An antibacterial and antiviral mask modified with cationic conjugated microporous polymer

Abstract

The invention discloses an antibacterial and antiviral mask based on a cationic conjugated microporous polymer, which includes an antibacterial and antiviral outer layer, an antibacterial and antiviral meltblown layer and a hygroscopic inner lining layer from outside to inside; the outer layer is a hydrophobic polypropylene spunbonded nonwoven fabric modified by a cationic conjugated microporous polymer film, the meltblown layer is a polypropylene meltblown nonwoven fabric modified by a cationic conjugated microporous polymer film, and the inner lining layer is a polypropylene spunbonded nonwoven fabric. The present invention modifies the cationic conjugated microporous polymer film on the outer layer and the meltblown layer of the mask, which can have antibacterial and antiviral activity by itself, and is not limited by light conditions. Under sunlight irradiation and dark conditions, it has a high antibacterial efficiency, can prevent secondary infection caused by improper removal, and has good lasting antibacterial and disease resistance, can achieve broad-spectrum and efficient antibacterial, and can be reused, which reduces the large consumption of disposable masks to a certain extent, and provides a new idea for the development of antibacterial and antiviral masks in the future.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial and antiviral masks, and particularly relates to an antibacterial and antiviral mask modified with a cationic conjugated microporous polymer. Background Art

[0002] When we breathe, talk, cough and sneeze, a large amount of respiratory secretions and saliva are released into the surrounding environment, forming microbial aerosols. These infectious aerosols are a collection of particles containing pathogens, which are very likely to be deposited in living spaces and infect susceptible people, leading to the occurrence of respiratory infectious diseases. Most pathogenic viruses, bacteria and fungi, such as H1N1 virus, Mycobacterium tuberculosis, Streptococcus pyogenes, Staphylococcus aureus, etc., can be transmitted through aerosols in the air. In addition, due to the continuous evolution of bacterial resistance and viral mutations, the role of existing drugs, vaccines and antibiotics is limited. In order to ensure that individuals are protected from infection, in addition to washing hands and maintaining a safe social distance, the use of personal protective equipment is also an important way to prevent the spread of infectious diseases. Masks are globally recognized as one of the personal protective equipment that can effectively prevent aerosol infection. Common masks are generally divided into two categories: ordinary masks and medical masks. Ordinary masks (dust masks, gauze masks and cotton masks, etc.) have a general filtering effect on droplets, dust, etc. in the air, and have almost no virus protection function. Medical masks can generally be divided into three categories: ordinary medical masks, medical surgical masks and medical protective masks, and their protection levels increase in sequence. Standard medical surgical masks are divided into three layers (SMS structure). The outer layer has a waterproof function to prevent droplets from entering the mask after splashing; the middle layer is the core layer of the mask, which can use its own ultra-fine pores and electrostatic effects to block and filter bacteria and viruses; the inner layer near the mouth and nose is used to absorb moisture and maintain a comfortable internal environment. The middle layer is generally made of a special material, which is called meltblown non-woven fabric, or meltblown fabric for short. Meltblown fabric is a kind of non-woven fabric made of polypropylene as raw material, which is blown into ultra-fine short fibers under the action of high-speed hot air and flies to the condensing net curtain belt or roller at a very high speed to form a criss-crossed fiber. The meltblown non-woven fabric produced by the meltblown method naturally has the characteristics of filtering bacteria and viruses, and its filtration rate is about 35%, but this does not meet the requirements of medical masks. The material needs to be treated with electret to make the fiber carry a charge, and use static electricity to capture pathogenic aerosols to achieve a filtration rate of more than 95%. Although the commonly used medical masks have high filtration properties, they lack antibacterial and antiviral activity, which allows bacteria or viruses to survive on the mask surface for a long time (up to 7 days), which can easily cause secondary infection. At the same time, the masks have a short service life and need to be replaced frequently and disposed of in large quantities. Based on the above shortcomings, it is an urgent need to develop masks with antibacterial and antiviral functions. The current research on antibacterial and antiviral masks mainly includes the following categories: (1) coating the mask surface with salt particles such as sodium chloride and potassium chloride; (2) modifying the mask surface with graphene oxide; (3) mixing metal nanoparticles into the raw materials to make the mask surface; (4) grafting photosensitizers onto the mask surface so that the mask produces reactive oxygen under light irradiation, thereby providing light-induced biocidal function.

[0003] Although different research methods have been used to give masks antibacterial and antiviral properties, these methods may have a series of problems such as low biocompatibility, complex manufacturing processes, slow and inefficient sterilization, and limitations on light conditions. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide an antibacterial and antiviral mask with a cationic conjugated microporous polymer modified on the outer layer and the melt-blown layer. The antibacterial and antiviral mask can achieve efficient antibacterial and antiviral effects by utilizing its own cationic side chains and photosensitivity, and is not limited by light conditions, and can produce good antibacterial and antiviral properties under both light and dark conditions.

[0005] To achieve the above-mentioned purpose, the cationic conjugated microporous polymer modified antibacterial and antiviral mask adopted by the present invention comprises, from outside to inside, an antibacterial and antiviral outer layer, an antibacterial and antiviral meltblown layer and a hygroscopic inner lining layer; the antibacterial and antiviral outer layer is a hydrophobic polypropylene spunbonded non-woven fabric modified with a cationic conjugated microporous polymer film; the antibacterial and antiviral meltblown layer is a polypropylene meltblown non-woven fabric modified with a cationic conjugated microporous polymer film; the hygroscopic inner lining layer is a polypropylene spunbonded non-woven fabric; the fiber fineness of the antibacterial and antiviral outer layer is 20 to 30 μm; the fiber fineness of the antibacterial and antiviral meltblown layer is 2 to 15 μm; the fiber fineness of the hygroscopic inner lining layer is 20 to 30 μm; the thickness of the cationic conjugated microporous polymer film on the antibacterial and antiviral outer layer (1) and the antibacterial and antiviral meltblown layer (2) is 10 to 500 nm.

[0006] The structural unit of the cationic conjugated microporous polymer is any one of the following formulas I to III:

[0007]

[0008]

[0009] In the formula, n is an integer of 1 to 20, X, Y, and Z each independently represent N or CH, and R is selected from Any one of, m is an integer from 1 to 18, R1 is selected from Any one of the following, wherein p is an integer from 0 to 3, and q is an integer from 1 to 8.

[0010] Furthermore, it is preferred that the thickness of the cationic conjugated microporous polymer film on the antibacterial and antiviral outer layer and the antibacterial and antiviral meltblown layer is 100 to 500 nm.

[0011] The preparation method of the above-mentioned antibacterial and antiviral outer layer and antibacterial and antiviral meltblown layer is as follows: dissolve monomer 1 and monomer 2 in an organic solvent, add a metal catalyst, and after complete dissolution, add a homogeneous catalyst, react in the dark for 2 to 5 hours to obtain a cationic conjugated microporous polymer reaction liquid; spray the reaction liquid onto a formed hydrophobic polypropylene spunbond non-woven fabric and a polypropylene meltblown non-woven fabric, wash them with methanol and chloroform in turn, and vacuum dry them to obtain a hydrophobic polypropylene spunbond non-woven fabric modified with a cationic conjugated microporous polymer and a polypropylene meltblown non-woven fabric modified with a cationic conjugated microporous polymer film, namely, an antibacterial and antiviral outer layer and an antibacterial and antiviral meltblown layer, respectively.

[0012] The structural formula of the monomer 1 is any one of formula a, b, and c:

[0013]

[0014] In formula a, b, and c, X, Y, and Z each independently represent N or CH.

[0015] The structural formula of the above monomer 2 is: Wherein, n is an integer from 1 to 20, and R is selected from Any one of, m is an integer from 1 to 18, R1 is selected from Any one of the following, wherein p is an integer from 0 to 3, and q is an integer from 1 to 8.

[0016] Furthermore, it is preferred that the structural formula of the monomer 2 is any one of formulas d, e, and f:

[0017]

[0018] The metal catalyst is any one of cuprous iodide, bis(triphenylphosphine)palladium dichloride, and palladium acetate catalysts, or a combination of two of them; the homogeneous catalyst is any one of isopropylamine, 4-dimethylaminopyridine, and triethylamine; and the organic solvent is any one of acetonitrile, N,N-dimethylformamide, dioxane, methanol, and tetrahydrofuran, or a combination of two of them.

[0019] Furthermore, the molar ratio of the monomer 1 to the monomer 2, the metal catalyst, and the homogeneous catalyst is preferably 1:1-1.5:0.1-0.8:2-3.

[0020] Furthermore, it is preferred that the vacuum drying temperature is 50 to 120° C. and the time is 8 to 15 hours.

[0021] The antibacterial and antiviral mask modified with cationic conjugated microporous polymers of the present invention has two main antibacterial principles: passive mode and active mode. On the one hand, the cationic conjugated microporous polymer itself can be used as a photosensitizer to produce active oxygen components in a photodynamic process under the stimulation of sunlight, causing irreversible damage to bacteria and viruses, while improving the antibacterial efficiency and overcoming the drug resistance problem of bacteria and viruses. This mode is called the active mode; on the other hand, the quaternary ammonium salt side chain of the cationic conjugated microporous polymer can be anchored to the surface of bacteria or viruses through electrostatic interactions, destroying the cell membrane or capsid of bacteria and viruses, thereby causing leakage of cytoplasm, or interfering with the viral genome content or structural units, resulting in the decomposition of the virus, ensuring that it can still achieve a good bactericidal effect in the dark or weak light. This process is called antibacterial and antiviral in passive mode. Based on the above principles, the cationic conjugated microporous polymer modified antibacterial and antiviral mask can achieve efficient antibacterial and antiviral effects through the synergistic active and passive modes under sunlight exposure, and can continue to perform antibacterial work through the passive mode at night or in cloudy and rainy weather, providing basic antibacterial and antiviral effects.

[0022] The beneficial effects of the present invention are as follows:

[0023] (1) The antibacterial and antiviral mask modified by the cationic conjugated microporous polymer of the present invention is of SMS structure, wherein a cationic conjugated microporous polymer film is grown on the outer layer and the melt-blown layer fiber layer, and the thickness thereof is about 10 to 500 nm, which gives the original mask surface layer antibacterial and antiviral properties. The antibacterial and antiviral mask formed can prevent secondary infection caused by improper removal, and at the same time, it has the advantage of being reusable, which reduces the large consumption of disposable masks to a certain extent;

[0024] (2) The cationic conjugated microporous polymers (CMPs) of the present invention are a type of organic porous polymers composed of light elements such as C, H, N, and O. The antibacterial and antiviral masks modified with the CMPs have good biocompatibility. The special feature is that the conjugated microporous polymer is a π-π conjugated network structure formed by alternating double bonds or triple bonds with single bonds. On the one hand, CMPs can be used as a photosensitizer to produce active oxygen components under light conditions and cause nonspecific and irreversible damage to bacteria and viruses, avoiding the problem of drug resistance; on the other hand, through the customization of molecular network building blocks, CMPs can introduce different functional groups into the polymer skeleton to enhance its ability to kill bacteria and viruses;

[0025] (3) The cationic conjugated microporous polymer modified antibacterial and antiviral mask of the present invention has the same killing effect on Gram-negative bacteria such as Escherichia coli, Gram-positive bacteria such as Staphylococcus aureus, pathogenic fungi such as Candida albicans, and viruses such as SARS-CoV-2. Under sunlight, it can achieve a bacterial lethality of more than 90% in just 10 minutes (95% and 99% respectively for Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus); under dark conditions, the anti The antibacterial and antiviral mask can achieve an antibacterial efficiency of more than 90% in 25 minutes (killing 90% and 99% of Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus respectively), and has basically good antibacterial and antiviral effects; after 8 consecutive uses, whether in dark or light conditions, its antibacterial rate still remains above 90% (the antibacterial rate for Escherichia coli is maintained at more than 90%, and the antibacterial rate for Staphylococcus aureus is maintained at more than 99%), and has good long-lasting antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic structural diagram of an antibacterial and antiviral mask modified with a cationic conjugated microporous polymer of the present invention;

[0027] Figure 2 This is a graph showing the change in the antibacterial rate of the antibacterial and antiviral mask modified with a cationic conjugated microporous polymer prepared in Example 1 against Escherichia coli over time;

[0028] Figure 3 This is a graph showing the change in the antibacterial rate of the antibacterial and antiviral mask modified with a cationic conjugated microporous polymer prepared in Example 1 against Staphylococcus aureus over time;

[0029] Figure 4 The antibacterial rate of the antibacterial and antiviral mask modified with the cationic conjugated microporous polymer prepared in Example 1 against Escherichia coli at different times of use;

[0030] Figure 5 The antibacterial rate of the antibacterial and antiviral mask modified with the cationic conjugated microporous polymer prepared in Example 1 against Staphylococcus aureus at different times of use;

[0031] Figure 6 This is a field emission scanning electron microscope image of Escherichia coli and Staphylococcus aureus on the antibacterial and antiviral mask modified with a cationic conjugated microporous polymer prepared in Example 1. DETAILED DESCRIPTION

[0032] The present invention is described in detail below with reference to the accompanying drawings and embodiments, but the protection scope of the present invention is not limited to these embodiments.

[0033] Example 1

[0034] like Figure 1 As shown, the cationic conjugated microporous polymer modified antibacterial and antiviral mask of this embodiment includes an antibacterial and antiviral outer layer 1, an antibacterial and antiviral meltblown layer 2 and a hygroscopic inner lining layer 3 from the outside to the inside; the antibacterial and antiviral outer layer 1 is a hydrophobic polypropylene spunbond non-woven fabric modified with a cationic conjugated microporous polymer film; the antibacterial and antiviral meltblown layer 2 is a polypropylene meltblown non-woven fabric modified with a cationic conjugated microporous polymer film; the hygroscopic inner lining layer 3 is a polypropylene spunbond non-woven fabric; the fiber fineness of the antibacterial and antiviral outer layer 1 is 20 to 30 μm; the fiber fineness of the antibacterial and antiviral meltblown layer 2 is 2 to 15 μm; the fiber fineness of the hygroscopic inner lining layer 3 is 20 to The thickness of the cationic conjugated microporous polymer film on the hydrophobic polypropylene spunbond nonwoven fabric modified by the cationic conjugated microporous polymer film and the polypropylene meltblown nonwoven fabric modified by the cationic conjugated microporous polymer film is 400 to 500 nm, and the structural unit of the cationic conjugated microporous polymer is shown in Formula I, wherein n=1, X=Y=Z=CH, and R is R1 is m=6, p=0.

[0035] The preparation method of the hydrophobic polypropylene spunbond nonwoven fabric modified by the cationic conjugated microporous polymer film and the polypropylene meltblown nonwoven fabric modified by the cationic conjugated microporous polymer film is as follows: 16 mL of N, N-dimethylformamide, 46 mg (0.12 mmol) of monomer 1-a-1 and 145 mg (0.18 mmol) of monomer 2-d-1 are added to a 50 mL centrifuge tube, and after complete dissolution, 11.4 mg (0.06 mmol) of cuprous iodide and 16.8 mg (0.024 mmol) bis(triphenylphosphine)palladium dichloride, and finally adding 500 μL (0.36 mmol) triethylamine, and reacting in the dark for 2 hours to obtain a cationic conjugated microporous polymer; the reaction solution is evenly sprayed onto the formed hydrophobic polypropylene spunbond non-woven fabric and the polypropylene melt-blown non-woven fabric, and washed with methanol and chloroform three times in sequence, and finally placed in a vacuum drying oven at 80° C. for 10 hours; after repeating the above spraying, washing, and drying processes twice, a cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond non-woven fabric and a cationic conjugated microporous polymer film-modified polypropylene melt-blown non-woven fabric are respectively obtained.

[0036] The synthetic route and method of the above monomer 1-a-1 are:

[0037]

[0038] 1. Add 2 g (3 mmol) of 1,3,5-tri-(4-iodophenyl)benzene (compound 1), 240 mg (0.9 mmol) of triphenylphosphine, 180 mg (0.9 mmol) of cuprous iodide, 320 mg (0.45 mmol) of bis(triphenylphosphine)palladium dichloride and 1 mL (27 mmol) of trimethylsilyl acetylene to a 50 mL round-bottom flask, then add 10 mL of tetrahydrofuran and 3 mL of triethylamine, react at room temperature for 5 h, extract, dry and concentrate, and separate by column chromatography to obtain compound 2;

[0039] 2. Add 2.5 g (4.2 mmol) of compound 2 and 3.4 g (25.2 mmol) of potassium carbonate into a 50 mL round-bottom flask, then add 6 mL of methanol and 10 mL of dichloromethane, react at room temperature for 5 h, extract, dry and concentrate, and separate by column chromatography to obtain monomer 1-a-1.

[0040] The synthetic route and method of the above monomer 2-d-1 are as follows:

[0041]

[0042] 1. Add 0.78 g (2 mmol) of 1,4-dimethoxy-2,5-diiodobenzene (compound 3) to a 50 mL round-bottom flask, dissolve it with 5 mL of dichloromethane, add 6 mL (6 mmol) of boron tribromide and 5 mL of dichloromethane to a dropping funnel, place the reaction mixture at -78 ° C, add a mixture of boron tribromide and dichloromethane dropwise, react at room temperature for 24 hours, quench the reaction mixture with ice water, extract, dry and concentrate it, and then separate it by column chromatography to obtain compound 4;

[0043] 2. Add 1.8 g (5 mmol) of compound 4, 12.2 g (50 mmol) of 1,6-dibromohexane, 3.44 g (25 mmol) of potassium carbonate, 131.4 mg (0.5 mmol) of 18-crown ether-6 and 20 mL of acetone to a 50 mL round-bottom flask, react at room temperature for 5 h, extract, dry and concentrate, and separate by column chromatography to obtain compound 5;

[0044] 3. Add 0.688 g (1 mmol) of compound 5, 5 mL of dichloromethane and 10 mL of trimethylamine into a 25 mL round-bottom flask and react at room temperature for 48 h. The resulting precipitate is recrystallized and centrifuged to obtain monomer 2-d-1.

[0045] Example 2

[0046] The structure of the antibacterial and antiviral mask modified with a cationic conjugated microporous polymer in this embodiment is the same as that in Example 1, wherein the thickness of the cationic conjugated microporous polymer film on the hydrophobic polypropylene spunbonded non-woven fabric modified with a cationic conjugated microporous polymer film and the polypropylene melt-blown non-woven fabric modified with a cationic conjugated microporous polymer film is 400 to 500 nm, and the structural unit of the cationic conjugated microporous polymer is shown in Formula I, wherein n=1, X=Y=Z=CH, and R is R1 is m=2, p=0.

[0047] The preparation method of the above-mentioned cationic conjugated microporous polymer film modified hydrophobic polypropylene spunbond nonwoven fabric and cationic conjugated microporous polymer film modified polypropylene meltblown nonwoven fabric is as follows: 16 mL of N, N-dimethylformamide, 46 mg (0.12 mmol) of monomer 1-a-1 and 141 mg (0.18 mmol) of monomer 2-f-1 are added to a 50 mL centrifuge tube, and after complete dissolution, 11.4 mg (0.06 mmol) of cuprous iodide and 16.8 mg (0.024 mmol) bis(triphenylphosphine)palladium dichloride, and finally adding 500 μL (0.36 mmol) triethylamine, and reacting in the dark for 2 hours to obtain a cationic conjugated microporous polymer; the reaction solution is evenly sprayed onto the formed hydrophobic polypropylene spunbond non-woven fabric and the polypropylene melt-blown non-woven fabric, and washed with methanol and chloroform three times in sequence, and finally placed in a vacuum drying oven for drying at 80° C. for 5 hours; after repeating the above spraying, washing, and drying process twice, a cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond non-woven fabric and a cationic conjugated microporous polymer film-modified polypropylene melt-blown non-woven fabric are respectively obtained.

[0048] The synthetic route of the above monomer 2-f-1 is as follows:

[0049]

[0050] In the synthesis method, only equimolar Replace Br(CH2)6Br in Example 1, and the other steps are the same as the synthesis method of monomer 2-d-1.

[0051] Example 3

[0052] The structure of the antibacterial and antiviral mask modified with a cationic conjugated microporous polymer in this embodiment is the same as that in Example 1, wherein the thickness of the cationic conjugated microporous polymer film on the hydrophobic polypropylene spunbonded non-woven fabric modified with a cationic conjugated microporous polymer film and the polypropylene melt-blown non-woven fabric modified with a cationic conjugated microporous polymer film is 100 to 200 nm, and the structural unit of the cationic conjugated microporous polymer is shown in Formula I, wherein n=1, X=Y=Z=N, and R is R1 is m=6, p=0.

[0053] The preparation method of the above-mentioned cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond nonwoven fabric and cationic conjugated microporous polymer film-modified polypropylene meltblown nonwoven fabric is as follows: 16 mL of N, N-dimethylformamide, 24.4 mg (0.06 mmol) of monomer 1-a-2 and 72.5 mg (0.09 mmol) of After the monomer 2-d-1 is completely dissolved, 5.7 mg (0.03 mmol) of cuprous iodide and 8.4 mg (0.012 mmol) of bis(triphenylphosphine)palladium dichloride are added, and finally 250 μL (0.18 mmol) of triethylamine is added, and the reaction is carried out in the dark for 2 hours to obtain a cationic conjugated microporous polymer; the reaction solution is evenly sprayed onto the formed hydrophobic polypropylene spunbond non-woven fabric and the polypropylene melt-blown non-woven fabric, and the fabric is washed with methanol and chloroform three times in sequence, and finally placed in a vacuum drying oven and dried at 80° C. for 10 hours; after repeating the above spraying, washing and drying process twice, a cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond non-woven fabric and a cationic conjugated microporous polymer film-modified polypropylene melt-blown non-woven fabric are obtained, respectively.

[0054] The synthetic route and method of the above monomer 1-a-2 are:

[0055]

[0056] 1. Add 2 g (3 mmol) of compound 7, 247 mg (0.9 mmol) of triphenylphosphine, 192 mg (0.9 mmol) of cuprous iodide, 343 mg (0.45 mmol) of bis(triphenylphosphine)palladium dichloride and 1.2 mL (27 mmol) of trimethylsilyl acetylene to a 50 mL round-bottom flask, then add 10 mL of tetrahydrofuran and 3 mL of triethylamine, react at room temperature for 10 h, extract, dry and concentrate, and separate by column chromatography to obtain compound 8;

[0057] 2. Add 2.5 g (4.2 mmol) of compound 8 and 3.8 g (25.2 mmol) of potassium carbonate into a 50 mL round-bottom flask, then add 6 mL of methanol and 10 mL of dichloromethane, react at room temperature for 10 h, extract, dry and concentrate, and separate by column chromatography to obtain monomer 1-a-2.

[0058] Example 4

[0059] The structure of the antibacterial and antiviral mask modified with the cationic conjugated microporous polymer of this embodiment is the same as that of Example 1. The structural unit of the cationic conjugated microporous polymer is shown in Formula II, wherein n=1, X=Y=Z=CH, and R is R1 is m=6, p=0.

[0060] The preparation method of the above-mentioned cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond nonwoven fabric and cationic conjugated microporous polymer film-modified polypropylene meltblown nonwoven fabric is as follows: 16 mL of N, N-dimethylformamide, 45 mg (1.2 mmol) of monomer 1-b-1 and 145 mg (1.8 mmol) of monomer 2-d-1 are added to a 50 mL centrifuge tube, and after they are completely dissolved, 11.4 mg (0.06 mmol) of cuprous iodide and 16.8 mg (0.024 mmol) of Bis(triphenylphosphine)palladium dichloride, and finally add 500 μL (0.36 mmol) of triethylamine, react for 2 hours in the dark to obtain a cationic conjugated microporous polymer; the reaction solution is evenly sprayed onto the formed hydrophobic polypropylene spunbond non-woven fabric and polypropylene melt-blown non-woven fabric, washed three times with methanol and chloroform in sequence, and finally placed in a vacuum drying oven and dried at 80°C for 5 hours; after repeating the above spraying, washing and drying process twice, a cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond non-woven fabric and a cationic conjugated microporous polymer film-modified polypropylene melt-blown non-woven fabric are obtained respectively.

[0061] The synthetic route and method of the above monomer 1-b-1 are:

[0062]

[0063] 10 mL of toluene was added to a 50 mL round-bottom flask, and after deoxygenation by N2 for 30 min, 2 g (3 mmol) of 1,3,5-tri-(4-iodophenyl)benzene (Compound 1), 1.58 g (5 mmol) of tributyl vinyl tin, 12.4 mg (0.06 mmol) of 2,6-di-tert-butylphenol, and 96 mg (0.135 mmol) of bis(triphenylphosphine) palladium dichloride were added, and the mixture was heated to 100 ° C for 10 h. After the reaction, the reaction solution was cooled to room temperature, and then 17 mL of 2 mol / L KF aqueous solution was added and stirred overnight. The resulting mixture was extracted, dried, concentrated, and separated by column chromatography to obtain monomer 1-b-1.

[0064] Example 5

[0065] The structure of the antibacterial and antiviral mask modified with the cationic conjugated microporous polymer of this embodiment is the same as that of Example 1. The structural unit of the cationic conjugated microporous polymer is shown in Formula III, wherein n=1, X=Y=Z=CH, and R is R1 is m=6, p=0.

[0066] The preparation method of the hydrophobic polypropylene spunbond nonwoven fabric modified by the cationic conjugated microporous polymer film and the polypropylene meltblown nonwoven fabric modified by the cationic conjugated microporous polymer film is as follows: 16 mL of N, N-dimethylformamide, 18 mg (0.12 mmol) of monomer 1-c-1 and 145 mg (0.18 mmol) of monomer 2-d-1 are added to a 50 mL centrifuge tube, and after they are completely dissolved, 11.4 mg (0.06 mmol) of cuprous iodide and 16.8 mg (0.024 mmol) bis(triphenylphosphine)palladium dichloride, and finally adding 500 μL (0.36 mmol) triethylamine, and reacting in the dark for 2 hours to obtain a cationic conjugated microporous polymer; the reaction solution is evenly sprayed onto the formed hydrophobic polypropylene spunbond non-woven fabric and the polypropylene melt-blown non-woven fabric, and washed with methanol and chloroform three times in sequence, and finally placed in a vacuum drying oven for drying at 80° C. for 5 hours; after repeating the above spraying, washing, and drying process twice, a cationic conjugated microporous polymer film-modified hydrophobic polypropylene spunbond non-woven fabric and a cationic conjugated microporous polymer film-modified polypropylene melt-blown non-woven fabric are respectively obtained.

[0067] The synthetic route and method of the above monomer 1-c-1 are as follows:

[0068]

[0069] 1. Add 1.37 g (3 mmol) of compound 9, 240 mg (0.9 mmol) of triphenylphosphine, 180 mg (0.9 mmol) of cuprous iodide, 320 mg (0.45 mmol) of bis(triphenylphosphine)palladium dichloride and 1 mL (27 mmol) of trimethylsilyl acetylene to a 50 mL round-bottom flask, then add 10 mL of tetrahydrofuran and 3 mL of triethylamine, react at room temperature for 5 h, extract, dry and concentrate, and separate by column chromatography to obtain compound 10;

[0070] 2. Add 1.54 g (4.2 mmol) of compound 10 and 3.4 g (25.2 mmol) of potassium carbonate into a 50 mL round-bottom flask, then add 4 mL of methanol and 6 mL of dichloromethane, react at room temperature for 5 h, extract, dry and concentrate, and separate by column chromatography to obtain monomer 1-c-1.

[0071] The antibacterial properties of the antibacterial and antiviral mask modified with the cationic conjugated microporous polymer prepared in Example 1 above were tested, and the specific experiments and results are as follows:

[0072] Primary Staphylococcus aureus and Escherichia coli stored at -80°C were spread onto BHI agar plates and LB agar plates, and incubated overnight in a watertight incubator at 37°C for first generation activation. Single colonies on the agar plates were picked and placed in 20 mL of culture medium, and incubated in a shaker at a constant temperature of 37°C for 12 hours until their logarithmic growth phase. Bacteria in the logarithmic growth phase were collected by centrifugation, and then washed three times with sterilized 0.9% NaCl saline. After removing the supernatant, 0.9% NaCl saline was added to obtain a bacterial suspension.

[0073] The bacterial suspension was diluted to 1 × 10 6 CFU / mL, take 20μL and drop it on a 1.5 cm*1.5 cm antibacterial and antiviral mask cloth, and place it in the dark or under light (white light source 100mW / cm 2 After treatment for 1, 2.5, 5, 10, 15, 20, 25, and 30 minutes under simulated sunlight conditions, the bacteria on the mask cloth were scraped with a cotton swab and smeared on an agar plate, which was placed in a water-tight incubator at 37°C and incubated overnight. The antibacterial rate of the antibacterial and antiviral mask of the present invention against Escherichia coli and Staphylococcus aureus was calculated using the plate count method. At the same time, a commercial disposable medical surgical mask was used as a control group, and the above experimental process was repeated. The results are shown in Figure 2 and Figure 3 .

[0074] Depend on Figure 2 and Figure 3 It can be seen that under dark conditions, the antibacterial and antiviral mask modified by the cationic conjugated microporous polymer can achieve an antibacterial rate of 90% and 99% or more against Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus at 25 minutes; under simulated sunlight, it can produce a killing effect of 95% and 99% or more against Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus at only 10 minutes; while for ordinary disposable medical surgical masks, whether in dark or light conditions, the antibacterial activity changes slightly, only about 40%. The experimental results show that the antibacterial and antiviral mask modified by the cationic conjugated microporous polymer in the present invention has good antibacterial activity and high antibacterial efficiency against both Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus.

[0075] The bacterial suspension was diluted to 1 × 10 6 CFU / mL, take 20μL and drop it on a 1.5 cm*1.5 cm antibacterial and antiviral mask cloth, and place it in the dark or under light (white light source 100mW / cm 2After 30 minutes of treatment under simulated sunlight conditions, use a cotton swab to scrape the bacteria on the mask cloth and apply it to the agar plate. After repeating this process 8 times, place the agar plate in a water-tight incubator at 37°C and incubate overnight. The antibacterial rate of the antibacterial and antiviral mask against Escherichia coli and Staphylococcus aureus was calculated using the plate count method. At the same time, a commercial disposable medical surgical mask was used as the control group and the above experimental process was repeated. The results are shown in Figure 4 and Figure 5 .

[0076] The experimental results show that after 8 consecutive uses, the antibacterial and antiviral mask modified with cationic conjugated microporous polymers maintained an antibacterial rate of more than 90% against Escherichia coli and an antibacterial rate of more than 99% against Staphylococcus aureus, whether in dark or light conditions, proving that it has good long-lasting antibacterial properties.

[0077] The bacterial suspension was diluted to 1 × 10 6 CFU / mL, take 20μL and drop it on a 1.5 cm*1.5 cm antibacterial and antiviral mask cloth, and place it in the dark or under light (white light source 100mW / cm 2 After being treated for 30 minutes under simulated sunlight conditions, the mask cloth coated with the bacterial solution was immersed in glutaraldehyde phosphate buffer solution, fixed for 12 hours at 4°C, washed more than 3 times with 10mM PBS solution (pH=7.4), and then dehydrated step by step with 30%, 50%, 60%, 70%, 80%, 90%, and 100% ethanol at 4°C for 10 minutes. Each gradient was repeated twice, and finally the cloth was immersed in tert-butanol solution for storage. At the same time, a commercial disposable medical surgical mask was used as the control group, and the above experimental process was repeated. The results of field emission scanning electron microscopy are shown in Figure 6 .Depend on Figure 6 It can be seen that both Escherichia coli and Staphylococcus aureus showed membrane fusion and membrane rupture on the cationic conjugated microporous polymer mask, indicating that the mask has good antibacterial properties; under light conditions, the bacteria were basically completely dead, indicating that in the dual antibacterial mode driven by sunlight, the cationic conjugated microporous polymer mask exhibited a more excellent synergistic antibacterial effect.

Claims

1. An antibacterial and antiviral mask modified with a cationic conjugated microporous polymer, characterized in that: From the outside to the inside, the antibacterial and antiviral outer layer (1), the antibacterial and antiviral meltblown layer (2) and the hygroscopic inner lining layer (3); the antibacterial and antiviral outer layer (1) is a hydrophobic polypropylene spunbonded non-woven fabric modified with a cationic conjugated microporous polymer film; the antibacterial and antiviral meltblown layer (2) is a polypropylene meltblown non-woven fabric modified with a cationic conjugated microporous polymer film; the hygroscopic inner lining layer (3) is a polypropylene spunbonded non-woven fabric; the fiber fineness of the antibacterial and antiviral outer layer (1) is 20 to 30 μm; the fiber fineness of the antibacterial and antiviral meltblown layer (2) is 2 to 15 μm; the fiber fineness of the hygroscopic inner lining layer (3) is 20 to 30 μm; the thickness of the cationic conjugated microporous polymer film on the antibacterial and antiviral outer layer (1) and the antibacterial and antiviral meltblown layer (2) is 10 to 500 nm; The structural unit of the cationic conjugated microporous polymer is any one of the following formulas I to III: In the formula, n is an integer of 1 to 20, X, Y, and Z each independently represent N or CH, and R is selected from Any one of, m is an integer from 1 to 18, R1 is selected from Any one of the following, wherein p is an integer from 0 to 3, and q is an integer from 1 to 8.

2. The antibacterial and antiviral mask modified with a cationic conjugated microporous polymer according to claim 1, characterized in that: The thickness of the cationic conjugated microporous polymer film on the antibacterial and antiviral outer layer (1) and the antibacterial and antiviral melt-blown layer (2) is 100 to 500 nm.

3. The antibacterial and antiviral mask modified with a cationic conjugated microporous polymer according to claim 1 or 2, characterized in that: The preparation method of the antibacterial and antiviral outer layer (1) and the antibacterial and antiviral meltblown layer (2) is as follows: dissolving monomer 1 and monomer 2 in an organic solvent, adding a metal catalyst, and after complete dissolution, adding a homogeneous catalyst, reacting in the dark for 2 to 5 hours to obtain a cationic conjugated microporous polymer reaction liquid; spraying the reaction liquid onto a formed hydrophobic polypropylene spunbond non-woven fabric and a polypropylene meltblown non-woven fabric, washing with methanol and chloroform in turn, and vacuum drying to obtain a hydrophobic polypropylene spunbond non-woven fabric modified with a cationic conjugated microporous polymer and a polypropylene meltblown non-woven fabric modified with a cationic conjugated microporous polymer film, namely, the antibacterial and antiviral outer layer (1) and the antibacterial and antiviral meltblown layer (2); The structural formula of the monomer 1 is any one of formula a, b, and c: In formula a, b, and c, X, Y, and Z each independently represent N or CH; The structural formula of the monomer 2 is: Wherein, n is an integer from 1 to 20, and R is selected from Any one of, m is an integer from 1 to 18, R1 is selected from Any one of, p is an integer from 0 to 3, q ​​is an integer from 1 to 8; The metal catalyst is any one of cuprous iodide, bistriphenylphosphine palladium dichloride, and palladium acetate catalysts, or a combination of two of them; the homogeneous catalyst is any one of isopropylamine, 4-dimethylaminopyridine, and triethylamine.

4. The antibacterial and antiviral mask modified with a cationic conjugated microporous polymer according to claim 3, characterized in that: The structural formula of the monomer 2 is any one of formulas d, e, and f: 。 5. The cationic conjugated microporous polymer modified antibacterial and antiviral mask according to claim 3, characterized in that: The molar ratio of the monomer 1 to the monomer 2, the metal catalyst and the homogeneous catalyst is 1:1-1.5:0.1-0.8:2-3.

6. The cationic conjugated microporous polymer modified antibacterial and antiviral mask according to claim 3, characterized in that: The organic solvent is any one or a combination of two of acetonitrile, N,N-dimethylformamide, dioxane, methanol and tetrahydrofuran.

7. The cationic conjugated microporous polymer modified antibacterial and antiviral mask according to claim 3, characterized in that: The vacuum drying is carried out at a temperature of 50 to 120° C. and for a time of 8 to 15 hours.

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