A biocompatible bactericidal and anti-adhesive PET material, its preparation method and application

Abstract

The present invention relates to a biocompatible bactericidal and anti-adhesive PET material. Amino groups are introduced onto the surface of the PET material through the ammonolysis reaction of polyethyleneimine and PET, and then bornyl 4-formylbenzoate is grafted onto the surface of the PET material through Schiff base bonds, obtaining a biocompatible bactericidal and anti-adhesive PET material. The preparation method of the biocompatible bactericidal and anti-adhesive PET material in the present invention is simple, can effectively kill bacteria, resist the adhesion of fungi and has good biocompatibility.

Description

Technical Field

[0001] The present invention belongs to the field of antibacterial polymer materials, and relates to a biocompatible bactericidal and anti-adhesive PET material, a preparation method thereof and an application thereof. Background Art

[0002] Polyethylene terephthalate (PET) materials are widely used in industries such as clothing, packaging, and medical due to their excellent properties. With the development of science and technology and the improvement of people's awareness of medical health, higher hygiene and safety requirements are put forward for daily PET products, and the demand for antibacterial PET materials is continuously expanding. PET materials are very easy to become a breeding ground for microorganisms, thus causing microbial cross-infection, triggering diseases, and endangering people's health. Therefore, it is very necessary to carry out antibacterial modification on PET materials. Summary of the Invention

[0003] One of the purposes of the present invention is to provide a biocompatible bactericidal and anti-adhesive PET material, which can kill bacteria, resist the adhesion of fungi and has the characteristics of biocompatibility.

[0004] Another purpose of the present invention is to provide a preparation method of the above-mentioned biocompatible bactericidal and anti-adhesive PET material. In this preparation method, amino groups are introduced onto the PET surface through the ammonolysis reaction of polyethyleneimine and the PET material, and then bornyl 4-formylbenzoate is grafted onto the PET surface through Schiff base bonds, thereby obtaining a biocompatible bactericidal and anti-adhesive PET material.

[0005] For this reason, in the first aspect of the present invention, a biocompatible bactericidal and anti-adhesive PET material is provided, which is formed by grafting bornyl 4-formylbenzoate onto the surface of a polyethyleneimine-modified PET material through Schiff base bonds, and its structure is shown in formula (I):

[0006]

[0007] In formula (I), n is the number of repeating units of polyethyleneimine, and the value is a positive integer.

[0008] In the present invention, the bornyl 4-formylbenzoate includes one or more of L-bornyl 4-formylbenzoate, D-bornyl 4-formylbenzoate, and iso-bornyl 4-formylbenzoate.

[0009] In the present invention, the surface of the polyethyleneimine-modified PET material contains amino groups, and its structure is shown in formula (II):

[0010]

[0011] In formula (II), n is the number of repeating units of polyethyleneimine, and the value is a positive integer.

[0012] In the present invention, the biocompatible bactericidal and anti-adhesive PET material can kill bacteria and prevent the adhesion of fungi.

[0013] The second aspect of the present invention provides a method for preparing the biocompatible bactericidal and anti-adhesive PET material as described in the first aspect of the claims, which includes:

[0014] Step C: Under heating conditions, immerse the PET material in a polyethyleneimine stock solution and continuously stir and react, wash, and dry to obtain a polyethyleneimine-modified PET material;

[0015] Step D: Under heating conditions, immerse the polyethyleneimine-modified PET material in a bornyl 4-formylbenzoate stock solution and continuously stir and react, wash, and dry to obtain the biocompatible bactericidal and anti-adhesive PET material.

[0016] In some embodiments of the present invention, the polyethyleneimine stock solution is prepared by dissolving polyethyleneimine in the first solvent; preferably, the concentration of the polyethyleneimine stock solution is 5 wt% - 20 wt%.

[0017] In some embodiments of the present invention, the bornyl 4-formylbenzoate stock solution is prepared by dissolving bornyl 4-formylbenzoate in the second solvent; preferably, the concentration of the bornyl 4-formylbenzoate stock solution is 5 wt% - 20 wt%.

[0018] In the present invention, the first solvent and the second solvent are the same or different, and each independently includes one or more of dimethylformamide, dimethylacetamide, dichloromethane, tetrahydrofuran, acetone, butanone, methanol, ethanol, n-propanol, n-butanol, ethyl acetate, and dimethyl sulfoxide.

[0019] According to the present invention, the molecular weight of the polyethyleneimine is 100 - 70000; preferably, the molecular weight of the polyethyleneimine is 300 - 10000.

[0020] According to the present invention, in Step C and Step D, the reaction temperature is 5 - 100 °C, preferably 25 - 60 °C; and / or, the reaction time is 0.5 - 48 h, preferably 5 - 24 h; and / or, the immersion bath ratio is 1:(10 - 100), preferably 1:(10 - 60).

[0021] The third aspect of the present invention provides the application of the biocompatible bactericidal and anti-adhesive PET material as described in the first aspect of the present invention or the biocompatible bactericidal and anti-adhesive PET material prepared by the preparation method as described in the second aspect of the present invention in the preparation of bactericidal and anti-adhesive PET products.

[0022] In some embodiments of the present invention, the biocompatible antibacterial and anti-adhesive PET products include PET fibers and fiber products, PET films and related film products; further preferably, the PET film products include plastic bottles, packaging bags and medical catheters.

[0023] In the present invention, amino groups are introduced onto the surface of PET through the ammonolysis reaction of polyethyleneimine and PET material, and then bornyl 4-formylbenzoate is grafted onto the surface of PET through Schiff base bonds, endowing the antibacterial PET material with bactericidal properties, anti-fungal adhesion properties and low cytotoxicity, thereby obtaining a biocompatible antibacterial and anti-adhesive PET material.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: by using a simple two-step method, polyethyleneimine of the bactericidal unit is introduced into the PET material through the ammonolysis reaction, and then the bornyl derivative is introduced through efficient Schiff base bonds, overcoming the defects of the traditional method of modifying PET with poor antibacterial durability, poor anti-fungal adhesion performance and low cytotoxicity. The biocompatible antibacterial and anti-adhesive PET material obtained by the present invention can be used as an antibacterial material in fields including medicine, food and hygiene, etc., and has great development potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be further described in detail below with reference to the accompanying drawings:

[0026] Figure 1 Shows the structure of the biocompatible antibacterial and anti-adhesive PET material in the present invention.

[0027] Figure 2 Is the infrared image of the biocompatible antibacterial and anti-adhesive PET material in Example 1 of the present invention.

[0028] Figure 3 Is the schematic diagram of the preparation process of the biocompatible antibacterial and anti-adhesive PET material in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] To make the present invention easy to understand, the present invention will be described in detail below. However, before describing the present invention in detail, it should be understood that the present invention is not limited to the specific embodiments described. It should also be understood that the terms used herein are only for describing the specific embodiments and do not represent restrictive.

[0030] When a numerical range is provided, it should be understood that each intermediate value between the upper and lower limits of the range and any other specified or intermediate value in the specified range is covered by the present invention. The upper and lower limits of these smaller ranges can be independently included in the smaller ranges and are also covered by the present invention, subject to any express exclusionary limits in the specified range. When a specified range includes one or both of the limits, ranges excluding either or both of the included limits are also included in the present invention.

[0031] Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.

[0032] Ⅰ. Terms

[0033] As used herein, the term "PET" refers to polyethylene terephthalate.

[0034] As used herein, the term "PET product" refers to various products of PET, including PET fibers and fiber products, PET films and related film products; the PET films and related film products include plastic bottles, packaging bags, medical catheters, etc.

[0035] As used herein, the term "PEI" refers to poly(ethylene imine).

[0036] Accordingly, as used herein, the term "PEI-PET" refers to a PET material modified with poly(ethylene imine), and its structure is shown in formula (Ⅱ).

[0037] As used herein, the term "BF" refers to bornyl 4-formylbenzoate.

[0038] Accordingly, as used herein, the term "BF-PEI-PET" refers to a biocompatible antibacterial and anti-adhesive PET material formed by grafting bornyl 4-formylbenzoate onto the surface of a PET material modified with poly(ethylene imine) through a Schiff base bond, and its structure is shown in formula (Ⅰ).

[0039] As used herein, the terms "about", "approximately", "substantially" and "mainly", when used in combination with a range of components, concentrations, temperatures or other physical or chemical properties or characteristics, cover variations that may exist in the upper and / or lower limits of the range of the property or characteristic, including, for example, variations caused by rounding, measurement methods or other statistical variations. As used herein, with respect to numerical values related to amounts, weights, etc., "about" as defined is plus or minus 1% of each specific value. For example, the term "about 10%" should be understood as "9% to 11%".

[0040] Ⅱ. Embodiments

[0041] At present, there are several methods for preparing antibacterial PET materials: First, an antibacterial agent is physically blended with a PET material to obtain a composite antibacterial material; Second, an antibacterial agent is modified or grafted on the material surface to obtain a composite antibacterial material with antibacterial properties.

[0042] The inventors of the present invention have found through research that there are still many defects in the antibacterial PET materials prepared by the above existing methods. On the one hand, the antibacterial agent doped by the physical blending method will gradually be released over time, and the antibacterial performance will weaken; on the other hand, the antibacterial agents commonly used for surface modification often exhibit high cytotoxicity and poor anti-fungal adhesion performance. Therefore, how to maintain the bactericidal performance of antibacterial PET materials, improve the anti-fungal adhesion performance and reduce cytotoxicity is a major challenge at present. In view of this, the inventors of the present invention have conducted a large number of studies on the antibacterial technology of PET.

[0043] The inventors of the present invention have found through research that amino groups are introduced onto the PET surface through the ammonolysis reaction of polyethyleneimine and PET materials, and then bornyl 4-formylbenzoate is grafted onto the PET surface through Schiff base bonds, overcoming the defects of the traditional method of modifying PET with poor antibacterial persistence, poor anti-fungal adhesion performance and low cytotoxicity, and making a PET material that can kill bacteria, resist the adhesion of fungi and has biocompatibility. The present invention is based on the above findings.

[0044] Therefore, the biocompatible bactericidal and anti-adhesive PET material involved in the first aspect of the present invention is formed by grafting two compounds, polyethyleneimine and bornyl 4-formylbenzoate, through a two-step method.

[0045] Specifically, the biocompatible bactericidal and anti-adhesive PET material is formed by grafting bornyl 4-formylbenzoate onto the surface of a polyethyleneimine-modified PET material through Schiff base bonds. Therefore, it can also be understood as a modified PET material. The structure of the biocompatible bactericidal and anti-adhesive PET material is shown in formula (Ⅰ) (see Figure 1 ):

[0046]

[0047] In formula (Ⅰ), n is the number of repeating units of polyethyleneimine, and the value is a positive integer.

[0048] In the present invention, the bornyl 4-formylbenzoate includes one or more of L-bornyl 4-formylbenzoate, D-bornyl 4-formylbenzoate and Iso-bornyl 4-formylbenzoate.

[0049] In the present invention, the molecular weight of the polyethyleneimine is 100 - 70000; preferably, the molecular weight of the polyethyleneimine is 300 - 10000; more preferably, the molecular weight of the polyethyleneimine can be 300, 600, 1200, 1800, 2100, 5000, 10000, etc.

[0050] In the present invention, the surface of the polyethyleneimine-modified PET material contains amino groups, and its structure is shown in formula (Ⅱ):

[0051]

[0052] In formula (Ⅱ), n is the number of repeating units of polyethyleneimine, and the value is a positive integer.

[0053] In the present invention, the biocompatible bactericidal and anti-adhesive PET material can kill bacteria and prevent fungal adhesion.

[0054] The schematic diagram of the preparation process of the biocompatible bactericidal and anti-adhesive PET material according to the first aspect of the present invention involved in the second aspect of the present invention is as Figure 3 shown. It can be seen from Figure 3 that the preparation method of the biocompatible bactericidal and anti-adhesive PET material in the present invention includes the following steps:

[0055] Step A, prepare a polyethyleneimine stock solution;

[0056] Step B, prepare a bornyl 4-formylbenzoate stock solution;

[0057] Step C, under heating conditions, immerse the PET material in the polyethyleneimine stock solution and continuously stir and react, wash, and dry to obtain the polyethyleneimine-modified PET material;

[0058] Step D, under heating conditions, immerse the polyethyleneimine-modified PET material in the bornyl 4-formylbenzoate stock solution and continuously stir and react, wash, and dry to obtain the biocompatible bactericidal and anti-adhesive PET material.

[0059] It has been found that the molecular weight of PEI, the type of solvent, the concentration of the stock solution, the reaction time, and the bath ratio all affect the grafting ratio of PEI and borneol, thereby affecting the balance of the bactericidal efficiency, anti-fungal adhesion efficiency, and biocompatibility of the modified PET material; the research results show that under the following reaction conditions, the prepared biocompatible bactericidal and anti-adhesive PET material has good bactericidal and anti-adhesive properties.

[0060] (1) The molecular weight of the polyethyleneimine described is 100 - 70,000; preferably, the molecular weight of the polyethyleneimine is 300 - 10,000; more preferably, the molecular weight of the polyethyleneimine can be 300, 600, 1200, 1800, 2100, 5000, 10,000, etc.

[0061] (2) In step A, the polyethyleneimine stock solution is prepared by dissolving polyethyleneimine in the first solvent; preferably, the concentration of the polyethyleneimine stock solution is 5wt% - 20wt%.

[0062] (3) In step B, the borneol 4 - formylbenzoate stock solution is prepared by dissolving borneol 4 - formylbenzoate in the second solvent; preferably, the concentration of the borneol 4 - formylbenzoate stock solution is 5wt% - 20wt%.

[0063] (4) The first solvent and the second solvent are the same or different, and each independently includes one or several of dimethylformamide, dimethylacetamide, dichloromethane, tetrahydrofuran, acetone, butanone, methanol, ethanol, n - propanol, n - butanol, ethyl acetate, and dimethyl sulfoxide.

[0064] (5) In steps C and D, the temperature of the reaction is 5 - 100°C, preferably 25 - 60°C; and / or, the reaction time is 0.5 - 48 h, preferably 5 - 24 h.

[0065] (6) In some embodiments of the present invention, in steps C and D, the bath ratio of the immersion is 1:(10 - 100), preferably 1:(10 - 60).

[0066] In some embodiments of the present invention, in steps C and D, the drying includes air - drying and / or drying in an oven; preferably, the temperature of the drying in the oven ≤130°C, preferably 80 - 130°C.

[0067] In some embodiments of the present invention, in steps C and D, the washing includes soaking in dichloromethane solution and ethanol solution in sequence at room temperature for 0.1 - 10 h, preferably 5 - 10 h, and performing ultrasonic treatment for 5 - 30 min, preferably 20 - 30 min after each soaking.

[0068] The present invention introduces amino groups onto the PET surface through the ammonolysis reaction of polyethyleneimine and PET material, and then grafts borneol 4 - formylbenzoate onto the PET surface through Schiff base bonds. The antibacterial PET material is endowed with bactericidal performance, antifungal adhesion performance, and low cytotoxicity, and a biocompatible antibacterial and anti - adhesion PET material is obtained.

[0069] The third aspect of the present invention provides the use of the biocompatible bactericidal and anti-adhesive PET material as described in the first aspect of the present invention or the biocompatible bactericidal and anti-adhesive PET material prepared by the preparation method as described in the second aspect of the present invention in the preparation of bactericidal and anti-adhesive PET products.

[0070] The PET products described in the present invention are various products of PET. For example, they include PET fibers and fiber products, PET films and related film products; preferably, the PET films and related film products include plastic bottles, packaging bags, medical catheters, etc.

[0071] The bacteriostatic or antibacterial test and biocompatibility test methods in the present invention are as follows:

[0072] Determination of anti-fungal adhesion performance: Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm, and after sterilization by irradiating both sides under ultraviolet light for 1 h, co-culture them with fungi.

[0073] Specifically, place the material face up flat on the malt extract agar medium, 1-2 cm away from the center of the petri dish, and then add 10 μL of fungal liquid [fungal spore liquid, containing spores (1-5)×10 8 cells / mL] at the center of the petri dish, and carry out constant temperature and humidity culture at 30 °C with a relative humidity of 85% ± 5% for 30 days, and observe and record the contamination situation on the surface of the textile with a camera. The evaluation criteria for the anti-mold effect are shown in Table 1. Among them, when the coverage area of mold on the surface of the control sample is greater than 60% (i.e., the anti-mold effect reaches level 4), and no mold growth can be observed with the naked eye on the surface of the blank test sample, the test is judged to be valid, otherwise the test is invalid.

[0074] Table 1 Evaluation criteria for anti-mold effect

[0075] Mildew condition Mildew proof grade No obvious mildew under magnifying glass 0 Sparse mildew growth or local growth, with the coverage area on the sample surface less than 10% 1 The coverage area of mildew on the sample surface is less than 30% (10% - 30%) 2 The coverage area of mildew on the sample surface is less than 60% (30% - 60%) 3 The coverage area of mildew on the sample surface reaches or exceeds 60% 4

[0076] Determination of antibacterial performance: After sterilizing the blank PET material and the bactericidal and anti-adhesive PET material by irradiating both sides under ultraviolet light for 1 h, then co-culture them with bacteria.

[0077] Specifically, first prepare a bacterial concentration of (1.5-3)×10 5CFU / mL broth bacterial suspension (prepared with tryptone soya broth medium), add 50 mL of the broth bacterial suspension into Erlenmeyer flasks containing (1±0.1) g of blank PET material, (1±0.1) g of antibacterial and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which serves as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, take 100 μL and spread it on a plate, culture at 37±2 °C for 24 h, perform plate colony counting, and calculate the antibacterial rate according to formula (II) or (III):

[0078] R(%) = [(A - B) / A]×100% (II)

[0079] R(%) = [(C - B) / C]×100% (III)

[0080] In formulas (II) and (III):

[0081] R—the antibacterial rate of the sample;

[0082] A—the concentration of the bacterial suspension (CFU / mL) after the blank PET material acts on the bacterial suspension for 24 h;

[0083] B—the concentration of the bacterial suspension (CFU / mL) after the antibacterial and anti-adhesive PET material acts on the bacterial suspension for 24 h;

[0084] C—the concentration of the bacterial suspension after only inoculating bacteria for 24 h.

[0085] Test of biocompatibility: After sterilizing the blank PET material and the antibacterial and anti-adhesive PET material by irradiating both sides under an ultraviolet lamp for 1 h, then co-culture them with L929 cells.

[0086] Specifically, soak 1±0.1 g of the sterilized material in 2 mL of 1640 medium for 24 hours. After adding 10% fetal bovine serum, 100 units / mL penicillin, and 100 μg / mL streptomycin, the extract is used as a complete cell culture medium. L929 mouse fibroblast cells are cultured in the conditioned medium at 37 °C in a humid environment of 95% air and 5% carbon dioxide. After culturing for 48 hours, the cell viability is determined by colorimetry. The relative growth rate (RGR) of the cells is calculated as RGR(%) = Abs490 样品 / Abs490 对照 ×100, where Abs490 样品 and Abs490 对照 are the absorbances of the sample and the reference at 490 nm respectively.

[0087] Table 2. Relationship between the relative growth rate of cells and the cytotoxicity grade.

[0088] Relative cell growth rate Cytotoxicity grade ≥100 0 ≥80 1 ≥50 2 ≥30 3 ≥0 4

[0089] Ⅲ. Examples

[0090] The present invention will be specifically described below through specific examples. Unless otherwise specified, the experimental methods described below are all conventional laboratory methods. Unless otherwise specifically stated, the experimental materials described below can be obtained from commercial channels.

[0091] The fungal or bacterial strains used in the antifungal or antibacterial experiments include:

[0092] Aspergillus niger (ATCC 16404); Staphylococcus aureus (ATCC 25923); wherein the term "ATCC" refers to the American Type Culture Collection. All of the above strains were purchased from the China Center for Industrial Culture Collection. L929 mouse fibroblasts were purchased from the IBMS Cell Resource Center of CAMS / PUMC in Beijing, China. Each strain was separately used as an experimental strain to conduct antifungal experiments, antibacterial experiments or biocompatibility experiments on the test samples.

[0093] The malt extract (malt juice) agar medium used in the antifungal experiment, the nutrient agar medium used for bacterial counting in the antibacterial experiment, the TSB medium (tryptic soy broth) used for preparing bacterial suspensions, and the fetal bovine serum, penicillin and streptomycin used for preparing cell culture media were all purchased from Beijing Aoboxing Biotechnology Co., Ltd.

[0094] Example 1:

[0095] 1. Preparation of biocompatible bactericidal and anti-adhesive PET material:

[0096] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 10,000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0097] (2) Preparation of bornyl 4-formylbenzoate stock solution: Weigh 2 g of bornyl 4-formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of bornyl 4-formylbenzoate is 20 wt%), stir evenly, and set aside.

[0098] (3) At 60 °C, immerse the PET material in the polyethyleneimine stock solution from step (1) (bath ratio 1:60) and stir continuously for 24 h. Then soak it successively in dichloromethane and ethanol solution for 10 h. After each soaking, ultrasonicate for 30 min, and then dry it at 130 °C to obtain the polyethyleneimine-modified PET material.

[0099] (4) At 60 °C, immerse the PET material from step (3) in the borneol 4-formylbenzoate stock solution from step (2) (bath ratio 1:60) and stir continuously for 24 h. Then soak it successively in dichloromethane and ethanol solution for 10 h. After each soaking, ultrasonicate for 30 min, and then dry it at 130 °C to obtain the biocompatible antibacterial and anti-adhesive PET material.

[0100] The prepared PET material was analyzed using an attenuated total reflection infrared spectrometer (Spectrum100 spectrometer from Perkin-Elmer, USA), and the results are as Figure 2 shown. It can be seen from the figure that the biocompatible antibacterial and anti-adhesive PET material was successfully synthesized.

[0101] 2. Antibacterial performance test:

[0102] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of antibacterial and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, and take 100 μL for plate spreading. Culture at 37 ± 2 °C for 24 h and perform plate colony counting. The antibacterial rate reaches 99.99%.

[0103] 3. Determination of anti-fungal adhesion performance:

[0104] Cut the blank PET material and the antibacterial and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under ultraviolet light for 1 h, co-culture with fungi for 30 days and observe the contamination situation on the material surface. The corresponding mildew resistance grade is 0.

[0105] 4. Biocompatibility test:

[0106] After sterilizing the blank PET material and the antibacterial and anti-adhesive PET material by irradiating both sides with ultraviolet light for 1 h, 1 ± 0.1 g of the sterilized material was immersed in 2 mL of 1640 medium and co-cultured with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade was grade 1.

[0107] Example 2:

[0108] 1. Preparation of biocompatible antibacterial and anti-adhesive PET material:

[0109] (1) Preparation of polyethyleneimine stock solution: Weigh 1.5 g of polyethyleneimine with a molecular weight of 10,000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 15 wt%), stir evenly, and set aside.

[0110] (2) Preparation of bornyl 4-formylbenzoate stock solution: Weigh 1.5 g of bornyl 4-formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of bornyl 4-formylbenzoate is 15 wt%), stir evenly, and set aside.

[0111] (3) At 50 °C, immerse the PET material in the polyethyleneimine stock solution prepared in step (1) (the bath ratio is 1:60) and stir continuously for 5 h, then soak it in dichloromethane and ethanol solution for 5 h successively. After each soaking, ultrasonicate for 20 min, and then dry it at 130 °C to obtain polyethyleneimine-modified PET material.

[0112] (4) At 50 °C, immerse the PET material in step (3) into the bornyl 4-formylbenzoate stock solution prepared in step (2) (the bath ratio is 1:60) and stir continuously for 5 h, then soak it in dichloromethane and ethanol solution for 5 h successively. After each soaking, ultrasonicate for 20 min, and then dry it at 130 °C to obtain biocompatible antibacterial and anti-adhesive PET material.

[0113] 2. Antibacterial performance test:

[0114] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to each of the Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of antibacterial and anti-adhesive PET material, and no sample. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at the "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, and take 100 μL for plate coating. Culture at 37 ± 2 °C for 24 h, and perform plate colony counting. The antibacterial rate reaches 99.99%.

[0115] 3. Determination of anti-fungal adhesion performance:

[0116] Cut the blank PET material and the bactericidal and anti - sticking PET material into circular samples with a diameter of 10.0±0.1 mm. After sterilization by irradiating both sides under an ultraviolet lamp for 1 h, co - culture with fungi for 30 days and observe the contamination situation on the material surface. The corresponding mold - proof grade is 2.

[0117] 4. Test of biocompatibility:

[0118] After sterilizing the blank PET material and the bactericidal and anti - sticking PET material by irradiating both sides under an ultraviolet lamp for 1 h, soak 1±0.1 g of the sterilized material in 2 mL of 1640 medium and co - culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 2.

[0119] Example 3:

[0120] 1. Preparation of biocompatible bactericidal and anti - sticking PET material:

[0121] (1) Preparation of polyethyleneimine stock solution: Weigh 1 g of polyethyleneimine with a molecular weight of 10000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 10 wt%), stir evenly and set aside.

[0122] (2) Preparation of bornyl 4 - formylbenzoate stock solution: Weigh 1 g of bornyl 4 - formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of bornyl 4 - formylbenzoate is 10 wt%), stir evenly and set aside.

[0123] (3) At 40 °C, immerse the PET material in the polyethyleneimine stock solution prepared in step (1) (the bath ratio is 1:30), stir continuously for 5 h, then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 20 min, and dry it at 100 °C to obtain polyethyleneimine - modified PET material.

[0124] (4) At 40 °C, immerse the PET material in step (3) into the bornyl 4 - formylbenzoate stock solution in step (2) (the bath ratio is 1:30), stir continuously for 5 h, then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 20 min, and dry it at 100 °C to obtain biocompatible bactericidal and anti - sticking PET material.

[0125] 2. Antibacterial performance test:

[0126] First, prepare a bacterial concentration of (1.5 - 3)×10 5CFU / mL broth bacterial suspension (prepared with tryptone soy broth medium), add 50 mL of broth bacterial suspension to Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of bactericidal and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, take 100 μL and spread it on a plate, culture at 37 ± 2 °C for 24 h, and perform plate colony counting. The antibacterial rate reaches 99.99%.

[0127] 3. Determination of anti-fungal adhesion performance:

[0128] Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under ultraviolet light for 1 h, co-culture with fungi for 30 days to observe the contamination situation on the material surface. The corresponding mold-proof grade is 2.

[0129] 4. Test of biocompatibility:

[0130] After sterilization by irradiating both sides of the blank PET material and the bactericidal and anti-adhesive PET material under ultraviolet light for 1 h, soak 1 ± 0.1 g of the sterilized material in 2 mL of 1640 medium and co-culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 2.

[0131] Example 4:

[0132] 1. Preparation of biocompatible bactericidal and anti-adhesive PET material:

[0133] (1) Preparation of polyethyleneimine stock solution: Weigh 0.5 g of polyethyleneimine with a molecular weight of 10000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 5 wt%), stir evenly, and set aside.

[0134] (2) Preparation of borneol 4-formylbenzoate stock solution: Weigh 0.5 g of borneol 4-formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of borneol 4-formylbenzoate is 5 wt%), stir evenly, and set aside.

[0135] (3) At 60 °C, immerse the PET material in the polyethyleneimine stock solution in step (1) (bath ratio is 1:20), stir continuously for 24 h, then soak it in dichloromethane and ethanol solution for 8 h in turn. After each soaking, ultrasonicate for 25 min, and dry it at 80 °C to obtain polyethyleneimine-modified PET material.

[0136] (4) Under the condition of 60 °C, the PET material in step (3) is immersed in the borneol 4-formylbenzoate stock solution in step (2) (the bath ratio is 1:20), and stirred continuously for 24 h, then soaked in dichloromethane and ethanol solution for 8 h in turn. After each soaking, ultrasonic treatment is carried out for 25 min, and then dried at 80 °C to obtain a biocompatible antibacterial and anti-adhesive PET material.

[0137] 2. Antibacterial performance test:

[0138] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to a triangular flask containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of antibacterial and anti-adhesive PET material, and a triangular flask without a sample respectively. Take 1 mL of the inoculum from the triangular flask without a sample and make a 10-fold dilution, which is used as the number of bacteria without a sample at the "0" contact time. Fix the other triangular flasks on a shaking table, shake for 1 h, then take out and dilute, and take 100 μL for plate coating, and culture at 37 ± 2 °C for 24 h for plate colony counting. The antibacterial rate reaches 92.85%.

[0139] 3. Determination of anti-fungal adhesion performance:

[0140] Specifically, cut the blank PET material and the antibacterial and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization treatment by irradiating both sides under ultraviolet light for 1 h, co-culture with fungi for 30 days to observe the contamination situation on the material surface. The corresponding anti-mildew grade is 3.

[0141] 4. Biocompatibility test:

[0142] After sterilization treatment by irradiating both sides of the blank PET material and the antibacterial and anti-adhesive PET material under ultraviolet light for 1 h, soak 1 ± 0.1 g of the sterilized material in 2 mL of 1640 medium and co-culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 2.

[0143] Example 5:

[0144] 1. Preparation of biocompatible antibacterial and anti-adhesive PET material:

[0145] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 300 and dissolve it in 10 mL of solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0146] (2) Preparation of borneol 4-formylbenzoate stock solution: Weigh 2 g of borneol 4-formylbenzoate and dissolve it in 10 mL of solvent II (the concentration of borneol 4-formylbenzoate is 20 wt%), stir evenly, and set aside.

[0147] (3) Under the condition of 60 °C, immerse the PET material in the polyethyleneimine stock solution of step (1) (bath ratio is 1:60) and stir continuously for 24 h, then soak it in dichloromethane and ethanol solution for 10 h in sequence. After each soaking, ultrasonicate for 30 min, and then dry it at 100 °C to obtain the polyethyleneimine-modified PET material.

[0148] (4) Under the condition of 60 °C, immerse the PET material in step (3) into the bornyl 4-formylbenzoate stock solution of step (2) (bath ratio is 1:60) and stir continuously for 24 h, then soak it in dichloromethane and ethanol solution for 10 h in sequence. After each soaking, ultrasonicate for 30 min, and then dry it at 100 °C to obtain the bactericidal and anti-adhesive PET material.

[0149] 2. Antibacterial performance test:

[0150] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soya broth medium). Add 50 mL of the broth bacterial suspension to Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of bactericidal and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, and take 100 μL for spread plating on a plate, and culture at 37 ± 2 °C for 24 h for plate colony counting. The antibacterial rate reaches 45.20%.

[0151] 3. Determination of anti-fungal adhesion performance:

[0152] Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under ultraviolet light for 1 h, co-culture with fungi for 30 days to observe the contamination situation on the material surface. The corresponding mold-proof grade is 4.

[0153] 4. Biocompatibility test:

[0154] After sterilization by irradiating both sides of the blank PET material and the bactericidal and anti-adhesive PET material under ultraviolet light for 1 h, soak 1 ± 0.1 g of the sterilized material in 2 mL of 1640 medium and co-culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 2.

[0155] Example 6:

[0156] 1. Preparation of biocompatible bactericidal and anti-adhesive PET material:

[0157] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 5000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0158] (2) Preparation of bornyl 4-formylbenzoate stock solution: Weigh 2 g of bornyl 4-formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of bornyl 4-formylbenzoate is 20 wt%), stir evenly, and set aside.

[0159] (3) At 25 °C, immerse the PET material in the polyethyleneimine stock solution prepared in step (1) (bath ratio 1:60) and stir continuously for 24 h. Then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 30 min, and dry it at 100 °C to obtain polyethyleneimine-modified PET material.

[0160] (4) At 25 °C, immerse the PET material in step (3) into the bornyl 4-formylbenzoate stock solution in step (2) (bath ratio 1:60) and stir continuously for 24 h. Then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 30 min, and dry it at 100 °C to obtain biocompatible antibacterial and anti-adhesive PET material.

[0161] 2. Antibacterial performance test:

[0162] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of antibacterial and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute. Take 100 μL and spread it on a plate, and culture it at 37 ± 2 °C for 24 h, and perform plate colony counting. The antibacterial rate reaches 92.20%.

[0163] 3. Determination of anti-fungal adhesion performance:

[0164] Cut the blank PET material and the antibacterial and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under ultraviolet light for 1 h, co-culture with fungi for 30 days and observe the contamination situation on the material surface. The corresponding mold-proof grade is 2. The PET material

[0165] 4. Biocompatibility test:

[0166] After sterilizing the blank PET material and the antibacterial and anti-adhesive PET material by irradiating both sides under an ultraviolet lamp for 1 h, 1 ± 0.1 g of the sterilized material was immersed in 2 mL of 1640 medium and co-cultured with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade was 2.

[0167] Example 7:

[0168] 1. Preparation of biocompatible antibacterial and anti-adhesive PET material:

[0169] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 5000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0170] (2) Preparation of bornyl 4-formylbenzoate stock solution: Weigh 2 g of bornyl 4-formylbenzoate and dissolve it in 10 mL of Solvent II (the concentration of bornyl 4-formylbenzoate is 20 wt%), stir evenly, and set aside.

[0171] (3) At 50 °C, immerse the PET material in the polyethyleneimine stock solution prepared in step (1) (the bath ratio is 1:10), stir continuously for 12 h, then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 30 min, and then dry it at 100 °C to obtain polyethyleneimine-modified PET material.

[0172] (4) At 50 °C, immerse the PET material in step (3) into the bornyl 4-formylbenzoate stock solution prepared in step (2) (the bath ratio is 1:10), stir continuously for 12 h, then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 30 min, and then dry it at 100 °C to obtain biocompatible antibacterial and anti-adhesive PET material.

[0173] 2. Antibacterial performance test:

[0174] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to the Erlenmeyer flasks containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of antibacterial and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the Erlenmeyer flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at "0" contact time. Fix the other Erlenmeyer flasks on a shaking incubator, shake for 1 h, then take out and dilute, and take 100 μL for plate coating, and culture at 37 ± 2 °C for 24 h for plate colony counting. The antibacterial rate reached 85.20%.

[0175] 3. Determination of anti-fungal adhesion performance:

[0176] Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under an ultraviolet lamp for 1 h, co-culture with fungi for 30 days and observe the contamination situation on the material surface. The corresponding mold-proof grade is 2.

[0177] 4. Test of biocompatibility:

[0178] After sterilizing the blank PET material and the bactericidal and anti-adhesive PET material by irradiating both sides under an ultraviolet lamp for 1 h, soak 1 ± 0.1 g of the sterilized material in 2 mL of 1640 medium and co-culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 2.

[0179] Comparative Example 1:

[0180] 1. Preparation of polyethyleneimine-modified PET material:

[0181] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 5000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0182] (2) At 50 °C, immerse the PET material into the polyethyleneimine stock solution in step (1) (the bath ratio is 1:10), stir continuously for 12 h, then soak it in dichloromethane and ethanol solution for 10 h in sequence. After each soaking, ultrasonicate for 30 min, and dry it at 100 °C to obtain the polyethyleneimine-modified PET material.

[0183] 2. Antibacterial performance test:

[0184] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3)×10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to a triangular flask containing (1 ± 0.1) g of the blank PET material, (1 ± 0.1) g of the bactericidal and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the triangular flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at the "0" contact time. Fix the other triangular flasks on a shaking incubator, shake for 1 h, then take out and dilute. Take 100 μL and spread it on a plate, and culture it at 37 ± 2 °C for 24 h for plate colony counting. The antibacterial rate reaches 65.2%.

[0185] 3. Determination of anti-fungal adhesion performance:

[0186] Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under an ultraviolet lamp for 1 h, co-culture with fungi for 30 days to observe the contamination of the material surface. The corresponding mold-proof grade is 4.

[0187] 4. Test of biocompatibility:

[0188] After sterilizing the blank PET material and the bactericidal and anti-adhesive PET material by irradiating both sides under an ultraviolet lamp for 1 h, soak 1 ± 0.1 g of the sterilized material in 2 mL of 1640 medium and co-culture with L929 cells for 48 hours to determine the cytotoxicity grade. The cytotoxicity grade is 4.

[0189] Comparative Example 2:

[0190] 1. Preparation of polyethyleneimine-modified PET material:

[0191] (1) Preparation of polyethyleneimine stock solution: Weigh 2 g of polyethyleneimine with a molecular weight of 10,000 and dissolve it in 10 mL of Solvent I (the concentration of polyethyleneimine is 20 wt%), stir evenly, and set aside.

[0192] (2) At 50 °C, immerse the PET material in the polyethyleneimine stock solution prepared in step (1) (the bath ratio is 1:10), stir continuously for 12 h, then soak it in dichloromethane and ethanol solution for 10 h successively. After each soaking, ultrasonicate for 30 min, and dry it at 100 °C to obtain the polyethyleneimine-modified PET material.

[0193] 2. Antibacterial performance test:

[0194] First, prepare a broth bacterial suspension with a bacterial concentration of (1.5 - 3) × 10 5 CFU / mL (prepared with tryptone soy broth medium). Add 50 mL of the broth bacterial suspension to a triangular flask containing (1 ± 0.1) g of blank PET material, (1 ± 0.1) g of bactericidal and anti-adhesive PET material, and no sample respectively. Take 1 mL of the inoculum from the triangular flask without sample and make a 10-fold dilution, which is used as the number of bacteria without sample at "0" contact time. Fix the other triangular flasks on a shaking incubator, shake for 1 h, then take out and dilute, and take 100 μL for plate coating, and culture at 37 ± 2 °C for 24 h for plate colony counting. The antibacterial rate reaches 99.9%.

[0195] 3. Determination of anti-fungal adhesion performance:

[0196] Cut the blank PET material and the bactericidal and anti-adhesive PET material into circular samples with a diameter of 10.0 ± 0.1 mm. After sterilization by irradiating both sides under an ultraviolet lamp for 1 h, co-culture with fungi for 30 days to observe the contamination of the material surface. The corresponding mold-proof grade is 4.

[0197] 4. Biocompatibility testing:

[0198] After sterilizing the blank PET material and the anti-adhesive PET material by irradiating the front and back sides of the material under UV light for 1 hour, 1±0.1g of the sterilized material was immersed in 2mL 1640 culture medium and co-cultured with L929 cells for 48 hours to determine the cytotoxicity level. The cytotoxicity level was 4.

[0199] It should be noted that the embodiments described above are only preferred embodiments of the present invention, which are used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A preparation method of a biocompatible bactericidal and anti-adhesive PET material, characterized in that, The steps are as follows: (1) Preparation of polyethyleneimine stock solution: Weigh polyethyleneimine with a molecular weight of 10,000 and dissolve it in Solvent I, stir evenly to obtain a polyethyleneimine stock solution with a concentration of 20 wt%; (2) Preparation of bornyl 4-formylbenzoate stock solution: Weigh bornyl 4-formylbenzoate and dissolve it in Solvent II, stir evenly to obtain a bornyl 4-formylbenzoate stock solution with a concentration of 20 wt%; (3) Immerse the PET material in the polyethyleneimine stock solution in step (1) at 40 - 60 °C, with a bath ratio of 1:60, continuously stir for 5 - 24 h, and obtain the polyethyleneimine-modified PET material after drying; (4) Immerse the PET material in step (3) in the bornyl 4-formylbenzoate stock solution in step (2) at 40 - 60 °C, with a bath ratio of 1:60, continuously stir for 5 - 24 h, and obtain the biocompatible, bactericidal and anti-adhesive PET material after drying.

2. According to the preparation method described in claim 1, Solvent I and Solvent II are the same or different, and each independently includes one or more of dimethylformamide, dimethylacetamide, dichloromethane, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, n-propanol, n-butanol, ethyl acetate and dimethyl sulfoxide.

3. A biocompatible bactericidal and anti-adhesive PET material, characterized in that, Prepared by using the method described in claim 1 or 2.

4. Use of the biocompatible, bactericidal and anti-adhesive PET material described in claim 3 in the preparation of biocompatible, bactericidal and anti-adhesive PET products.

Images