Modified fiber, antibacterial hydrophobic fabric, and preparation method and application thereof

Abstract

The invention discloses a modified fiber, an antibacterial and hydrophobic fabric, and a preparation method and application thereof. Hollow polystyrene microspheres and an olefin compound having a double-end vinyl structure are reacted in water in the presence of an oil-soluble initiator to generate first modified microspheres. The first modified microspheres are then reacted with an alkoxysilane compound containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of a water-soluble initiator to generate second modified microspheres. The second modified microspheres are then reacted with a hydrocarbon ammonium halide compound containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of an oil-soluble initiator to generate a polymer modifier. The polymer modifier is applied to a fiber matrix or a fabric matrix having terminal active groups and reacted to generate the modified fiber or fabric. The modified fiber or fabric prepared by the method of the invention can not only achieve excellent antibacterial and hydrophobic dual functions, but also achieve good effects in properties such as bonding strength, thermal stability, and chemical stability, and is suitable for preparing antibacterial and hydrophobic dual-functional materials.

Description

Technical Field

[0001] The present invention relates to the field of modified fibers, in particular to fibers or fabrics having dual antibacterial and hydrophobic functions, and more particularly to fibers or fabrics modified with polymer materials to impart multifunctionality while also having excellent bonding strength and other properties. The present invention specifically relates to a modified fiber, an antibacterial and hydrophobic fabric, and a preparation method and application thereof. Background Art

[0002] In the field of fibers or fabrics, functional fibers or fabrics have received more and more attention and applications. Currently, they are basically single-functional fibers or fabrics. When it is desired to realize two or even more functions on fibers or fabrics, the usual practice is to coat materials with multiple functions on the fibers or fabrics simultaneously or in steps. However, this practice usually has the following problems: unexpected reactions may occur between the functional materials, resulting in the loss of corresponding functions; the functional materials are prone to overlapping with each other, resulting in the inability to truly exert the corresponding functions; a larger amount of addition is required to effectively realize each function, which on the one hand increases the cost of raw materials, and on the other hand, the application of too many functional materials can easily cause the air permeability of the fiber to decrease seriously, hindering its application in clothing and other fields; the bonding force between the functional materials and the fiber matrix or fabric is insufficient, which can easily cause the functional materials to fall off or break when subjected to external forces; the functional fibers or fabrics produced have insufficient performance in thermal stability, chemical stability, water resistance and other properties, making it difficult to adapt to more demanding application environments. At present, there has been no report on fibers or fabrics that are both effective in antibacterial and hydrophobic, while maintaining their respective properties without interfering with each other, achieving a perfect combination of dual functions and high breathability, thermal stability, chemical stability and other properties. Summary of the Invention

[0003] The purpose of the present invention is to overcome one or more deficiencies in the prior art and to provide a method for preparing modified fibers, wherein the modified fibers prepared by the method not only have excellent antibacterial and hydrophobic dual functions, but also have better properties such as bonding strength, thermal stability, and chemical stability.

[0004] The present invention also provides a method for preparing an antibacterial and hydrophobic fabric. The antibacterial and hydrophobic fabric prepared by the method can not only achieve excellent antibacterial and hydrophobic dual functions, but also achieve good effects in properties such as bonding strength, thermal stability, and chemical stability.

[0005] The present invention also provides an application of the modified fiber or antibacterial hydrophobic fabric prepared by the above method in the preparation of antibacterial and hydrophobic dual-functional materials. Furthermore, the antibacterial and hydrophobic dual-functional materials can be applied in medical and sanitary products, marine antifouling, etc.

[0006] In order to achieve the above object, a technical solution adopted by the present invention is:

[0007] A method for preparing a modified fiber, comprising:

[0008] (1) allowing hollow polystyrene microspheres and an olefin compound having a molecular weight of less than 300 and a double-end vinyl structure to react in water in the presence of an oil-soluble initiator to generate first modified microspheres;

[0009] (2) reacting the first modified microspheres and an alkoxysilane compound having a molecular weight of less than 500 and containing an acryloxy group or an alkyl acryloxy group in water in the presence of a water-soluble initiator to produce second modified microspheres;

[0010] (3) reacting the second modified microspheres and a hydrocarbon ammonium halide compound having a molecular weight of less than 800 and containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of an oil-soluble initiator to produce a polymer modifier;

[0011] (4) applying the polymer modifier to a fiber matrix having terminal active groups to react and generate modified fibers; wherein the terminal active groups include hydroxyl groups.

[0012] In the present invention, in step (1), the use of the hollow polystyrene microspheres can reduce sedimentation problems and improve dispersion stability. When the low molecular weight olefin compound is mixed with the hollow polystyrene microspheres, since it is in a system with water as a solvent, the olefin compound will swell in the internal structure of the hollow polystyrene microspheres, the wall thickness of the hollow polystyrene microspheres will increase, and the hardness will increase. At the same time, the presence of the oil phase initiator can initiate polymerization, so that not only the olefin compound can be grafted onto the polystyrene microspheres, but also the product of the olefin compound polymerization can be grafted onto the polystyrene microspheres. After the reaction, the hardness of the hollow polystyrene microspheres increases and the hollow pores become smaller. In addition, since the olefin compound has a double-end vinyl structure, the first modified microspheres can retain part of the end vinyl group, so as to facilitate subsequent grafting modification through the residual carbon-carbon double bond.

[0013] In some preferred embodiments of the present invention, in step (1), the average particle size of the hollow polystyrene microspheres is 200-600 nm, further 380-420 nm.

[0014] In some preferred embodiments of the present invention, in step (1), the olefin compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (I);

[0015] In formula (I), R1 is a substituted or unsubstituted group as follows: 、C 2-10 Alkylene.

[0016] Furthermore, in formula (I), the substituents used can be methyl, ethyl, propyl, fluorine and the like, and the number of substituents can be 1, 2 or 3.

[0017] According to some preferred aspects of the present invention, in formula (I), R1 is , ethylene, propylene, butylene, pentylene or hexylene.

[0018] According to a specific aspect of the present invention, in step (1), the olefin compound comprises divinylbenzene (DVB).

[0019] In some preferred embodiments of the present invention, in step (2), the alkoxysilane compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (II);

[0020] In formula (II), R2 is H or C 1-6 Alkyl, R3 is C 1-6 Alkylene, R4, R5, R6 are independently selected from C 1-6 alkyl.

[0021] According to some preferred aspects of the present invention, in formula (II), R2 is H, methyl, ethyl or propyl, R3 is methylene, ethylene, propylene, butylene, pentylene or hexylene, and R4, R5 and R6 are independently selected from methyl, ethyl or propyl.

[0022] According to a specific aspect of the present invention, in step (2), the alkoxysilane compound comprises γ-methacryloxypropyltrimethoxysilane (MPS).

[0023] In the present invention, in step (2), a small molecular weight alkoxysilane compound is used as an organic compound modifier to modify the first modified microspheres. The modification process is carried out in water and a water-soluble initiator is used. When the small molecular weight alkoxysilane compound containing an acryloyloxy group or an alkylacryloyloxy group is added to the reaction system, in the initial stage of the reaction, the alkoxysilane compound will swell the polymer shell of the first modified microspheres and undergo free radical polymerization in the shell to form a polymer. As the reaction proceeds, the formed polymer chain segments will undergo hydrolysis (alkoxy groups are hydrolyzed and separated to obtain silanol groups) and condensation reaction to form silicon compounds. This process induces phase separation between the polymer and the silicon compound, causing the silicon compound to gradually aggregate into a gel and form a protruding structure, and the generated second modified microspheres still retain some terminal vinyl groups. One end of the particles of this structure is a silicon compound with reactive silanol groups that can be anchored to the fiber, and the other end is a hydrophobic copolymer that can be grafted with an antibacterial polymer. Therefore, it can not only achieve covalent bonds, hydrogen bonds and strong anchoring effects with the fiber substrate, but also provide hydrophobic and antibacterial functions for the modified fiber.

[0024] In some preferred embodiments of the present invention, in step (3), the hydrocarbyl ammonium halide compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (III);

[0025] In formula (III), X is halogen, R7, R8, and R9 are independently selected from C 1-6 Alkyl; or, X is halogen, R7 does not exist, R8, R9 are connected and the N to which they are connected together forms a 4-10 membered heterocyclic ring; or, R7, X does not exist, R8, R9 are independently selected from C 1-6 alkyl;

[0026] R 10 C 1-20 Alkylene, R 11 H or C 1-6 alkyl.

[0027] According to some preferred aspects of the present invention, in formula (III), X is bromine or chlorine, and R7, R8, and R9 are independently selected from methyl, ethyl, or propyl; or, X is bromine or chlorine, R7 is absent, and R8 and R9 are connected and form a pyridine ring with the N to which they are commonly connected; or, R7 and X are absent, and R8 and R9 are independently selected from methyl, ethyl, or propyl.

[0028] According to some preferred aspects of the present invention, in formula (III), R 10 is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene, heptadecylene or octadecylene, R 11 is H, methyl, ethyl or propyl.

[0029] Furthermore, in step (3), the hydrocarbon ammonium halide compound is selected from 12-methacryloyloxy dodecyl pyridinium bromide (MDPB), 2-methacryloyloxy ethyl trimethyl ammonium chloride, dimethylamino hexadecyl methacrylate (CH2=C(CH3)-C(=O)-O-(CH2) 16 -N(CH3)2, referred to as DMAHDM) or a combination of one or more.

[0030] In the present invention, in step (3), a small molecular weight hydrocarbon ammonium halide compound containing acryloyloxy or alkylacryloyloxy is used as a further modifier (by utilizing the olefinic bond contained therein to graft with the terminal vinyl group on the second modified microsphere). On the one hand, it can impart antibacterial properties to the polymer modifier, and on the other hand, it can make the grafted groups stably and evenly dispersed on the particle surface of the polymer modifier, and coexist with other functional groups without affecting each other.

[0031] According to some preferred aspects of the present invention, in step (1), based on 100 parts by total weight of the hollow polystyrene microspheres and the olefin compound, the amount of the hollow polystyrene microspheres is 60-90 parts, and the amount of the olefin compound is 10-40 parts.

[0032] According to some preferred aspects of the present invention, in step (2), the mass ratio of the first modified microspheres to the alkoxysilane compound is 1:0.5-2.0. Further, in step (2), the mass ratio of the first modified microspheres to the alkoxysilane compound is 1:0.6-1.4. In some embodiments of the present invention, in step (2), the mass ratio of the first modified microspheres to the alkoxysilane compound is 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, etc.

[0033] According to some preferred aspects of the present invention, in step (3), the mass ratio of the second modified microspheres to the hydrocarbyl ammonium halide compound is 1:0.5-1.5. Further, in step (3), the mass ratio of the second modified microspheres to the hydrocarbyl ammonium halide compound is 1:0.8-1.2.

[0034] According to a specific aspect of the present invention, in step (3), the mass ratio of the second modified microspheres to the hydrocarbon ammonium halide compound is 1:1.

[0035] In some embodiments of the present invention, the oil-soluble initiator in step (1) and step (3) is independently selected from one or more combinations of dibenzoyl peroxide (BPO), ethylene glycol diglycidyl ether, tert-butyl peroxypivalate (BPP), diisopropyl peroxydicarbonate (IPP), dicyclohexyl peroxydicarbonate (DCPD), azobisisobutyronitrile (AIBN), azobisisoheptylonitrile (ABVN), dibenzoyl peroxide, and N,N′-dimethylaniline.

[0036] In some embodiments of the present invention, in step (1), the amount of the oil-soluble initiator added is 0.01%-2.0% of the total mass of the hollow polystyrene microspheres and the olefin compound, and can further be 0.1%-1.5%.

[0037] In some embodiments of the present invention, in step (3), the amount of the oil-soluble initiator added is 0.5%-4.0% of the total mass of the second modified microspheres and the hydrocarbon ammonium halide compound, and can further be 1%-3%.

[0038] In some embodiments of the present invention, the water-soluble initiator in step (2) is a combination of one or more selected from potassium persulfate (KPS), diaryl iodonium salts, and triaryl sulfonium salts.

[0039] In some embodiments of the present invention, in step (2), the amount of the water-soluble initiator added is 0.1%-1.0% of the total mass of the first modified microspheres and the alkoxysilane compound, and can further be 0.2%-0.8%.

[0040] According to some preferred aspects of the present invention, in step (1) and step (2), the reactions are respectively carried out in the presence of a surfactant.

[0041] Furthermore, the surfactant includes anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, etc.

[0042] In some embodiments of the present invention, the anionic surfactant includes but is not limited to sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, etc. In some embodiments of the present invention, the cationic surfactant includes but is not limited to benzalkonium chloride, amine salts, etc.

[0043] In some embodiments of the present invention, the nonionic surfactant includes but is not limited to polysorbate (Tween, such as Tween 20, Tween 80), fatty acid glyceride, polyethylene glycol (PEG) derivatives, etc.

[0044] In some embodiments of the present invention, the zwitterionic surfactant includes but is not limited to betaine (such as cocamidopropyl betaine), imidazoline, and the like.

[0045] In some embodiments of the present invention, in step (1), the added amount of the surfactant accounts for 0.5%-5.0% of the total mass of the hollow polystyrene microspheres and the olefin compound, and can further be 0.5%-3.0%.

[0046] In some embodiments of the present invention, in step (2), the added amount of the surfactant accounts for 1%-8% of the total mass of the first modified microspheres and the alkoxysilane compound, and can further be 2%-6%.

[0047] According to some preferred aspects of the present invention, in step (1) to step (3), the reaction is carried out at 50-90° C. Further, in step (1) to step (3), the reaction is carried out at 65-85° C.

[0048] According to some preferred aspects of the present invention, the grafted weight percentage of the olefin compound in the first modified microspheres after the reaction is 5 wt.%-40 wt.%, and further can be 6 wt.%-36 wt.%. In the present invention, the grafted weight percentage of the olefin compound after the reaction refers to the percentage of the weight of the olefin compound and / or the weight of the olefin compound grafted onto the hollow polystyrene microspheres after polymerization of the olefin compound, as a percentage of the weight of the first modified microspheres, thereby reflecting the grafted amount.

[0049] According to some preferred aspects of the present invention, in the polymer modifier, the grafted weight percentage of the hydrocarbyl ammonium halide compound after the reaction is 2 wt.%-30 wt.%, and can further be 2 wt.%-30 wt.%. In the present invention, the grafted weight percentage of the hydrocarbyl ammonium halide compound after the reaction refers to the percentage of the weight of the hydrocarbyl ammonium halide compound grafted onto the second modified microspheres by the reaction with the polymer modifier, thereby reflecting the grafted amount.

[0050] In some embodiments of the present invention, in step (1), the method of preparing the first modified microspheres includes: mixing and emulsifying the raw materials, and then heating to initiate a polymerization reaction to generate the first modified microspheres.

[0051] Furthermore, during the preparation of the first modified microspheres, the raw materials are mixed and emulsified to form an emulsion, which is then stirred for 1-12 hours and then heated to initiate a polymerization reaction. After 2-16 hours, a copolymer dispersion is obtained. Furthermore, the mixture can be rinsed multiple times with anhydrous ethanol and deionized water to remove unpolymerized olefin compound monomers, and then freeze-dried to obtain the copolymer, i.e., the first modified microspheres.

[0052] In some embodiments of the present invention, in step (2), the method for preparing the second modified microspheres includes: preparing the first modified microspheres into a seed emulsion, preparing the alkoxysilane compound into a monomer emulsion, and then dropwise adding the monomer emulsion into the seed emulsion. After the dropwise addition, heating the mixture to react and generating the second modified microspheres.

[0053] Furthermore, the monomer emulsion contains an alkoxysilane compound, a water-soluble initiator, a surfactant and water.

[0054] Furthermore, the seed emulsion contains first modified microspheres and water.

[0055] Furthermore, during the preparation of the second modified microspheres, the reaction time is controlled to be 10-24 hours; furthermore, after the reaction is completed, the microspheres can be rinsed multiple times with anhydrous ethanol and deionized water, and freeze-dried to obtain the second modified microspheres.

[0056] In some embodiments of the present invention, in step (3), the method for preparing the polymer modifier includes: preparing the second modified microspheres into an emulsion, then mixing the emulsion with other raw materials, and heating the mixture to react to generate the polymer modifier.

[0057] Furthermore, in the process of preparing the polymer modifier spheres, the reaction time is controlled to be 0.2-3h; further, after the reaction is completed, the spheres can be rinsed multiple times with anhydrous ethanol and deionized water, and freeze-dried to obtain the polymer modifier.

[0058] In some embodiments of the present invention, in step (4), the fiber matrix having terminal active groups is obtained by subjecting the fiber to treatment with an alkaline reagent or an acidic reagent; or

[0059] In step (4), the method for preparing the fiber matrix having terminal active groups includes:

[0060] The fiber is treated with an alkaline reagent or an acidic reagent to obtain a pretreated fiber; the pretreated fiber is immersed in a sodium alginate aqueous solution to react and form a sodium alginate modified fiber matrix;

[0061] The sodium alginate modified fiber matrix is immersed in a silane coupling agent aqueous solution to react and generate the fiber matrix with terminal active groups.

[0062] In some embodiments of the present invention, the alkaline agent may be an alkali metal hydroxide, and the fiber may be treated in the form of an aqueous solution, for example, a sodium hydroxide aqueous solution with a mass concentration of 2% to 5% may be used.

[0063] In some embodiments of the present invention, the mass concentration of the sodium alginate aqueous solution is 5%-20%. Furthermore, the immersion temperature in the sodium alginate aqueous solution is 40-50°C.

[0064] In some embodiments of the present invention, the mass concentration of the silane coupling agent aqueous solution is 5%-30%. Furthermore, the immersion temperature in the silane coupling agent aqueous solution is 60-80°C.

[0065] In some embodiments of the present invention, the silane coupling agent used in the silane coupling agent aqueous solution includes but is not limited to 3-aminopropyltriethoxysilane (APTES), γ-methacryloxypropyltrimethoxysilane (KH570), γ-aminopropyltriethoxysilane (KH550), etc.

[0066] In the present invention, after treatment with acid and alkali reagents, the fiber can obtain reactive active groups, and practice has shown that if sodium alginate and silane coupling agents are further used for modification (using the hydroxyl groups they contain or the hydroxyl groups obtained after hydrolysis to react with the active groups on the fiber after treatment with acid and alkali reagents, or to form hydrogen bonds and other forces), the polymer modifier in the form of particles can be better combined with the fiber matrix.

[0067] In some embodiments of the present invention, the fiber may be PET fiber, etc. Further, it may be three-dimensional composite hollow fiber, ES fiber, cotton fiber, etc.

[0068] In some embodiments of the present invention, in step (4), the method for preparing the modified fiber includes: immersing the fiber matrix having terminal active groups in an aqueous solution of a polymer modifier, and heating the solution for reaction, wherein the mass content of the polymer modifier in the aqueous solution of the polymer modifier is 5%-50%.

[0069] In some embodiments of the present invention, the polymer modifier aqueous solution is obtained by dispersing the polymer modifier in water, and the mass content of the polymer modifier in the polymer modifier aqueous solution is 10%-40%.

[0070] In some embodiments of the present invention, in step (4), the reaction is carried out at 50-90° C. Further, the reaction can be carried out at 65-85° C.

[0071] In some embodiments of the present invention, in step (4), the reaction is carried out under ultrasonic conditions.

[0072] In some embodiments of the present invention, in step (4), after the reaction is completed, the fiber is taken out, rinsed multiple times with anhydrous ethanol and deionized water, and then dried to obtain the modified fiber.

[0073] In some embodiments of the present invention, the average particle size of the polymer modifier is 0.5-1 μm.

[0074] Another technical solution provided by the present invention is a modified fiber produced by the above-mentioned method for preparing the modified fiber.

[0075] In some embodiments of the present invention, the surface water contact angle (WCA) of the modified fiber is greater than 145°, or even greater than 150°, and the water sliding angle (SA) is less than 7°.

[0076] Another technical solution provided by the present invention is a method for preparing an antibacterial hydrophobic fabric, the method comprising:

[0077] (1) allowing hollow polystyrene microspheres and an olefin compound having a molecular weight of less than 300 and a double-end vinyl structure to react in water in the presence of an oil-soluble initiator to generate first modified microspheres;

[0078] (2) reacting the first modified microspheres and an alkoxysilane compound having a molecular weight of less than 500 and containing an acryloxy group or an alkyl acryloxy group in water in the presence of a water-soluble initiator to produce second modified microspheres;

[0079] (3) reacting the second modified microspheres and a hydrocarbon ammonium halide compound having a molecular weight of less than 800 and containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of an oil-soluble initiator to produce a polymer modifier;

[0080] (4) applying the polymer modifier to a fabric substrate, reacting to generate an antibacterial and hydrophobic fabric; wherein the fabric substrate includes terminal active groups;

[0081] Alternatively, the preparation method comprises: using the modified fiber described above as a raw material to produce the antibacterial and hydrophobic fabric through a weaving process.

[0082] Another technical solution provided by the present invention is the use of the modified fiber described above in the preparation of an antibacterial and hydrophobic dual-functional material.

[0083] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0084] Based on the problems existing in the preparation of existing multifunctional fibers or fabrics, the present invention proposes for the first time a method using hollow polystyrene microspheres as the starting raw material and sequentially modifying them with three specific compounds. In this way, a polymer modifier is obtained that is both effectively antibacterial and hydrophobic, while maintaining the respective properties without interfering with each other, thereby achieving a perfect combination of dual functions. After applying the polymer modifier to the modified fiber or fabric, it also gives the modified fiber or fabric excellent thermal stability, chemical stability, and high air permeability, and has strong water wash resistance and high bonding strength. After 200 cycles of rinsing, its mechanical properties, hydrophobic properties and antibacterial properties are all maintained at 90% or even above 95%, and it also has excellent stability in acidic and alkaline environments, so that the modified fiber or fabric of the present invention can be used in more harsh environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 TEM image of the first modified microsphere-1 prepared in Example 1 of the present invention;

[0086] Figure 2 TEM image of polymer modifier-2 prepared in Example 8 of the present invention;

[0087] Figure 3 This is an SEM image of the modified fabric (antibacterial and hydrophobic fabric) prepared in Example 10 of the present invention;

[0088] Figure 4 The photographs show the wettability of the modified fabric prepared in Example 12 of the present invention tested by dropping a methylene blue aqueous solution, coffee, tea, milk, juice, and cola respectively on the surface;

[0089] Figure 5 This is the water contact angle image of the modified fabric prepared in Comparative Example 1 of the present invention;

[0090] Figure 6 The photographs show that methylene blue aqueous solution, coffee, tea, milk, juice and cola were dropped onto the surface of the modified fabric prepared in Comparative Example 1 of the present invention to test its wettability. DETAILED DESCRIPTION

[0091] The above scheme is further described below in conjunction with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following examples; the implementation conditions adopted in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in routine experiments.

[0092] Unless otherwise specified in the following examples, all raw materials were purchased from commercial sources or prepared by conventional methods in the art.

[0093] In the following, hollow polystyrene microspheres (PS) were purchased from Rohm and Haas with the brand HP433; sodium alginate was purchased from Sinopharm with a molecular weight of approximately 150 kDa; PET fiber was purchased from Shenghong Fiber with a specification of 400D; and the operating parameters of the thermogravimetric analysis (TGA) were: operating range 50-400°C, heating rate 10°C / min, nitrogen atmosphere, and nitrogen flow rate 40-50 mL / min.

[0094] Example 1: This example provides a preparation method for the first modified microspheres, which comprises: mixing 90 parts of hollow polystyrene microspheres (PS), 10 parts of divinylbenzene (DVB), 1 part of initiator azobisisobutyronitrile (AIBN), 2 parts of sodium dodecyl sulfate (SDS) and 100 parts of water, and emulsifying under ultrasonic action for 5 minutes to form a DVB emulsion. At room temperature, the above raw materials are mechanically stirred at 350r / min for 8 hours, heated to 75°C to initiate the polymerization reaction, and after 10 hours, a PS / PDVB copolymer dispersion is obtained. After the reaction is completed, rinse with anhydrous ethanol and deionized water 3 times to wash away the unpolymerized DVB monomer, and freeze-dry to obtain the product, the first modified microspheres. Thermogravimetric analysis (TGA) measured that the grafting content of divinylbenzene was about 8.45wt.%, recorded as the first modified microsphere-1, and its TEM image is shown in FIG. Figure 1 As shown, from Figure 1 It can be seen that the particle size of the first modified microspheres is about 400 nm and has a hollow structure.

[0095] Example 2: This example provides a method for preparing first modified microspheres. The method comprises mixing 80 parts of hollow polystyrene microspheres (PS), 20 parts of divinylbenzene (DVB), 1 part of azobisisobutyronitrile (AIBN) as an initiator, 2 parts of sodium dodecyl sulfate (SDS), and 100 parts of water. The mixture is ultrasonically emulsified for 5 minutes to form a DVB emulsion. The mixture is then mechanically stirred at 350 rpm for 8 hours at room temperature and heated to 75°C to initiate polymerization. After 10 hours, a PS / PDVB copolymer dispersion is obtained. After the reaction, the mixture is rinsed three times with anhydrous ethanol and deionized water to remove unpolymerized DVB monomer. The product is then freeze-dried to obtain the first modified microspheres. Thermogravimetric analysis (TGA) determined that the divinylbenzene graft content was approximately 15.62 wt.%. The product is designated as first modified microsphere-2.

[0096] Example 3: This example provides a method for preparing first modified microspheres. The method comprises mixing 60 parts of hollow polystyrene microspheres (PS), 40 parts of divinylbenzene (DVB), 1 part of azobisisobutyronitrile (AIBN) as an initiator, 2 parts of sodium dodecyl sulfate (SDS), and 100 parts of water. The mixture is ultrasonically emulsified for 5 minutes to form a DVB emulsion. The mixture is then mechanically stirred at 350 rpm for 8 hours at room temperature and heated to 75°C to initiate polymerization. After 10 hours, a PS / PDVB copolymer dispersion is obtained. After the reaction, the mixture is rinsed three times with anhydrous ethanol and deionized water to remove unpolymerized DVB monomer. The product is then freeze-dried to obtain the first modified microspheres. Thermogravimetric analysis (TGA) determined that the divinylbenzene graft content was approximately 32.05 wt.%. The product is designated as first modified microsphere-3.

[0097] Example 4: This example provides a method for preparing a second modified microsphere, the preparation method comprising: 45 parts of the first modified microsphere-1, 45 parts of γ-methacryloxypropyltrimethoxysilane (MPS), 5 parts of sodium dodecyl sulfate (SDS), and 0.5 parts of potassium persulfate, mixing the sodium dodecyl sulfate (SDS) with water to form an SDS aqueous solution with a concentration of approximately 0.24 wt.%, and mixing the potassium persulfate (KPS) with water to form a KPS aqueous solution with a concentration of approximately 1 wt.%;

[0098] MPS and KPS aqueous solutions (1 wt.%) were mixed with SDS aqueous solution (0.24 wt.%) and ultrasonically emulsified for 5 min to form an MPS monomer emulsion;

[0099] The first modified microsphere-1 was dispersed in water, the solid content was adjusted to 37.5%, and ultrasonic emulsification was performed for 5 minutes to form a first modified microsphere-1 seed emulsion;

[0100] The MPS monomer emulsion was added dropwise to the first modified microsphere-1 seed emulsion using a peristaltic pump at a constant rate (addition time approximately 30 minutes). After the addition was complete, the reaction was maintained at 75°C for 18 hours. After the reaction, the product was rinsed three times with anhydrous ethanol and deionized water, and freeze-dried to obtain the second modified microsphere-1 product.

[0101] Example 5: This example provides a method for preparing a second modified microsphere, the preparation method comprising: 45 parts of the first modified microsphere-2, 45 parts of γ-methacryloxypropyltrimethoxysilane (MPS), 5 parts of sodium dodecyl sulfate (SDS), and 0.5 parts of potassium persulfate; sodium dodecyl sulfate (SDS) is prepared with water to form an SDS aqueous solution with a concentration of about 0.24 wt.%, and potassium persulfate (KPS) is prepared with water to form a KPS aqueous solution with a concentration of about 1 wt.%;

[0102] MPS and KPS aqueous solutions (1 wt.%) were mixed with SDS aqueous solution (0.24 wt.%) and ultrasonically emulsified for 5 min to form an MPS monomer emulsion;

[0103] The first modified microsphere-2 was dispersed in water, the solid content was adjusted to 37.5%, and ultrasonic emulsification was performed for 5 minutes to form a first modified microsphere-2 seed emulsion;

[0104] The MPS monomer emulsion was added dropwise to the first modified microsphere-2 seed emulsion using a peristaltic pump at a constant rate (addition time approximately 30 minutes). After the addition was complete, the reaction was maintained at 75°C for 18 hours. After the reaction, the product was rinsed three times with anhydrous ethanol and deionized water, and freeze-dried to obtain the second modified microsphere-2 product.

[0105] Example 6: This example provides a method for preparing a second modified microsphere, the preparation method comprising: 45 parts of the first modified microsphere-3, 45 parts of γ-methacryloxypropyltrimethoxysilane (MPS), 5 parts of sodium dodecyl sulfate (SDS), and 0.5 parts of potassium persulfate; sodium dodecyl sulfate (SDS) is prepared with water to form an SDS aqueous solution with a concentration of about 0.24 wt.%, and potassium persulfate (KPS) is prepared with water to form a KPS aqueous solution with a concentration of about 1 wt.%;

[0106] MPS and KPS aqueous solutions (1 wt.%) were mixed with SDS aqueous solution (0.24 wt.%) and ultrasonically emulsified for 5 min to form an MPS monomer emulsion;

[0107] The first modified microsphere-3 was dispersed in water, the solid content was adjusted to 37.5%, and ultrasonic emulsification was performed for 5 minutes to form a first modified microsphere-3 seed emulsion;

[0108] The MPS monomer emulsion was added dropwise to the first modified microsphere-3 seed emulsion using a peristaltic pump at a constant rate (addition time approximately 30 minutes). After the addition was complete, the mixture was kept at 75°C for 18 hours. After the reaction, the mixture was rinsed three times with anhydrous ethanol and deionized water, and freeze-dried to obtain the second modified microsphere-3 product.

[0109] Example 7: This example provides a method for preparing a polymer modifier. The method comprises dispersing 20 parts of a second modified microsphere-1 in water, ultrasonically dispersing the microspheres for 5 minutes, then adding the dispersed emulsion, 20 parts of 12-methacryloyloxydodecylpyridinium ammonium bromide (MDPB), and 1 part of azobisisobutyronitrile (AIBN) to a flask. The mixture is heated to 75°C and mechanically stirred at 300 rpm for 1 hour. After the reaction, the mixture is rinsed three times with anhydrous ethanol and deionized water, and freeze-dried to obtain the product, polymer modifier-1. The grafted content of MDPB was estimated by thermogravimetric analysis (TGA) under a nitrogen atmosphere during heating, and the grafted content was approximately 5.60%.

[0110] Example 8: This example provides a method for preparing a polymer modifier, which comprises dispersing 20 parts of the second modified microsphere-2 in water, ultrasonically dispersing for 5 minutes, then adding the dispersed emulsion, 20 parts of 12-methacryloyloxydodecylpyridinium ammonium bromide (MDPB), and 1 part of azobisisobutyronitrile (AIBN) into a flask, heating to 75°C, and mechanically stirring at 300 rpm for 1 hour. After the reaction, the product is rinsed with anhydrous ethanol and deionized water three times, and freeze-dried to obtain the product polymer modifier-2, the TEM image (transmission electron microscopy image) of which is shown in FIG. Figure 2As shown, the size of the second modified microspheres increased to 700 nm compared to the 400 nm of the first modified microspheres. The silicon compound was clearly well separated from the first modified microspheres, protruding from the microspheres. The grafted MDPB content was estimated by thermogravimetric analysis (TGA) under a nitrogen atmosphere using mass loss during heating, and was found to be approximately 11.5%.

[0111] Example 9: This example provides a method for preparing a polymer modifier. The method comprises dispersing 20 parts of the second modified microspheres-3 in water, ultrasonically dispersing for 5 minutes, then adding the dispersed emulsion, 20 parts of 12-methacryloyloxydodecylpyridinium ammonium bromide (MDPB), and 1 part of azobisisobutyronitrile (AIBN) to a flask. The mixture is heated to 75°C and mechanically stirred at 300 rpm for 1 hour. After the reaction, the mixture is rinsed three times with anhydrous ethanol and deionized water, and freeze-dried to obtain the product, polymer modifier-3. The grafted content of MDPB was estimated by thermogravimetric analysis (TGA) under a nitrogen atmosphere during heating, and the grafted content was approximately 23.4%.

[0112] In the following embodiments, a fiber matrix having terminal active groups is prepared by the following method: PET fiber is immersed in a sodium hydroxide aqueous solution with a mass concentration of 2% for 30 minutes at a soaking temperature of 25°C, and is taken out after the soaking to obtain a pretreated fiber; the pretreated fiber is immersed in a sodium alginate aqueous solution with a mass concentration of 5% at a soaking temperature of 45°C for 30 minutes, and is taken out after the soaking to obtain a sodium alginate modified fiber matrix; the sodium alginate modified fiber matrix is immersed in a 3-aminopropyltriethoxysilane (APTES) aqueous solution with a mass concentration of 20% at a soaking temperature of 70°C for 12 hours, and is taken out after the soaking to obtain a fiber matrix having terminal active groups.

[0113] Example 10: This example provides a method for preparing a modified fabric (antibacterial and hydrophobic fabric). The method comprises: adding 2 parts of the polymer modifier 1 prepared above to 5 parts of deionized water, dispersing the mixture to obtain a mixed solution; then, using a knitting machine, interweaving warp and weft yarns of a fiber matrix having terminal active groups to form a fabric. The fabric is cut into a predetermined size (4 x 4 cm) and placed in the mixed solution. After heating to 75°C and ultrasonically treating for 15 minutes, the sample is removed and rinsed three times with ethanol and deionized water, and dried at 75°C for 1 hour to obtain a modified fabric, namely, an antibacterial and hydrophobic fabric. See the SEM image (scanning electron microscope image) for details. Figure 3 As shown, in the surface morphology structure of the modified fabric, the particles can be well distributed on the surface of the fabric substrate.

[0114] The hydrophobic properties of the antibacterial hydrophobic fabric produced according to the present invention were tested using an OCA20 contact angle meter, resulting in a water contact angle (WCA) of 150.5 ± 1°. Dynamic flow testing revealed an antibacterial rate of 78.5%, demonstrating the excellent antibacterial properties of the antibacterial hydrophobic fabric produced according to the present invention. The data are listed in Table 1.

[0115] Using a universal material testing machine, the stretching speed (100 mm / min) was set according to GB / T 3923.1, and the measured elongation at break was 76%, indicating that the antibacterial and hydrophobic fabric prepared in the present invention has good elasticity and extensibility.

[0116] The thermal stability of the hydrophobicity of the antibacterial hydrophobic fabric prepared by the present invention was tested by far infrared radiation. The hydrophobicity of the sample was hardly changed by contact angle measuring instrument OCA20, and the excellent thermal stability was maintained. The obtained data are listed in Table 4.

[0117] Example 11: This example provides a method for preparing a modified fabric (antimicrobial and hydrophobic fabric). The method comprises: adding 2 parts of the polymer modifier-2 prepared above to 5 parts of deionized water, dispersing the mixture to obtain a mixed solution; then, using a knitting machine, weaving warp and weft yarns of a fiber matrix having terminal active groups to form a fabric. The fabric is then cut into pieces (4 x 4 cm) and placed into the mixed solution. After heating to 75°C and ultrasonically treating for 15 minutes, the sample is removed, rinsed three times with ethanol and deionized water, and dried at 75°C for 1 hour to obtain the modified fabric, i.e., the antimicrobial and hydrophobic fabric.

[0118] The hydrophobic properties of the antibacterial hydrophobic fabric produced according to the present invention were tested using an OCA20 contact angle meter, resulting in a water contact angle (WCA) of 153.2 ± 1°. Dynamic flow testing revealed an antibacterial rate of 85.9%, demonstrating the excellent antibacterial properties of the antibacterial hydrophobic fabric produced according to the present invention. The data are listed in Table 1.

[0119] Using a universal material testing machine, the stretching speed (100 mm / min) was set according to GB / T 3923.1, and the measured elongation at break was 79%, indicating that the antibacterial and hydrophobic fabric prepared in the present invention has good elasticity and extensibility.

[0120] The thermal stability of the hydrophobicity of the antibacterial hydrophobic fabric prepared by the present invention was tested by far infrared radiation. The hydrophobicity of the sample was hardly changed by contact angle measuring instrument OCA20, and the excellent thermal stability was maintained. The obtained data are listed in Table 4.

[0121] Example 12: This example provides a method for preparing a modified fabric (antimicrobial and hydrophobic fabric). The method comprises: adding 2 parts of the polymer modifier-3 prepared above to 5 parts of deionized water, dispersing the mixture to obtain a mixed solution; then, using a knitting machine, interweaving warp and weft yarns of a fiber matrix having terminal active groups to form a fabric. The fabric is then cut into pieces (4 x 4 cm) and placed into the mixed solution. After heating to 75°C and ultrasonically treating for 15 minutes, the sample is removed, rinsed three times with ethanol and deionized water, and dried at 75°C for 1 hour to obtain the modified fabric, i.e., the antimicrobial and hydrophobic fabric.

[0122] The hydrophobicity of the antibacterial hydrophobic fabric prepared by the present invention was tested using a contact angle meter OCA20, and the water contact angle (WCA) was measured to be 151.6±1°. In addition, methylene blue aqueous solution, coffee, juice, tea, cola, and milk were dropped on the surface of the modified fabric to test its wettability (see Figure 4 The results show that the antibacterial fabric has good hydrophobicity. Dynamic flow testing measured an antibacterial rate of 99.6%, demonstrating the excellent antibacterial properties of the antibacterial hydrophobic fabric prepared by the present invention. The obtained data are listed in Table 1.

[0123] Using a universal material testing machine, the tensile speed was set at 100 mm / min according to GB / T 3923.1, and the elongation at break was measured to be 75%, indicating that the antibacterial and hydrophobic fabric prepared in the present invention has good elasticity and extensibility.

[0124] The thermal stability of the hydrophobicity of the antibacterial hydrophobic fabric prepared by the present invention was tested by far infrared radiation. The hydrophobicity of the sample was hardly changed by the contact angle measuring instrument OCA20, and the excellent thermal stability was maintained. The obtained data are listed in Table 4.

[0125] Comparative Example 1: This example provides a method for preparing a modified fabric, which comprises: weaving warp and weft yarns of a fiber matrix having terminal active groups using a knitting machine to form a modified fabric.

[0126] The water contact angle (WCA) of the modified fabric was measured by contact angle meter OCA20 and was 16.2±1° (see Figure 5 In addition, methylene blue aqueous solution, coffee and juice were dropped on the surface of the modified fabric to test its wettability (see Figure 6 The modified fabric exhibited significant wetting and dispersion, as shown in Figure 1. Dynamic flow testing revealed an antibacterial rate of 1.5%, as reported in Table 1. Using a universal testing machine, the elongation at break was measured to be 23%, using a set tensile speed.

[0127] The thermal stability of the hydrophobicity was tested using far-infrared radiation. Tests using an OCA20 contact angle meter revealed that the hydrophobicity of the samples remained virtually unchanged, demonstrating excellent thermal stability. The data are listed in Table 4.

[0128] Comparative Example 2: This example provides a method for preparing a modified fabric. The method comprises: adding two parts of the second modified microspheres prepared above to five parts of deionized water, dispersing the solution to obtain a mixed solution; then, using a knitting machine, interweaving warp and weft yarns of a fiber matrix having terminal reactive groups to form a fabric. The fabric is then cut into a predetermined size (4 x 4 cm) and placed into the mixed solution. After heating to 75°C and ultrasonicating for 15 minutes, the sample is removed, rinsed three times with ethanol and deionized water, and dried at 75°C for one hour to obtain a modified fabric.

[0129] The hydrophobic properties of the modified fabric were measured using an OCA20 contact angle meter, with a water contact angle (WCA) of 149 ± 1°. The antibacterial rate data were obtained through dynamic flow testing and are listed in Table 1.

[0130] Using a universal material testing machine, a certain tensile speed was set for stretching, and the elongation at break was measured to be 78%.

[0131] The thermal stability of the hydrophobicity of the modified fabric was tested using far infrared radiation. The hydrophobicity of the above sample was tested using the contact angle meter OCA20, which showed that the hydrophobicity did not change much, and the excellent thermal stability was maintained. The obtained data are listed in Table 4.

[0132] Comparative Example 3: This example provides a method for preparing a modified fabric. The method comprises: adding two parts of the first modified microspheres prepared above to five parts of deionized water, dispersing the solution to obtain a mixed solution; then, using a knitting machine, interweaving warp and weft yarns of a fiber matrix having terminal reactive groups to form a fabric. The fabric is then cut into pieces (4 x 4 cm) and placed into the mixed solution. After heating to 75°C and ultrasonicating for 15 minutes, the sample is removed, rinsed three times with ethanol and deionized water, and dried at 75°C for one hour to obtain a modified fabric.

[0133] The water contact angle (WCA) of the modified fabric was measured using an OCA20 contact angle meter and was 90.5 ± 1°. Using a universal materials testing machine, stretching at a set speed resulted in an elongation at break of 20%. Dynamic flow testing revealed an antibacterial rate of 3.5%.

[0134] Comparative Example 4: This example provides a method for preparing a modified fabric, which is basically the same as Example 12, except that the polymer modifier is different. Specifically, γ-methacryloxypropyltrimethoxysilane is not used for modification during the preparation of the polymer modifier in this comparative example.

[0135] Furthermore, the polymer modifier used in this comparative example was prepared according to the following method: the first modified microsphere-3 was prepared by the method of Example 3; 20 parts of the first modified microsphere-3 were dispersed in water and ultrasonically dispersed for 5 minutes, and then the dispersed emulsion, 20 parts of 12-methacryloyloxydodecylpyridinium ammonium bromide (MDPB), and 1 part of azobisisobutyronitrile (AIBN) were added to a flask, the temperature was raised to 75° C., and mechanical stirring was carried out at 300 r / min for 1 hour. After the reaction, the product was rinsed with anhydrous ethanol and deionized water three times, and freeze-dried to obtain the product polymer modifier;

[0136] The rest is the same as Example 12.

[0137] The water contact angle of the modified fabric was measured at 135.9 ± 1° using an OCA20 contact angle meter. Using a universal materials testing machine, the elongation at break was 22% at a set tensile speed. Dynamic flow testing revealed an antibacterial rate of 70.6%.

[0138] Performance test: (1) The test results of the hydrophobicity, antibacterial property and elongation at break of the modified fabrics obtained in Examples 10-12 and Comparative Examples 1-4 are shown in Table 1.

[0139]

[0140] (2) The test results of the chemical stability of the modified fabrics obtained in Example 12 and Comparative Examples 1-4 are shown in Table 2. The test method for chemical stability is as follows: each modified fabric is immersed in solutions with different pH values (hydrochloric acid with a pH value of 5, sodium hydroxide aqueous solution with a pH value of 9) and salt water (26.5 wt.% NaCl aqueous solution, pH value of 7), and its performance is tested after 12 hours.

[0141]

[0142] (3) The abrasion resistance of the modified fabrics obtained in Example 12 and Comparative Examples 1-4 (the samples were circularly pasted with transparent tape). The test results are shown in Table 3.

[0143]

[0144] (4) Air permeability test: Using a YG461E digital air permeability meter, cut five specimens from different locations on the sample fabric. Place the specimens flat on the test head to avoid wrinkles or stretching, and secure them with a clamp. The test results are shown in Table 4.

[0145]

[0146] As can be seen from Tables 1 to 4 above, the modified fabric or modified fiber made using the specific polymer modifier of the present invention not only achieves excellent antibacterial and hydrophobic dual functions, but also gives the modified fiber or fabric excellent thermal stability, chemical stability, high air permeability, strong water washability, high bonding strength, and after 200 cycles of rinsing, its mechanical properties, hydrophobic properties and antibacterial properties are maintained at 90% or even above 95%, and it also has excellent stability in acid, alkali and salt environments, thereby enabling the modified fiber or fabric of the present invention to be used in more harsh environments.

[0147] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

[0148] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

Claims

1. A method for preparing modified fiber, characterized in that: The preparation method comprises: (1) allowing hollow polystyrene microspheres and an olefin compound having a molecular weight of less than 300 and a double-end vinyl structure to react in water in the presence of an oil-soluble initiator to generate first modified microspheres; The olefin compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (I); In formula (I), R1 is a substituted or unsubstituted group as follows: 、C 2-10 alkylene; (2) reacting the first modified microspheres and an alkoxysilane compound having a molecular weight of less than 500 and containing an acryloxy group or an alkyl acryloxy group in water in the presence of a water-soluble initiator to produce second modified microspheres; The alkoxysilane compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (II); In formula (II), R2 is H or C 1-6 Alkyl, R3 is C 1-6 Alkylene, R4, R5, R6 are independently selected from C 1-6 alkyl; (3) reacting the second modified microspheres and a hydrocarbon ammonium halide compound having a molecular weight of less than 800 and containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of an oil-soluble initiator to produce a polymer modifier; The hydrocarbyl ammonium halide compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (III); In formula (III), X is halogen, R7, R8, and R9 are independently selected from C 1-6 Alkyl; or, X is halogen, R7 does not exist, R8, R9 are connected and the N to which they are connected together forms a 4-10 membered heterocyclic ring; or, R7, X does not exist, R8, R9 are independently selected from C 1-6 alkyl; R 10 C 1-20 Alkylene, R 11 H or C 1-6 alkyl; (4) applying the polymer modifier to a fiber matrix having terminal active groups to react and generate modified fibers; wherein the terminal active groups include hydroxyl groups.

2. The method for preparing the modified fiber according to claim 1, characterized in that: In formula (I), R1 is , ethylene, propylene, butylene, pentylene or hexylene; and / or, In formula (II), R2 is H, methyl, ethyl or propyl, R3 is methylene, ethylene, propylene, butylene, pentylene or hexylene, and R4, R5 and R6 are independently selected from methyl, ethyl or propyl; and / or, In formula (III), X is bromine or chlorine, R7, R8, and R9 are independently selected from methyl, ethyl, or propyl; or, X is bromine or chlorine, R7 is absent, R8 and R9 are connected and form a pyridine ring with the N to which they are connected; or, R7 and X are absent, and R8 and R9 are independently selected from methyl, ethyl, or propyl; R 10 is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene, heptadecylene or octadecylene, R 11 is H, methyl, ethyl or propyl.

3. The method for preparing modified fiber according to claim 1 or 2, characterized in that: In step (1), the olefin compound comprises divinylbenzene; and / or, in step (2), the alkoxysilane compound comprises γ-methacryloyloxypropyltrimethoxysilane; and / or, in step (3), the hydrocarbon ammonium halide compound comprises a combination of one or more selected from 12-methacryloyloxydodecylpyridinium ammonium bromide, 2-methacryloyloxyethyltrimethylammonium chloride, and dimethylaminohexadecyl methacrylate.

4. The method for preparing modified fiber according to claim 1, characterized in that: In step (1), based on the total weight of the hollow polystyrene microspheres and the olefin compound as 100 parts, the amount of the hollow polystyrene microspheres is 60-90 parts, and the amount of the olefin compound is 10-40 parts; and / or, In step (2), the mass ratio of the first modified microspheres to the alkoxysilane compound is 1:0.5-2.0; and / or, In step (3), the mass ratio of the second modified microspheres to the hydrocarbon ammonium halide compound is 1:0.5-1.

5.

5. The method for preparing modified fiber according to claim 1, characterized in that: The oil-soluble initiator in step (1) and step (3) is independently selected from one or more combinations of dibenzoyl peroxide, ethylene glycol diglycidyl ether, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptylonitrile, and N,N′-dimethylaniline; and / or, The water-soluble initiator in step (2) is a combination of one or more selected from potassium persulfate, diaryliodonium salts, and triarylsulfonium salts; and / or, In step (1)-step (2), the reaction is further carried out in the presence of a surfactant; and / or, In steps (1) to (3), the reactions are carried out at 50-90°C, respectively.

6. The method for preparing modified fiber according to claim 1, characterized in that: In the first modified microspheres, the graft weight proportion of the olefin compound after the reaction is 5wt.%-40wt.%; and / or, in the polymer modifier, the graft weight proportion of the hydrocarbon ammonium halide compound after the reaction is 2wt.%-30wt.%.

7. The method for preparing modified fiber according to claim 1, characterized in that: In step (1), the embodiment of preparing the first modified microspheres includes: mixing and emulsifying the raw materials, and then heating to initiate a polymerization reaction to generate the first modified microspheres; and / or, In step (2), the embodiment of preparing the second modified microspheres includes: preparing the first modified microspheres into a seed emulsion, preparing the alkoxysilane compound into a monomer emulsion, and then dropwise adding the monomer emulsion into the seed emulsion, and after the dropwise addition, heating the reaction to generate the second modified microspheres; and / or, In step (3), the implementation method of preparing the polymer modifier includes: preparing the second modified microspheres into an emulsion, then mixing it with other raw materials, heating and reacting it to generate the polymer modifier.

8. The method for preparing modified fiber according to claim 1, characterized in that: In step (4), the fiber matrix having terminal active groups is obtained by subjecting the fiber to treatment with an alkaline reagent or an acidic reagent; or, In step (4), the method for preparing the fiber matrix having terminal active groups includes: The fiber is treated with an alkaline reagent or an acidic reagent to obtain a pretreated fiber; soaking the pretreated fiber in a sodium alginate aqueous solution to react and generate a sodium alginate modified fiber matrix; The sodium alginate modified fiber matrix is immersed in a silane coupling agent aqueous solution to react and generate the fiber matrix with terminal active groups.

9. The method for preparing modified fiber according to claim 1, characterized in that: In step (4), the embodiment of preparing the modified fiber includes: soaking the fiber matrix having terminal active groups in an aqueous solution of a polymer modifier, heating the solution for reaction, wherein the mass content of the polymer modifier in the aqueous solution is 5%-50%; and / or, In step (4), the reaction is carried out at 50-90°C; and / or, The average particle size of the polymer modifier is 0.5-1 μm.

10. A modified fiber produced by the method for producing a modified fiber according to any one of claims 1 to 9.

11. A method for preparing an antibacterial hydrophobic fabric, characterized in that: The preparation method comprises: (1) allowing hollow polystyrene microspheres and an olefin compound having a molecular weight of less than 300 and a double-end vinyl structure to react in water in the presence of an oil-soluble initiator to generate first modified microspheres; The olefin compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (I); In formula (I), R1 is a substituted or unsubstituted group as follows: 、C 2-10 alkylene; (2) reacting the first modified microspheres and an alkoxysilane compound having a molecular weight of less than 500 and containing an acryloxy group or an alkyl acryloxy group in water in the presence of a water-soluble initiator to produce second modified microspheres; The alkoxysilane compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (II); In formula (II), R2 is H or C 1-6 Alkyl, R3 is C 1-6 Alkylene, R4, R5, R6 are independently selected from C 1-6 alkyl; (3) reacting the second modified microspheres and a hydrocarbon ammonium halide compound having a molecular weight of less than 800 and containing an acryloyloxy group or an alkylacryloyloxy group in water in the presence of an oil-soluble initiator to produce a polymer modifier; The hydrocarbyl ammonium halide compound is a combination of one or more compounds selected from the group consisting of compounds represented by formula (III); In formula (III), X is halogen, R7, R8, and R9 are independently selected from C 1-6 Alkyl; or, X is halogen, R7 does not exist, R8, R9 are connected and the N to which they are connected together forms a 4-10 membered heterocyclic ring; or, R7, X does not exist, R8, R9 are independently selected from C 1-6 alkyl; R 10 C 1-20 Alkylene, R 11 H or C 1-6 alkyl; (4) applying the polymer modifier to a fabric substrate, reacting to generate an antibacterial and hydrophobic fabric; wherein the fabric substrate includes terminal active groups; Alternatively, the preparation method comprises: using the modified fiber according to claim 10 as a raw material to produce the antibacterial and hydrophobic fabric through a weaving process.

12. Use of the modified fiber according to claim 10 or the antibacterial hydrophobic fabric prepared by the method for preparing the antibacterial hydrophobic fabric according to claim 11 in preparing an antibacterial and hydrophobic dual-functional material.

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