Antibacterial waterborne polyurethane material, preparation method thereof and application of antibacterial waterborne polyurethane material in preparation of medical catheters

By introducing raw materials such as acrylate polyethylene glycol dopamine and terminal hydroxy polyvinylpyrrolidone into polyurethane materials, the problem of polyurethane materials being prone to adhere to bacteria and proteins in medical catheters is solved, and the effect of improving hydrophilicity, lubricity and anticoagulation performance is achieved, simplifying the preparation process and reducing costs.

CN120192499APending Publication Date: 2025-06-24HUAIAN KAIYUE TECH DEV
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Patent Information

Application Number
CN202510313518.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-03-17
Publication Date
2025-06-24

AI Technical Summary

Technical Problem

Polyurethane materials are prone to adhere to bacteria and proteins in human tissues in medical catheters, resulting in risk of infection. The existing surface modification methods are complex, costly and difficult to guarantee product quality.

Method used

The hydrophilic components of polyethylene glycol dopamine and terminal hydroxy polyvinylpyrrolidone are introduced into the polyurethane molecular chain through polycondensation reaction to improve the hydrophilicity and lubricity of polyurethane materials, and the anticoagulation effect of polyethylene glycol is used to improve the anticoagulation performance.

Benefits of technology

It effectively reduces the adhesion of polyurethane materials, improves its hydrophilicity, lubricity and anticoagulation properties, enhances the safety and operability of medical catheters, simplifies the preparation process and reduces costs.

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Abstract

The invention belongs to the technical field of biomedical polyurethane materials, and particularly discloses an antibacterial waterborne polyurethane material, a preparation method of the antibacterial waterborne polyurethane material and application of the antibacterial waterborne polyurethane material in preparation of medical catheters. 8 to 15% of oligomeric polyether glycol; 1-3% of oligomeric hydroxyl-terminated polybutadiene; 2-4% of acrylate polyethylene glycol dopamine; 2 to 4% of hydroxyl-terminated polyvinylpyrrolidone; 2-6% of a hydrophilic chain extender containing a tertiary amine group; 1 to 3 percent of acrylic acid-2-hydroxyethyl ester; 2-6% of a 1, 3, 4, 5-trihydroxybenzoic acid neutralizer; 0.1 to 0.5 percent of an organic bismuth catalyst; 10 to 15% of acetone; and the balance of water. According to the waterborne polyurethane material provided by the invention, acrylate polyethylene glycol dopamine and hydroxyl-terminated polyvinylpyrrolidone are adopted in the raw materials, so that the hydrophilicity and lubricity of the waterborne polyurethane material can be effectively and synergistically improved, and the adhesion of the waterborne polyurethane material is reduced; and the anticoagulation performance of polyethylene glycol can be improved by using the anticoagulation effect of polyethylene glycol.
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Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical polyurethane materials, and particularly relates to an antibacterial aqueous polyurethane material, a preparation method thereof, and an application thereof in the preparation of medical catheters. Background Art

[0002] Medical catheters are precision medical devices used to deliver gases, liquids, and solids into the body during disease treatment. As a passage connecting the inside and outside of the human body, medical catheters not only require good biocompatibility but also special mechanical properties.

[0003] Polyurethane elastomers have received extensive attention due to their good mechanical stability, biocompatibility, and elasticity. However, polyurethane itself does not have anti-fouling properties and has hydrophobic characteristics, resulting in its easy adhesion to bacteria and substances such as proteins in human tissues. When used as a medical catheter, it is prone to infection risks, severely restricting its application.

[0004] In view of the deficiencies of polyurethane materials, surface modification of polyurethane medical catheters by coating is commonly used in the prior art to improve their hydrophilicity, antibacterial properties, etc., thereby reducing the infection risk during use. For example, Chinese Patent CN101711894 discloses a surface-grafted modified polyurethane medical catheter and a preparation method thereof. A polyvinylpyrrolidone modified layer is formed on the surface of the polyurethane catheter through ultraviolet irradiation graft polymerization reaction, and then further complexed with iodine (I). The obtained modified coating is chemically bonded to the surface of the PU catheter, thereby improving the hydrophilicity and lubricity of the catheter, enhancing its biocompatibility and anticoagulant properties, and endowing the polyurethane medical catheter with anti-infection performance and bactericidal ability. Through this surface modification method, although the medical catheter can have special functions and meet the use requirements, the preparation steps are relatively cumbersome, the raw material cost is relatively high, and the product quality is difficult to guarantee, making it not easy to be popularized and applied. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an antibacterial aqueous polyurethane material. By using acrylate polyethylene glycol dopamine and hydroxyl-terminated polyvinylpyrrolidone in the raw materials for preparing the polyurethane material, it can not only effectively synergistically improve the hydrophilicity and lubricity of the aqueous polyurethane material and reduce its adhesiveness, but also utilize the anticoagulant effect of polyethylene glycol to enhance its anticoagulant performance. Moreover, the preparation method is simple, which can effectively solve the problems in the background art. This polyurethane material can be used as a raw material for preparing medical catheters, providing guarantee for the safe popularization and application of medical catheters.

[0006] The present invention is achieved through the following technical solutions: An antibacterial aqueous polyurethane material is prepared from the following raw materials in weight percentages: Diisocyanate 15 - 20%; Oligomeric polyether diol 8 - 15%; Oligomeric hydroxyl - terminated polybutadiene 1 - 3%; Acrylate polyethylene glycol dopamine 2 - 4%; Hydroxyl - terminated polyvinylpyrrolidone 2 - 4%; Hydrophilic chain extender containing tertiary amine group 2 - 6%; 2 - Hydroxyethyl acrylate 1 - 3%; 3,4,5 - Trihydroxybenzoic acid neutralizer 2 - 6%; Organic bismuth catalyst 0.1 - 0.5%; Acetone 10 - 15%; The balance is water.

[0007] A further improvement of the present invention is: The diisocyanate is one or a mixture of two or more of isophorone diisocyanate, hexamethylene diisocyanate or 4,4 - dicyclohexylmethane diisocyanate.

[0008] A further improvement of the present invention is: The oligomeric polyether diol is one or a mixture of two or more of polypropylene glycol 2000, polypropylene glycol 3000, polypropylene glycol 4000, polytetramethylene ether glycol 1000, polytetramethylene ether glycol 2000 or polytetramethylene ether glycol 2900.

[0009] A further improvement of the present invention is: The average molecular weight of the acrylate polyethylene glycol dopamine is 2000.

[0010] A further improvement of the present invention is: The hydrophilic chain extender containing tertiary amine group is one or a mixture of two or more of N - methyldiethanolamine, N - ethyldiethanolamine, N - propyldiethanolamine or N - butyldiethanolamine.

[0011] A further solution of the present invention is: A preparation method of an antibacterial aqueous polyurethane material, the operation steps are as follows: S1. Mix the diisocyanate and the oligomeric polyether diol and stir; S2. Add the oligomeric hydroxyl - terminated polybutadiene, acrylate polyethylene glycol dopamine and hydroxyl - terminated polyvinylpyrrolidone and stir; S3. Add the organic bismuth catalyst, acetone, the hydrophilic chain extender containing tertiary amine group and 2 - hydroxyethyl acrylate and stir; S4. Add 3,4,5 - trihydroxybenzoic acid for neutralization reaction; S5. Add water and stir until emulsified and dispersed. After the system becomes a translucent and homogeneous liquid, heat the system and then keep it warm, and remove acetone under low pressure to obtain the waterborne polyurethane material.

[0012] Further, in S1, the stirring temperature is 80 - 90 °C, and the stirring time is 0.5 - 1 h; And / or, in S2, the stirring time is 0.5 - 1 h; And / or, in S3, the stirring time is 1.5 - 3 h; And / or, in S4, the neutralization reaction temperature is 45 - 55 °C, and the reaction time is 20 - 30 min; And / or, in S5, the heat preservation temperature is 50 - 60 °C.

[0013] Furthermore, in S1, the stirring temperature is 85 °C, and the stirring time is 0.5 h; And / or, in S2, the stirring time is 0.5 h; And / or, in S3, the stirring time is 2 h; And / or, in S4, the neutralization reaction temperature is 50 °C, and the reaction time is 30 min; And / or, in S5, the heat preservation temperature is 55 °C.

[0014] A further scheme of the present invention is as follows: Application of the antibacterial waterborne polyurethane material in the preparation of medical catheters, which is characterized by including the following steps: (1) Add a radical initiator and a waterborne defoaming agent to the antibacterial waterborne polyurethane material, and stir evenly to obtain a mixed emulsion; (2) Immerse the medical catheter forming mold into the mixed emulsion, dip and lift it, and demold after drying to obtain a medical catheter.

[0015] Further, in step (1), the radical initiator is one or a mixture of two or more of tert-butyl peroxybenzoate, dicumyl peroxide, and tert-butyl peroxy pivalate; And / or, in step (2), the lifting speed is 100 - 2000 μm / s. Beneficial effects

[0016] Compared with the prior art, the present invention has the following obvious advantages: I. The present invention provides an antibacterial aqueous polyurethane material. Acrylate polyethylene glycol dopamine and hydroxy-terminated polyvinylpyrrolidone are innovatively used in the raw materials. By utilizing the polycondensation reaction between the hydroxyl groups on their molecules and isocyanates, hydrophilic components of polyethylene glycol and polyvinylpyrrolidone with good biocompatibility are in-situ introduced onto the polyurethane molecular chain, which can effectively synergistically improve the hydrophilicity and lubricity of the polyurethane material, reduce its adhesiveness, and further improve the operability of the medical catheter prepared therefrom during use, enhancing the comfort of patients. In addition, the anticoagulant effect of polyethylene glycol can be utilized to enhance the anticoagulant performance of the polyurethane material.

[0017] II. For the aqueous polyurethane material provided by the present invention, polybutadiene molecular chains are introduced into the polyurethane backbone to improve its low-temperature flexibility; a 3,4,5-trihydroxybenzoic acid neutralizer with antibacterial function is also introduced, which can form quaternary ammonium salts with the tertiary amine groups on the hydrophilic chain extender, effectively synergistically enhancing the antibacterial performance of the polyurethane material; acrylate is introduced into the molecular chain of the aqueous polyurethane through functionalized polyols, and further polymerization and crosslinking occur during the subsequent forming and drying process of preparing the medical catheter, enabling the medical catheter to have good water resistance.

[0018] III. The aqueous polyurethane material provided by the present invention can also be applied to the preparation of medical catheters. The dip-coating and pulling method is adopted. This preparation method not only has low investment, is convenient to operate, energy-saving and environmentally friendly, but also the diameter and wall thickness of the prepared medical catheter can be changed by adjusting the diameter of the metal rod mold and the pulling speed, etc., which is relatively simple and has broad application prospects. Detailed Embodiment

[0019] The present invention will be introduced in detail below in combination with embodiments.

[0020] In the specific embodiment of the present invention, acrylate polyethylene glycol dopamine with a molecular weight of 2000 is used. Embodiment 1

[0021] 1. The raw materials used for the aqueous polyurethane material in this embodiment are as follows (calculated by weight percentage): Isophorone diisocyanate 16%, oligomeric polyether diol 12% (including 10% polypropylene glycol 3000 and 2% polytetramethylene ether glycol 1000), oligomeric hydroxy-terminated polybutadiene 2%, acrylate polyethylene glycol dopamine 1%, hydroxy-terminated polyvinylpyrrolidone 2%, N-ethyldiethanolamine 3%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 4%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0022] 2. Preparation of the aqueous polyurethane material (emulsion) Isophorone diisocyanate, polypropylene glycol 3000, and polytetramethylene ether glycol 1000 were stirred and reacted at 85 °C for 0.5 h; Oligo-terminally hydroxy polybutadiene, acrylate polyethylene glycol dopamine, and terminally hydroxy polyvinylpyrrolidone were added, and the stirring reaction was continued for 0.5 h; An organic bismuth catalyst, acetone, N-ethyldiethanolamine, and 2-hydroxyethyl acrylate were added, and the stirring reaction was continued for 2 h; 3,4,5-Trihydroxybenzoic acid was added at 50 °C for neutralization reaction for 30 min; Finally, water was added and stirred until emulsified and dispersed. After the system became a translucent homogeneous liquid, the system was heated and maintained at 55 °C, and acetone was removed under low pressure to obtain an aqueous polyurethane emulsion.

[0023] 3. Preparation of medical catheter 1% of tert-butyl peroxybenzoate and 0.5% of aqueous defoamer (calculated by weight percentage) were added to the aqueous polyurethane emulsion and stirred evenly to obtain a mixed emulsion; The metal mold for forming the medical catheter was immersed in the mixed emulsion, impregnated, pulled up at a speed of 200 μm / s, dried at 110 °C, and demolded to obtain a medical catheter. Example 2

[0024] 1. The raw materials used for the aqueous polyurethane material in this example are as follows: (calculated by weight percentage) Hexamethylene diisocyanate 15%, oligo polyether diol 10% (including 8% polypropylene glycol 4000 and 2% polytetramethylene ether glycol 2000), oligo-terminally hydroxy polybutadiene 2%, acrylate polyethylene glycol dopamine 3%, terminally hydroxy polyvinylpyrrolidone 2%, N-methyldiethanolamine 3%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 4%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0025] 2. Preparation of aqueous polyurethane material (emulsion) Hexamethylene diisocyanate, polypropylene glycol 4000, and polytetramethylene ether glycol 2000 were stirred and reacted at 85 °C for 0.5 h; Oligo-terminally hydroxy polybutadiene, acrylate polyethylene glycol dopamine, and terminally hydroxy polyvinylpyrrolidone were added, and the stirring reaction was continued for 0.5 h; An organic bismuth catalyst, acetone, N-methyldiethanolamine, and 2-hydroxyethyl acrylate were added, and the stirring reaction was continued for 2 h; 3,4,5-Trihydroxybenzoic acid was added at 50 °C for neutralization reaction for 30 min; Finally, add water and stir until emulsified and dispersed. After the system becomes a semi-transparent and homogeneous liquid, heat the system and maintain it at 55°C, and remove acetone under low pressure to obtain an aqueous polyurethane emulsion.

[0026] 3. Preparation of medical catheter Add 1% tert-butyl peroxy pivalate and 0.5% aqueous defoamer (calculated by weight percentage) to the aqueous polyurethane emulsion, and stir evenly to obtain a mixed emulsion. Immerse the metal mold for forming the medical catheter into the mixed emulsion, impregnate it, lift it at a speed of 400 μm / s, dry it at 110°C, and then demold it to obtain a medical catheter. Example 3

[0027] 1. The raw materials of the aqueous polyurethane material used in this example are as follows: (calculated by weight percentage) 4,4'-dicyclohexylmethane diisocyanate 20%, oligomeric polyether diol 12% (including 9% polypropylene glycol 2000 and 3% polytetramethylene ether glycol 2900), oligomeric hydroxyl-terminated polybutadiene 2%, acrylate polyethylene glycol dopamine 1%, hydroxyl-terminated polyvinylpyrrolidone 4%, N-butyl diethanolamine 3%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 4%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0028] 2. Preparation of aqueous polyurethane material (emulsion) Stir and react 4,4'-dicyclohexylmethane diisocyanate, polypropylene glycol 2000 and polytetramethylene ether glycol 2900 at 85°C for 0.5 h. Add oligomeric hydroxyl-terminated polybutadiene, acrylate polyethylene glycol dopamine and hydroxyl-terminated polyvinylpyrrolidone, and continue to stir and react for 0.5 h. Add organic bismuth catalyst, acetone, N-butyl diethanolamine and 2-hydroxyethyl acrylate, and continue to stir and react for 2 h. Add 3,4,5-trihydroxybenzoic acid at 50°C for neutralization reaction for 30 min. Finally, add water and stir until emulsified and dispersed. After the system becomes a semi-transparent and homogeneous liquid, heat the system and maintain it at 55°C, and remove acetone under low pressure to obtain an aqueous polyurethane emulsion.

[0029] 3. Preparation of medical catheter Add 1% dicumyl peroxide and 0.5% aqueous defoamer (calculated by weight percentage) to the aqueous polyurethane emulsion, and stir evenly to obtain a mixed emulsion. Immerse the metal mold for forming the medical catheter into the mixed emulsion, impregnate it, lift it at a speed of 500 μm / s, dry it at 110°C, and then demold it to obtain a medical catheter. Example 4

[0030] 1. In this example, the raw materials of the waterborne polyurethane material are as follows (calculated by weight percentage): Isophorone diisocyanate 16%, oligomeric polyether diol 10% (including 8% polypropylene glycol 3000 and 2% polytetramethylene ether glycol 2000), oligomeric hydroxyl-terminated polybutadiene 2%, acrylate polyethylene glycol dopamine 1%, hydroxyl-terminated polyvinylpyrrolidone 4%, N-ethyldiethanolamine 5%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 7%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0031] 2. Preparation of the waterborne polyurethane material (emulsion) React isophorone diisocyanate, polypropylene glycol 3000 and polytetramethylene ether glycol 2000 by stirring at 85 °C for 0.5 h; Add oligomeric hydroxyl-terminated polybutadiene, acrylate polyethylene glycol dopamine and hydroxyl-terminated polyvinylpyrrolidone, and continue stirring and reacting for 0.5 h; Add organic bismuth catalyst, acetone, N-propyldiethanolamine and 2-hydroxyethyl acrylate, and continue stirring and reacting for 2 h; Add 3,4,5-trihydroxybenzoic acid at 50 °C for neutralization reaction for 30 min; Finally, add water and stir until emulsified and dispersed. After the system becomes a translucent homogeneous liquid, heat the system, keep it at 55 °C, and remove acetone under low pressure to obtain the waterborne polyurethane emulsion.

[0032] 3. Preparation of the medical catheter Add 1% tert-butyl peroxybenzoate and 0.5% water-based defoamer (calculated by weight percentage) to the waterborne polyurethane emulsion, stir evenly to obtain a mixed emulsion; Immerse the metal mold for forming the medical catheter into the mixed emulsion, impregnate, lift it at a speed of 100 μm / s, dry it at 110 °C, and then demold to obtain the medical catheter.

[0033] Comparative Example 1 1. In this comparative example, the raw materials of the waterborne polyurethane material are as follows (calculated by weight percentage): Isophorone diisocyanate 16%, oligomeric polyether diol 12% (including 10% polypropylene glycol 3000 and 2% polytetramethylene ether glycol 1000), oligomeric hydroxyl-terminated polybutadiene 2%, hydroxyl-terminated polyvinylpyrrolidone 3%, N-ethyldiethanolamine 3%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 4%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0034] 2. Preparation of aqueous polyurethane material (emulsion) Isophorone diisocyanate, polypropylene glycol 3000 and polytetramethylene ether glycol 1000 were stirred and reacted at 85 °C for 0.5 h; Oligo-terminally hydroxy polybutadiene and hydroxy-terminated polyvinylpyrrolidone were added, and stirring and reaction were continued for 0.5 h; Organic bismuth catalyst, acetone, N-ethyldiethanolamine and 2-hydroxyethyl acrylate were added, and stirring and reaction were continued for 2 h; 3,4,5-Trihydroxybenzoic acid was added at 50 °C for neutralization reaction for 30 min; Finally, water was added and stirred until emulsified and dispersed. After the system became a translucent homogeneous liquid, the system was heated and maintained at 55 °C, and acetone was removed under low pressure to obtain an aqueous polyurethane emulsion.

[0035] 3. Preparation of medical catheter 1% tert-butyl peroxybenzoate and 0.5% aqueous defoaming agent (calculated by weight percentage) were added to the aqueous polyurethane emulsion and stirred evenly to obtain a mixed emulsion; The metal mold for forming the medical catheter was immersed in the mixed emulsion, impregnated, pulled up at a speed of 200 μm / s, dried at 110 °C, and demolded to obtain a medical catheter.

[0036] Comparative Example 2 1. The raw materials used for the aqueous polyurethane material in this comparative example are as follows: (calculated by weight percentage) Isophorone diisocyanate 16%, oligo polyether diol 12% (including 10% polypropylene glycol 3000 and 2% polytetramethylene ether glycol 1000), oligo-terminally hydroxy polybutadiene 2%, acrylate polyethylene glycol dopamine 3%, N-ethyldiethanolamine 3%, 2-hydroxyethyl acrylate 3%, 3,4,5-trihydroxybenzoic acid neutralizer 4%, organic bismuth catalyst 0.2%, acetone 12%, and the balance is water.

[0037] 2. Preparation of aqueous polyurethane material (emulsion) Isophorone diisocyanate, polypropylene glycol 3000 and polytetramethylene ether glycol 1000 were stirred and reacted at 85 °C for 0.5 h; Oligo-terminally hydroxy polybutadiene and acrylate polyethylene glycol dopamine were added, and stirring and reaction were continued for 0.5 h; Organic bismuth catalyst, acetone, N-ethyldiethanolamine and 2-hydroxyethyl acrylate were added, and stirring and reaction were continued for 2 h; 3,4,5-Trihydroxybenzoic acid was added at 50 °C for neutralization reaction for 30 min; Finally, add water and stir until emulsified and dispersed. After the system becomes a translucent and homogeneous liquid, heat the system and maintain it at 55 °C, and remove acetone under low pressure to obtain an aqueous polyurethane emulsion.

[0038] 3. Preparation of medical catheter Add 1% tert-butyl perbenzoate and 0.5% aqueous defoamer (calculated by weight percentage) to the aqueous polyurethane emulsion, and stir evenly to obtain a mixed emulsion; Immerse the metal mold for forming the medical catheter into the mixed emulsion, impregnate it, lift it at a speed of 200 μm / s, dry it at 110 °C, and then demold it to obtain a medical catheter.

[0039] Carry out relevant tests on the hydrophilicity, antibacterial property, lubricity and fracture resistance of the medical catheters produced in the above Examples 1-4 and Comparative Examples 1-2 respectively, and detect their water contact angles, antibacterial rates, dynamic friction coefficients and tensile strengths. The methods used are as follows: Water contact angle test: Drop 5.0 μL of deionized water on the surface of the medical catheter, and measure it with a contact angle measuring instrument of model JC2000C2. The measurement temperature is 20 ± 1 °C, and the humidity is 50 ± 2%. Take 5 points for each sample respectively, and calculate the average value of the contact angle.

[0040] Antibacterial rate: Conduct according to the test regulations of GB / T 21866-2008.

[0041] Surface dynamic friction coefficient test: Conduct according to the test regulations of GB / T 10006-2021.

[0042] Tensile strength test: Film the aqueous polyurethane mixed emulsion prepared in the above Examples 1-4 and Comparative Examples 1-2 on the surface of a flat metal mold, dry it at 110 °C, and then demold it to obtain an aqueous polyurethane film of the same material as the medical catheter. Then, according to GB / T1040.3-2006, test the tensile strength of the aqueous polyurethane film.

[0043] The test results are shown in Table 1 below: Table 1 Performance test results of water contact angle, antibacterial rate, dynamic friction coefficient and tensile strength

[0044] Conclusion: Comparing the data of Example 1 and Example 4, it can be seen that as the content of the hydrophilic chain extender containing tertiary amine groups in the raw materials increases, the amount of 3,4,5-trihydroxybenzoic acid neutralizer required increases, and the formed cationic quaternary ammonium salts increase. The water contact angle of the obtained aqueous polyurethane material decreases, the antibacterial rate increases, and the hydrophilicity and antibacterial property are effectively improved; Comparing the data of Comparative Example 1 and Comparative Examples 1-2, it can be seen that, compared with the individual effects of acrylate polyethylene glycol dopamine and hydroxy-terminated polyvinylpyrrolidone, the dynamic friction coefficient of the waterborne polyurethane material prepared under their synergistic effect is lower, and the lubricity is effectively improved; Comparing the data of Comparative Example 1 and Example 2, it can be seen that as the amount of acrylate polyethylene glycol dopamine in the raw materials increases, the dynamic friction coefficient of the obtained waterborne polyurethane material decreases, and the lubricity is effectively improved; comparing the data of Comparative Example 1 and Example 3, it can be seen that as the amount of hydroxy-terminated polyvinylpyrrolidone in the raw materials increases, the dynamic friction coefficient of the obtained waterborne polyurethane material decreases significantly, and the lubricity is significantly improved; Comparing the data of Comparative Examples 1-4 and Comparative Examples 1-2, it can be seen that as the number of polymerizable double bond functional groups introduced (including oligomeric hydroxy-terminated polybutadiene, acrylate polyethylene glycol dopamine, and 2-hydroxyethyl acrylate) increases, the tensile strength of the obtained waterborne polyurethane material increases, and the anti-fracture ability is improved.

[0045] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. An antibacterial waterborne polyurethane material, characterized in that: It is prepared from the following raw materials in weight percentage: Diisocyanate 15-20%; Oligopolyether diol 8-15%; Oligomeric hydroxy-terminated polybutadiene 1-3%; Polyethylene glycol dopamine acrylate 2-4%; Hydroxyl-terminated polyvinyl pyrrolidone 2-4%; 2-6% hydrophilic chain extender containing tertiary amine groups; 2-Hydroxyethyl acrylate 1-3%; 3,4,5-trihydroxybenzoic acid neutralizer 2-6%; Organic bismuth catalyst 0.1-0.5%; Acetone 10-15%; The balance is water.

2. The antibacterial waterborne polyurethane material according to claim 1, characterized in that: The diisocyanate is one or a mixture of two or more of isophorone diisocyanate, hexamethylene diisocyanate or 4,4-dicyclohexylmethane diisocyanate.

3. The antibacterial waterborne polyurethane material according to claim 1, characterized in that: The oligomeric polyether diol is one of polypropylene glycol 2000, polypropylene glycol 3000, polypropylene glycol 4000, polytetramethylene ether glycol 1000, polytetramethylene ether glycol 2000 or polytetramethylene ether glycol 2900, or a mixture of two or more thereof.

4. The antibacterial waterborne polyurethane material according to claim 1, characterized in that: The average molecular weight of the acrylate polyethylene glycol dopamine is 2000.

5. The antibacterial waterborne polyurethane material according to claim 1, characterized in that: The hydrophilic chain extender containing tertiary amine groups is one of N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine or N-butyldiethanolamine, or a mixture of two or more thereof.

6. A method for preparing the antibacterial waterborne polyurethane material according to any one of claims 1 to 5, characterized in that: The steps are as follows: S1, mixing diisocyanate and oligomeric polyether diol, and stirring; S2, adding oligomeric hydroxy-terminated polybutadiene, acrylate polyethylene glycol dopamine and hydroxy-terminated polyvinyl pyrrolidone, and stirring; S3, adding an organic bismuth catalyst, acetone, a hydrophilic chain extender containing a tertiary amine group and 2-hydroxyethyl acrylate, and stirring; S4, adding 3,4,5-trihydroxybenzoic acid to carry out neutralization reaction; S5. Add water and stir until emulsified and dispersed. After the system becomes a translucent uniform liquid, heat the system and then keep it warm, remove acetone at low pressure, and obtain a water-based polyurethane material.

7. The method for preparing an antibacterial waterborne polyurethane material according to claim 6, characterized in that: In S1, the stirring temperature is 80-90°C and the stirring time is 0.5-1h; and / or, in S2, the stirring time is 0.5-1h; and / or, in S3, the stirring time is 1.5-3h; and / or, in S4, the neutralization reaction temperature is 45-55° C., and the reaction time is 20-30 min; And / or, in S5, the insulation temperature is 50-60°C.

8. The method for preparing an antibacterial waterborne polyurethane material according to claim 7, characterized in that: In S1, the stirring temperature is 85 °C and the stirring time is 0.5 h; And / or, in S2, the stirring time is 0.5h; And / or, in S3, the stirring time is 2h; and / or, in S4, the neutralization reaction temperature is 50° C. and the reaction time is 30 min; And / or, in S5, the insulation temperature is 55°C.

9. Use of the antibacterial waterborne polyurethane material according to any one of claims 1 to 5 in the preparation of medical catheters, characterized in that: The following steps are involved: (1) adding a free radical initiator and an aqueous defoamer to the antibacterial waterborne polyurethane material, stirring evenly to obtain a mixed emulsion; (2) Dipping the medical catheter forming mold into the mixed emulsion, dipping, pulling, drying and then demoulding to obtain the medical catheter.

10. The use according to claim 9, characterized in that: In step (1), the free radical initiator is one or a mixture of two or more of tert-butyl perbenzoate, diisopropylbenzene peroxide or tert-butyl perpentyl valerate; And / or, in step (2), the pulling speed is 100-2000 μm / s.

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