Lubricating antibacterial additive, preparation method thereof and antibacterial polyurethane material with lubricating function

Abstract

The invention provides a lubricating antibacterial additive and a preparation method thereof, and an antibacterial polyurethane material with a lubricating function, and belongs to the technical field of lubricating materials. The chitosan quaternary ammonium salt is used as a basic structure, and the chitosan quaternary ammonium salt has excellent antibacterial performance, good water solubility and hygroscopicity and good biocompatibility; the sodium lauroyl sarcosinate and the sodium lauroyl glutamate are amino acid type surfactants, are mild in performance, small in irritation and good in biodegradability, and have good emulsifying, wetting and foaming performance. Anions of sodium lauroyl sarcosinate and / or sodium lauroyl glutamate are / is used as modified groups, and the obtained lubricating and antibacterial additive has excellent antibacterial performance and biocompatibility of chitosan quaternary ammonium salt, also has excellent hydration capacity and can convert polyurethane into a hydrophilic material. The lubricating antibacterial agent is added into a polyurethane material as a lubricating antibacterial additive, and meanwhile, the problems that a polyurethane catheter is high in friction coefficient and easy to breed bacteria are effectively solved.

Description

Technical Field

[0001] The 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 a lubricating function. Background Art

[0002] Medical catheters are widely used in interventional surgery, nursing and other scenarios. However, most of these medical devices are made of hydrophobic materials. When entering the human body, the surface of the device and the human tissue produce greater friction, causing damage to the human cavity tissue, causing adverse reactions and complications, and thus causing additional pain to the patient. In addition, greater friction will increase the difficulty of operation for medical staff, which is not conducive to 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 a preparation method thereof, and an antibacterial polyurethane material with lubricating function. The antibacterial lubricating additive provided by the present invention can give polyurethane good lubricating and antibacterial properties.

[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, 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 1-20%.

[0017] Preferably, the molecular weight of the chitosan quaternary ammonium salt is 10000 to 500000 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 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 application of the antibacterial polyurethane material with lubricating function in preparing a medical urinary catheter.

[0026] The present invention provides a lubricating antibacterial additive having a structure shown in Formula 1. The present invention is based on chitosan quaternary ammonium salt, which has excellent antibacterial properties, good water solubility and hygroscopicity and good biocompatibility; sodium lauroyl sarcosinate and sodium lauroyl glutamate are both amino acid surfactants, which have mild properties, low irritation and good biodegradability, and have good emulsification, wetting, foaming and other properties. The present invention uses the anion of sodium lauroyl sarcosinate and / or sodium lauroyl glutamate as a modifying group, and the obtained lubricating antibacterial additive has both the excellent antibacterial properties and biocompatibility of chitosan quaternary ammonium salt and excellent hydration ability, and can convert polyurethane into a hydrophilic material. It is added to a polyurethane material as a lubricating antibacterial additive, and the problems of high friction coefficient and easy bacterial growth of polyurethane urinary catheters are effectively solved at the same time.

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

[0028] The present invention provides an antibacterial polyurethane material with lubricating function. The present invention uses the above lubricating antibacterial additive to modify the polyurethane material commonly used in catheters, giving the material lubricating and antibacterial functions, which can greatly reduce the friction between the surface of medical devices and human tissues, reduce the damage to human tissues during use, and improve the portability of doctors' operations and the comfort of patients. At the same time, the modified material has good antibacterial activity, can kill bacteria on the surface of the catheter, avoid excessive use of bactericides or antibiotics, and extend the service life of the catheter. 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 structure is shown in Formula 2-1 or Formula 2-2, the anion R having the structure shown in Formula 2-1 or Formula 2-2 - 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 ungrafted quaternary ammonium salt in 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 grafted quaternary ammonium salt in 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, 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 10000-500000 g / mol, more preferably 50000-250000 g / mol, and further preferably 100000-150000 g / mol. In the present invention, the degree of substitution of the chitosan quaternary ammonium salt is preferably 50-99%, more preferably 70%-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 special requirements for the mixing method, and a mixing method well known in the art can be used, such as stirring and mixing.

[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 the amino acid surfactant aqueous solution, and performs an ion exchange reaction to obtain a lubricating antibacterial additive having a structure shown in Formula 1. In the present invention, the molar ratio of the chitosan quaternary ammonium salt functional group to the amino acid surfactant is preferably 1:1-10, more preferably 1:0.5-5, and further preferably 1:1-3.

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

[0048] In the present invention, after the ion exchange, the obtained ion exchange reaction liquid 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 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 application of the antibacterial polyurethane material with lubricating function in preparing a medical urinary catheter.

[0054] The lubricating antibacterial additive and its preparation method, and an antibacterial polyurethane material with lubricating function provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0055] Example 1

[0056] (1) 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 were added to a 500 mL round-bottom flask and heated 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 a sodium lauroyl sarcosinate aqueous solution.

[0058] (3) After mixing the 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 sodium lauroyl sarcosinate is 1:1) for 72 hours, and the resulting product is washed and dried multiple times to obtain an antibacterial lubricating additive.

[0059] (4) The antibacterial lubricating additive obtained in (3) is mixed with polyurethane in a DMF solution, and the mixing weight ratio of the antibacterial lubricating additive to the polyurethane is 10 / 90. The obtained 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) Dissolve 15.63 g of the sodium lauroyl sarcosinate 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 sodium lauroyl sarcosinate is 1:2) for 72 hours, and 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 mixed with polyurethane in a DMF solution, and the mixing weight ratio of the antibacterial lubricating additive to the polyurethane is 15 / 85. The obtained 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) Dissolve 5.8 g of the sodium lauroyl glutamate 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 is carried out at room temperature (the molar ratio of the quaternary ammonium salt group in the chitosan quaternary ammonium salt to sodium lauroyl glutamate is 1:0.6) for 72 hours, and the resulting product is washed and dried multiple times to obtain an antibacterial lubricating additive.

[0069] (4) The antibacterial lubricating additive obtained in (3) is mixed with polyurethane in a DMF solution, and the mixing weight ratio of the antibacterial lubricating additive to the polyurethane is 20 / 80. The obtained 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 lubrication function obtained in Examples 1 to 3. The friction pair contact mode 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 lubrication 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 for leaching at 37°C for 24 h 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 the cell count was performed to adjust the cell concentration to 1×10 5 / mL, take 100μL and inoculate it into a 96-well plate, culture it overnight at 37℃ in a 5% CO2 constant temperature incubator to allow the cells to grow attached to the wall. After adding 100μL of the extract and culturing for 24h, remove the culture medium, wash it three times with sterile PBS buffer, add 100μL of 10% CCK-8 solution to each well, add 100μL of complete culture medium to the blank wells around the test well as the background group, culture it in a constant temperature incubator at 5% CO2, 37℃ for 2h, take it out and use an enzyme reader to detect the absorbance value of each well at 450nm. The cytotoxicity of the cell viability test sample is calculated by 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 h 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 for later use. 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. Incubate the test sample in a constant temperature and humidity incubator at 37°C and 90% humidity 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 1.5min to make the bacteria adhering to the surface of the test sample fall off. Then spread the PBS solution containing bacteria on the LB agar culture, culture it overnight at 37°C, 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 antibacterial polyurethane material with lubricating function obtained in Examples 1 to 3 was used as a test sample, and the polyurethane without antibacterial lubricating additive was used as a control sample. The water contact angle of the polyurethane material surface before and after modification was measured using a contact angle meter. The sample was fixed on a clean glass slide after drying, and 6 μL of distilled water was dropped onto the surface of the polyurethane material before and after modification. The water contact angle of each sample was photographed respectively, and 3 different positions were taken for testing and the average value was taken.

[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 material with lubrication function obtained in Examples 1 to 3

[0082]

[0083] It can be seen from Table 1 that 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 principle of the present invention. These improvements and modifications should also be regarded as 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, 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 an ion exchange reaction is performed 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 10000-500000 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 1-50%.

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 1:1-10; 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 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 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.

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