An embedded N-substituted benzisothiazolinone and N-substituted ciprofloxacin antimicrobial polyurethane acrylate film material

Abstract

The application discloses an embedded N-substituted benzisothiazolinone and N-substituted ciprofloxacin antibacterial polyurethane acrylate film material, and belongs to the field of organic antibacterial coating.The application introduces double bonds into benzisothiazolinone structural units and ciprofloxacin structural units by respectively functionalizing benzisothiazolinone and ciprofloxacin N-substituted alkenyl groups, grafts N-substituted alkenyl functionalized benzisothiazolinone derivatives (NBT) and ciprofloxacin derivatives (NCP) into a polyurethane acrylate main chain at the same time, and utilizes excellent antibacterial properties of NBT on staphylococcus aureus and excellent antibacterial properties of NCP on escherichia coli to prepare a broad-spectrum antibacterial material, and a corresponding antibacterial coating can be used for modifying a substrate surface.

Description

TECHNICAL FIELD

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

[0002] Pathogenic microorganisms such as bacteria 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 the service life to be shortened, but also easily infects humans with pathogenic microorganisms such as bacteria when they come into contact with the pathogenic microorganisms, thereby endangering human health. The antibacterial polymer coating as a functional film material not only enhances the service life of the substrate and resists the growth of pathogenic microorganisms such as bacteria, but also is beneficial to human health. The antibacterial agent grafted in the antibacterial film material prepared in the patent involves benzisothiazolinone and ciprofloxacin antibacterial units.

[0003] Benzisothiazolinone is an organic antibacterial agent. The antibacterial mechanism of benzisothiazolinone is that the S-N bond interacts with the mercapto group (such as the thiol of the active site cysteine of the protein) in the enzyme of the bacteria, forms an S-S bond, destroys the enzyme activity, inhibits the growth of the bacteria, and ultimately leads 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 quinolone antibacterial agents. Ciprofloxacin binds to subunit A of the DNA gyrase of bacteria, inhibits the cutting and linking functions of the enzyme, and prevents the replication of bacterial DNA, thereby showing antibacterial action, especially excellent bacteriostatic effect on gram-negative bacteria. (STRUGA M, ROSZKOWSKI P, 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 strong bacteriostatic effect on gram-positive bacteria, and the ciprofloxacin structural unit has strong bactericidal effect on gram-negative bacteria. By combining the advantages of the two antibacterial structural units, the application discloses a polyurethane acrylate antibacterial coating containing benzisothiazolinone derivatives and ciprofloxacin derivatives.

[0004] Document 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 nanometer antibacterial material, in which 1,2-benzisothiazolin-3-yl anion (BIT-COO - ) is inserted into two-dimensional nanoparticle Mg-Al layered double hydroxide (LDH) through the process of ion exchange to achieve the controlled release of benzisothiazolinone. The two-dimensional nanoparticle wrapped with antibacterial anion is mixed with acrylate to synthesize LDH@BIT-COOH coating through ultrasonic dispersion and mechanical stirring, which has inactivation effect on Escherichia coli within 6h and on Staphylococcus aureus within 12h. However, the coating has the risk of small molecule antibacterial agent BIT-COO - 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 a benzisothiazolinone grafted polyurethane antibacterial coating. Through click chemistry reaction, azide functionalized polyurethane (PU-N3) is reacted with alkyne functionalized benzisothiazolinone (BIT-Al) to prepare grafted benzisothiazolinone antibacterial polyurethane (PU-BIT). The antibacterial polyurethane has excellent antibacterial property on Staphylococcus aureus, but poor antibacterial effect on 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 uses 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), to prepare a double-layer film on a titanium (Ti) substrate. Studies have shown that the coating film has a double-layer film structure, and the antibacterial effect is achieved by gradually releasing CIP through the micropores on the surface. The ciprofloxacin released by the coating causes problems 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. After acryloylation of the ciprofloxacin molecule, the ciprofloxacin molecule is covalently fixed to the surface of the vinyl-functionalized Fe3O4 nanoparticles by graft copolymerization with acrylic acid to prepare the corresponding composite nanomaterial. In this nanomaterial, only the ciprofloxacin structural unit is covalently grafted to the surface of the nanoparticles.

[0008] In the aforementioned published documents, there is no mention of covalently grafting the ciprofloxacin structural unit and the benzisothiazolinone to the polyurethane acrylate backbone.

[0009] In the preparation of benzisothiazolinone and ciprofloxacin antibacterial structural units, Chinese patent (CN114940665A A benzisothiazolinone compound used as a bactericide and a preparation method thereof) discloses a preparation method of benzisothiazolinone compounds. Under the action of p-toluenesulfonic acid, benzisothiazolinone reacts with aliphatic aldehyde and aliphatic alcohol to prepare benzisothiazolinone derivatives with different chain lengths, providing a new idea for the development of new bactericides. Chinese patent (CN113440523 A Chitosan-modified benzisothiazolinone polylactic acid nanosphere and its preparation method and application) discloses a technology in which benzisothiazolinone is modified with chitosan to prepare benzisothiazolinone polylactic acid nanospheres. The nanospheres prepared by the invention can effectively improve the transmembrane transport rate of the nanocarrier system and the antibacterial activity. Chinese patent (CN113440523 A A propiophenone derivative of ciprofloxacin and a preparation method and application thereof) discloses a technology in which the fluorinated quinolone skeleton and the propiophenone skeleton are effectively combined to construct a new fluorinated quinolone "chalcone-like" compound, which increases the resistance to drug resistance and can be applied to antitumor drug therapy. These patents provide ideas for the development of benzisothiazolinone and ciprofloxacin antibacterial agents.

[0010] Chinese patent (CN113440523 A Amphiphilic arginine block ciprofloxacin copolymer, nanoparticle and preparation method and application thereof) discloses a technology in which arginine is used as the hydrophilic segment and ciprofloxacin is used as the hydrophobic segment to construct an amphiphilic copolymer (PAC), which forms a positively charged nanoparticle (PAC@NPs) with arginine fragments as the shell and ciprofloxacin fragments as the core in solution. Nanoparticles with this structure have excellent resistance to drug resistance, providing a new idea for containing the spread of bacterial drug resistance.

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

[0012] The technology disclosed in the previous patent (CN 114573762 A A polyurethane acrylate polymer containing benzisothiazolinone derivatives with antibacterial properties and a preparation method) of the laboratory synthesizes N-substituted benzisothiazolinone derivatives containing different olefin chain lengths by olefinizing benzisothiazolinone, utilizes the excellent antibacterial property of benzisothiazolinone against Staphylococcus aureus, and embeds benzisothiazolinone into polyurethane acrylate to prepare an antibacterial coating through ultraviolet light curing. The antibacterial coating in the invention has excellent antibacterial effect against Staphylococcus aureus, but poor antibacterial effect against Escherichia coli. However, the invention does not involve embedding ciprofloxacin derivatives into polyurethane acrylate.

[0013] In the preparation method disclosed in the foregoing patent, ciprofloxacin structural units and benzisothiazolinone are not covalently grafted onto the polyurethane acrylate main chain.

[0014] Based on the previous research of the laboratory, the invention first grafts benzisothiazolinone derivatives (NBT) and ciprofloxacin derivatives (NCP) onto the polyurethane acrylate main chain through chemical bonds, utilizes the excellent inactivation of benzisothiazolinone against Gram-positive bacteria and the excellent inactivation of ciprofloxacin against Gram-negative bacteria, N-substitutes benzisothiazolinone and ciprofloxacin through allyl bromide and acryloyl chloride to prepare N-substituted benzisothiazolinone derivatives (NBT) and N-substituted ciprofloxacin derivatives (NCP), and explores the antibacterial activity of polyurethane acrylate antibacterial coatings with different proportions of NBT and NCP against Staphylococcus aureus and Escherichia coli. SUMMARY

[0015] The invention provides a structure of antibacterial polyurethane acrylate coating simultaneously grafted with benzisothiazolinone and ciprofloxacin structural units 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 antibacterial agents while avoiding the loss of small molecules.

[0016] The polyurethane acrylate antibacterial coating synthesized in the invention is an antibacterial polyurethane acrylate film material simultaneously grafted with different proportions of benzisothiazolinone and ciprofloxacin antibacterial units. The benzisothiazolinone structural unit refers to N-substituted benzisothiazolinone, and the ciprofloxacin antibacterial unit refers to N-substituted ciprofloxacin. The benzisothiazolinone and ciprofloxacin are grafted onto the polyurethane acrylate main chain through carbon-carbon double bond radical polymerization to prepare the antibacterial polyurethane acrylate film material, which has the following formula (1) structure:

[0017] R1:

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

[0019]

[0020] The wavy line represents a chemical bond connection not written out

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

[0022] Formula (1) is a structure formula of a polyurethane acrylate antibacterial coating, wherein at least one of the three branches in R1 is single-carbon-bonded with an N-substituted benzisothiazolinone or an N-substituted ciprofloxacin. 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 2-50, preferably 25-45.

[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 with the structure shown in monomer D corresponding to block D;

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

[0027] (4) mixing the R1 polymer, monomer D, monomer E, and 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 to obtain a polyurethane acrylate prepolymer;

[0028] Monomer A

[0029] Monomer B Monomer C Monomer D Monomer E

[0030] (5) After the polyurethane acrylate prepolymer prepared in step (4) is cured by ultraviolet light, a coating with antibacterial properties corresponding to formula (1) is formed.

[0031] Further preferably, the mass ratio of the polyurethane polymer R1, the active diluent monomers (A+B+C), and the antibacterial small molecules (D+E) ranges from 5:4.99:0.01 to 5:4.94:0.06; the sum of the mass 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 monomers A, B, and C is 5:3:1.7 to 5:3:2, preferably 5:3:2; the mass of the antibacterial small molecules, i.e., the benzisothiazolinone derivative and the ciprofloxacin derivative, is 5:1 to 7:1, preferably 5:1.

[0032] The experimental results show that the polyurethane acrylate antibacterial coating simultaneously grafted with NBT and NCP has excellent killing performance on gram-positive bacteria and gram-negative bacteria. Typically, when the antibacterial coating prepared by adding 5wt% of the benzisothiazolinone derivative and 1wt% of the ciprofloxacin derivative, the antibacterial effect on 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 application has more excellent comprehensive antibacterial effect. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively. 1 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively. 13 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively.

[0034] Figure 2 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively. 1 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively. 13 The H NMR chart (a) and the C NMR chart (b) of the antibacterial small molecule NBT prepared in the examples are shown in Figures 1 and 2, respectively.

[0035] Figure 3 The total reflection attenuated infrared spectrograms of the PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% coatings prepared in the examples are shown in Figure 3.

[0036] Figure 4 The thermodynamic stability test chart of the PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, and PUA-(NBT-NCP)-6wt% coatings prepared in the examples is shown in Figure 4, (a) is TGA, and (b) is DTG.

[0037] Figure 5Figure 1. Zone of inhibition test chart for PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, PUA-(NBT-NCP)-6wt% coatings prepared in the examples;

[0038] Figure 6 Figure 2. Bacterial plate count test chart for PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, PUA-(NBT-NCP)-6wt% coatings prepared in the examples;

[0039] Figure 7 Figure 3. Bacterial cell viability chart for PUA, PUA-(NBT-NCP)-1wt%, PUA-(NBT-NCP)-3wt%, PUA-(NBT-NCP)-6wt% coatings prepared in the examples; BacLight TM DETAILED DESCRIPTION:

[0040] Antibacterial polyurethane acrylate coatings with simultaneous grafting of different proportions of benzisothiazolinone and ciprofloxacin structural units, one of which is shown in (1):

[0041]

[0042] wherein R1 is:

[0043]

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

[0045] (1) According to the method reported in Chinese patent (CN114940665 A Benzisothiazolinone compound used as a bactericide and its preparation method), R1 polymer is prepared, one of the typical structures is shown in (2):

[0046] (2) According to the method reported in Chinese patent (CN114940665 A Benzisothiazolinone compound used as a bactericide and its preparation method), benzisothiazolinone derivatives with the structure shown in monomer D are 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.), the cyclopyracycline derivative with the structure shown in monomer E was prepared;

[0048] (4) The R1 polymer, monomer D, monomer E, and commercially available active diluent monomers A, B, and C corresponding to blocks A, B, and C were mixed with a photoinitiator 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) was cured by ultraviolet light to form a coating with antibacterial properties.

[0052] Further, 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; wherein the mass ratio of the active diluent monomers A, B, and C is in the range of 5:3:1.7 to 5:3:2, and preferably 5:3:2; the mass of the antibacterial small molecules benzisothiazolinone derivative and cyclopyracycline derivative is in the range of 5:1 to 7:1, and preferably 5:1.

[0053] Example 1

[0054] 5.6 mmol (1.25 g) of isophorone diisocyanate (IPDI) was weighed into a 50 ml three-necked flask, 0.03 eq of catalyst dibutyltin dilaurate was added, and mechanical stirring was carried out under vacuum at 45°C, followed by dropwise addition of 2.8 mmol (8.39 g) of polyether polyol HSH330N. After the dropwise 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 while stirring for 0.5 h. After the mixture was cooled to room temperature, the polymer R1 was prepared.

[0055] To the above polymer R110g, 10 g of reactive diluent (isobornyl methacrylate, i.e. monomer A: 1,6-hexanediol diacrylate, i.e. monomer B: trimethylolpropane triacrylate, i.e. monomer C, mass ratio = 5:3:2) was added, and after stirring for 30 minutes, a transparent and uniform liquid prepolymer was obtained.

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

[0057] According to the method of Example 1, by changing the total content of ciprofloxacin derivative and benzisothiazolinone derivative, a series of polyurethane acrylate antibacterial coatings with different proportions of benzisothiazolinone structural units and ciprofloxacin structural units were prepared, and were named PUA-(NBT-NCP)-xwt%, where xwt% is the total mass of benzisothiazolinone structural units and ciprofloxacin structural units in the main chain, xwt% is set to 1wt%, 3wt%, 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 antibacterial performance test

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

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

[0061] (2) Attenuated total reflection infrared (FT-IR) test

[0062] The antibacterial coatings prepared in the examples were tested by attenuated total reflection infrared, and the test results are shown in Figure 3As shown; for polyurethane without added antibacterial agents, the antibacterial coating is at 741 cm⁻¹. -1 The bending vibration absorption peak of NBT with o-phthalic disubstituted form appeared at 1730 cm⁻¹. 1 The absorption peak for the C=O stretching vibration of carboxylic acid in ciprofloxacin is present at 1630 cm⁻¹. -1 No stretching vibration absorption peaks were observed in the carbon-carbon double bonds (C=C) of compounds NBT and NCP; the stretching vibration absorption peak of the -NCO group of IPDI near 2270 cm⁻¹ disappeared. Spectral analysis indicates that the prepared antibacterial coating was completely cured, and NBT and NCP were embedded in the main chain.

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

[0064] Thermodynamic stability tests were performed on the antibacterial coatings prepared in the examples, and the test results are as follows: Figure 4 As shown, the coating begins to degrade significantly at 300℃, exhibiting good thermal stability. The addition of small amounts of antibacterial agents NBT and NCP has little impact on the overall thermal stability of the coating.

[0065] (4) Antibacterial performance test

[0066] The antibacterial coatings prepared in the examples were subjected to inhibition zone tests, plate count tests, and... BacLight TM Bacterial cell viability test.

[0067] The inhibition zone test involved diluting the bacterial suspension (Gram-negative Escherichia coli) to 10⁻⁶. -7 CFU.mL -1 Take 100 μL of the diluted bacterial solution and spread it onto a petri dish. Before testing, sterilize the coating under UV light for 30 minutes, cut it into small squares, place them on the petri dish coated with bacterial solution, and incubate at 37°C for 24 hours. Observe whether an inhibition zone is formed. The test results are as follows. Figure 5 As shown, the results indicate that no antibacterial zone was generated in the coating, suggesting that the NBT and NCP of the contact antibacterial material in this coating are completely embedded in the polyurethane backbone.

[0068] Plate count test: The bacterial suspensions (corresponding to E. coli and S. aureus, respectively) were diluted to 10⁻⁶. -7 CFU.mL -1 The sterilized small square coatings were placed in bacterial suspension and incubated at 37°C for 3 hours. The coatings were then removed, the surface was slowly rinsed with PBS, and the coatings were ultrasonically shaken in PBS solution. 100 μL of the shaken liquid was then spread onto solid culture dishes and incubated at 37°C for 24 hours. Colonies on the culture dishes were observed. Coatings without added antibacterial agents were used as a 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%. It is shown that the prepared coating film has high efficiency and broad-spectrum antibacterial property.

[0069] Taking E. coli as an example, the coating film was subjected to BacLight TM Bacterial cell activity test, the bacterial solution was diluted to 10 -7 CFU / mL -1 After sterilization, the small square coating film was placed in the bacterial solution and incubated at 37°C for 3h, and then the coating film was taken out and slowly rinsed with PBS. The coating film was dyed with PI and SYTO-9 under light shielding, incubated at 37°C for 30min, and then rinsed with PBS, and the fluorescence state of the bacteria was observed under a confocal microscope. The test results are shown in Figure 7 As shown, when the added mass of NBT-NCP is 6wt%, almost all the red patterns are observed under the microscope, indicating that the antibacterial property of the coating is excellent.

Claims

1. An embedded N-substituted benzisothiazolinone and N-substituted ciprofloxacin antibacterial polyurethane acrylate polymer, characterized by, To graft different proportion of benzisothiazolinone, ciprofloxacin antibacterial unit of antibacterial polyurethane acrylate film material, the benzisothiazolinone structural unit refers to N-substituted benzisothiazolinone, the ciprofloxacin antibacterial unit refers to N-substituted ciprofloxacin, by carbon-carbon double bond radical polymerization graft to polyurethane acrylate main chain, the preparation of antibacterial polyurethane acrylate film material; The structural formula of the polymer is shown as formula (1): Formula (1): wherein R1: m has a value ranging from 1 to 100; corresponding to the main structure of a triol except H. The preparation method comprises the following steps: (1) preparing the polymer corresponding to R1; (2) preparing the benzisothiazolinone derivative of the structure shown by monomer D corresponding to block D; (3) preparing the ciprofloxacin derivative of the structure shown by monomer E corresponding to block E; (4) mixing R1 polymer, monomer D, monomer E, and 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, and adding a photoinitiator to obtain a polyurethane acrylate prepolymer; Monomer A Monomer B Monomer C Monomer D Monomer E (5) forming a coating with antibacterial performance corresponding to formula (1) after ultraviolet curing of the polyurethane acrylate prepolymer prepared in step (4); The mass ratio of polyurethane polymer R1, active diluent monomers A+B+C, and 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 mass of active diluent monomers A+B+C and antibacterial small molecules D+E is equal to polyurethane polymer R1; wherein the mass ratio of active diluent monomers A, B and C is 5:3:1.7 to 5:3:2, and the mass ratio of antibacterial small molecules benzisothiazolinone derivative and ciprofloxacin derivative is 5:1 to 7:

1.

2. The polymer according to claim 1, characterized in that The polymer is composed of groups R1, blocks A, B, C, D and E, the terminal of the three-branch structure of R1 is a double bond, and the structures of R1 and blocks A, B, C, D and E are as follows, wherein blocks D and E graft 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 correspond to polymerization degrees a, b, c, d and e respectively, and the values are in the range of 2 to 50 with the required polymerization degree adjustment.

4. The polymer according to claim 3, characterized in that, The values of a, b, c, d and e are in the range of 25 to 45.

5. The polymer according to claim 1, characterized in that, The mass ratio of active diluent monomers A, B and C is 5:3:2, and the mass ratio of antibacterial small molecules benzisothiazolinone derivative and ciprofloxacin derivative is 5:

1.

6. The polymer of any one of claims 1-5 is directly used as an antibacterial film or antibacterial coating.

7. Use according to claim 6, characterized in that, The polymer is directly used as an antibacterial film or antibacterial coating.

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