A lubricating antibacterial additive and its preparation method, an antibacterial polyurethane material with lubricating function

Abstract

The present invention provides a lubricating antibacterial additive and a preparation method thereof, as well as an antibacterial polyurethane material with lubricating function, belonging to the technical field of lubricating materials. The present invention is based on a chitosan quaternary ammonium salt as its basic structure. The chitosan quaternary ammonium salt has excellent antibacterial properties, good water solubility and hygroscopicity, and good biocompatibility. Sodium lauroyl sarcosinate and sodium lauroyl glutamate are both amino acid surfactants with mild properties, low irritation, good biodegradability, and good emulsification, wetting, and foaming properties. The present invention uses the anions of sodium lauroyl sarcosinate and / or sodium lauroyl glutamate as modifying groups. The resulting lubricating antibacterial additive has the excellent antibacterial properties and biocompatibility of the chitosan quaternary ammonium salt, while also having excellent hydration capacity and the ability to convert polyurethane into a hydrophilic material. When added to a polyurethane material as a lubricating antibacterial additive, the problems of high friction coefficient and easy bacterial growth in polyurethane urinary catheters are effectively solved.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating materials, and in particular to a lubricating antibacterial additive and a preparation method thereof, and an antibacterial polyurethane material with lubricating function. Background Art

[0002] Medical catheters are widely used in interventional surgeries, nursing care, and other settings. However, these medical devices are often made of hydrophobic materials. When inserted into the human body, significant friction occurs between the device surface and tissue, damaging the urethra, causing adverse reactions and complications, and resulting in additional pain for the patient. Furthermore, this increased friction increases operational difficulty for medical personnel, hindering the smooth progress of treatment. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a lubricating antibacterial additive and its preparation method, and an antibacterial polyurethane material with lubricating function. The antibacterial lubricating additive provided by the present invention can impart good lubricating and antibacterial properties to polyurethane.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a lubricating antibacterial additive having a structure shown in Formula 1:

[0006]

[0007] The anion R in formula 1 - Having the structure shown in Formula 2-1 and / or Formula 2-2;

[0008]

[0009] In formula 1, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, and m and n are both integers.

[0010] Preferably, the method comprises the following steps:

[0011] Mixing a chitosan quaternary ammonium salt having a structure shown in Formula 3 with water to obtain a chitosan quaternary ammonium salt aqueous solution;

[0012]

[0013] In formula 3, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, m and n are both integers;

[0014] Mixing an amino acid surfactant with water to obtain an amino acid surfactant aqueous solution; the amino acid surfactant is sodium lauroyl sarcosinate and / or sodium lauroyl glutamate;

[0015] The chitosan quaternary ammonium salt aqueous solution is mixed with an amino acid surfactant aqueous solution, and an ion exchange reaction is performed to obtain a lubricating antibacterial additive having a structure shown in Formula 1.

[0016] Preferably, the mass concentration of the chitosan quaternary ammonium salt aqueous solution is 1 to 20%.

[0017] Preferably, the molecular weight of the chitosan quaternary ammonium salt is 10,000 to 500,000 g / mol;

[0018] The substitution degree of the chitosan quaternary ammonium salt is 50-99%.

[0019] Preferably, the mass concentration of the amino acid surfactant aqueous solution is 1 to 50%.

[0020] Preferably, the molar ratio of the chitosan quaternary ammonium salt functional group to the amino acid surfactant is 1:1 to 10;

[0021] The temperature of the ion exchange reaction is 0° C. to 100° C., and the time is 0.5 to 120 hours.

[0022] The present invention provides application of the above-mentioned lubricating and antibacterial additive as an antibacterial lubricating additive for polyurethane.

[0023] Preferably, it comprises polyurethane and the lubricating antibacterial additive according to claim 1 or the lubricating antibacterial additive prepared by the preparation method according to any one of claims 2 to 6.

[0024] Preferably, the mass ratio of the lubricating antibacterial additive to the polyurethane is (1-50):(99-50).

[0025] The present invention provides the use of the antibacterial polyurethane material with lubricating function in the preparation of medical urinary catheters.

[0026] The present invention provides a lubricating antibacterial additive having a structure shown in Formula 1. The present invention uses chitosan quaternary ammonium salt as its basic structure. Chitosan quaternary ammonium salt has excellent antibacterial properties, good water solubility and hygroscopicity, and good biocompatibility. Sodium lauroyl sarcosinate and sodium lauroyl glutamate are both amino acid surfactants with mild properties, low irritation, good biodegradability, and good emulsification, wetting, and foaming properties. The present invention uses the anions of sodium lauroyl sarcosinate and / or sodium lauroyl glutamate as modifying groups. The resulting lubricating antibacterial additive has both the excellent antibacterial properties and biocompatibility of chitosan quaternary ammonium salt and excellent hydration capacity, capable of converting polyurethane into a hydrophilic material. Adding the lubricating antibacterial additive to a polyurethane material as a lubricating antibacterial additive effectively solves the problems of high friction coefficient and easy bacterial growth in polyurethane urinary catheters.

[0027] The present invention provides a method for preparing the above-mentioned lubricating antibacterial additive. The present invention adopts an ion exchange method to prepare the lubricating antibacterial additive, which has simple operation, low cost, and is easy to achieve industrial batch production.

[0028] The present invention provides an antibacterial polyurethane material with lubricating properties. The invention uses the aforementioned lubricating and antibacterial additive to modify the polyurethane material commonly used in urinary catheters, imparting lubricating and antibacterial properties to the material. This significantly reduces friction between the surface of the medical device and human tissue, minimizing damage to human tissue during use, improving operator convenience and patient comfort. Furthermore, the modified material exhibits excellent antibacterial activity, killing bacteria on the catheter surface, preventing overuse of antiseptics or antibiotics, and extending the catheter's service life. DETAILED DESCRIPTION

[0029] The present invention provides a lubricating antibacterial additive having a structure shown in Formula 1:

[0030]

[0031] The anion R in formula 1 - Having the structure shown in Formula 2-1 and / or Formula 2-2; In the present invention, when the anion R - When the structures shown in Formula 2-1 and Formula 2-2 are present, the anions R - Exist in different structural units;

[0032]

[0033] In formula 1, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, and m and n are both integers.

[0034] In the present invention, m represents the number of repeating units of the ungrafted quaternary ammonium salt in the chitosan quaternary ammonium salt; m is preferably 0 to 300, more preferably 0 to 50. In the present invention, n represents the number of repeating units of the grafted quaternary ammonium salt in the complexed chitosan quaternary ammonium salt; m+n is preferably 10 to 800, more preferably 100 to 500. n / m+n is preferably 0.5 to 0.99, more preferably 0.7 to 0.99.

[0035] The present invention provides a method for preparing the above-mentioned lubricating antibacterial additive, comprising the following steps:

[0036] Mixing a chitosan quaternary ammonium salt having a structure shown in Formula 3 with water to obtain a chitosan quaternary ammonium salt aqueous solution;

[0037]

[0038] In formula 3, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, m and n are both integers;

[0039] Mixing an amino acid surfactant with water to obtain an amino acid surfactant aqueous solution; the amino acid surfactant is sodium lauroyl sarcosinate and / or sodium lauroyl glutamate;

[0040] The chitosan quaternary ammonium salt aqueous solution is mixed with an amino acid surfactant aqueous solution and subjected to an ion exchange reaction to obtain a surfactant having a structure shown in Formula 1.

[0041] Unless otherwise specified, the raw materials used in the present invention are all commercially available.

[0042] The present invention mixes a chitosan quaternary ammonium salt having a structure shown in Formula 3 with water to obtain a chitosan quaternary ammonium salt aqueous solution. In the present invention, the molecular weight of the chitosan quaternary ammonium salt is preferably 10,000 to 500,000 g / mol, more preferably 50,000 to 250,000 g / mol, and further preferably 100,000 to 150,000 g / mol. In the present invention, the degree of substitution of the chitosan quaternary ammonium salt is preferably 50 to 99%, more preferably 70 to 99%.

[0043] In the present invention, the water is preferably deionized water. In the present invention, the mixing is preferably heated mixing, and the temperature of the heated mixing is preferably 45°C. In the present invention, the mass concentration of the chitosan quaternary ammonium salt aqueous solution is preferably 1-20%, more preferably 5-10%; as a specific embodiment of the present invention, the mass concentration of the chitosan quaternary ammonium salt aqueous solution is 1%, 5%, 8%, 10%, 15% or 20%.

[0044] The present invention mixes an amino acid surfactant with water to obtain an amino acid surfactant aqueous solution. In the present invention, the water is preferably deionized water. The present invention has no particular requirements for the mixing method, and any mixing method known in the art can be used, specifically, stirring.

[0045] In the present invention, the mass concentration of the amino acid surfactant aqueous solution is preferably 1-50%, more preferably 10-40%; as a specific embodiment of the present invention, the mass concentration of the amino acid surfactant aqueous solution is 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%.

[0046] The present invention mixes the chitosan quaternary ammonium salt aqueous solution with an amino acid surfactant aqueous solution and performs an ion exchange reaction to obtain a lubricating antibacterial additive having a structure represented by Formula 1. In the present invention, the molar ratio of the chitosan quaternary ammonium salt functional group to the amino acid surfactant is preferably 1:1 to 10, more preferably 1:0.5 to 5, and even more preferably 1:1 to 3.

[0047] The present invention has no special requirements for the mixing method, and any mixing method well known in the art can be used, such as stirring. In the present invention, the temperature of the ion exchange is preferably 0°C to 100°C, more preferably 20°C to 60°C, and even more preferably room temperature; the time of the ion exchange is preferably 0.5 to 120 hours, more preferably 10 to 60 hours. As a specific embodiment of the present invention, the time of the ion exchange is 0.5 hours, 1 hour, 12 hours, 24 hours, 36 hours, 48 ​​hours, 60 hours, 72 hours, 84 hours, 96 hours, 108 hours, or 120 hours.

[0048] In the present invention, after the ion exchange, the ion exchange reaction solution is preferably washed and dried. In the present invention, the washing is preferably water washing, and the drying is preferably freeze drying.

[0049] The present invention provides application of the above-mentioned lubricating and antibacterial additive as an antibacterial lubricating additive for polyurethane.

[0050] The present invention provides an antibacterial polyurethane material with lubricating function, comprising polyurethane and the above-mentioned lubricating antibacterial additive. In the present invention, the lubricating antibacterial additive is distributed on the surface and inside of the polyurethane material.

[0051] In the present invention, the mass ratio of the lubricating antibacterial additive to the polyurethane is preferably (1-50):(99-50); as a specific embodiment of the present invention, the mass ratio of the lubricating antibacterial additive to the polyurethane is 10:90, 15:85 or 20:80.

[0052] The present invention has no special requirements on the molding method of the antibacterial polyurethane material with lubricating function, and any molding method well known in the art can be used.

[0053] The present invention provides the use of the antibacterial polyurethane material with lubricating function in the preparation of medical urinary catheters.

[0054] The following describes in detail a lubricating antibacterial additive and a preparation method thereof, and an antibacterial polyurethane material with lubricating function provided by the present invention in conjunction with the embodiments. However, these embodiments should not be construed as limiting the scope of protection of the present invention.

[0055] Example 1

[0056] (1) Add 12.0 g of chitosan quaternary ammonium salt with a molecular weight of 100,000 g / mol and a degree of substitution of 90% and 250 g of deionized water to a 500 mL round-bottom flask and heat at 45°C for 24 h until completely dissolved.

[0057] (2) 6.32 g of the sodium lauroyl sarcosinate was dissolved in 50 mL of deionized water to obtain an aqueous solution of sodium lauroyl sarcosinate.

[0058] (3) After mixing the above two aqueous solutions, an ion exchange reaction was carried out at room temperature (the molar ratio of the quaternary ammonium salt group in the chitosan quaternary ammonium salt to the sodium lauroyl sarcosinate was 1:1) for 72 hours. The obtained product was washed and dried multiple times to obtain an antibacterial lubricating additive.

[0059] (4) The antibacterial lubricating additive obtained in (3) is blended with polyurethane in a DMF solution, wherein the blending mass ratio of the antibacterial lubricating additive to the polyurethane is 10 / 90. The resulting solution is spread on a film and dried to obtain an antibacterial polyurethane material with lubricating function.

[0060] Example 2

[0061] (1) 15.0 g of chitosan quaternary ammonium salt with a molecular weight of 300,000 g / mol and a degree of substitution of 99% and 250 g of deionized water were added to a 500 mL round-bottom flask and heated at 45°C for 24 h until completely dissolved.

[0062] (2) 15.63 g of the sodium lauroyl sarcosinate was dissolved in 100 mL of deionized water to obtain a sodium lauroyl sarcosinate aqueous solution.

[0063] (3) After mixing the above two aqueous solutions, an ion exchange reaction is carried out at room temperature (the molar ratio of the quaternary ammonium salt group in the chitosan quaternary ammonium salt to the sodium lauroyl sarcosinate is 1:2) for 72 hours. The resulting product is washed and dried multiple times to obtain an antibacterial lubricating additive.

[0064] (4) The antibacterial lubricating additive obtained in (3) is blended with polyurethane in a DMF solution, wherein the blending mass ratio of the antibacterial lubricating additive to the polyurethane is 15 / 85. The resulting solution is spread on a film and dried to obtain an antibacterial polyurethane material with lubricating function.

[0065] Example 3

[0066] (1) 15.0 g of chitosan quaternary ammonium salt with a molecular weight of 400,000 g / mol and a degree of substitution of 75% and 250 g of deionized water were added to a 500 mL round-bottom flask and heated at 45°C for 24 h until completely dissolved.

[0067] (2) 5.8 g of the sodium lauroyl glutamate was dissolved in 50 mL of deionized water to obtain a sodium lauroyl glutamate aqueous solution.

[0068] (3) After mixing the above two aqueous solutions, an ion exchange reaction was carried out at room temperature (the molar ratio of the quaternary ammonium salt group in the chitosan quaternary ammonium salt to sodium lauroyl glutamate was 1:0.6) for 72 hours. The obtained product was washed and dried multiple times to obtain an antibacterial lubricating additive.

[0069] (4) The antibacterial lubricating additive obtained in (3) is blended with polyurethane in a DMF solution, with the blending mass ratio of the antibacterial lubricating additive to the polyurethane being 20 / 80. The resulting solution is spread on a film and dried to obtain an antibacterial polyurethane material with lubricating function.

[0070] Performance Testing

[0071] (1) Friction coefficient test: A CSM friction and wear tester was used to evaluate the tribological properties of the antibacterial polyurethane materials with lubricating function obtained in Examples 1 to 3. The contact mode of the friction pair of the CSM friction and wear tester is point contact. The upper sample is a PDMS ball, and the lower sample is an antibacterial polyurethane material with lubricating function, which is fixed in the test area of ​​the CSM. Physiological saline was dripped into the contact area of ​​the upper and lower samples for testing. The test frequency was 1 Hz, the test load was 5 N, the friction distance was 6 mm, and the test time was 600 s. Each sample was tested at least 3 times and the average value was taken. The test results were compared with the polyurethane material without the addition of antibacterial lubricating additives.

[0072] (2) Cytotoxicity test: The antibacterial polyurethane material with lubricating function obtained in Examples 1 to 3 was cut into 3 cm × 2 cm rectangular strips as test samples, washed and dried, and then placed in 2 mL of complete culture medium and extracted at 37°C for 24 hours to obtain an extract. The material extract was subjected to a cytotoxicity test using the CCK-8 method. L929 cells in the logarithmic growth phase were taken and counted, and the cell concentration was adjusted to 1×10 5 100 μL of the extract was inoculated into a 96-well plate and cultured overnight at 37°C in a 5% CO2 incubator to allow the cells to adhere and grow. After adding 100 μL of the extract and culturing for 24 hours, the culture medium was removed and washed three times with sterile PBS buffer. 100 μL of a 10% CCK-8 solution was added to each well. 100 μL of complete culture medium was added to the blank wells surrounding the test wells as a background control. The plates were incubated in a 5% CO2 incubator at 37°C for 2 hours. The absorbance of each well was measured at 450 nm using a microplate reader. The cytotoxicity of the cell viability test samples was calculated using formula (a).

[0073]

[0074] (3) Antibacterial performance test: Escherichia coli and Staphylococcus aureus were used as experimental strains. First, the bacteria were inoculated into MH broth medium and cultured at 37°C for 12 hours to allow the bacteria to reach the logarithmic growth phase. After centrifugation, the bacterial solution was diluted with MH broth to 5×10 5 CFU / mL is set aside. Cut the test sample into a 1.5cm×1.5cm square membrane and place it in a 6-well plate. Add 25μL of the above bacterial suspension to the center area of ​​the membrane surface and cover it with a 1cm×1cm polyethylene (PE) film. Place the test sample in a constant temperature and humidity incubator at 37°C and 90% humidity and incubate for 24 hours. Then take out the test sample together with the PE cover film and place it in a 50mL sterile centrifuge tube. Add 5mL of PBS solution and vortex for 1.5 minutes to make the bacteria adhering to the surface of the test sample fall off. Then spread the PBS solution containing bacteria on LB agar culture, culture at 37°C overnight, and count the number of colonies. The calculation formula for the antibacterial rate is shown in formula b:

[0075] Antibacterial rate (%) = (BC) / B × 100 formula b;

[0076] In formula b, B: average number of bacteria recovered from blank control samples;

[0077] C: Average number of bacteria recovered from antibacterial samples.

[0078] (4) Water contact angle test:

[0079] The antimicrobial polyurethane materials with lubricating properties obtained in Examples 1-3 were used as test samples, while a polyurethane without antimicrobial lubricating additives was used as a control. The water contact angles of the modified and unmodified polyurethane materials were measured using a contact angle meter. After drying, the samples were mounted on a clean glass slide. 6 μL of distilled water was dripped onto the surfaces of the modified and unmodified polyurethane materials. The water contact angles of each sample were measured at three different locations and the average value was calculated.

[0080] The performance test results of the antibacterial polyurethane materials with lubricating function obtained in Examples 1 to 3 are shown in Table 1.

[0081] Table 1 Performance test results of the antibacterial polyurethane materials with lubricating function obtained in Examples 1 to 3

[0082]

[0083] As can be seen from Table 1, the antibacterial lubricating additive provided by the present invention can impart good lubricating and antibacterial properties to polyurethane.

[0084] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A lubricating antibacterial additive, characterized in that: It has the structure shown in formula 1: The anion R in formula 1 - Having the structure shown in Formula 2-1 and / or Formula 2-2; In formula 1, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, and m and n are both integers.

2. The method for preparing the lubricating antibacterial additive according to claim 1, characterized in that: The following steps are involved: Mixing a chitosan quaternary ammonium salt having a structure shown in Formula 3 with water to obtain a chitosan quaternary ammonium salt aqueous solution; In formula 3, m>0, n>0, m+n=10-800, n / m+n=0.5-0.99, m and n are both integers; Mixing an amino acid surfactant with water to obtain an amino acid surfactant aqueous solution; the amino acid surfactant is sodium lauroyl sarcosinate and / or sodium lauroyl glutamate; The chitosan quaternary ammonium salt aqueous solution is mixed with an amino acid surfactant aqueous solution and subjected to an ion exchange reaction to obtain a lubricating antibacterial additive having a structure shown in Formula 1.

3. The preparation method according to claim 2, characterized in that The mass concentration of the chitosan quaternary ammonium salt aqueous solution is 1-20%.

4. The preparation method according to claim 2 or 3, characterized in that The molecular weight of the chitosan quaternary ammonium salt is 10,000 to 500,000 g / mol; The substitution degree of the chitosan quaternary ammonium salt is 50-99%.

5. The preparation method according to claim 2, characterized in that The mass concentration of the amino acid surfactant aqueous solution is 1 to 50%.

6. The preparation method according to claim 2, characterized in that The molar ratio of the chitosan quaternary ammonium salt functional group to the amino acid surfactant is 1:1 to 10; The temperature of the ion exchange reaction is 0° C. to 100° C., and the time is 0.5 to 120 hours.

7. Use of the lubricating and antibacterial additive according to claim 1 or the lubricating and antibacterial additive prepared by the preparation method according to any one of claims 2 to 6 as an antibacterial lubricating additive for polyurethane.

8. An antibacterial polyurethane material with lubricating function, characterized in that: The invention comprises polyurethane and the lubricating antibacterial additive according to claim 1 or the lubricating antibacterial additive prepared by the preparation method according to any one of claims 2 to 6.

9. The antibacterial polyurethane material with lubricating function according to claim 8, characterized in that: The mass ratio of the lubricating antibacterial additive to the polyurethane is (1-50):(99-50).

10. Use of the antibacterial polyurethane material with lubricating function according to claim 8 or 9 in the preparation of medical urinary catheters.

Images