Odorless antibacterial polymer-based composite material and preparation method thereof

Abstract

The invention relates to an odorless antibacterial polymer-based composite material and a preparation method thereof. The odorless antibacterial polymer-based composite material comprises the following components in parts by weight: 20-30 parts of modified water-borne epoxy resin, 5-20 parts of a water-borne epoxy resin curing agent, 5-10 parts of a dispersing agent, 5-10 parts of a defoaming agent, 5-10 parts of a flatting agent, 5-10 parts of a coalescing agent, 5-10 parts of modified glass fibers, 20-30 parts of filler, 5-10 parts of an antibacterial agent, 3-8 parts of an antioxidant and 20-30 parts of water. The coating has excellent properties, such as good adhesiveness, corrosion resistance, good mechanical properties, good antibacterial property, good weather resistance, water resistance and the like. And the modified tetrapod-like zinc oxide whisker is compounded with the ethylene bis-dithiocarbamic acid zinc, so that the problem of poor compatibility with the odorless antibacterial polymer-based composite material when the modified tetrapod-like zinc oxide is independently added is solved, the surface hardness of the odorless antibacterial polymer-based composite material is increased, and the service life of the odorless antibacterial polymer-based composite material is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial composite materials, in particular to an odorless antibacterial polymer-based composite material and a preparation method thereof. Background Art

[0002] Polymer-based composites (PMCs) are materials composed of a polymer matrix and other reinforcing materials. They offer advantages such as lightweight, high strength, and corrosion resistance, and are widely used in various fields. However, as their application continues to expand, the antibacterial properties of PMCs have become an important consideration.

[0003] Epoxy floor paint has good water and oil resistance, chemical corrosion resistance, high hardness, high wear resistance, excellent adhesion, etc., and has beautiful colors, stain resistance, easy maintenance, and excellent overall comprehensive performance. It is widely used in modern buildings such as factories, shopping malls, garages, home decoration, etc., and plays an important role in the flooring industry.

[0004] Traditional water-based epoxy floor paints, in addition to their insufficient weather resistance for outdoor use, urgently need further improvement in their construction process. For example, in certain construction environments with frequent rain, a water-based epoxy floor paint with a fast curing speed, good hardness and scratch resistance within 24 hours, and a moderate pot life is needed. However, the disadvantages of traditional water-based epoxy floor paints are slow drying speed and long recoating time. Further improving the drying speed (such as a shorter surface drying time) and hardening time of water-based epoxy floor paints, while ensuring the product's wear resistance, hardness, adhesion, scratch resistance, and chemical resistance, has become another development direction for water-based epoxy floor paints.

[0005] Tetrapod-shaped zinc oxide whiskers, or T-ZnO whiskers for short, are a specialized form of zinc oxide with a regular, three-dimensional, four-needle structure. Specifically, the whisker consists of a core from which four needle-like crystals extend radially, each of which is a single-crystal microfiber. This unique three-dimensional structure endows them with numerous special functions, including thermal conductivity, piezoelectricity, pressure sensitivity, wave and sound absorption, vibration reduction, antibacterial properties, algae control, and catalysis. The nano-activity of the tetrapod-shaped zinc oxide tips can effectively kill and eliminate bacteria and their debris. Composite antimicrobial agents and materials formulated with an appropriate amount of needle-shaped zinc oxide have a kill rate exceeding 99% against common bacteria, including Staphylococcus aureus, Escherichia coli, Candida albicans, and Salmonella.

[0006] A significant portion of the T-ZnO whisker tip is nanoscale or finer. Its nanoactive components are highly effective in killing and removing bacteria and their debris, and can also decompose bacterial toxins, resulting in a significant antibacterial effect. Furthermore, a significant portion of the T-ZnO whisker lattice contains highly oxidative atomic oxygen, which disrupts the biological activity and metabolic reproduction of most bacteria, achieving its antibacterial effect. Zinc oxide whisker samples doped with iron, copper, and silver exhibited excellent antibacterial and formaldehyde-decomposing properties. Testing has shown that T-ZnO whisker resin-based composites have a 99% kill rate against Escherichia coli and Pseudomonas aeruginosa.

[0007] T-ZnO whiskers offer excellent wear resistance and improve the anti-slip properties of materials. Tests have shown that their application to rubber, coatings, and plastics can achieve satisfactory anti-slip effects. Furthermore, T-ZnO whiskers effectively convert absorbed mechanical energy into heat, providing a significant damping effect. Furthermore, T-ZnO whiskers absorb acoustic vibrations and convert them into heat, giving the material a sound-absorbing property and achieving a sound-insulating effect. Finally, they can be used in air fresheners and deodorizers.

[0008] CN106811006B discloses a waterborne epoxy floor paint composition for outdoor use and a preparation method. This invention discloses a waterborne epoxy floor paint composition for outdoor use. The composition comprises two components, A and B, with a mass ratio of A:B = (80-150):100. Component A is an acrylic-based hybrid modified waterborne epoxy resin with an epoxy equivalent weight of 800-1500. The waterborne epoxy floor paint of this invention is a waterborne system that contains no VOCs, making it a green and environmentally friendly waterborne epoxy floor paint. However, this waterborne epoxy floor paint lacks antibacterial properties and exhibits poor overall performance.

[0009] CN102578148B discloses a method for improving the antibacterial properties of tetrapod-shaped zinc oxide whiskers. The synthesis steps of this invention are as follows: A. Adding white powdery tetrapod-shaped zinc oxide whiskers to an aqueous solution of potassium sodium tartrate to form a paste or suspension, stirring for 10-30 minutes. The molar ratio of potassium sodium tartrate to tetrapod-shaped zinc oxide whiskers is (0.1-1):100. Then, while stirring, slowly add an aqueous solution of copper chloride in an amount equimolar to the potassium sodium tartrate. Stirring is continued for 30-60 minutes. Finally, filtering, washing, and drying the mixture yields a tetrapod-shaped zinc oxide whisker composite powder with nano-copper tartrate deposited in situ on the surface. B. Heating the composite powder to 270-300°C in a hydrogen atmosphere, maintaining the temperature for 15-60 minutes, and cooling to room temperature. Although this invention patent improves the antibacterial properties of four-needle silver oxide whiskers by surface modification, the preparation process may not meet the purification standards and may leave toxic and harmful substances such as copper oxide. Summary of the Invention

[0010] The present invention provides an odorless antibacterial polymer-based composite material, and the preparation steps are as follows, calculated in parts by weight: Step 1: First add 20-30 parts of water to a container, then add 5-10 parts of dispersant and 5-10 parts of defoamer, stir for 3-5 minutes, and stir at a speed of 200-300 rpm; then add 20-30 parts of filler and 5-10 parts of modified glass fiber, stir for 40-60 minutes, and stir at a speed of 900-1000 rpm; until the slurry fineness is less than 40 μm, then add 5-20 parts of water-based epoxy resin curing agent, 5-10 parts of leveling agent, 5-10 parts of antibacterial agent, and 3-8 parts of antioxidant, stir for 10-20 minutes, and stir at a speed of 200-300 rpm to obtain component A; Step 2: Mix 20-30 parts of modified waterborne epoxy resin and 5-10 parts of film-forming aid, stirring for 30-40 minutes at a stirring speed of 800-900 rpm to obtain component B; Step 3: Component A and component B are mixed and stirred, with the mixing mass ratio of component A to component B being (100-180):100, the stirring time being 30-40 min, and the stirring speed being 800-900 rpm; thereby obtaining the odorless antibacterial polymer-based composite material.

[0011] The modified waterborne epoxy resin is made of an emulsifier and an epoxy resin, wherein the epoxy resin is at least one of bisphenol A epoxy resin, E51 epoxy resin, E44 epoxy resin, alicyclic epoxy resin, bisphenol F epoxy resin, and novolac epoxy resin; more preferably, the epoxy resin is bisphenol A epoxy resin.

[0012] The emulsifier is at least one of pure acrylic emulsion, acetic acid acrylic emulsion, and styrene acrylic emulsion; more preferably, the emulsifier is styrene acrylic emulsion.

[0013] The mass ratio of the epoxy resin to the emulsifier is 100:(10-20); more preferably, the mass ratio of the epoxy resin to the emulsifier is 100:15.

[0014] The waterborne epoxy resin curing agent is at least one of polyamide, isophorone diamine, cyclohexanediamine, methylcyclopentanediamine, polyoxypropylene triamine, and polyethylene oxide diamine; more preferably, the waterborne epoxy resin curing agent is polyamide.

[0015] The dispersant is at least one of DISPERS-188A, BYK-180, BYK-190, EFKA-4560, W-511, FA-182, EFKA-4550, and W-518; more preferably, the dispersant is BYK-190.

[0016] The defoaming agent is at least one of HS-334, LG-20GB, SXP-120, LG-10, CF-328, CF-698, Foamex 1488, and BYK-020; more preferably, the defoaming agent is Foamex 1488.

[0017] The leveling agent is at least one of BYK-346, BLD-533, BLD-511, San Nopco 621N, TEGO Twin 4100, W-77, W-461, BYK-333, and TEGO Twin 4000; more preferably, the leveling agent is BYK-333.

[0018] The film-forming aid is at least one of ethanol, methoxybutanol, and benzyl alcohol; more preferably, the film-forming aid is benzyl alcohol.

[0019] The modified glass fiber preparation method is as follows, in parts by weight: S1: immerse 5-10 parts of glass fiber in 10-20 parts of 3-5% by mass hydrofluoric acid aqueous solution for 20-50 seconds, continue to clean and dry, and then set aside; S2: mixing the glass fiber treated in step S1 with 2-3 parts of alkoxysilane, 1-2 parts of end-capping agent, 20-30 parts of organic solvent, and 1-2 parts of catalyst at 40-80° C. for 2-3 hours to obtain modified glass fiber.

[0020] The glass fiber has a diameter of 20 to 60 μm and a length of 50 to 300 mm; more preferably, the glass fiber has a diameter of 30 μm and a length of 100 mm.

[0021] The alkoxysilane is at least one of dimethoxymethylvinylsilane, vinyltriethoxysilane, propenyltriethoxysilane, and phenyltriethoxysilane; more preferably, the siloxysilane is dimethoxymethylvinylsilane.

[0022] The end-capping agent is at least one of hexamethyldisiloxane, methyltriethoxysilane, and tetramethyldivinyldisiloxane; more preferably, the end-capping agent is methyltriethoxysilane.

[0023] The organic solvent is at least one of tetrahydrofuran, methanol, toluene, n-hexane, and chloroform; more preferably, the organic solvent is toluene.

[0024] The catalyst is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and perchloric acid; more preferably, the catalyst is phosphoric acid.

[0025] The mass fraction of the phosphoric acid is 3-5%; more preferably, the mass fraction of the phosphoric acid is 5%.

[0026] The filler is at least one of rutile titanium dioxide, talc, mica, quartz powder, and nano-alumina; more preferably, the filler is rutile titanium dioxide.

[0027] The antimicrobial agent is at least one of suberic acid-modified tetrapod-shaped zinc oxide whiskers, nano-zinc oxide, zinc ethylenebisdithiocarbamate, and zinc pyrithione. Preferably, the antimicrobial agent is a mixture of zinc ethylenebisdithiocarbamate and suberic acid-modified tetrapod-shaped zinc oxide in a mass ratio of (1-3):1.

[0028] The preparation method of the suberic acid modified tetrapod-shaped zinc oxide whiskers is as follows, in parts by weight: X1: Add 5-10 parts of suberic acid to 30-50 parts of anhydrous ethanol and ultrasonicate at a frequency of 20-50 kHz for 30-50 minutes to completely dissolve and disperse the suberic acid in the anhydrous ethanol. X2 adds 5 to 10 parts of dry tetrapod-shaped zinc oxide whiskers to X1, ultrasonically oscillates at a frequency of 20 to 50 kHz for 30 to 50 min, continues stirring at 40 to 50°C for 30 to 60 min, and at a stirring speed of 500 to 800 r / min. After filtration, suberic acid-modified tetrapod-shaped zinc oxide whiskers are obtained.

[0029] The antioxidant is at least one of antioxidant 1010, antioxidant 168, 2,6-di-tert-butyl-p-cresol, N,N'-di-sec-butyl-p-phenylenediamine, and trisnonylphenyl phosphite; more preferably, the antioxidant is trisnonylphenyl phosphite.

[0030] The functions of the main raw materials in the present invention are described as follows: Waterborne epoxy resin curing agent: The mechanism of action of waterborne epoxy curing agents in odorless, antimicrobial polymer-based composites primarily involves curing and crosslinking reactions. 1. First, the waterborne epoxy curing agent undergoes a ring-opening reaction with the epoxy groups in the epoxy resin, generating hydroxyl groups, which then react with the epoxy groups to form ether bonds. This process tightly bonds the curing agent and epoxy resin, forming a network structure. 2. Second, the multifunctional groups in the waterborne epoxy curing agent undergo cross-linking reactions with reactive groups such as hydroxyl groups and ether bonds in the epoxy resin, forming a three-dimensional network structure that enhances the physical and chemical properties of the coating. The cross-linking reaction improves the coating's hardness, toughness, wear resistance, and corrosion resistance. 3. Furthermore, waterborne epoxy curing agents enhance the coating's application and drying properties. Waterborne epoxy curing agents accelerate the coating's drying process, reduce application waiting time, and improve the coating's chemical stability. Furthermore, they enhance the material's physical properties and resistance, making the floor easier to clean and more durable.

[0031] In summary, the mechanism of action of waterborne epoxy curing agent in odorless antibacterial polymer-based composite materials is to improve the performance and construction performance of the coating through curing reaction and cross-linking reaction, and to improve the hardness, toughness, wear resistance, corrosion resistance and other properties of the coating film.

[0032] Wetting and dispersing agent BYK-190: When pigments are dispersed in epoxy resin, the resin's viscosity limits their dispersion efficiency. If the curing agent contains surfactant segments and possesses a certain degree of wetting and dispersing ability, a dispersant can theoretically be omitted. However, considering the compatibility of the conductive pigment with other ingredients and the need for quick dispersion, a suitable wetting and dispersing agent is essential. The mechanism of action of the wetting and dispersing agent BYK-190 in odorless, antimicrobial polymer-based composites primarily involves wetting, dispersing, and stabilizing. 1. First, BYK-190's wetting action helps odorless, antimicrobial polymer-based composites better wet pigments and fillers, improving the coating's leveling and workability. 2. Second, BYK-190's dispersing effect prevents pigment flocculation, stabilizing the hue and tinting strength of coatings and pigment pastes while reducing color floating and blooming in pigment mixtures, which helps enhance the color intensity and hiding power of the coating film. 3. Furthermore, BYK-190 has a stabilizing effect, increasing the system's storage stability. It deflocculates pigments through steric stabilization. Due to the small particle size of deflocculated pigments, high gloss and enhanced color intensity are achieved. The hiding power of transparent pigments is also enhanced. Furthermore, the reduced viscosity improves flowability, allowing for increased pigment content.

[0033] In summary, the mechanism of action of the wetting and dispersing agent BYK-190 in odorless antibacterial polymer-based composites is to improve the performance and construction performance of the coating through wetting, dispersion and stabilization, and to enhance the gloss, color intensity and hiding power of the coating film.

[0034] Defoamer Foamex 1488: Defoamers require special attention because some of the ingredients have surface activity, which can easily form foam; air can be entrapped during application; paint films lack density and contain micropores; and film thickness affects the rate of foam generation and removal. A combined defoamer and defoamer is more effective. The defoamer Foamex 1488's mechanism of action in odorless antimicrobial polymer-based composites is primarily to reduce the surface tension of the foam, destabilize it, and thus eliminate it. The production and application of odorless antimicrobial polymer-based composites, involving multiple chemicals and complex reaction processes, can easily generate bubbles or foam. These bubbles can severely impact the fluidity, application performance, and film quality of the coating. Defoamer Foamex 1488 is a silicone polymer with low surface tension and excellent defoaming properties. It effectively eliminates bubbles in odorless antimicrobial polymer-based composites, improving the fluidity and application performance of the coating. The mechanism of action of the defoamer Foamex 1488 includes the following aspects: 1. Reducing surface tension: The defoamer Foamex 1488 has a low surface tension and can effectively wet the surface of the foam, reducing the elasticity of the foam and making it easier to burst; 2. Destroying foam stability: The defoamer Foamex 1488 can penetrate into the foam, change the local surface tension of the foam, and cause the foam to burst; 3. Preventing foam regeneration: The defoamer Foamex 1488 can inhibit the regeneration of foam, thereby maintaining the stability and construction performance of the coating.

[0035] In summary, the mechanism of action of the defoamer Foamex 1488 in odorless antibacterial polymer-based composite materials is to eliminate bubbles by reducing surface tension, destroying foam stability and inhibiting foam regeneration, thereby improving the fluidity and construction performance of the coating and improving the coating film quality.

[0036] Leveling agent BYK-333: Water has a relatively high surface tension, which significantly reduces substrate wetting. However, it ensures that the coating film fully leveled within a limited timeframe, ensuring uncompromised gloss. The mechanism of action of BYK-333 in odorless, antimicrobial polymer-based composites primarily involves reducing surface tension, improving wettability, and eliminating orange peel or Bénard cells caused by surface tension differences during the drying process. 1. Surface tension reduction: BYK-333 requires a certain degree of compatibility with the system and a lower surface tension than the system. This allows it to migrate across the surface of the paint film and exert its leveling effect. 2. Wettability improvement: BYK-333 reduces the surface tension of coatings and printing inks, improving substrate wetting and preventing craters. In water-based systems, it improves anti-blocking properties. 3. It eliminates orange peel or Bénard cells caused by surface tension differences during the drying process. This primarily reduces the surface tension of the coating film, improving surface tension consistency across the coating, thereby eliminating these differences.

[0037] In addition, the leveling agent BYK-333 can also improve the leveling properties of the coating system, making the coating surface smooth and increasing the gloss.

[0038] In summary, the mechanism of action of the leveling agent BYK-333 in odorless antibacterial polymer-based composites is to improve the leveling of the coating and the surface quality of the coating film by reducing surface tension, improving wettability, and eliminating orange peel or Bénard vortices caused by surface tension differences during the drying process.

[0039] Coal-forming agent benzyl alcohol: Coal-forming agents reduce MFFT, adjust system viscosity, and benefit surface appearance. A good coalescing agent should meet the following requirements: 1. Good hydrolytic stability; 2. Low freezing point; 3. Appropriate volatility; 4. Good coagulation efficiency; and 5. Environmentally friendly.

[0040] The mechanism of action of the film-forming aid benzyl alcohol in odorless antimicrobial polymer-based composites is primarily to plasticize epoxy resins and reduce the brittleness of low-molecular-weight epoxy resins after film formation. 1. Benzyl alcohol, as a solvent for salicylic acid, participates in the curing reaction of epoxy resins. During this process, benzyl alcohol plasticizes the epoxy resins, reducing their brittleness after film formation. This improves the coating's flexibility and durability, thereby extending its service life. 2. Benzyl alcohol also enhances the coating's application performance and drying speed. It accelerates the coating's drying process, reduces application waiting time, and improves the coating's chemical stability.

[0041] It is important to note that the use of coalescents must strictly adhere to product and environmental compatibility principles to ensure their stability in the coating and that they do not cause adverse effects on the environment or human health. Furthermore, the amount of benzyl alcohol added should be carefully considered to avoid excessive use, which can lead to performance degradation.

[0042] In general, the role of the film-forming aid benzyl alcohol in odorless antibacterial polymer-based composites is to improve the quality and service life of the coating by improving its flexibility and durability, improving construction performance and drying speed.

[0043] Glass fiber: The mechanism of action of glass fiber in odorless antibacterial polymer-based composite materials mainly includes enhancing their strength and hardness, improving heat resistance, and enhancing wear resistance. 1. First, glass fiber has the characteristics of high strength and high hardness, which can effectively increase its compressive strength and wear resistance. Adding an appropriate amount of glass fiber to the odorless antibacterial polymer-based composite material can make it more durable and less susceptible to damage by external forces; 2. Second, glass fiber has a high melting point and high temperature resistance, which can effectively improve the heat resistance of the odorless antibacterial polymer-based composite material. In high temperature environments, the glass fiber in the odorless antibacterial polymer-based composite material can act as a reinforcing material to prevent it from deforming or cracking due to high temperature; 3. In addition, glass fiber can also improve the construction performance and drying speed of the coating. It can speed up the drying speed of the coating, reduce construction waiting time, and improve the stability of the chemical properties of the coating.

[0044] In summary, the mechanism of action of glass fiber in odorless and antibacterial polymer-based composite materials is to improve the quality and service life by enhancing its strength and hardness, improving temperature resistance and enhancing wear resistance.

[0045] Filler rutile titanium dioxide: The mechanism of action of filler rutile titanium dioxide in odorless antibacterial polymer-based composites mainly includes improving hiding power, enhancing white color retention and increasing wear resistance. 1. First, rutile titanium dioxide has high hiding power and can effectively cover its surface defects and unevenness. This makes its surface smoother and flatter, improving its aesthetics and comfort of use; 2. Secondly, rutile titanium dioxide has excellent weather resistance and stability, which can enhance its white color retention. Even under harsh environmental conditions, such as ultraviolet rays and humidity, rutile titanium dioxide can maintain stable color and performance; 3. Finally, rutile titanium dioxide can also increase its wear resistance and effectively resist friction and wear, which makes it more durable and less prone to wear and scratches.

[0046] In summary, the mechanism of action of filler rutile titanium dioxide in odorless antibacterial polymer-based composites is to improve their quality and performance by improving hiding power, enhancing white retention and increasing wear resistance.

[0047] Tetrapod-modified zinc oxide whiskers with antimicrobial agent suberic acid: 1. The properties and application characteristics of tetrapod-shaped zinc oxide whiskers are similar to those of silicon carbide and potassium titanate whiskers, but there are few reports on them. Tetrapod-shaped zinc oxide whiskers exhibit a three-dimensional, four-needle shape: a core from which four needle-like crystals extend radially. Each needle is a single-crystal microfiber, and the angle between any two needles is 109°. The diameter of the whisker's central body ranges from 0.7 to 1.4 µm, the diameter of the needle base ranges from 0.5 to 14 µm, and the length ranges from 3 to 200 µm. It is the only crystal discovered to date with a three-dimensional structure. 2. T-ZnO whiskers also possess high strength, high modulus (with an elastic modulus of 350 GPa), and high-temperature resistance (resistant to 1720°C). These unique properties make it easy to achieve three-dimensional uniform distribution and isotropy when used as composite reinforcements or coating additives, advantages that one-dimensional whiskers struggle to achieve. 3. Related research has found that T-ZnO whiskers also exhibit excellent properties such as vibration damping, noise reduction, wave absorption, antistatic properties, and antibacterial properties. T-ZnO whiskers possess a three-dimensional tetrahedral structure, while conventional whiskers, such as silicon carbide whiskers and potassium titanate whiskers, are needle- or rod-shaped, with a fibrous, one-dimensional shape similar to glass and carbon fibers, primarily used as reinforcement materials. 4. Research has shown that these conventional one-dimensional, fibrous whiskers are difficult to achieve a three-dimensional uniform distribution within a matrix material, resulting in anisotropic properties in the composite material. T-ZnO whiskers, however, achieve a uniform three-dimensional distribution within the matrix material, imparting isotropic mechanical properties to the composite material, thereby eliminating or reducing anisotropy and improving sliding and frictional properties. They can also serve as reinforcements for plastics, rubber, coatings, and adhesives. A significant portion of the T-ZnO whisker tips are nanoscale or finer, and their nanoactive components effectively kill and remove bacteria and their debris, as well as decompose bacterial toxins, resulting in a significant antibacterial effect. Furthermore, a significant portion of the T-ZnO whisker lattice contains highly oxidizing atomic oxygen, which disrupts the biological activity and metabolic reproduction of most bacteria, achieving its antibacterial effect. Zinc oxide whisker samples doped with iron, copper, and silver exhibited excellent antibacterial and formaldehyde-degrading properties. Testing has shown that T-ZnO whisker resin-based composites have a 99% kill rate against Escherichia coli and Pseudomonas aeruginosa.

[0048] Antioxidant trisnonylphenyl phosphite: The antioxidant trisnonylphenyl phosphite's mechanism of action in odorless antimicrobial polymer-based composite materials is primarily to inhibit the generation of free radicals and terminate chain reactions, thereby preventing aging and fading of the coating. 1. During the construction of odorless antimicrobial polymer-based composite materials, due to the involvement of multiple chemical substances and complex reaction processes, free radicals are easily generated, leading to aging and fading of the coating. The antioxidant trisnonylphenyl phosphite can effectively inhibit the generation of free radicals and terminate chain reactions, thereby preventing aging and fading of the coating. 2. In addition, the antioxidant trisnonylphenyl phosphite can also improve the weather resistance and yellowing resistance of the coating. It can enhance the chemical stability of the coating, allowing it to maintain stable performance in harsh environments such as ultraviolet light and humidity.

[0049] In summary, the mechanism of action of the antioxidant trinonylphenyl phosphite in odorless antibacterial polymer-based composite materials is to prevent the aging and fading of the coating by inhibiting the generation of free radicals and terminating the chain reaction, thereby improving the weather resistance and yellowing resistance of the coating and extending its service life.

[0050] Beneficial effects of the present invention: 1. The antimicrobial agent of the present invention is an inorganic zinc antimicrobial agent, tetrapod-modified zinc oxide whiskers, combined with an organic zinc antimicrobial agent, zinc ethylenebisdithiocarbamate. Its antimicrobial properties are superior to those of conventional antimicrobial agents, and it is environmentally friendly and durable. It also overcomes the poor compatibility of modified tetrapod-modified zinc oxide whiskers with odorless antimicrobial polymer-based composites when added alone. Furthermore, it improves the surface hardness of the odorless antimicrobial polymer-based composite, extending its service life. 2. The odorless antibacterial polymer-based composite material of the present invention does not contain any VOCs, and is a green and environmentally friendly odorless antibacterial polymer-based composite material; 3. The odorless antibacterial polymer-based composite material of the present invention has a compatibility between the various materials, resulting in a pencil hardness of ≥1 H after 24 hours of curing, and has higher mechanical properties than conventional odorless antibacterial polymer-based composite materials; 4. The odorless antibacterial polymer-based composite material of the present invention further improves the toughness of the paint film while substantially not reducing the hardness of the paint film, and has good scratch resistance after one day of curing, achieving a balance between the hardness and toughness of the paint film. By reducing the amount of organic thickener used, the water resistance of the odorless antibacterial polymer-based composite material is improved, further improving the weather resistance and overall performance of the odorless antibacterial polymer-based composite material. DETAILED DESCRIPTION

[0051] In order to further understand the present invention, the following describes in detail an odorless antibacterial polymer-based composite material and a preparation method thereof provided by the present invention in conjunction with embodiments.

[0052] In the following statements: Bisphenol A epoxy resin: Model: E-03, source: Hubei Shishun Biotechnology Co., Ltd.

[0053] Styrene acrylic emulsion: Product number: Y17677, source: Shanghai Yuanye Biotechnology Co., Ltd.

[0054] Polyamide: Product number: TB07339, source: Hubei Tuobang Chemical Co., Ltd.

[0055] Dispersant: Model DISPERBYK-190, sourced from BYK, Germany.

[0056] Defoaming agent: Model Foamex 1488, source: Digo Company.

[0057] Leveling agent: Model DISPERBYK-333, sourced from BYK, Germany.

[0058] Rutile titanium dioxide: particle size is 300 mesh.

[0059] Glass fiber: 30 μm in diameter and 100 mm in length.

[0060] Nano zinc oxide: Model: ZT-J20, average particle size is 20 nm, source: Zhejiang Zhiti Nano Micro New Materials Co., Ltd.

[0061] Zinc ethylenebisdithiocarbamate: CAS number: 12122-67-7.

[0062] Tetrapod-shaped zinc oxide whiskers: Model: JC-07-01, Chengdu Tianyou Jingchuang Technology Co., Ltd. Example 1

[0063] An odorless antibacterial polymer-based composite material, the preparation steps are as follows: Step 1: Add 20.0 g of water to a 500 mL beaker, then add 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stir for 5 min at a stirring speed of 300 rpm; then add 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber, stir for 40 min at a stirring speed of 900 rpm; until the slurry fineness is 20 μm, then add 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 6.0 g of suberic acid-modified tetrapodal zinc oxide, and 3.0 g of antioxidant trisnonylphenyl phosphite, stir for 10 min at a stirring speed of 200 rpm to obtain component A; Step 2: 20.0 g of modified waterborne epoxy resin and 5.0 g of film-forming aid benzyl alcohol were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain component B; Step 3: 37.5 g of component A and 25.0 g of component B were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0064] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, with a mass ratio of 100:15, and the modified waterborne epoxy resin is prepared by mixing.

[0065] The epoxy resin is bisphenol A epoxy resin.

[0066] The emulsifier is styrene acrylic emulsion.

[0067] The modified glass fiber preparation method is as follows: S1: Immerse 6 g of glass fiber in 15 g of 3% hydrofluoric acid aqueous solution for 30 seconds, then continue cleaning and drying for later use; S2: The glass fiber treated in step S1 is mixed with 3 g of dimethoxymethylvinylsilane, 2 g of methyltriethoxysilane, 25 g of toluene, and 2 g of a 5% by mass phosphoric acid aqueous solution at 70° C. for 2 h to obtain a modified glass fiber.

[0068] The preparation method of the suberic acid modified tetrapod-shaped zinc oxide whiskers is as follows: X1: Add 6 g of suberic acid to 50 mL of anhydrous ethanol and ultrasonicate at a frequency of 35 kHz for 40 min to completely dissolve and disperse the suberic acid in the anhydrous ethanol. X2 added 6 g of dried tetrapod-shaped zinc oxide whiskers to X1, subjected to ultrasonic oscillation at a frequency of 30 KHz and an ultrasonic time of 50 min, and continued stirring at 45°C for 40 min at a stirring speed of 600 r / min. After filtration, suberic acid-modified tetrapod-shaped zinc oxide whiskers were obtained. Example 2

[0069] An odorless antibacterial polymer-based composite material, the preparation steps are as follows: Step 1: Add 20.0 g of water to a 500 mL beaker, then add 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stir for 5 min at a stirring speed of 300 rpm; then add 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber, stir for 40 min at a stirring speed of 900 rpm; until the slurry fineness reaches 20 μm, then add 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 6.0 g of nano zinc oxide, and 3.0 g of antioxidant trisnonylphenyl phosphite, stir for 10 min at a stirring speed of 200 rpm; Step 2: 20.0 g of modified waterborne epoxy resin and 5.0 g of film-forming aid benzyl alcohol were mixed and stirred for 30 min at a stirring speed of 800 rpm; Step 3: 37.5 g of component A and 25.0 g of component B were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0070] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, the mass ratio of the two is 100:15, and the modified waterborne epoxy resin is prepared by mixing; The epoxy resin is bisphenol A epoxy resin; The emulsifier is styrene acrylic emulsion; The method for preparing the modified glass fiber is the same as that in Example 1 and will not be described again here. Example 3

[0071] An odorless antibacterial polymer-based composite material, the preparation steps are as follows: Step 1: Add 20.0 g of water to a 500 mL beaker, then add 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stir for 5 min at a stirring speed of 300 rpm; then add 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber, stir for 40 min at a stirring speed of 900 rpm; until the slurry fineness reaches 20 μm, then add 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 6.0 g of zinc ethylenebisdithiocarbamate, and 3.0 g of antioxidant trisnonylphenyl phosphite, stir for 10 min at a stirring speed of 200 rpm; Step 2: 20.0 g of modified waterborne epoxy resin and 5.0 g of film-forming aid benzyl alcohol were mixed and stirred for 30 min at a stirring speed of 800 rpm; Step 3: 37.5 g of component A and 25.0 g of component B were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0072] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, the mass ratio of the two is 100:15, and the modified waterborne epoxy resin is prepared by mixing; The epoxy resin is bisphenol A epoxy resin; The emulsifier is styrene acrylic emulsion; The method for preparing the modified glass fiber is the same as that in Example 1 and will not be described again here. Example 4

[0073] An odorless antibacterial polymer-based composite material, the preparation steps are as follows: Step 1: Add 20.0 g of water to a 500 mL beaker, then add 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stir for 5 min at a stirring speed of 300 rpm; then add 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber, stir for 40 min at a stirring speed of 900 rpm; until the slurry fineness is 20 μm, then add 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 6.0 g of zinc pyrithione, and 3.0 g of antioxidant trisnonylphenyl phosphite, stir for 10 min at a stirring speed of 200 rpm; Step 2: 20.0 g of modified waterborne epoxy resin and 5.0 g of film-forming aid benzyl alcohol were mixed and stirred for 30 min at a stirring speed of 800 rpm; Step 3: 37.5 g of component A and 25.0 g of component B were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0074] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, the mass ratio of the two is 100:15, and the modified waterborne epoxy resin is prepared by mixing; The epoxy resin is bisphenol A epoxy resin; The emulsifier is styrene acrylic emulsion; The method for preparing the modified glass fiber is the same as that in Example 1 and will not be described again here. Example 5

[0075] An odorless antibacterial polymer-based composite material, the preparation steps are as follows: Step 1: Add 20.0 g of water to a 500 mL beaker, then add 5.0 g of dispersant BYK-190 and 5.0 g of defoamer Foamex 1488, stir for 5 min at a stirring speed of 300 rpm; then add 20.0 g of filler rutile titanium dioxide and 6.0 g of modified glass fiber, stir for 40 min at a stirring speed of 900 rpm; until the slurry fineness is 20 μm, then add 5.0 g of polyamide, 5.0 g of leveling agent BYK-333, 4.0 g of ethylenebisdithiocarbamate zinc, 2.0 g of suberic acid-modified tetrapodal zinc oxide, and 3.0 g of antioxidant trisnonylphenyl phosphite, stir for 10 min at a stirring speed of 200 rpm; Step 2: 20.0 g of modified waterborne epoxy resin and 5.0 g of film-forming aid benzyl alcohol were mixed and stirred for 30 min at a stirring speed of 800 rpm; Step 3: 37.5 g of component A and 25.0 g of component B were mixed and stirred for 30 min at a stirring speed of 800 rpm to obtain the odorless antibacterial polymer-based composite material.

[0076] The modified waterborne epoxy resin is a mixture of epoxy resin and emulsifier, with a mass ratio of 100:15, and the modified waterborne epoxy resin is prepared by mixing.

[0077] The epoxy resin is bisphenol A epoxy resin.

[0078] The emulsifier is styrene acrylic emulsion.

[0079] The method for preparing the modified glass fiber is the same as that in Example 1 and will not be described again here.

[0080] The suberic acid-modified tetrapod-shaped zinc oxide is the same as that in Example 1 and will not be described again here.

[0081] Test Item 1: Basic performance test of odorless antibacterial polymer-based composite materials The test was carried out in accordance with the standard "GB / T 22374-2018 Floor Coating Materials".

[0082] Table 1 Basic performance test of odorless antibacterial polymer-based composite materials

[0083] Through the performance tests of Examples 1-5 in Table 1, it can be found that Example 5 has the best performance. It also shows that adding suberic acid-modified tetrapodal zinc oxide combined with an organic zinc antibacterial agent zinc ethylenebisdithiocarbamate to the odorless antibacterial polymer-based composite material can improve its surface hardness, which can be seen from the hardness in the above test; from the adhesion size in the above table, it can be seen that adding the inorganic antibacterial agent suberic acid-modified tetrapodal zinc oxide combined with an organic zinc antibacterial agent zinc ethylenebisdithiocarbamate to the odorless antibacterial polymer-based composite material can improve its compatibility problem in the odorless antibacterial polymer-based composite material, so that the composite antibacterial agent has better compatibility in the odorless antibacterial polymer-based composite material than adding suberic acid-modified tetrapodal zinc oxide alone.

[0084] The possible reasons for the above changes are: 1. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate are compatible with water-based epoxy resin, thereby improving the stability of the system; 2. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate can chemically react with water-based epoxy resin to form a network structure, thereby improving the surface hardness of the odorless antibacterial polymer-based composite material; 3. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate can enhance the wear resistance and weather resistance of the odorless antibacterial polymer-based composite material, thereby improving its service life; 4. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate can reduce the surface tension of the odorless antibacterial polymer-based composite material coating, improve the wettability and fluidity of the coating, thereby improving the surface smoothness and hardness of the odorless antibacterial polymer-based composite material coating.

[0085] In summary, adding the inorganic antibacterial agent tetrapod-modified zinc oxide with suberic acid combined with the organic zinc antibacterial agent zinc ethylenebisdithiocarbamate into the odorless antibacterial polymer-based composite material can improve the compatibility problem of suberic acid-modified tetrapod-shaped zinc oxide added alone to the odorless antibacterial polymer-based composite material, and at the same time improve the surface hardness, wear resistance and weather resistance of the odorless antibacterial polymer-based composite material.

[0086] Test Item 2: Scratch resistance test of odorless antibacterial polymer-based composite materials The test was conducted in accordance with the standard GB / T 9279.1-2015 Determination of scratch resistance of paints and varnishes Part 1 Constant load method. The corresponding paint films were made from the odorless antibacterial polymer-based composite materials of Examples 1-5 above, and then subjected to the scratch test.

[0087] The substrate should be steel plate with a thickness of 0.8 mm and comply with the requirements of ISO 1514. The size of the substrate should be 200 mm × 100 mm. Substrate preparation and coating: The substrate was prepared according to ISO 1514, and then coated with the material prepared in the above example according to the specified method.

[0088] Drying and Conditioning: Painted test panels should be dried (or baked) and cured under the specified conditions and for the specified time. Before testing, condition the painted test panels at a temperature of (23±2)°C and a relative humidity of (50±5)°C (as specified in ISO 3270) for at least 16 hours.

[0089] The thickness of the dry coating is determined in μm using a method specified in ISO 2808.

[0090] Clamp a painted test panel onto the test panel holder with the test surface facing upwards. Position the test panel so that the distance between the scratches is at least 5 mm and the scratches are at least 10 mm from the edge of the test panel.

[0091] Table 2 Scratch resistance test of odorless antibacterial polymer-based composite materials

[0092] As shown in Table 2 above, the odorless antibacterial polymer-based composite material prepared in Example 5 exhibits the best scratch resistance. Possible reasons for this are: 1. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate both possess antibacterial properties, effectively inhibiting bacterial growth and thus improving the antibacterial properties of the odorless antibacterial polymer-based composite material. Furthermore, these antibacterial agents can form a network structure, enhancing the hardness and wear resistance of the coating, thereby improving scratch resistance. 2. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate can reduce the surface tension of the coating, improving its wettability and fluidity, thereby improving its surface smoothness and scratch resistance. 3. Suberic acid-modified tetrapodal zinc oxide and zinc ethylenebisdithiocarbamate can enhance the chemical corrosion resistance of the odorless antibacterial polymer-based composite material, thereby improving its durability and scratch resistance.

[0093] In summary, combining the inorganic zinc antimicrobial agent, tetrapod-modified zinc oxide (SSO), with the organic zinc antimicrobial agent, zinc ethylenebisdithiocarbamate, can enhance the antimicrobial properties, surface hardness, wear resistance, and durability of odorless antimicrobial polymer-based composites, thereby improving their scratch resistance. This is likely due to the ability of these antimicrobial agents to form a network structure, reduce the surface tension of the coating, and enhance the hardness and wear resistance of the coating.

[0094] Test Item 3: Aging resistance test of odorless antibacterial polymer-based composite materials The test is carried out in accordance with the standards "GB / T 1865-2009 Paints and varnishes - Artificial weathering and artificial radiation exposure to filtered xenon arc radiation" and "GB / T-1766-2008 Paints and varnishes - Rating method for coating degradation".

[0095] This standard uses a numerical scale of 0 to 5 to assess the degree and amount of damage, with "0" indicating no damage and "5" indicating severe damage. The four grades (1, 2, 3, and 4) should be determined to provide optimal differentiation across the entire grade range. If necessary, intermediate half-grades may be used to record all observed phenomena in more detail.

[0096] Table 3 Aging resistance test of odorless antibacterial polymer-based composite materials

[0097] It can be seen from Table 3 above that the odorless antibacterial polymer-based composite material prepared in Example 5 has the best aging resistance test result, and the comprehensive performance evaluation reaches level 0. Its aging resistance is far superior to that of Examples 1-4. The possible reasons are: 1. Suberic acid-modified tetrapod-shaped zinc oxide and ethylenebisdithiocarbamate zinc both have antibacterial properties, thereby improving the antibacterial properties of the odorless antibacterial polymer-based composite material. At the same time, these antibacterial agents can form a network structure, enhance the hardness and wear resistance of the coating, thereby improving the aging resistance; 2. Suberic acid-modified tetrapodal zinc oxide and ethylenebisdithiocarbamate zinc can reduce the surface tension of the coating, improve the wettability and fluidity of the coating, thereby improving the surface smoothness and aging resistance of the coating; 3. Suberic acid-modified tetrapodal zinc oxide and ethylenebisdithiocarbamate zinc can capture free radicals and inhibit oxidation reactions, thereby slowing down the aging process of the coating and improving aging resistance; 4. Suberic acid-modified tetrapodal zinc oxide and ethylenebisdithiocarbamate zinc can enhance the chemical corrosion resistance of odorless antibacterial polymer-based composites, thereby improving their durability and aging resistance.

[0098] In summary, the addition of an inorganic zinc antimicrobial agent, tetrapod-modified zinc oxide (SS) modified with suberic acid, combined with an organic zinc antimicrobial agent, zinc ethylenebisdithiocarbamate, to an odorless antimicrobial polymer-based composite material can enhance its antimicrobial properties, surface hardness, wear resistance, and durability, thereby improving its aging resistance. This is likely due to the ability of these antimicrobial agents to form a network structure, reduce the surface tension of the coating, capture free radicals, and enhance the hardness and wear resistance of the coating.

[0099] Test Example 4: Antifungal test of odorless antibacterial polymer-based composite materials The antibacterial rate reaches 50%, which meets the national standard. The test bacteria used are Escherichia coli ( Escherichia coli )ASI.90 and Staphylococcus aureus ( Staphylococcus aureus )ASI.89.

[0100] The antibacterial activity was determined according to the standard GB / T 21866-2008 Determination of antibacterial activity and antibacterial effect of antibacterial coatings (paint films).

[0101] This method involves quantitatively inoculating bacteria onto a sample plate to be tested. Using a film-based method, the bacteria are evenly contacted with the sample plate. After a certain period of incubation, the number of viable bacteria on the sample plate is detected, and the antibacterial rate of the sample plate is calculated. Antibacterial testing must be conducted in a laboratory that meets the laboratory biosafety management and facility conditions requirements specified in GB 19489.

[0102] Main equipment: constant temperature incubator (37±1)℃, refrigerator (0~5)℃, clean bench, pressure steam sterilizer, electric drying oven, balance (accuracy 0.01 g), sterilized petri dishes, sterilized test tubes, sterilized pipettes, inoculating loops, alcohol lamp.

[0103] Preparation of coating panels: Sampling should be performed in accordance with the requirements of GB / T 3186. The substrate used for the test panels should generally be the same as the actual substrate in use (e.g., cement, wood, metal, or plastic). The coating film should be produced in accordance with the requirements of GB / T 1727. The coating is generally applied in two coats, with the second coat applied after the first coat has dried to the touch. The total wet film thickness should be less than 100 μm. The panels should be flat and free of rust. Cut the coated panels into 10 50 mm x 50 mm panels and disinfect them before testing.

[0104] Antibacterial rate calculation formula: R =( B - C ) / B ×100 Where, R - Antibacterial rate, expressed in (%), with the value rounded to four significant figures, in accordance with the provisions of GB / T 1250; B ——Average number of bacteria recovered from blank control plates after 24 hours (cfu / plate); C ——Average number of recovered bacteria on the antibacterial coating sample after 24 hours (cfu / plate).

[0105] A qualitative method is used in which the test drug diffuses in the agar plate, inhibiting the growth of bacteria around it to form a transparent circle. Observing the size of the transparent circle formed by the surrounding bacterial growth can indicate the antibacterial effect of the antifungal and antimicrobial agent.

[0106] This test method involves applying an antimicrobial agent in a specific manner to the surface of a culture medium containing agar for the bacterial culture used in the test. Once applied, the antimicrobial agent diffuses in a three-dimensional pattern within the culture medium. If the antimicrobial agent inhibits the growth and reproduction of the test bacteria, a transparent ring forms near it. The size of this ring can be used to evaluate the agent's ability to inhibit bacterial growth. The standard for "Antibacterial Plastic (Composite) Flexible Packaging" (T / SHBX 012-2021) stipulates that a transparent ring greater than 99% indicates a strong ability to resist bacterial growth, while a transparent ring greater than 90% indicates a moderate resistance to bacterial growth.

[0107] Table 4 Antibacterial test of odorless antibacterial polymer-based composite materials Test items Antibacterial rate (Escherichia coli) / % Antibacterial rate (Staphylococcus aureus) / % Example 1 91.51 92.13 Example 2 90.32 91.35 Example 3 85.53 90.18 Example 4 90.51 91.34 Example 5 99.42 99.83 As shown in Table 4, Example 5 has the best antibacterial effect, followed by Example 1. This indicates that the inorganic zinc antibacterial agent, tetrapod-modified zinc oxide, combined with the organic zinc antibacterial agent, zinc ethylenebisdithiocarbamate, exhibits the best antibacterial performance. Possible reasons for this are: 1. The synergistic effect between tetrapod-modified zinc oxide and zinc ethylenebisdithiocarbamate produces a synergistic effect when combined, enhancing the antibacterial effect; 2. The mechanism of action of tetrapod-modified zinc oxide and zinc ethylenebisdithiocarbamate is more comprehensive. They can inhibit the growth of both bacteria and molds, exhibiting a broader antibacterial spectrum; 3. The tetrapod-modified zinc oxide and zinc ethylenebisdithiocarbamate exhibit greater stability. They are more compatible with waterborne epoxy resins, less prone to separation and precipitation, and thus maintain the long-lasting antibacterial properties; and 4. The antibacterial effects of tetrapod-modified zinc oxide and zinc ethylenebisdithiocarbamate are more rapid. They can quickly inhibit the growth of bacteria and prevent microorganisms from damaging odorless antimicrobial polymer-based composites.

[0108] In summary, the antibacterial properties of tetrapod-modified inorganic zinc antibacterial agent suberic acid-modified zinc oxide combined with organic zinc antibacterial agent zinc ethylenebisdithiocarbamate are better than those of nano zinc oxide, tetrapod-modified inorganic zinc antibacterial agent zinc ethylenebisdithiocarbamate, and zinc pyrithione, mainly due to their synergistic effect, comprehensive antibacterial spectrum, high stability and rapid antibacterial effect.

[0109] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, replacements, and improvements made within the principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an odorless antibacterial polymer-based composite material, characterized in that: The method comprises the following steps, in parts by weight: Step 1: First add 20-30 parts of water to a container, then add 5-10 parts of dispersant and 5-10 parts of defoamer, stir for 3-5 minutes, and stir at a speed of 200-300 rpm; then add 20-30 parts of filler and 5-10 parts of modified glass fiber, stir for 40-60 minutes, and stir at a speed of 900-1000 rpm; until the slurry fineness is less than 40 μm, then add 5-20 parts of water-based epoxy resin curing agent, 5-10 parts of leveling agent, 5-10 parts of antibacterial agent, and 5-8 parts of antioxidant, stir for 10-20 minutes, and stir at a speed of 200-300 rpm to obtain component A; Step 2: Mix 20-30 parts of modified waterborne epoxy resin and 5-10 parts of film-forming aid, stirring for 30-40 minutes at a stirring speed of 800-900 rpm to obtain component B; Step 3: Component A and component B are mixed and stirred, with the mixing mass ratio of component A to component B being (100-180):100, the stirring time being 30-40 min, and the stirring speed being 800-900 rpm; thereby obtaining the odorless antibacterial polymer-based composite material.

2. The method for preparing the odorless antibacterial polymer-based composite material according to claim 1, characterized in that: The modified waterborne epoxy resin is made of an emulsifier and an epoxy resin, wherein the epoxy resin is at least one of bisphenol A epoxy resin, E51 epoxy resin, E44 epoxy resin, alicyclic epoxy resin, bisphenol F epoxy resin, and novolac epoxy resin; the emulsifier is at least one of pure acrylic emulsion, acetic acid acrylic emulsion, and styrene acrylic emulsion; the mass ratio of the epoxy resin to the emulsifier is 100:(10-20); and the waterborne epoxy resin curing agent is at least one of polyamide, isophorone diamine, cyclohexanediamine, methylcyclopentanediamine, polyoxypropylene triamine, and polyethylene oxide diamine.

3. The method for preparing the odorless antibacterial polymer-based composite material according to claim 1, characterized in that: The dispersant is at least one of DISPERS-188A, BYK-180, BYK-190, EFKA-4560, W-511, FA-182, EFKA-4550, and W-518; the defoamer is at least one of HS-334, LG-20GB, SXP-120, LG-10, CF-328, BYK-011, Foamex 1488, and BYK-020; the leveling agent is at least one of BYK-346, BLD-533, BLD-511, San Nopco 621N, TEGOTwin 4100, W-77, W-461, BYK-333, and TEGO Twin 4000; and the film-forming aid is at least one of ethanol, methoxybutanol, and benzyl alcohol.

4. The method for preparing the odorless antibacterial polymer-based composite material according to claim 1, characterized in that: The modified glass fiber preparation method is as follows, in parts by weight: S1: immerse 5-10 parts of glass fiber in 10-20 parts of 3-5% by mass hydrofluoric acid aqueous solution for 20-50 seconds, continue to clean and dry, and then set aside; S2: mixing the glass fiber treated in step S1 with 2-3 parts of alkoxysilane, 1-2 parts of end-capping agent, 20-30 parts of organic solvent, and 1-2 parts of catalyst at 40-80° C. for 2-3 hours to obtain modified glass fiber.

5. The method for preparing the odorless antibacterial polymer-based composite material according to claim 4, characterized in that: The glass fiber has a diameter of 20-60 μm and a length of 50-300 mm.

6. The method for preparing an odorless polymer-based composite material according to claim 4, wherein: The alkoxysilane is at least one of dimethoxymethylvinylsilane, vinyltriethoxysilane, propenyltriethoxysilane, and phenyltriethoxysilane; the end-capping agent is at least one of hexamethyldisiloxane, methyltriethoxysilane, and tetramethyldivinyldisiloxane; the organic solvent is at least one of tetrahydrofuran, methanol, toluene, n-hexane, and chloroform; the catalyst is at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and perchloric acid; and the mass fraction of the catalyst is 3-5%.

7. The method for preparing an odorless polymer-based composite material according to claim 1, wherein: The filler is at least one of rutile titanium dioxide, talc, mica, quartz powder, and nano-alumina; the antibacterial agent is at least one of suberic acid-modified tetrapod-shaped zinc oxide whiskers, nano-zinc oxide, zinc ethylenebisdithiocarbamate, and zinc pyrithione; and the antioxidant is at least one of antioxidant 1010, antioxidant 168, 2,6-di-tert-butyl-p-cresol, N,N'-di-sec-butyl-p-phenylenediamine, and trisnonylphenyl phosphite.

8. The method for preparing the odorless antibacterial polymer-based composite material according to claim 7, characterized in that: The antibacterial agent is prepared by mixing zinc ethylenebisdithiocarbamate and suberic acid-modified tetrapod-shaped zinc oxide in a mass ratio of (1-3):

1.

9. The method for preparing the odorless antibacterial polymer-based composite material according to claim 7 or 8, characterized in that: The suberic acid modified tetrapod-shaped zinc oxide whisker is prepared as follows, in parts by weight: X1: Add 5-10 parts of suberic acid to 30-50 parts of anhydrous ethanol and ultrasonicate at a frequency of 20-50 kHz for 30-50 minutes to completely dissolve and disperse the suberic acid in the anhydrous ethanol. X2 adds 5 to 10 parts of dry tetrapod-shaped zinc oxide whiskers to X1, ultrasonically oscillates at a frequency of 20 to 50 kHz for 30 to 50 min, continues stirring at 40 to 50°C for 30 to 60 min, and at a stirring speed of 500 to 800 r / min. After filtration, suberic acid-modified tetrapod-shaped zinc oxide whiskers are obtained.

10. An odorless antibacterial polymer-based composite material, characterized by: Prepared by the method according to any one of claims 1 to 9.

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