A polycation-pi antibacterial agent and a preparation method and application thereof

Abstract

The application belongs to the technical field of antibacterial agents, and relates to a polycation-pi antibacterial agent and a preparation method and application thereof. The antibacterial agent has a controllable sequence structure, a polymer main chain is composed of alternating hydrophobic segments and hydrophilic segments, guanidine salts are regularly arranged, surface positive charges are concentratedly distributed, and multiple interactions of cation-pi, hydrogen bonds and pi-pi stacking can be generated between molecules of the antibacterial agent. The preparation method is as follows: under catalyst or non-catalyst conditions, polycation guanidine salts and compounds with benzene rings in a molar ratio of 0.8-1.2:1 are subjected to melt polymerization or solution polymerization, and the polycation-pi antibacterial agent is obtained. The application is that the antibacterial agent is used to finish fabric to obtain antibacterial fabric, and the fabric is made of hydrophobic fibers. The preparation method of the antibacterial agent is simple, and the antibacterial fabric with durable antibacterial, directional moisture permeability and refrigeration effect can be prepared by using the antibacterial agent.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial agent technology, and relates to a polycationic-π antibacterial agent, its preparation method and application. Background Technology

[0002] With the frequent outbreaks of epidemics, pathogenic microorganisms in droplets / aerosols pose a serious threat to human health, and existing clothing and other fabrics often lead to the cultivation and spread of bacteria and viruses. Developing appropriate methods to imbue fabrics with antimicrobial properties to address this escalating threat can reduce cross-infection of diseases, alleviate the economic burden on families and society, and has broad application prospects.

[0003] Antimicrobial agents are a prerequisite for the preparation of antimicrobial fabrics. Commonly used antimicrobial agents include inorganic and organic agents. Among inorganic antimicrobial agents, silver nanoparticles and copper nanoparticles and their metal oxides, which possess broad-spectrum and highly effective antimicrobial properties, are widely used. However, a problem exposed by these nanoparticles is that nanoscale metals can cause cytotoxicity and genotoxicity to organisms when infiltrated into the environment. Chitosan, as a representative of natural antimicrobial agents, tends to be eco-friendly and is abundant on Earth. However, its application is limited because chitosan is sensitive to the pH of the finishing solution and has poor adhesion to fabrics without cross-linking agents. Quaternary ammonium compounds, halogenated amines, guanidine salts, and triclosan are widely used as organic antibacterial agents. However, the structural properties of their macromolecular chains limit intermolecular interactions, making physical adsorption onto fabrics difficult. Therefore, grafting is commonly used to fix them onto fabrics to obtain wash-resistant antibacterial fabrics. Grafting typically employs highly reactive crosslinking agents and involves complex processes, leading to significant waste of antibacterial agents, equipment modification issues, and substantial energy consumption. Furthermore, long-term use of quaternary ammonium compounds and triclosan can cause bacteria to develop resistance. Halogenated amines and triclosan possess high antibacterial efficacy, but they are highly toxic, have an irritating odor, and pose negative health risks.

[0004] The prior art mainly forms small molecule compounds by functionalizing the end group of the guanidine salt antibacterial agent containing aromatic ring. For example, patent CN104230760B proposes a preparation method of N-aryl substituted biguanide hydrobromide compound, which is to covalently bond benzene rings at both ends of the biguanide salt to form a small molecule compound. However, the antibacterial effect of such small molecule compounds is poor, and the fastness for fabric finishing is not high. Patent application CN105566547A proposes a preparation method of guanidine-based high molecular weight antibacterial agent, which is realized by copolymerization of guanidine salt functionalized maleic anhydride and styrene. Patent with application number CN202410769129.2 proposes an antibacterial and deodorizing particle prepared by grafting halogenated hydrocarbon with benzene ring based on polyhexamethylene guanidine salt. However, the position of the aromatic ring in these antibacterial agents is on the side chain of the polymer, and the antibacterial effect is limited, and the preparation process is complex. The antibacterial performance of the guanidine salt antibacterial agent containing aromatic ring needs to be further improved. At the same time, the washing resistance and friction resistance of the antibacterial fabric prepared by using such antibacterial agent are poor. SUMMARY

[0005] The purpose of the present application is to solve the problems in the prior art, and to provide a polycation-π antibacterial agent and a preparation method and application thereof.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] A polycation-π antibacterial agent, the structural formula is one of the following formulas A~F:

[0008]

[0009]

[0010] In the formula, n1, n2 and n4 are in the range of 1-10, n3 and n5 are in the range of 2-50, X - is Cl - , PO4 - , NO3 - , CO3 - 2 or C6H5SO3 - , -M is -OH, -COOCH3 or -Cl.

[0011] As a preferred technical solution:

[0012] The polycation-π antibacterial agent has a number average molecular weight of 500-20000 Da, a minimum inhibitory concentration of 1-128 μg / mL, and a minimum bactericidal concentration of 1-256 μg / mL.

[0013] The application also provides a method for preparing the polycation-pi antibacterial agent, which comprises melt polymerization or solution polymerization of the polycation guanidine salt and the benzene ring-containing compound in a molar ratio of 0.8-1.2:1 under catalytic or non-catalytic conditions.

[0014] The cationic guanidine salt has a structure as shown in any one of the following formulas I-V:

[0015] ;

[0016] The benzene ring-containing compound has a structure as shown in any one of the following formulas I-IV:

[0017] .

[0018] As a preferred technical solution,

[0019] The melt polymerization process of the method comprises the following steps: firstly, heating to 100-160 DEG C under stirring, then reacting for 2-12 h, then heating to 150-260 DEG C, then reacting for 1-5 h, and finally, vacuumizing to a vacuum degree of less than or equal to 200 Pa, and then reacting for 0-10 h (the reaction time is 0, that is, no vacuumizing, and the operation is omitted).

[0020] The molar ratio of the cationic guanidine salt and the benzene ring-containing compound in the method is 0.8-1.2:1.

[0021] The solution polymerization uses one or more of dimethyl sulfoxide, N, N-dimethylformamide, water, isopropyl alcohol, methanol, ethanol and acetone as the solvent, the solution polymerization temperature is 0-130 DEG C, and the solution polymerization time is 0.5-20 h.

[0022] The catalyst used in the method is an acidic catalyst (HCl or H2SO4), an alkaline catalyst (NaOH) or a metal catalyst (aluminum or copper-based), and the catalyst is added in an amount of 0.01-0.5% of the total mass of the polycation guanidine salt and the benzene ring-containing compound.

[0023] The application also provides an antibacterial fabric, which is obtained by finishing (the finishing method can be dipping, spraying, etc.) a fabric with an antibacterial agent, the fabric is made of hydrophobic fibers, and the antibacterial agent is one or more of the following compounds A-F, and the structural formulas of the compounds A-F correspond to the following formulas A-F:

[0024]

[0025]

[0026] In the formula, n1, n2 and n4 are in a range of 1-10, n3 and n5 are in a range of 2-50, X -Cl - PO4 3- - NO3 - CO3 2- - or C6H5SO3 - M is -OH, -COOCH3 or -Cl.

[0027] As a preferred technical solution:

[0028] The antibacterial fabric as described above, the mass of the antibacterial agent is 1-5% of the mass of the fabric.

[0029] The antibacterial fabric as described above, the fabric is a polyethylene terephthalate fabric, a polytrimethylene terephthalate fabric, a polybutylene terephthalate fabric, a polybutylene terephthalate-adipate fabric, a polylactic acid fabric, a polyethylene fabric, a polypropylene fabric, a polyterephthalamide fabric, a poly-m-xylylene adipamide fabric, a heterocyclic polybenzimidazole fabric or a poly-p-phenylene benzobisoxazole fabric.

[0030] The antibacterial fabric as described above, the finishing is performed by spraying, and the antibacterial agent is only finished on one side of the fabric; the water evaporation rate of the antibacterial fabric is greater than 0.6 g / h; the temperature of the antibacterial fabric after being placed on a water-sprayed skin surface for 1 minute is at least 2℃ lower than that of the fabric before finishing.

[0031] After the antibacterial agent is sprayed on one side of the fabric, the sprayed side exhibits good wetting ability and small pores, while the un-sprayed side maintains poor hydrophilicity. Due to the difference in wetting ability and pore size between the two sides of the fabric, the obtained antibacterial fabric exhibits unidirectional moisture guiding ability, and a dry and cool microenvironment can be formed between the antibacterial fabric and the human body after wearing the antibacterial fabric.

[0032] Due to the unidirectional moisture guiding ability of the antibacterial fabric and the hydrophobic chain segments in the antibacterial agent can quickly spread water in space, when the human body sweats, the fabric can quickly absorb water from the skin surface and transport it from the inside to the outside of the fabric, and the water on the outside of the fabric evaporates to take away the heat of the human body, thereby reducing the temperature of the skin surface, so the antibacterial fabric has good refrigeration effect.

[0033] The antibacterial fabric as described above, the antibacterial rate of the antibacterial fabric on Escherichia coli, Staphylococcus aureus and Candida albicans is ≥97%; after 50 times of washing, the antibacterial rate of the antibacterial fabric on Escherichia coli, Staphylococcus aureus and Candida albicans is ≥90%; after 100 times of friction resistance test, the antibacterial rate of the antibacterial fabric on Escherichia coli, Staphylococcus aureus and Candida albicans is ≥90%.

[0034] Principle of the application:

[0035] The antibacterial performance of the antibacterial agent of the present application is superior to that of the prior art antibacterial agent under the premise that both contain "guanidine salt" and "aromatic ring", the main reason being that the antibacterial agent of the present application has a controllable sequence structure, the polymer main chain is composed of alternating hydrophobic segments and hydrophilic segments, which helps to form a relatively rigid one-dimensional structure of macromolecules with a certain molecular weight, which is very helpful to the bacteriostatic effect of the antibacterial agent. In addition, the guanidine salt is regularly arranged, and the surface positive charge is concentratedly distributed, which is also very helpful to the bacteriostatic effect of the antibacterial agent. The molecular chain of the antibacterial agent of the prior art is relatively short, which is a small molecular compound, and when it acts on bacteria, it is difficult to penetrate the bacterial cell membrane and kill bacteria, or the guanidine salt is difficult to form effective concentrated distribution of positive charges at the side group position of the polymer macromolecular chain, therefore, the antibacterial effect of the antibacterial agent of the prior art is relatively poor.

[0036] In addition, under the premise that both contain "guanidine salt" and "aromatic ring" in the structural formula, the antibacterial fabric prepared by using the antibacterial agent of the present application has more excellent water washing resistance and friction resistance, the main reasons are as follows:

[0037] (1) From the interaction between the molecular chains of the antibacterial agent, the antibacterial agent of the present application can produce cation-π, hydrogen bond and π-π stacking multiple interactions between molecules, as shown in Figure 1 , causing strong self-aggregation, which helps to form a stable antibacterial adhesive on the surface of the fabric (water washing resistance, friction resistance).

[0038] (2) The antibacterial agent of the present application can produce cation-π, hydrogen bond and π-π stacking multiple interactions with the fabric, thereby stably adhering to the surface of the fabric. Now taking the antibacterial agent as PXDAG (the structural formula corresponds to formula A) and the fabric as polyethylene terephthalate (PET) fabric as an example for description. In order to determine whether the cation-π and hydrogen bond interactions can promote the strong interfacial adhesion between PXDAG and PET, we first carried out density functional theory (DFT) simulation to prove the intrinsic stability of the PXDAG and PET system. The possible structures and electrostatic potential distribution of PET, PXDAG and PET / PXDAG were optimized by DFT Figure 2 (a). When PET / PXDAG is close, the intermolecular interaction energy is lower than that of two single molecules due to the cation-π interaction between the nitrogen cation and the benzene ring of adjacent molecules. The Gibbs free energy change (ΔG) of the PET / PXDAG composite material is -8.2 kcal / mol. In order to effectively show the non-covalent interaction, further analysis by molecular density based on Hirshfeld partitioning (IGMH) found that there were cation-π interactions and hydrogen bonds in PET / PXDAG, as shown in Figure 2 (b).

[0039] Two-dimensional nuclear magnetic spectroscopy further determined the interfacial interactions including hydrogen bonding network and cation-π. As shown in Figure 3, when the solution was added with 2M BHET (a model compound of PET) and PXDAG (a polycation-π antibacterial agent), a weak NOE appeared between the aromatic ring group and guanidinium group in BHET. These data further proved the existence of non-covalent interactions between benzene and guanidine, again indicating that cation-π and hydrogen bonding interactions may also exist in PET and PXDAG. The cation-π interaction and hydrogen bonding in PXDAG-PET will make the material exhibit strong non-covalent cohesion, dissipate more breaking energy, and significantly improve the interfacial fracture threshold.

[0040] Beneficial effects

[0041] The preparation method of the polycation-π antibacterial agent of the present application is simple, especially melt polymerization, which can introduce controllable sequences of aromatic rings into guanidine polymers in only one step reaction.

[0042] The polycation-π antibacterial agent of the present application introduces aromatic rings, increases multiple interactions between the fabric, and only needs simple adsorption to improve the washing fastness, without adding crosslinking agents, fastness agents, etc.

[0043] The antibacterial fabric of the present application can effectively inhibit bacteria, has long-lasting effect, and has remarkable washing resistance, showing the robust interaction between functional auxiliaries and fabrics achieved by chemical sequence structure design.

[0044] The antibacterial fabric developed by using the spraying technology in the present application has the function of spontaneous perspiration, the skin temperature is lower than the surrounding environment, and has good softness, appearance and wear resistance.

[0045] The antibacterial fabric of the present application can rapidly absorb moisture from the skin surface and transport from the inside of the fabric to the outside of the fabric, and due to the evaporation of water, the human body heat can be taken away, so that the effect of reducing the skin surface temperature can be achieved.

[0046] The raw materials used in the present application have low cost and simple preparation method, and the durable antibacterial, directional moisture permeable and refrigeration multifunctional fabric can be prepared on a large scale, which is helpful for industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 Figure 1 is a schematic diagram of the intermolecular forces of PXDAG (cation-π, hydrogen bonding, π-π stacking).

[0048] Figure 2 (a) is the structure and electrostatic potential distribution of PET, PXDAG and PET / PXDAG;

[0049] Figure 2 (b) is the IGMH analysis of the interaction in the PET / PXDAG system;

[0050] Figure 3(a) is a schematic diagram of cation-π interaction between PET and PXDAG;

[0051] Figure 3(b) is a 1H-1H NOESY spectrum of BHET and PXDAG mixture;

[0052] Figure 3(c) is an enlarged signal of coupling of Ha-He and Hb-He;

[0053] Figure 4 MALDI-TOF-MS spectrum of the polycation-π antibacterial agent of Example 1; 1 H-NMR spectrum;

[0054] Figure 5 MALDI-TOF-MS spectrum of the polycation-π antibacterial agent of Example 1;

[0055] Figure 6 MBC results of aqueous solution of PXDAG at concentrations of 64 μg / mL, 32 μg / mL and 16 μg / mL from left to right against S. aureus;

[0056] Figure 7 MBC results of aqueous solution of PXDAG at concentrations of 256 μg / mL, 128 μg / mL and 64 μg / mL from left to right against E. coli;

[0057] Figure 8 1H NMR spectrum of the polycation-π antibacterial agent of Example 2. DETAILED DESCRIPTION

[0058] The application will be further described below in connection with specific embodiments. It should be understood that these embodiments are intended to illustrate the application and not to limit the scope of the application. Furthermore, it should be understood that after reading the content of the present application, those skilled in the art could make various modifications or alterations to the application, and these equivalent forms should also fall within the scope of the appended claims.

[0059] Methods for detecting relevant indexes in examples and comparative examples:

[0060] Minimum inhibitory concentration and minimum bactericidal concentration of antibacterial agent: tested according to micro-doubling dilution method;

[0061] Water evaporation rate: tested according to standard GB / T 21655.1-2008 Textiles - Assessment of the water vapour permeability - Part 1: Single specimen method;

[0062] Temperature of antibacterial fabric placed on water-sprayed skin surface for 1 minute and temperature of untreated fabric placed on water-sprayed skin surface for 1 minute were measured using an infrared thermal imager (FOTRIC 315, USA) and analyzed using AnalyzIR software.

[0063] Antibacterial rate: Tested according to standard GB / T 20944.3-2008 Evaluation of antibacterial properties of textiles - Part 3: Vibration method.

[0064] Washing: Performed in accordance with standard GB / T 20944.3-2008 Evaluation of antimicrobial properties of textiles - Part 3: Vibration method.

[0065] Abrasion resistance test: The test shall be conducted in accordance with the standard test method for abrasion resistance of textile fabrics (Martindale abrasion tester method) of ASTM D4966-22.

[0066] Example 1

[0067] A method for preparing a polycationic-π antibacterial agent is as follows:

[0068] (1) Raw material preparation:

[0069] Cation guanidine salt: ;

[0070] Compounds containing a benzene ring: ;

[0071] (2) Preparation of antibacterial agents:

[0072] First, a cationic guanidine salt and a compound containing a benzene ring are mixed in a molar ratio of 1:1. Then, the mixture is heated to 100°C under stirring and reacted for 12 hours. Next, the mixture is heated to 190°C and reacted for 5 hours. Finally, the mixture is evacuated to a vacuum degree of 200 Pa and reacted for 10 hours to obtain the polycationic-π antibacterial agent.

[0073] The final polycationic-π antibacterial agent has the following structural formula:

[0074] ;

[0075] In the formula, n1=1, n2=1, n3=50, X - For Cl - ;

[0076] The polycationic-π antibacterial agent 1 H-NMR spectrum as shown Figure 4 As shown, the MALDI-TOF-MS spectrum is as follows: Figure 5The number average molecular weight is 10000 Da, the minimum inhibitory concentration is 8 μg / mL, and the minimum bactericidal concentration is 64 μg / mL. The MBC results of the aqueous solution of PXDAG at concentrations of 64 μg / mL, 32 μg / mL, and 16 μg / mL on Staphylococcus aureus are shown in Figure 6 The MBC results of the aqueous solution of PXDAG at concentrations of 256 μg / mL, 128 μg / mL, and 64 μg / mL on Escherichia coli are shown in Figure 7

[0077] Example 2

[0078] A preparation method of a polycation-π antibacterial agent is as follows:

[0079] (1) Preparation of raw materials:

[0080] Cationic guanidine salt:

[0081] Compound with benzene ring:

[0082] (2) Preparation of antibacterial agent:

[0083] First, the cationic guanidine salt and the compound with benzene ring are mixed at a molar ratio of 1.2:1, then heated to 160°C under stirring, reacted for 2 h, then heated to 260°C, reacted for 1 h, and finally vacuumized to a vacuum degree of -Pa, reacted for 1 h, to obtain the polycation-π antibacterial agent.

[0084] The polycation-π antibacterial agent finally prepared has a structural formula as follows:

[0085]

[0086] In the formula, n1=1, n2=1, n3=50, n4=6, X - is Cl -

[0087] The polycation-π antibacterial agent has a 1 H-NMR spectrum as shown in Figure 8 The number average molecular weight is 18800 Da, the minimum inhibitory concentration is 1 μg / mL, and the minimum bactericidal concentration is 1 μg / mL.

[0088] Example 3

[0089] A preparation method of a polycation-π antibacterial agent is as follows:

[0090] (1) Preparation of raw materials:

[0091] Cationic guanidine salt: ​​​​​​

[0092] a compound with a benzene ring: ;

[0093] Catalyst: HCl

[0094] (2) Preparation of the antibacterial agent:

[0095] First, the cationic guanidine salt, the compound with a benzene ring and the catalyst are mixed in a molar ratio of 0.9:1, then heated to 110°C under stirring, reacted for 2h, then heated to 190°C, reacted for 2h, and finally vacuumized to a vacuum degree of 200 Pa, reacted for 1h, to obtain the polycation-π antibacterial agent.

[0096] The catalyst is added in an amount of 0.01% of the total mass of the polycationic guanidine salt and the compound with a benzene ring.

[0097] The polycation-π antibacterial agent prepared finally has a structural formula as follows:

[0098] ;

[0099] In the formula, n1=1, n2=1, n3=20, X - is Cl - ;

[0100] The polycation-π antibacterial agent has a number average molecular weight of 5000 Da, a minimum inhibitory concentration of 4 μg / mL and a minimum bactericidal concentration of 4 μg / mL.

[0101] Example 4

[0102] A preparation method of a polycation-π antibacterial agent is as follows:

[0103] (1) Preparation of raw materials:

[0104] Cationic guanidine salt: ;

[0105] Compound with a benzene ring: ;

[0106] Catalyst: copper oxide

[0107] (2) Preparation of the antibacterial agent:

[0108] First, the cationic guanidine salt, the compound with a benzene ring and the catalyst are mixed in a molar ratio of 0.8:1, then heated to 130°C under stirring, reacted for 2h, then heated to 180°C, reacted for 5h, and finally vacuumized to a vacuum degree of -Pa, reacted for -h, to obtain the polycation-π antibacterial agent.

[0109] The amount of the catalyst added is 0.5% of the total mass of the polycation guanidine salt and the compound with benzene ring.

[0110] The polycation-π antibacterial agent prepared has the following structural formula:

[0111] ;

[0112] In the formula, n1=1, n2=1, n3=4, n4=6, X - is C6H5SO3 - ;

[0113] The polycation-π antibacterial agent has a number average molecular weight of 3000 Da, a minimum bacteriostatic concentration of 8 μg / mL, and a minimum bactericidal concentration of 8 μg / mL.

[0114] Example 5

[0115] A preparation method of a polycation-π antibacterial agent is as follows:

[0116] (1) Preparation of raw materials:

[0117] Cationic guanidine salt: ;

[0118] Compound with benzene ring: ;

[0119] Catalyst: NaOH

[0120] (2) Preparation of the antibacterial agent:

[0121] The polycation-π antibacterial agent is prepared by solution polymerization from the cationic guanidine salt and the compound with benzene ring in a molar ratio of 0.9:1, using isopropyl alcohol as the solvent, at a solution polymerization temperature of 0°C, and for a time of 0.5 h.

[0122] The amount of the catalyst added is 0.5% of the total mass of the polycation guanidine salt and the compound with benzene ring.

[0123] The polycation-π antibacterial agent prepared has the following structural formula:

[0124] ;

[0125] In the formula, n5=5, -M is -Cl, and X - is C6H5SO3 - ;

[0126] The polycation-π antibacterial agent has a number average molecular weight of 2000 Da, a minimum bacteriostatic concentration of 128 μg / mL, and a minimum bactericidal concentration of 256 μg / mL.

[0127] Example 6

[0128] A preparation method of a polycation-π antibacterial agent, specifically as follows:

[0129] (1) Raw material preparation:

[0130] Cationic guanidine salt: ;

[0131] Compound with benzene ring: ;

[0132] (2) Preparation of antibacterial agent:

[0133] The polycation-π antibacterial agent is prepared by solution polymerization from the cationic guanidine salt and the compound with benzene ring with a molar ratio of 0.8:1, and the solvent used is water, and the temperature of the solution polymerization is 90℃, and the time is 20h.

[0134] The polycation-π antibacterial agent finally prepared has a structural formula as follows:

[0135] ;

[0136] In the formula, n4=6, n5=13, -M is -COOCH3, X - is Cl - ;

[0137] The number average molecular weight of the polycation-π antibacterial agent is 5500Da, the minimum inhibitory concentration is 8μg / mL, and the minimum bactericidal concentration is 16μg / mL.

[0138] Example 7

[0139] A preparation method of an antibacterial fabric, specifically as follows: the antibacterial agent (the polycation-π antibacterial agent prepared in Example 1) is finished to the single side surface of the fabric (polyethylene terephthalate fabric) by spraying, so as to prepare the antibacterial fabric.

[0140] In the antibacterial fabric, the mass of the antibacterial agent is 1% of the mass of the fabric.

[0141] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.82 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.8℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 99.68%, 99.84% and 99.71% respectively, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans of the antibacterial fabric after 50 times of washing are 96.74%, 96.89% and 96.70% respectively, and the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans of the antibacterial fabric after 100 times of friction resistance test are 91.82%, 92.11% and 91.91% respectively.

[0142] Example 8

[0143] A preparation method of an antibacterial fabric, specifically: the antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 2) is finished on the single side surface of the fabric (polybutylene terephthalate-hexane adipate fabric) by spraying to prepare the antibacterial fabric.

[0144] In the antibacterial fabric, the mass of the antibacterial agent is 5% of the mass of the fabric.

[0145] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.65 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.2℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 98.75%, 99.56% and 97.72% respectively, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans of the antibacterial fabric after 50 times of washing are 96.29%, 96.37% and 95.55% respectively, and the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans of the antibacterial fabric after 100 times of friction resistance test are 93.35%, 93.73% and 93.66% respectively.

[0146] Example 9

[0147] A preparation method of an antibacterial fabric, specifically: the antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 3) is finished on the single side surface of the fabric (poly-lactic acid fabric) by spraying to prepare the antibacterial fabric.

[0148] In the antibacterial fabric, the mass of the antibacterial agent is 3.5% of the mass of the fabric.

[0149] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.68 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.2℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 98.29%, 98.79% and 98.40% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 95.99%, 96.34% and 95.74% respectively; after the antibacterial fabric is subjected to 100 times of rubbing test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 90.01%, 90.83% and 90.23% respectively.

[0150] Example 10

[0151] A preparation method of an antibacterial fabric, specifically: an antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 4) is finished to a single side surface of a fabric (a polyethylene fabric) in a spraying manner to prepare an antibacterial fabric.

[0152] In the antibacterial fabric, the mass of the antibacterial agent is 5% of the mass of the fabric.

[0153] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.72 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.3℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 97.85%, 98.32% and 97.60% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 95.42%, 95.87% and 95.18% respectively; after the antibacterial fabric is subjected to 100 times of rubbing test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 90.05%, 90.63% and 90.01% respectively.

[0154] Example 11

[0155] A preparation method of an antibacterial fabric, specifically: an antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 5) is finished to a single side surface of a fabric (a poly-m-phenylene isophthalamide fabric) in a spraying manner to prepare an antibacterial fabric.

[0156] In the antibacterial fabric, the mass of the antibacterial agent is 3.5% of the mass of the fabric.

[0157] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.76 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.4℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 99.71%, 99.83% and 99.44% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 98.39%, 98.64% and 98.03% respectively; after the antibacterial fabric is subjected to 100 times of rubbing test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 96.40%, 97.23% and 96.69% respectively.

[0158] Example 12

[0159] A preparation method of an antibacterial fabric, specifically: an antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 6) is finished on a single side surface of a fabric (heterocyclic polybenzimidazole fabric) in a spraying manner to prepare the antibacterial fabric.

[0160] In the antibacterial fabric, the mass of the antibacterial agent is 5% of the mass of the fabric.

[0161] The moisture evaporation rate of the finally prepared antibacterial fabric is 0.77 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.6℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 99.93%, 99.97% and 99.86% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 98.75%, 98.91% and 98.38% respectively; after the antibacterial fabric is subjected to 100 times of rubbing test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 97.25%, 97.65% and 97.10% respectively.

[0162] Example 13

[0163] A preparation method of an antibacterial fabric, specifically: an antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 2) is finished on a fabric (polyethylene terephthalate fabric) in an immersion manner to prepare the antibacterial fabric.

[0164] In the method, the bath ratio is 1:20, and the concentration of the antibacterial agent in the immersion solution is 10 g / L.

[0165] The moisture evaporation rate of the final antibacterial fabric is 0.1 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 0.1℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 99.78%, 99.85% and 99.63% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 95.65%, 96.87% and 96.22% respectively; after the antibacterial fabric is subjected to 100 times of friction resistance test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 91.46%, 91.85% and 91.28% respectively.

[0166] Example 14

[0167] A preparation method of an antibacterial fabric, specifically: an antibacterial agent (the poly-cation-π antibacterial agent prepared in Example 1) is finished on one side surface of a fabric (a poly-p-phenylene-benzobisoxazole fabric) by spraying to obtain an antibacterial fabric.

[0168] In the antibacterial fabric, the mass of the antibacterial agent is 3% of the mass of the fabric.

[0169] The moisture evaporation rate of the final antibacterial fabric is 0.77 g / h, the temperature of the antibacterial fabric after being placed on the skin surface sprayed with water for 1 minute is 2.4℃ lower than that of the fabric before finishing, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 99.35%, 99.58% and 99.22% respectively; after the antibacterial fabric is washed for 50 times, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 98.52%, 98.75% and 98.10% respectively; after the antibacterial fabric is subjected to 100 times of friction resistance test, the antibacterial rates on Escherichia coli, Staphylococcus aureus and Candida albicans are 96.33%, 96.72% and 95.54% respectively.

[0170] Comparative Example 1

[0171] A preparation method of an antibacterial fabric, which is basically the same as that in Example 14, except that the antibacterial agent used in the present comparative example is the N-aryl-substituted biguanide hydrobromide compound prepared in Example 1 of patent CN104230760B.

[0172] The final antibacterial fabric had a water evaporation rate of 0.35 g / h. The temperature of the antibacterial fabric after being placed on a water-sprayed skin surface for 1 minute was 0.87℃ lower than that of the untreated fabric after the same process. The antibacterial fabric exhibited inhibition rates of 82.18%, 82.56%, and 81.90% against Escherichia coli, Staphylococcus aureus, and Candida albicans, respectively. After 50 washes, the antibacterial fabric maintained inhibition rates of 62.88%, 63.67%, and 61.97% against the same bacteria. After 100 abrasion tests, the antibacterial fabric maintained inhibition rates of 37.91%, 38.40%, and 36.89% against the same bacteria.

[0173] Compared to Example 14, Comparative Example 1 exhibits a lower water evaporation rate, poorer fabric cooling effect, and inferior antibacterial, washability, and abrasion resistance. This is because the N-aryl-substituted biguanide hydrobromide compounds have a small molecular weight, and the hydrophobic benzene ring significantly affects their hydrophilicity, resulting in poor overall hydrophilicity of the antibacterial agent. Furthermore, due to their shorter molecular chains, the interaction force with the fabric is easily affected by external environmental factors such as friction and washing, leading to poor bonding strength with the fabric and consequently, poor washability and abrasion resistance.

[0174] Comparative Example 2

[0175] A method for preparing an antibacterial fabric is basically the same as in Example 14, except that the antibacterial agent used in this comparative example is the guanidine polymeric antibacterial agent prepared in Example 1 of patent application CN105566547A.

[0176] The final antibacterial fabric had a water evaporation rate of 0.46 g / h. The temperature of the antibacterial fabric after being placed on a water-sprayed skin surface for 1 minute was 0.95℃ lower than that of the untreated fabric after the same process. The antibacterial fabric exhibited inhibition rates of 91.06%, 91.98%, and 90.82% against Escherichia coli, Staphylococcus aureus, and Candida albicans, respectively. After 50 washes, the antibacterial fabric maintained inhibition rates of 69.83%, 70.36%, and 69.29% against Escherichia coli, Staphylococcus aureus, and Candida albicans, respectively. After 100 abrasion tests, the antibacterial fabric maintained inhibition rates of 56.59%, 57.22%, and 54.91% against Escherichia coli, Staphylococcus aureus, and Candida albicans, respectively.

[0177] Compared with Example 14, the moisture evaporation rate of Comparative Example 2 is low, the fabric cooling effect is poor, the antibacterial washing resistance is poor, and the friction resistance effect is poor. This is because although a guanidine high molecular type antibacterial agent is used, the position of the aromatic ring is on the polymer side chain, resulting in poor hydrophilic effect, so the moisture evaporation rate is low, and the fabric cooling effect is poor. In addition, the guanidine high molecular antibacterial agent has limited antibacterial effect, and the large steric hindrance side chain limits its direct stable interaction with the fabric, so the antibacterial effect of the fabric is poor after being affected by factors such as washing and friction.

Claims

1. An antibacterial fabric, made by treating a fabric with an antibacterial agent, wherein the fabric is made of hydrophobic fibers, characterized in that, The antibacterial agent is a polycationic-π antibacterial agent, which is one or more of compounds A to F, and the structural formulas of compounds A to F correspond to the following formulas A to F: In the formula, the values ​​of n1, n2, and n4 range from 1 to 10, and the values ​​of n3 and n5 range from 2 to 50. - For Cl - NO3 - or C6H5SO3 - -M can be -OH, -COOCH3 or -Cl.

2. The antibacterial fabric according to claim 1, characterized in that, The antibacterial agent should be 1-5% of the fabric weight.

3. The antibacterial fabric according to claim 1, characterized in that, The fabric is made of polyethylene terephthalate, propylene terephthalate, butylene terephthalate, butylene adipate, polylactic acid, polyethylene, polypropylene, polyterephthalamide, polyisophthalamide, heterocyclic polybenzimidazole, or poly(p-phenylenebenzobisoxazole).

4. The antibacterial fabric according to claim 1, characterized in that, The finishing process involves spraying, with the antibacterial agent applied only to one side of the fabric surface; the moisture evaporation rate of the antibacterial fabric is greater than 0.6 g / h; the temperature of the antibacterial fabric after being placed on a water-sprayed skin surface for 1 minute is at least 2°C lower than the temperature of the unfinished fabric after being placed on a water-sprayed skin surface for 1 minute.

5. The antibacterial fabric according to claim 1, characterized in that, The number average molecular weight of polycationic-π antibacterial agents is 500-20000 Da, the minimum inhibitory concentration is 1-128 μg / mL, and the minimum bactericidal concentration is 1-256 μg / mL.

6. The antibacterial fabric according to claim 1, characterized in that, The preparation method of polycationic-π antibacterial agent is as follows: under catalytic or catalyst-free conditions, polycationic guanidine salt and compound containing benzene ring are melt-polymerized or solution-polymerized in a molar ratio of 0.8-1.2:1 to obtain polycationic-π antibacterial agent; The structural formula of the guanidine salt is one of the following formulas i to iv: ； Compounds containing a benzene ring are one of the following formulas I to IV: 。 7. An antibacterial fabric according to claim 6, characterized in that, The melt polymerization process is as follows: First, the temperature is raised to 100-160℃ under stirring and reacted for 2-12 hours. Then, the temperature is raised to 150-260℃ and reacted for 1-5 hours. Finally, the vacuum is evacuated to a vacuum degree ≤200Pa and reacted for 0-10 hours.

8. An antibacterial fabric according to claim 6, characterized in that, The solvent used for solution polymerization is one or more of dimethyl sulfoxide, N,N-dimethylformamide, water, isopropanol, methanol, ethanol and acetone; the solution polymerization temperature is 0-130℃ and the time is 0.5-20h.

9. An antibacterial fabric according to claim 6, characterized in that, The catalyst is an acidic catalyst, a basic catalyst, or a metal catalyst, and the amount of catalyst added is 0.01-0.5% of the total mass of the polycationic guanidine salt and the compound with a benzene ring.

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