Construction method of host-guest of photodynamic / quaternary ammonium salt / boric acid antibacterial composite pet fiber coating

Abstract

The application discloses a kind of photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating host-guest construction method, methylated branched polyethylene imine, benzyl halogenated hydrocarbon and solvent are sequentially added, after reaction is finished, solvent is removed, and benzyl modified methylated branched polyethylene imine is obtained;Benzyl modified methylated branched polyethylene imine chloroform solution and photosensitizer aqueous solution are configured, are mixed and stirred, so that photosensitizer enters host product, is separated, is rotary evaporated, and benzyl modified methylated branched polyethylene imine with guest dye is obtained;The benzyl modified methylated branched polyethylene imine with guest dye is dissolved in organic solvent, 4-chloromethyl phenyl boronic acid is added and uniformly coated on the surface of PET fiber, PET fiber is placed on substrate, and photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating is obtained after solidification.The PET fiber prepared by the application has antibacterial effect, compared with other traditional small molecule antibacterial materials, has excellent chemical stability, non-volatility and long-term activity and the like.

Description

Technical Field

[0001] This invention relates to the field of antibacterial materials, and more particularly to a method for constructing a host-guest composite PET fiber coating based on photodynamic / quaternary ammonium salt / boric acid antibacterial properties. Background Technology

[0002] Infections caused by microorganisms such as bacteria, viruses, and fungi pose a significant threat to human health. Textile materials are ideal media for microbial growth and can potentially cause various cross-infectious diseases. Because ordinary textiles lack antibacterial properties, common fabrics can actually lead to the proliferation of various bacteria. To reduce cross-infection caused by pathogenic microorganisms, antibacterial finishing of textiles and antimicrobial materials has been extensively studied. Among numerous antibacterial agents, quaternary ammonium compounds and silver or silver-based compounds have received widespread attention as effective antibacterial agents in various fields.

[0003] Quaternary ammonium salts possess strong antibacterial properties, broad-spectrum antibacterial activity, and are readily available. Antibacterial materials prepared using quaternary ammonium salts exhibit good antibacterial performance and are widely used in many fields, including medicine, water treatment, and food. The effective bactericidal component of quaternary ammonium salts is a cationic group formed by the combination of an organic radical and a single particle. Quaternary ammonium salts adsorb bacteria and then utilize the nearby long carbon chains to disrupt the bacterial cell membrane, causing intracellular substances to leak out and leading to cell death.

[0004] The photosensitizer generates highly reactive oxygen species under light, causing non-specific cell damage and exhibiting broad-spectrum bactericidal activity. Furthermore, it does not induce drug resistance with repeated use and demonstrates good antibacterial properties against drug-resistant bacteria. This photodynamic antimicrobial chemotherapy is an effective and low-cost antibacterial strategy.

[0005] Boric acid's applications in medicine and healthcare primarily rely on its bactericidal and disinfectant properties against various bacteria and fungi. The antibacterial mechanism of boric acid involves its ability to bind to the glucose dihydroxyl groups of bacteria and fungi, as well as the -NH3 groups in proteins, thereby affecting microbial metabolism and disrupting cell wall permeability. Furthermore, its low acidity and minimal skin irritation make it commonly used for cleaning, hemostasis, anti-inflammatory effects, and bactericidal purposes in treating burns, scalds, otitis media, and dermatitis, particularly for cleaning skin, wounds, and mucous membranes.

[0006] Since the pioneering work on host-guest chemistry in the 1990s, dendritic host-guest chemistry has developed into an important field of supramolecular chemistry. Its encapsulation mechanism typically utilizes the interactions between the host and guest (including electrostatic attraction, hydrogen bonding, van der Waals forces, hydrophobic bonds, or dipole interactions) to encapsulate multifunctional guest molecules within dendritic host polymers, achieving polymer multifunctionality. Currently, host-guest chemistry has been applied in phase transfer, non-covalent functionalization, metal nanoparticle growth, and bioimaging. Unlike conventional hosts that specifically capture organic small molecules as guests in a one-to-one manner, dendritic polymers can non-specifically load one or more guests based on their molecular structure. In addition to organic guests, dendritic polymers can even load inorganic nanoparticles, forming organic-inorganic hybrids. Furthermore, due to their large chamber volume and numerous cavities, dendritic polymers can simultaneously encapsulate different types of guests. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for constructing a host-guest composite PET fiber coating based on photodynamic / quaternary ammonium salt / boric acid antibacterial properties.

[0008] The objective of this invention is achieved through the following technical solution: a method for constructing a host-guest composite PET fiber coating based on photodynamic / quaternary ammonium salt / boric acid antibacterial properties, comprising the following steps:

[0009] (1) Add 0.5-2g of methylated branched polyethyleneimine, 0.5-5g of benzyl halide and 5-15mL of solvent, and stir at 50-120℃ for 1-48h; after the reaction is completed, remove the solvent to obtain benzyl-modified methylated branched polyethyleneimine.

[0010] (2) The benzyl-modified methylated branched polyethyleneimine prepared in step (1) is dissolved in chloroform to prepare a chloroform solution of benzyl-modified methylated branched polyethyleneimine with a concentration of 0.003-0.018 g / mL; and a photosensitizer aqueous solution with a concentration of 0.0005-0.0025 g / mL is prepared; then 75-125 mL of the chloroform solution of the benzyl-modified methylated branched polyethyleneimine and 75-125 mL of the photosensitizer aqueous solution are mixed, the lower layer solution is separated and dried by rotary evaporation to obtain benzyl-modified methylated branched polyethyleneimine with guest dye;

[0011] (3) Dissolve 0.5-1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in an organic solvent, add 0.3-1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a substrate, and cure it at 50-90℃ for 1h-7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0012] Further, the benzyl halide is 3-methylbenzyl chloride, (5-bromopentyl)benzene, (5-chloropentyl)benzene, 1-chloro-2-phenylethane, 1-bromo-2-phenylethane, 1-chloro-3-phenylpropane, 1-bromo-3-phenylpropane, 4-isopropylbenzyl chloride, 4-isopropylbenzyl bromide, 4-phenyl-1-butyl bromide, or 4-phenyl-1-butyl chloride.

[0013] Furthermore, the photosensitizer aqueous solution is an aqueous solution of Bengal rose red, toluidine blue, indocyanine green, or methylene blue.

[0014] Further, the solvent is toluene, xylene, methanol, tetrahydrofuran, N,N-dimethylformamide, N,N-diethylformamide, cyclohexane, or chloroform.

[0015] Furthermore, the organic solvent is chloroform, toluene, or methanol.

[0016] The beneficial effects of this invention are: the branched quaternary ammonium salt with guest dye is introduced into the PET fiber system, and the 4-chloromethylphenylboronic acid added to the system also has antibacterial effect, so that the high-density quaternary ammonium salt structure can be obtained and excellent antibacterial ability can be guaranteed. Attached Figure Description

[0017] Figure 1 Infrared spectra of the host and guest components of pure PET fibers and the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3;

[0018] Figure 2 The diagram shows the antibacterial activity against Escherichia coli. Figure 2 (a) shows the antibacterial activity of pure PET fiber against Escherichia coli. Figure 2 (b) is an antibacterial diagram of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 against Escherichia coli;

[0019] Figure 3 The diagram shows the antibacterial activity against Staphylococcus aureus. Figure 3 (a) shows the antibacterial activity of pure PET fiber against Staphylococcus aureus. Figure 3 (b) is an antibacterial diagram of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 against Staphylococcus aureus;

[0020] Figure 4 The host-guest 1H NMR spectrum of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3;

[0021] Figure 5 The image shows the physical specimens of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0023] This invention provides a method for constructing a host-guest composite coating of photodynamic / quaternary ammonium salt / boric acid antibacterial PET fibers, comprising the following steps:

[0024] (1) Add 0.5-2g of methylated branched polyethyleneimine, 0.5-5g of benzyl halide and 5-15mL of solvent, and stir at 50-120℃ for 1-48h; after the reaction is completed, remove the solvent to obtain benzyl-modified methylated branched polyethyleneimine.

[0025] (2) The benzyl-modified methylated branched polyethyleneimine prepared in step (1) is dissolved in chloroform to prepare a chloroform solution of benzyl-modified methylated branched polyethyleneimine with a concentration of 0.003-0.018 g / mL; and a photosensitizer aqueous solution with a concentration of 0.0005-0.0025 g / mL is prepared; then 75-125 mL of the chloroform solution of the benzyl-modified methylated branched polyethyleneimine and 75-125 mL of the photosensitizer aqueous solution are mixed, the lower layer solution is separated and dried by rotary evaporation to obtain benzyl-modified methylated branched polyethyleneimine with guest dye;

[0026] (3) Dissolve 0.5-1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in an organic solvent, add 0.3-1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a substrate, and cure it at 50-90℃ for 1h-7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0027] Example 1

[0028] (1) 1g of methylated branched polyethyleneimine, 2.2428g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylformamide were stirred at 50℃ for 48h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylformamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0029] The 4-phenyl-1-butyl bromide is a benzyl halide; in this invention, the benzyl halide is 3-methylbenzyl chloride, (5-bromopentyl)benzene, (5-chloropentyl)benzene, 1-chloro-2-phenylethane, 1-bromo-2-phenylethane, 1-chloro-3-phenylpropane, 1-bromo-3-phenylpropane, 4-isopropylbenzyl chloride, 4-isopropylbenzyl bromide, 4-phenyl-1-butyl bromide, or 4-phenyl-1-butyl chloride.

[0030] The N,N-dimethylformamide is a solvent; in this invention, the solvent is toluene, xylene, methanol, tetrahydrofuran, N,N-dimethylformamide, N,N-diethylformamide, cyclohexane, or chloroform.

[0031] (2) Dissolve 0.3g of the benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.003g / mL, and at the same time prepare an aqueous solution of 0.0025g / mL of Bengal rose red; then mix and stir 75mL of the chloroform solution of the benzyl-modified methyl-branched polyethyleneimine and 75mL of the aqueous solution of Bengal rose red, and at this time, the photosensitizer enters the main product by mixing and stirring; then separate the solution using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0032] The Bengal rose red aqueous solution is a photosensitizer aqueous solution; in this invention, the photosensitizer aqueous solution is a Bengal rose red aqueous solution, a toluidine blue aqueous solution, an indocyanine green aqueous solution, or a methylene blue aqueous solution.

[0033] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 0.3g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 50℃ for 7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0034] Example 2

[0035] (1) 1g of methylated branched polyethyleneimine, 1.1214g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylformamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylformamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0036] (2) Dissolve 2.25g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 125mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.018g / mL, and at the same time prepare an aqueous solution of 0.0005g / mL of Bengal rose red; then mix and stir 125mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 125mL of the aqueous solution of Bengal rose red; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0037] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 90℃ for 1h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0038] Example 3

[0039] (1) 1g of methylated branched polyethyleneimine, 2.2428g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylformamide were stirred at 70℃ for 48h. After the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylformamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0040] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of 0.002g / mL of Bengal rose red; then mix and stir 100mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of Bengal rose red; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0041] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 70℃ for 12h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0042] Figure 1 Infrared spectra of the host and guest components of pure PET fibers and the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3. Figure 4 The image shows the 1H NMR spectrum of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3. Figure 1 As shown, the first line from top to bottom is "PET," which refers to pure PET fiber without added quaternary ammonium salt materials; the second line is "PDT-30," which is the host and guest material of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3. Figure 1 As can be seen from the data, the infrared spectra of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 are at 907 cm⁻¹. -1 The presence of absorption peaks indicates that the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 are grafted with quaternary ammonium salts. Meanwhile, from... Figure 4 As can be seen from the data, the host and guest 1H NMR spectra of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 show a shift peak at 3.48 belonging to the hydrogen on the quaternary ammonium salt, which also corroborates the synthesis of polyethyleneimine long carbon chain quaternary ammonium salt.

[0043] Figure 2 The image shows an antibacterial effect against Escherichia coli (E. coli). Figure 2 (a) shows the antibacterial activity of pure PET fiber against Escherichia coli. Figure 2 (b) is an antibacterial diagram of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 against Escherichia coli. The antibacterial rate of the host and guest components of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3 against Escherichia coli is 96.2%.

[0044] Figure 3 The diagram shows the antibacterial activity against Staphylococcus aureus (S. aurues). Figure 3 (a) shows the antibacterial activity of pure PET fiber against Staphylococcus aureus. Figure 3(b) Antibacterial properties of the host and guest components of the photodynamic / quaternary ammonium / boric acid antibacterial composite PET fiber coating prepared in Example 3 against Staphylococcus aureus. The host and guest components of the photodynamic / quaternary ammonium / boric acid antibacterial composite PET fiber coating prepared in Example 3 showed an antibacterial rate of 98.3% against Staphylococcus aureus. The host and guest components of the photodynamic / quaternary ammonium / boric acid antibacterial composite PET fiber coating prepared in Example 3, which contain a certain amount of benzyl-modified methylated branched polyethyleneimine with guest dye, exhibit excellent antibacterial properties.

[0045] Figure 5 The image shows the physical specimens of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating prepared in Example 3.

[0046] Example 4

[0047] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of xylene were stirred at 120℃ for 1h; after the reaction was completed, the xylene was removed by centrifugation of the precipitate to obtain benzyl-modified methylated branched polyethyleneimine.

[0048] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of 0.002g / mL of Bengal rose red; then mix and stir 100mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of Bengal rose red; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0049] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 90℃ for 2h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0050] Example 5

[0051] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylacetamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0052] (2) Dissolve 0.75g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 75mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of methylene blue with a concentration of 0.002g / mL; then mix and stir 75mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 75mL of the aqueous solution of methylene blue; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0053] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 90℃ for 5h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0054] Example 6

[0055] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylacetamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0056] (2) Dissolve 0.15g of the benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 150mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of methylene blue with a concentration of 0.002g / mL; then mix and stir 100mL of the chloroform solution of the benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of methylene blue; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0057] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 90℃ for 1d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0058] Example 7

[0059] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of toluene were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove the toluene, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0060] (2) Dissolve 0.1g of the benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of indocyanine green with a concentration of 0.002g / mL; then mix and stir 100mL of the chloroform solution of the benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of indocyanine green; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0061] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 90℃ for 3d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0062] Example 8

[0063] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylacetamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0064] (2) Dissolve 0.8g of the benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 80mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of indocyanine green with a concentration of 0.002g / mL; then mix and stir 80mL of the chloroform solution of the benzyl-modified methyl-branched polyethyleneimine and 80mL of the aqueous solution of indocyanine green; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0065] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 80℃ for 1h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0066] Example 9

[0067] (1) 1g of methylated branched polyethyleneimine, 1.3953g of 4-phenyl-1-butyl bromide and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylacetamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0068] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of methylene blue with a concentration of 0.002g / mL; then mix and stir 100mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of methylene blue; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0069] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 80℃ for 7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0070] Example 10

[0071] (1) 1g of methylated branched polyethyleneimine, 1.4335g of 4-phenyl-1-butyl chloride and 5mL of toluene were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove the toluene, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0072] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of 0.002g / mL of Bengal rose red; then mix and stir 100mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of Bengal rose red; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0073] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 85℃ for 1h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0074] Example 11

[0075] (1) 1g of methylated branched polyethyleneimine, 1.4335g of 1-chloro-2-phenylethane and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove N,N-dimethylacetamide, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0076] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 200mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.005g / mL, and at the same time prepare an aqueous solution of toluidine blue with a concentration of 0.002g / mL; then mix and stir 100mL of the chloroform solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of toluidine blue; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0077] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 85℃ for 7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0078] Example 12

[0079] (1) 1g of methylated branched polyethyleneimine, 1.4335g of 1-chloro-2-phenylethane and 5mL of N,N-dimethylacetamide were stirred at 120℃ for 1h; after the reaction was completed, N,N-dimethylacetamide was removed to obtain benzyl-modified methylated branched polyethyleneimine.

[0080] (2) Dissolve 0.75g of the benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 75mL of chloroform to prepare a chloroform solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of indocyanine green with a concentration of 0.002g / mL; then mix and stir 75mL of the chloroform solution of the benzyl-modified methyl-branched polyethyleneimine and 75mL of the aqueous solution of indocyanine green; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 40℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0081] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 1g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 85℃ for 1h to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0082] Example 13

[0083] (1) 1g of methylated branched polyethyleneimine, 1.4335g of 1-chloro-2-phenylethane and 5mL of chloroform were stirred at 120℃ for 1h; after the reaction was completed, the precipitate was centrifuged to remove the chloroform, and benzyl-modified methylated branched polyethyleneimine was obtained.

[0084] (2) Dissolve 1g of benzyl-modified methyl-branched polyethyleneimine prepared in step (1) in 100mL of chloroform to prepare a toluene solution of benzyl-modified methyl-branched polyethyleneimine with a concentration of 0.01g / mL, and at the same time prepare an aqueous solution of methylene blue with a concentration of 0.002g / mL; then mix and stir 100mL of the toluene solution of benzyl-modified methyl-branched polyethyleneimine and 100mL of the aqueous solution of methylene blue; then separate the layers using a separatory funnel, take the lower layer solution and dry it by rotary evaporation at 80℃ to obtain benzyl-modified methyl-branched polyethyleneimine with guest dye.

[0085] (3) Dissolve 1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in 5mL of chloroform, add 0.75g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a polytetrafluoroethylene vinyl plate, and cure it at 85℃ for 3d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

[0086] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for constructing a host-guest composite coating of photodynamic / quaternary ammonium salt / boric acid antibacterial PET fibers, characterized in that, Includes the following steps: (1) Add 0.5~2g of methylated branched polyethyleneimine, 0.5~5g of benzyl halide and 5~15mL of solvent, and stir at 50~120℃ for 1~48h; after the reaction is completed, remove the solvent to obtain benzyl-modified methylated branched polyethyleneimine; the benzyl halide is 3-methylbenzyl chloride, (5-bromopentyl)benzene, (5-chloropentyl)benzene, 1-chloro-2-phenylethane, 1-bromo-2-phenylethane, 1-chloro-3-phenylpropane, 1-bromo-3-phenylpropane, 4-isopropylbenzyl chloride, 4-isopropylbenzyl bromide, 4-phenyl-1-butyl bromide or 4-phenyl-1-butyl chloride; (2) Dissolve the benzyl-modified methylated branched polyethyleneimine prepared in step (1) in chloroform to prepare a chloroform solution of benzyl-modified methylated branched polyethyleneimine with a concentration of 0.003~0.018 g / mL; and prepare an aqueous photosensitizer solution with a concentration of 0.0005~0.0025 g / mL; then take 75~125 mL of the chloroform solution of the benzyl-modified methylated branched polyethyleneimine and 75~125 mL of the aqueous photosensitizer solution, separate the liquid, and dry the lower layer solution by rotary evaporation to obtain benzyl-modified methylated branched polyethyleneimine with guest dye; the aqueous photosensitizer solution is an aqueous solution of Bengal rose red, toluidine blue, indocyanine green or methylene blue. (3) Dissolve 0.5~1g of benzyl-modified methylated branched polyethyleneimine with guest dye prepared in step (2) in an organic solvent, add 0.3~1.5g of 4-chloromethylphenylboronic acid, coat it evenly on PET fiber and place it on a substrate, and cure it at 50~90℃ for 1h~7d to obtain the host and guest of the photodynamic / quaternary ammonium salt / boric acid antibacterial composite PET fiber coating.

2. The method for constructing a host-guest composite PET fiber coating based on a photodynamic / quaternary ammonium salt / boric acid antibacterial coating according to claim 1, characterized in that, The solvent is toluene, xylene, methanol, tetrahydrofuran, N,N-dimethylformamide, N,N-diethylformamide, cyclohexane, or chloroform.

3. The method for constructing the host-guest composite of photodynamic / quaternary ammonium salt / boric acid antibacterial PET fiber coating according to claim 1, characterized in that, The organic solvent is chloroform, toluene, or methanol.

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