Polyurethane modified by polyborneol ester phosphonium solid bactericide

Abstract

The invention discloses polyurethane modified by a solid bactericide of polyborneol ester phosphonium. The preparation method comprises the following steps that octaphosphino cage type oligomeric silsesquioxane and halogenated bornyl acetate react in an anhydrous solvent at the temperature of 10-50 DEG C for 12-24 hours, the molar ratio of phosphine groups to halogenated bornyl acetate groups is 1: (1-1.5), and the powdery antibacterial agent is obtained after precipitation, collection and drying. The antibacterial agent is added into thermoplastic polyurethane through primary mixing and mixing in an internal mixer to form a uniform and transparent polyurethane material, so that the material has antibacterial performance. The multi-quaternary phosphonium cation constructed on the basis of cage type oligomeric silsesquioxane has good antibacterial performance and environmental degradability, can be used in the fields of disinfectants, plastics, textile fabrics, medical instruments and the like, is different from common liquid water-soluble mono-quaternary phosphonium salt, is solid powder, cannot be dissolved in water but can be dissolved in ethanol, and can be used for preparing the antibacterial material. This makes it difficult to migrate and washable during use.

Description

Technical Field

[0001] This invention relates to the field of environmentally friendly materials, and more particularly to a polyurethane modified with phosphonium borneol ester as a solid bactericide. Background Technology

[0002] Octaphosphine-based cage-like oligomeric silsesquioxanes (CAS: 200200-88-0) exhibit high reactivity of phosphine functional groups, enabling them to participate in various chemical modification reactions. Simultaneously, the silicon-oxygen framework imparts excellent thermal stability, allowing the material to maintain stable performance at high temperatures. Physically, octaphosphine-based cage-like oligomeric silsesquioxanes possess good solubility in various organic solvents, facilitating processing and handling. Their rigid cage-like structure significantly enhances the material's mechanical strength and hardness. In terms of applications, octaphosphine-based cage-like oligomeric silsesquioxanes demonstrate multifaceted potential. The phosphine functional groups possess flame-retardant properties and can be modified into functional quaternary phosphonium groups, offering potential applications in conductive and antibacterial fields.

[0003] Quaternary phosphonium salts possess a contact antibacterial mechanism. Their positively charged phosphonium ions interact electrostatically with the negatively charged surface of bacterial cell membranes, disrupting cell membrane integrity and causing leakage of cell contents, thus achieving a bactericidal effect. Borneol structures possess a stereochemical antibacterial mechanism. Through their unique stereochemical configuration, borneol structures can specifically recognize and embed themselves in the hydrophobic regions of bacterial cell walls, interfering with normal cell wall synthesis. Combining these two components achieves a synergistic antibacterial mechanism, significantly enhancing the antibacterial effect.

[0004] Common quaternary phosphonium and quaternary ammonium salts are mostly liquids, and due to their high polarity, they have good water solubility. This makes them prone to migration or being dissolved and carried away by water when added to antibacterial materials. Therefore, there is a need for a solidified modification scheme that reduces water solubility to help quaternary phosphonium and quaternary ammonium salts exert better and more sustained effects in materials.

[0005] The purpose of this invention is to provide a solid bactericide-modified polyurethane, such as thermoplastic polyurethane materials commonly used in medical devices, based on phosphonium borneol ester. The method involves reacting an octaphosphine cage-type oligomeric silsesquioxane with haloacetic acid bornyl ester to obtain a bactericide in solid powder form that is insoluble in water. This product can be well dispersed in thermoplastic polyurethane at low mass fractions, maintaining the transparency of the material and possessing good practical value. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a polyurethane modified with phosphonium borneol ester as a solid bactericide.

[0007] The objective of this invention is achieved through the following technical solution: a polyurethane modified with phosphonium borneol ester as a solid bactericide, comprising the following steps: (1) React octaphosphine cage-type oligomeric silsesquioxane with haloacetic acid bornyl ester in anhydrous solvent at 10-50℃ for 12-24 hours; The molar ratio of phosphine groups to haloacetic acid bornone ester groups is 1:1-1.5; (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, which gives the material antibacterial properties. The mass ratio of antibacterial agent to thermoplastic polyurethane is 1:20-200; This material contains polyquaternary phosphonium cations, exhibiting excellent antibacterial properties and environmental degradability. It can be used in disinfectants, plastics, textiles, medical devices, and other fields.

[0008] Furthermore, the anhydrous solvent is anhydrous N,N-dimethylformamide, anhydrous dimethyl sulfoxide, anhydrous N,N-dimethylacetamide, anhydrous N-methylpyrrolidone, acetone, chloroform, etc., but is not limited to these. Furthermore, the haloacetic acid bornyl ester is chloroacetic acid bornyl ester (CAS: 75556-46-6), bromoacetic acid bornyl ester (CAS: 106973-67-5), iodoacetic acid bornyl ester (CAS: 106973-66-4), etc., but is not limited to these. The beneficial effects of this invention are: the material possesses multiple quaternary phosphonium cations, exhibiting excellent antibacterial properties; the ester bonds with adjacent electron-withdrawing quaternary phosphonium groups provide environmentally degradable characteristics; and the cage-like oligomeric silsesquioxane skeleton allows the bactericide to be in solid powder form, significantly reducing water solubility. This bactericide can be used in disinfectants, plastics, textiles, medical devices, and other fields. It exhibits good dispersibility in typical thermoplastic polyurethane polymers, making it suitable for use in medical catheter materials. Attached Figure Description

[0009] Figure 1 The NMR spectrum of 1H halogenated bornyl acetate is shown.

[0010] Figure 2 The 1H NMR spectrum of the polyquaternary phosphonium cation octoborneol phosphonium solid bactericide prepared for Experimental Example 1.

[0011] Figure 3(b) and (d) are bactericidal images of benzalkonium chloride solution, a commercially available disinfectant, against Escherichia coli and Staphylococcus aureus, respectively. (a) and (c) are bactericidal images of phosphonium arsenate solid bactericide prepared in Example 1 against Escherichia coli and Staphylococcus aureus, respectively. (Escherichia coli and Staphylococcus aureus were selected as the antibacterial test subjects. Bacterial culture procedure: The bacterial strain was spread on the surface of a solid culture medium, sealed with sealing film, inverted, and placed in a 37℃ incubator for 12 h. Then, independent colonies at the tail end of the colony were selected and inoculated into Luria-Bertani (LB) liquid medium, and then placed in a 37℃ incubator for 12 h at 180 rpm. Before the antibacterial experiment, the concentrated bacterial culture was diluted with clean LB liquid medium to the required concentration (ODS = ~0.05, ODE = ~0.1 at 600 nm wavelength). 5 mL of the diluted bacterial culture was injected into the first well of a 12-well plate. Then, 0.5 mL of LB liquid medium was taken from the first well, and 4.5 mL of LB liquid medium was added to it.) Use LB liquid medium to reduce the medium concentration in the well to 1 / 10 of the previous well. Repeat this process until the bacterial culture concentration is diluted to 10 times the initial concentration. -5 Times. Take 100 μL of the above 10 -5 A diluted bacterial solution was dropped onto the sample surface. Plastic wrap was slowly applied over the droplets, and the liquid was spread evenly. The sample was then placed in a 37°C constant temperature and humidity incubator for 24 hours. 5 mL of 0.85wt% NaCl solution was used to slowly rinse the antibacterial coating and plastic wrap surfaces to remove bacteria, ensuring thorough rinsing to obtain a NaCl mixture containing bacteria. 100 μL of this mixture was dropped onto the surface of a solid culture medium, spread evenly with a spreading stick, and then incubated at 37°C for 24 hours. The colony growth on the solid culture medium was observed and photographed. At a dilution of 10... -5 At the same time, comparisons (a) and (b) show that borneol phosphonium solid disinfectant has a stronger antibacterial effect against Escherichia coli than the commercially available disinfectant benzalkonium chloride, at a dilution of 10. -5 At the same time, the comparison in (c) and (d) shows that borneol phosphonium solid disinfectant has a stronger ability to fight Staphylococcus aureus than the commercially available disinfectant benzalkonium chloride. Figure 4 It is a uniform and transparent polyurethane sheet formed by mixing antibacterial agents and thermoplastic polyurethane in an internal mixer and then compressing it. Detailed Implementation

[0012] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0013] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available. Example 1

[0014] (1) Reaction of octaphosphine cage-type oligomeric silsesquioxane with chloroacetic acid bornyl ester in anhydrous N,N-dimethylformamide at 10°C for 24 hours; The molar ratio of phosphine group to chloroacetic acid bornone ester group is 1:1, and for every 1 g of phosphine group added, 0.92 g of chloroacetic acid bornone ester group is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The antibacterial agent is mixed with thermoplastic polyurethane (BASF Elastollan SP806) at a mass ratio of 1:20. Example 2

[0015] (1) Reaction of octaphosphine cage-type oligomeric silsesquioxane with chloroacetic acid bornyl ester in anhydrous N,N-dimethylacetamide at 50°C for 12 hours; The molar ratio of phosphine group to chloroacetic acid bornyl ester group is 1:1.5, and for every 1g of phosphine group added, 1.38g of chloroacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The mass ratio of antibacterial agent to thermoplastic polyurethane (BASF Elastollan SP806) is 1:200; Example 3

[0016] (1) The octaphosphine cage-type oligomeric silsesquioxane and iodoacetic acid bornyl ester were reacted in anhydrous N,N-dimethylacetamide at 20 °C for 20 hours; The molar ratio of phosphine group to iodoacetic acid bornyl ester group is 1:1.3, and for every 1g of phosphine group added, 1.67g of iodoacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The antibacterial agent is mixed with thermoplastic polyurethane (NEU Specialty Engineered Materials UR873A) at a mass ratio of 1:40. Example 4

[0017] (1) Reaction of octaphosphine cage-type oligomeric silsesquioxane with chloroacetic acid bornyl ester in anhydrous N-methylpyrrolidone at 22°C for 18 hours; The molar ratio of phosphine group to chloroacetic acid bornyl ester group is 1:1.4, and for every 1g of phosphine group added, 1.29g of chloroacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The antibacterial agent is mixed with thermoplastic polyurethane (NEU Specialty Engineered Materials UR873A) at a mass ratio of 1:60. Example 5

[0018] (1) The octaphosphine cage-type oligomeric silsesquioxane and iodoacetic acid bornyl ester were reacted in anhydrous N,N-dimethylformamide at 28 °C for 16 hours. The molar ratio of phosphine group to iodoacetic acid bornyl ester group is 1:1.3, and for every 1g of phosphine group added, 1.67g of iodoacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The antibacterial agent is mixed with thermoplastic polyurethane (Covestro Desmopan TPU 9665DU) at a mass ratio of 1:100. Example 6

[0019] (1) Reaction of octaphosphine cage-type oligomeric silsesquioxane with bromoacetic acid bornyl ester in anhydrous dimethyl sulfoxide at 32°C for 14 hours; The molar ratio of phosphine group to bromoacetic acid bornyl ester group is 1:1.4, and for every 1 g of phosphine group added, 1.53 g of bromoacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175 ℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The mass ratio of antibacterial agent to thermoplastic polyurethane (Covestro Desmopan TPU 9665DU) is 1:130; Example 7

[0020] (1) The octaphosphine cage-type oligomeric silsesquioxane and iodoacetic acid bornyl ester were reacted in anhydrous N-methylpyrrolidone at 34°C for 14 hours; The molar ratio of phosphine group to iodoacetic acid bornyl ester group is 1:1.2, and for every 1g of phosphine group added, 1.54g of iodoacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The mass ratio of antibacterial agent to thermoplastic polyurethane (Covestro Texin RxT70A 000000) is 1:160; Example 8

[0021] (1) Reaction of octaphosphine cage-type oligomeric silsesquioxane with bromoacetic acid bornyl ester in anhydrous dimethyl sulfoxide at 15°C for 22 hours; The molar ratio of phosphine group to bromoacetic acid bornyl ester group is 1:1.2, and for every 1g of phosphine group added, 1.31g of bromoacetic acid bornyl ester is added. (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175℃ to form a uniform and transparent polyurethane material, so that the surface of the material has antibacterial properties. The mass ratio of the antibacterial agent to thermoplastic polyurethane (Covestro Texin RxT70A 000000) is 1:180. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A solid biocide-modified polyurethane of polygermanium ester characterized in that, Includes the following steps: (1) Quaternization reaction of octaphosphine cage-type oligomeric silsesquioxane (CAS: 200200-88-0) and haloacetic acid bornyl ester in anhydrous solvent at 10-50 °C for 12-24 hours; The molar ratio of phosphine groups to haloacetic acid bornone ester groups is 1:1-1.5; (2) After precipitation, collection and drying, a powdered antibacterial agent is obtained. After initial mixing with polyurethane powder, it is placed in a mixer with a temperature set at 60-175 ℃ to form a uniform and transparent polyurethane material, which gives the material antibacterial properties. The mass ratio of antibacterial agent to thermoplastic polyurethane is 1:20-200.

2. A solid biocide-modified polyurethane according to claim 1, wherein, The solvent is N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, acetone, chloroform, etc., but is not limited to these.

3. A solid biocide-modified polyurethane according to claim 1, wherein, The haloacetic acid bornyl esters are chloroacetic acid bornyl ester (CAS: 75556-46-6), bromoacetic acid bornyl ester (CAS: 106973-67-5), iodoacetic acid bornyl ester (CAS: 106973-66-4), etc., but are not limited to these.

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