Antibacterial polyurethane acrylate film material embedded with N-substituted benzisothiazolinone and N-substituted ciprofloxacin

Abstract

The invention discloses an antibacterial polyurethane acrylate film material embedded with N-substituted benzisothiazolinone and N-substituted ciprofloxacin, and belongs to the field of organic antibacterial coatings. The preparation method comprises the following steps: respectively functionalizing N-substituted alkenyl of benzisothiazolinone and ciprofloxacin, introducing double bonds into a benzisothiazolinone structural unit and a ciprofloxacin structural unit, and simultaneously grafting an N-substituted alkenyl functionalized benzisothiazolinone derivative (NBT) and a ciprofloxacin derivative (NCP) into a polyurethane acrylate main chain, so as to obtain the high-molecular polymer. A broad-spectrum antibacterial material is prepared by utilizing the excellent antibacterial property of NBT on staphylococcus aureus and the excellent antibacterial property of NCP on escherichia coli, and a corresponding antibacterial coating can be used for modifying the surface of a base material.

Description

Technical field:

[0001] The invention discloses an antibacterial polyurethane acrylate film material structure with benzisothiazolinone and ciprofloxacin structural units grafted at different proportions simultaneously and a preparation method thereof, belonging to the technical field of organic antibacterial polymer film materials. Background technology:

[0002] Bacteria and other pathogenic microorganisms multiply and grow on the surface of substrates such as office supplies, furniture, and electronic equipment, which not only causes the surface of the substrate to fall off and shortens its service life, but also makes humans susceptible to infection with bacteria and other pathogenic microorganisms when in contact with them, which is harmful to health. As a functional membrane material, the antibacterial polymer coating not only enhances the service life of the substrate, resists the growth of bacteria and other pathogenic microorganisms, but also is beneficial to human health. The grafted antibacterial agent in the antibacterial membrane material prepared by this patent involves benzisothiazolinone and ciprofloxacin antibacterial units.

[0003] Benzisothiazolinone is an organic antibacterial agent. The antibacterial mechanism of Benzisothiazolinone is that the SN bond interacts with the sulfhydryl group of the enzyme in bacteria (such as the thiol of cysteine ​​in the active site of the protein) to form an SS bond, destroying the enzyme activity, inhibiting bacterial growth, and ultimately leading to cell death. (SILVA, V.; SILVA, C.; SOARES, P, et al. Isothiazolinone Biocides: Chemistry, Biological, and Toxicity Profiles. Molecules 2020, 25(4), 991). Ciprofloxacin belongs to the quinolone antibacterial agent. Ciprofloxacin binds to the DNA gyrase subunit A of bacteria, inhibits the enzyme's cutting and linking functions, and prevents the replication of bacterial DNA, thereby showing an antibacterial effect, especially against Gram-negative bacteria. It has excellent antibacterial effect. (STRUGA M, ROSZKOWSKIP, BIELENICA A, et al. N-Acylated Ciprofloxacin Derivatives: Synthesis and In Vitro Biological Evaluation as Antibacterial and Anticancer Agents. ACS Omega, 2023, 8(21), 18663-18684.). The benzisothiazolinone structural unit has a strong antibacterial effect on Gram-positive bacteria, and the ciprofloxacin structural unit has a strong bactericidal effect on Gram-negative bacteria. Combining the advantages of the two antibacterial structural units, this patent invents a polyurethane acrylate antibacterial coating containing benzisothiazolinone derivatives and ciprofloxacin derivatives.

[0004] Literature 1 (HAO X, ZHANG X, WANG W, et al. Controlled release of 1,2-benzisothiazolin-3-one-based anion encapsulated in Mg–Al layered double hydroxides for antibacterial and antifouling applications. Progress in Organic Coatings, 2024, 189, 108208.) discloses a two-dimensional nano antibacterial material, in which 1,2-benzisothiazolin-3-one anion (BIT-COO) is inserted into two-dimensional nanoparticle Mg-Al layered double hydroxide (LDH) through an ion exchange process. - ) to achieve controlled release of benzisothiazolinone. The two-dimensional nanoparticles encapsulating the antimicrobial anion were mixed with acrylate, and LDH@BIT-COOH coating was synthesized by ultrasonic dispersion and mechanical stirring. The coating had an inactivation effect on Escherichia coli within 6 hours and on Staphylococcus aureus within 12 hours. However, the coating contained the small molecule antimicrobial agent BIT-COOH. - Risk of leakage.

[0005] Document 2 (PENG K, DAI X, MAO H, et al. Development of direct contact-killing non-leaching antimicrobial polyurethanes through click chemistry. Journal of Coatings Technology and Research, 2018, 15 (6), 1239-1250.) discloses an antibacterial coating of benzisothiazolinone grafted polyurethane. Through click chemistry reaction, azide functionalized polyurethane (PU-N3) is reacted with alkynyl functionalized benzisothiazolinone (BIT-Al) to prepare grafted benzothiazolinone antibacterial polyurethane (PU-BIT). The antibacterial polyurethane has excellent antibacterial properties against Staphylococcus aureus, but poor antibacterial effect against Escherichia coli.

[0006] Document 3 (XU Q, XU Z, JIANG X, et al. Antibacterial coatings based on polycaprolactone and polyurethane with prolonged release of ciprofloxacin. Surface and Coatings Technology, 2021, 405: 126584.) discloses a ciprofloxacin sustained-release polycaprolactone and polyurethane antibacterial coating. The coating adopts low-energy electron beam dispersion (EBD) technology, with polycaprolactone (PCL) and ciprofloxacin hydrochloride (CIP) as the bottom layer and polyurethane (PU) as the upper layer (PCL: CIP / PU = 1: 1 / 1, mass ratio), and a double-layer film is prepared on a titanium (Ti) substrate. Studies have shown that the coating has a double-layer membrane structure and gradually releases CIP through the micropores on the surface to achieve antibacterial effect. The sustained-release ciprofloxacin in this coating causes trouble for people who are prone to allergies.

[0007] Document 4 (CHANG J, CHEN Y, ZHAO S, et al. Poly (N-acryloyl ciprofloxacin-co-acrylic acid) grafted magnetite nanoparticles for microbial decontamination of collagen solution: have we conquered the problem of antimicrobial residues? Polymer Chemistry, 2015, 6, 8150-8160.) discloses a magnetically recyclable nanocomposite material. After acrylation of ciprofloxacin molecules, the ciprofloxacin molecules are covalently fixed on the surface of vinyl-functionalized Fe3O4 nanoparticles by graft copolymerization with acrylic acid to prepare the corresponding composite nanomaterial. The nanomaterial only involves the covalent grafting of ciprofloxacin structural units onto the surface of nanoparticles.

[0008] In the aforementioned publicly reported documents, there is no reference to covalently grafting ciprofloxacin structural units and benzisothiazolinone onto the main chain of polyurethane acrylate.

[0009] In the preparation of benzisothiazolinone and ciprofloxacin antibacterial structural units, Chinese patent (CN114940665A A benzisothiazolinone compound used as a bactericide and its preparation method) discloses a preparation method of benzisothiazolinone compounds. Under the action of p-toluenesulfonic acid, benzisothiazolinone is reacted with fatty aldehydes and fatty alcohols to prepare benzisothiazolinone derivatives of different chain lengths, which provides ideas for further developing new bactericides. In the technology disclosed in Chinese patent (CN113440523 A A chitosan-modified benzisothiazolinone polylactic acid nanosphere and its preparation method and application), benzisothiazolinone is modified with chitosan to prepare benzisothiazolinone polylactic acid nanospheres. The nanospheres prepared by this invention can effectively improve the transmembrane operation rate and antibacterial activity of the nanocarrier system. The technology disclosed in the Chinese patent (CN113440523A, a ciprofloxacin acrylone derivative, its preparation method and application) realizes the effective combination of the fluoroquinolone skeleton and the acrylone skeleton, constructs a new fluoroquinolone "chalcone-like" compound, increases the resistance to drug resistance, and can be applied to anti-tumor drug treatment. These patents provide ideas for the development of benzisothiazolinone and ciprofloxacin antibacterial agents.

[0010] In the technology disclosed in the Chinese patent (CN113440523 A amphiphilic arginine-block ciprofloxacin copolymer, nanoparticles and preparation method and application thereof), an amphiphilic copolymer (PAC) is constructed with arginine as the hydrophilic segment and ciprofloxacin as the hydrophobic segment, and positively charged nanoparticles (PAC@NPs) with arginine segments as the shell and ciprofloxacin segments as the core are formed by self-assembly in the solution. Nanoparticles with this structure have excellent resistance to drug resistance, providing a new idea for curbing the spread of bacterial drug resistance.

[0011] In the technology disclosed in a Chinese patent (CN 110463719 A Ciprofloxacin metal complex-polyenol complex and its preparation method and application), ciprofloxacin, a compound containing a sub-group metal element and an oxide containing a transition metal are mixed to prepare a solution, which is then mixed with a polyenol solution to prepare a ciprofloxacin metal complex-polyenol complex, which has a good sustained-release antibacterial effect.

[0012] In the technology disclosed in the previous patent of our laboratory (CN 114573762 A A polyurethane acrylate polymer containing benzisothiazolinone derivatives with antibacterial properties and preparation method), benzisothiazolinone is olefinized to synthesize N-substituted benzisothiazolinone derivatives with different olefin chain lengths, and benzisothiazolinone is embedded in polyurethane acrylate by utilizing its excellent antibacterial property against Staphylococcus aureus, and an antibacterial coating is prepared by UV curing. The antibacterial coating in this invention has excellent antibacterial effect against Staphylococcus aureus, but poor antibacterial effect against Escherichia coli, but the invention does not involve embedding ciprofloxacin derivatives into polyurethane acrylate.

[0013] In the preparation methods disclosed in the aforementioned patents, there is no reference to covalently grafting ciprofloxacin structural units and benzisothiazolinone onto the main chain of polyurethane acrylate.

[0014] Based on the previous research of our laboratory, the present invention is the first to embed benzisothiazolinone derivatives (NBT) and ciprofloxacin derivatives (NCP) into the main chain of polyurethane acrylate by chemical bond grafting. Utilizing the excellent inactivation of benzisothiazolinone against Gram-positive bacteria and the excellent inactivation of ciprofloxacin against Gram-negative bacteria, benzisothiazolinone and ciprofloxacin are N-substituted olefinized with allyl bromide and acryloyl chloride to prepare N-substituted benzisothiazolinone derivatives (NBT) and N-substituted ciprofloxacin derivatives (NCP), and the antibacterial activity of polyurethane acrylate antibacterial coatings simultaneously grafted with NBT and NCP in different proportions against Staphylococcus aureus and Escherichia coli is investigated. Summary of the invention:

[0015] The invention provides a structure of an antibacterial polyurethane acrylate coating with benzisothiazolinone and ciprofloxacin structural units grafted simultaneously and a preparation method thereof. The prepared antibacterial film material has high efficiency, low toxicity and broad-spectrum antibacterial properties and expands the use range of the antibacterial agent while avoiding the loss of small molecules.

[0016] The polyurethane acrylate antibacterial coating synthesized by the present invention is an antibacterial polyurethane acrylate film material with benzisothiazolinone and ciprofloxacin antibacterial units grafted at different proportions at the same time, wherein the benzisothiazolinone structural unit refers to N-substituted benzisothiazolinone, and the ciprofloxacin antibacterial unit refers to N-substituted ciprofloxacin, which are grafted onto the polyurethane acrylate main chain through carbon-carbon double bond free radical polymerization, and the polyurethane acrylate film material with antibacterial properties comprises the following formula (1):

[0017] R1:

[0018] The value range of m is 1-100; The corresponding structure is the main structure of the triol except H.

[0019]

[0020] Wavy lines represent unwritten chemical bonds.

[0021] R1 is a polyurethane prepolymer with a three-branch structure, and each branch end is a carbon-carbon double bond. In formula (1), each branch end forms a carbon-carbon single bond connection, and the mass percentage of R1 in formula (1) is 35%-65%.

[0022] Formula (1) is a structural formula of a polyurethane acrylate antibacterial coating, wherein at least one of the three branches in R1 is connected to N-substituted benzisothiazolinone or N-substituted ciprofloxacin by a single carbon bond. Formula (1) includes five blocks A, B, C, D, and E, and the corresponding polymerization degrees a, b, c, d, and e can be adjusted according to the required polymerization degree, and the value range is 2 to 50, preferably 25 to 45.

[0023] Block A: Block B: Block C: Block D: Block E: The preparation method comprises the following steps:

[0024] (1) preparing a polymer corresponding to R1;

[0025] (2) preparing a benzisothiazolinone derivative having a structure shown in monomer D corresponding to block D;

[0026] (3) preparing a ciprofloxacin derivative having a structure shown in monomer E corresponding to block E;

[0027] (4) adding a photoinitiator to the R1 polymer, the monomer D, the monomer E, the reactive diluent monomer A corresponding to the block A, the reactive diluent monomer B corresponding to the block B, and the reactive diluent monomer C corresponding to the block C, and mixing to obtain a polyurethane acrylate prepolymer;

[0028] Monomer A

[0029] Monomer B Monomer C Monomer D Monomer E

[0030] (5) The polyurethane acrylate prepolymer prepared in step (4) is cured by ultraviolet light to form a coating having antibacterial properties corresponding to formula (1).

[0031] Further preferably, the mass ratio of the polyurethane polymer R1, the active diluent monomer (A+B+C), and the antibacterial small molecule (D+E) is in the range of 5:4.99:0.01 to 5:4.94:0.06; the sum of the masses of the active diluent monomer (A+B+C) and the antibacterial small molecule (D+E) is equal to the polyurethane polymer R1; wherein the mass ratio of the active diluent A, B, and C monomers is 5:3:1.7 to 5:3:2, preferably 5:3:2; the mass ratio of the antibacterial small molecule benzisothiazolinone derivatives and ciprofloxacin derivatives is 5:1 to 7:1, preferably 5:1.

[0032] The experimental results show that the polyurethane acrylate antibacterial coating grafted with NBT and NCP has excellent killing performance against Gram-positive bacteria and Gram-negative bacteria. Typically, the antibacterial coating prepared when the addition content of benzisothiazolinone derivatives is 5wt% and the addition content of ciprofloxacin derivatives is 1wt%, the antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli reaches 99.99%. Compared with the antibacterial coatings prepared in the literature and related patents, the antibacterial coating prepared in the present invention has a better comprehensive antibacterial effect. Description of the drawings:

[0033] Figure 1 is the antibacterial small molecule NBT prepared in the embodiment 1 H NMR spectra (a) and 13 C NMR spectrum (b);

[0034] Figure 2 is the antibacterial small molecule NCP prepared in the embodiment 1 H NMR spectra (a) and 13 C NMR spectrum (b);

[0035] Figure 3 Total reflection attenuated infrared spectra of PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% coatings prepared in the examples;

[0036] Figure 4 Thermodynamic stability test diagrams of PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% coatings prepared in the examples, (a) is TGA, (b) is DTG;

[0037] Figure 5The antibacterial zone test diagram of four coatings of PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% prepared in the embodiment;

[0038] Figure 6 This is a test chart of the bacterial plate count method for preparing PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% coatings in the examples;

[0039] Figure 7 The PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, PUA-(NBT-NCP)-6wt% coatings prepared in the examples BacLight TM Diagram of bacterial cell activity. Specific implementation method:

[0040] The antibacterial polyurethane acrylate coating is grafted with different proportions of benzisothiazolinone and ciprofloxacin structural units, one of which has a structure as shown in (1):

[0041]

[0042] Where R1 is:

[0043]

[0044] The preparation method of the antibacterial polyurethane acrylate coating with benzisothiazolinone and ciprofloxacin structural units grafted at different proportions simultaneously includes but is not limited to the following steps:

[0045] (1) According to the method disclosed in a Chinese patent (CN114940665 A: A benzisothiazolinone compound used as a fungicide and its preparation method), an R1 polymer is prepared, one of the typical structures of which is shown in FIG. (2);

[0046] (2) According to the method disclosed in Chinese patent (CN114940665 A A benzisothiazolinone compound used as a fungicide and its preparation method), a benzisothiazolinone derivative with the structure shown in monomer D was prepared;

[0047] (3) According to the method reported in the literature (CHANG J, CHEN Y, XU Z, et al. Switchable Control of Antibiotic Activity: A Shape-Shifting "Tail" Strategy. Bioconjugate Chemistry, 2018, 29 (1): 74-82.), a ciprofloxacin derivative having the structure shown in monomer E was prepared;

[0048] (4) Add a photoinitiator to the R1 polymer, monomer D, monomer E, and commercially available active diluent monomer A corresponding to block A, active diluent monomer B corresponding to block B, and active diluent monomer C corresponding to block C (monomers A, B, and C are all purchased from Anage Chemical Co., Ltd.) to obtain a polyurethane acrylate prepolymer.

[0049] Monomer A

[0050] Monomer B Monomer C Monomer D Monomer E

[0051] (5) The polyurethane acrylate prepolymer prepared in step (4) is cured by ultraviolet light to form a coating with antibacterial properties.

[0052] Furthermore, the mass ratio of the polyurethane polymer R1, the active diluent monomer (A+B+C), and the antibacterial small molecule (D+E) is in the range of 5:4.99:0.01 to 5:4.94:0.06; the mass ratio of the active diluent A, B, and C monomers is 5:3:1.7 to 5:3:2, preferably 5:3:2; the mass ratio of the antibacterial small molecule benzisothiazolinone derivatives and ciprofloxacin derivatives is 5:1 to 7:1, preferably 5:1.

[0053] Example 1

[0054] 5.6 mmol (1.25 g) of isophorone diisocyanate (IPDI) was weighed and added to a 50 ml three-necked flask, and 0.03 eq of catalyst dibutyltin dilaurate was added. The mixture was mechanically stirred under vacuum at 45°C, and then 2.8 mmol (8.39 g) of polyether polyol HSH330N was added dropwise. After the addition was completed, the reaction was continued for 1.5 h. After the reaction was complete, 3 mmol (0.36 g) of hydroxyethyl acrylate was added to the system, and the temperature was maintained and stirred for 0.5 h. After the mixture was cooled to room temperature, polymer R1 was obtained.

[0055] 10 g of active diluent (mass ratio of isobornyl methacrylate, i.e. monomer A: 1,6-hexanediol diacrylate, i.e. monomer B: trimethylolpropane triacrylate, i.e. monomer C = 5:3:2) was added to 10 g of the above polymer R1, and after stirring for 30 minutes, a transparent and uniform liquid prepolymer was obtained.

[0056] Take 1g of polyurethane acrylate prepolymer solution, 1.6mg of ciprofloxacin derivative (NCP), 8.4mg of benzisothiazolinone derivative (NBT), add trace amounts of acetic acid and dichloromethane to promote the dissolution of the ciprofloxacin derivative, then add 0.03eq of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), stir well to obtain a transparent liquid. The liquid sample is coated on a polycarbonate plate and cured under ultraviolet light to obtain a coating PUA-(NBT-NCP)-1wt% with antibacterial properties.

[0057] According to the method of Example 1, a series of polyurethane acrylate antibacterial coatings simultaneously grafted with different proportions of benzisothiazolinone structural units and ciprofloxacin structural units were prepared by changing the total added content of ciprofloxacin derivatives and benzisothiazolinone derivatives, and named PUA-(NBT-NCP)-xwt%, wherein xwt% is the total added mass of benzisothiazolinone structural units and ciprofloxacin structural units in the main chain, and xwt% is set to 1wt%, 3wt%, and 6wt% here; corresponding to the prepared antibacterial coatings PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, PUA-(NBT-NCP)-6wt% and the blank control PUA coating, respectively.

[0058] Test characterization and antimicrobial performance testing

[0059] (1) 1 H NMR and 13 C NMR testing

[0060] The preparation of the antibacterial small molecules NBT and NCP in the example was detected by nuclear magnetic resonance. 1 H NMR and 13 C NMR test results are as follows Figure 1 and Figure 2 As shown, the solvent selected is CDCl3; from the spectrum analysis, it can be obtained that the antibacterial small molecules NBT and NCP are successfully prepared.

[0061] (2) Total reflection attenuated infrared (FT-IR) test

[0062] The antibacterial coating prepared in the embodiment was subjected to a total reflection attenuation infrared test, and the test results are as follows: Figure 3As shown; for polyurethane without adding antimicrobial agent, the antimicrobial coating is at 741cm -1 The bending vibration absorption peak of NBT's disubstituted phthalate appears at 1730 cm- 1 There is a C=O stretching vibration absorption peak of carboxylic acid in ciprofloxacin at 1630 cm -1 No stretching vibration absorption peak of carbon-carbon double bond (C=C) in compounds NBT and NCP was observed; the stretching vibration absorption peak of -NCO group of IPDI disappeared near 2270cm-1. From the spectrum analysis, it can be seen that the prepared antibacterial coating is completely cured, and NBT and NCP are embedded in the main chain.

[0063] (3) Thermodynamic stability test (TGA, DTG)

[0064] The thermodynamic stability test of the antibacterial coating prepared in the embodiment is carried out, and the test results are as follows: Figure 4 As shown in the figure, the coating begins to degrade significantly at 300°C and has good thermal stability. Adding a small amount of antibacterial agents NBT and NCP has little effect on the overall thermal stability of the coating.

[0065] (4) Antibacterial performance test

[0066] The antibacterial coating prepared in the embodiment was subjected to the inhibition zone test, plate count test and BacLight TM Bacterial cell viability test.

[0067] In the inhibition zone test, the bacterial solution (Gram-negative bacteria Escherichia coli) was diluted to 10 -7 CFU.mL -1 , take 100uL of the diluted bacterial solution and apply it on the culture dish. Sterilize the coating under ultraviolet light for 30 minutes before testing, cut it into small squares, place it on the culture dish coated with bacterial solution, and culture it at 37℃ for 24 hours to observe whether there is an inhibition zone. The test results are as follows Figure 5 As shown, the results show that the coating film does not produce an inhibition zone, indicating that the coating is a contact antibacterial material, and NBT and NCP are completely embedded in the polyurethane main chain.

[0068] Plate count test: dilute the bacterial solution (corresponding to E. coli and S. aureus) to 10 -7 CFU.mL -1 Place the sterilized small square coating in the bacterial solution and culture it at 37℃ for 3h, take out the coating, slowly rinse the surface with PBS, place it in the PBS solution for ultrasonic vibration, take 100uL of the liquid after vibration and apply it on the solid culture dish, culture it at 37℃ for 24h, observe the colonies on the culture dish, and use the coating without adding antimicrobial agent as the blank control. The test results are as follows Figure 6As shown, when the added mass of NBT-NCP is 6wt%, the antibacterial rate against E. coli and S. aureus reaches 99.99%, indicating that the prepared coating has high efficiency and broad-spectrum antibacterial properties.

[0069] Taking E.coli as an example, the coating was BacLight TM Bacterial cell activity test, dilute the bacterial solution to 10 -7 CFU.mL -1 Place the sterilized small square coating in the bacterial solution and culture it at 37℃ for 3h, take out the coating and slowly rinse the surface with PBS. Stain the coating with PI and SYTO-9 in the dark, culture it at 37℃ for 30min, then rinse it with PBS and observe the fluorescence state of bacteria with a co-fluorescence microscope. The test results are as follows: Figure 7 As shown, when the added mass of NBT-NCP is 6wt%, the patterns observed under the microscope are almost all red, indicating that the coating has excellent antibacterial properties.

Claims

1. An antimicrobial polyurethane acrylate polymer embedded with N-substituted benzisothiazolinone and N-substituted ciprofloxacin, characterized in that: The invention relates to an antibacterial polyurethane acrylate film material with benzisothiazolinone and ciprofloxacin antibacterial units grafted at different proportions at the same time, wherein the benzisothiazolinone structural unit refers to N-substituted benzisothiazolinone, and the ciprofloxacin antibacterial unit refers to N-substituted ciprofloxacin, which are grafted onto the polyurethane acrylate main chain through carbon-carbon double bond free radical polymerization to obtain a polyurethane acrylate film material with antibacterial properties; a structural formula of the polymer is shown in formula (1): Formula (1): Where R1: The value range of m is 1-100; The corresponding structure is the main structure of the triol except H.

2. The polymer according to claim 1, characterized in that The polymer is composed of a group R1, blocks A, B, C, D, and E. The three-branch structure of R1 ends with a double bond. The structures of R1 and blocks A, B, C, D, and E are as follows, wherein blocks D and E are grafted with benzisothiazolinone and ciprofloxacin structural units, respectively: Group R1: Block A: Block B: Block C: Block D: Block E:

3. The polymer according to claim 1, characterized in that The five blocks A, B, C, D, and E have corresponding polymerization degrees a, b, c, d, and e, respectively, which can be adjusted according to the required polymerization degree, and the value range is 2 to 50, preferably 25 to 45.

4. The method for preparing the polymer according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) preparing a polymer corresponding to R1; (2) preparing a benzisothiazolinone derivative having a structure shown in monomer D corresponding to block D; (3) preparing a ciprofloxacin derivative having a structure shown in monomer E corresponding to block E; (4) adding a photoinitiator to the R1 polymer, the monomer D, the monomer E, the reactive diluent monomer A corresponding to the block A, the reactive diluent monomer B corresponding to the block B, and the reactive diluent monomer C corresponding to the block C, and mixing to obtain a polyurethane acrylate prepolymer; Monomer A Monomer B Monomer C Monomer D Monomer E (5) The polyurethane acrylate prepolymer prepared in step (4) is cured by ultraviolet light to form a coating having antibacterial properties corresponding to formula (1).

5. The method according to claim 4, characterized in that The mass ratio of the polyurethane polymer R1, the active diluent monomers A+B+C, and the antibacterial small molecules D+E is in the range of 5:4.99:0.01 to 5:4.94:0.06; the sum of the masses of the active diluent monomers A+B+C and the antibacterial small molecules D+E is equal to the polyurethane polymer R1; wherein the mass ratio of the active diluent A, B, and C monomers is 5:3:1.7 to 5:3:2, preferably 5:3:2; the mass ratio of the antibacterial small molecule benzisothiazolinone derivatives and ciprofloxacin derivatives is 5:1 to 7:1, preferably 5:

1.

6. Use of the polymer according to any one of claims 1 to 3 directly as an antibacterial film or antibacterial coating.

7. The use according to claim 6, characterized in that Used to prepare antibacterial films or antibacterial coatings that are killing Gram-positive bacteria and Gram-negative bacteria.

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