 Product 27 14.6 Product 28 18 Product 29 21.83 Product 30 23.3 Product 31 30.4 Product 32 21.83

[0191] The test results of the above products 1-12 and curcumin against Staphylococcus aureus are shown in Table 2.

[0192] Table 2 Results of the product's anti-Staphylococcus aureus test

[0193]

[0194]

[0195] The test results of the soaking solutions of the above products 18 and 29 against Staphylococcus aureus are shown in Table 3.

[0196] Table 3. Results of the anti-Staphylococcus aureus test of the product soaking solution.

[0197] soaking solution Thin film quality PBS solution Soaking time Antibacterial effect (%) Product 18 0.1g 5mL 6 hours 60 Product 18 0.1g 5mL 1 day 70 Product 18 0.1g 5mL 7 days 80 Product 18 0.1g 5mL 60 days 86 Product 29 0.1g 5mL 6 hours 80 Product 29 0.1g 5mL 1 day 90 Product 29 0.1g 5mL 7 days 92 Product 29 0.1g 5mL 60 days 97

[0198] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A curcumin-based polyurethane material, characterized in that, The raw materials for preparing the curcumin-based polyurethane material include: curcumin chain extender and polyetheramine-modified curcumin; The general structural formula of the curcumin chain extender is shown in formula (1) below: （1）； Where R is a residue of a compound that has one or more hydroxyl groups at its terminal or side chain; The general structural formula of the polyetheramine-modified curcumin is shown in formula (2) below: （2）； Where n1 is an integer from 1 to 50, and R0 is an H or -CH3 group.

2. The curcumin-based polyurethane material according to claim 1, characterized in that, The curcumin chain extender is selected from one or more of the following compounds: 、 、 、 、 、 、 。 3. The curcumin-based polyurethane material according to claim 1, characterized in that, The polyetheramine-modified curcumin is selected from one or more of the following compounds: 、 、 、 、 。 4. The method for preparing the curcumin-based polyurethane material according to any one of claims 1-3, characterized in that, Includes the following steps: The curcumin chain extender was dissolved in a polar solvent and then mixed with a diol, diisocyanate, and HDI trimer to react and obtain curcumin polyurethane prepolymer. The polyetheramine-modified curcumin and curcumin polyurethane prepolymer are mixed and reacted to obtain the curcumin-based polyurethane material.

5. The preparation method according to claim 4, characterized in that, The preparation method of the curcumin chain extender includes the following steps: Curcumin is dissolved in a polar solvent and then mixed with a compound containing one or more hydroxyl groups at the end or on the side chain and an alkaline catalyst to obtain the curcumin chain extender.

6. The preparation method according to claim 4, characterized in that, The general structural formula of the curcumin polyurethane prepolymer is shown in equation (4) below: （4）； Where R1 is one or more diisocyanate residues from TDI, HDI, MDI, and IPDI, R2 is a diol residue, m2 is an integer from 10 to 50, m3 is an integer from 10 to 50, m4 is an integer from 1 to 50, and E is a polyurethane repeating unit segment.

7. The preparation method according to claim 4, characterized in that, The preparation method of the polyetheramine-modified curcumin includes the following steps: Curcumin and polyetheramine are mixed in a polar solvent and reacted to obtain the polyetheramine-modified curcumin.

8. The use of the curcumin-based polyurethane material according to any one of claims 1-3 in medical devices or food packaging.

9. A prosthesis, characterized in that, Including the curcumin-based polyurethane material as described in any one of claims 1-3.

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