An antibacterial polypropylene meltblown fabric based on inorganic-organic hybridization and its preparation method and application

Abstract

The present invention provides an antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization, and a preparation method and application thereof, which belongs to the technical field of antibacterial meltblown cloth. The preparation method of the polypropylene composite masterbatch provided by the present invention is to prepare the composite masterbatch by melt blending and granulating the compound antibacterial agent with the polypropylene resin; the compound antibacterial agent is nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride. The antibacterial polypropylene meltblown cloth provided by the present invention is prepared from the polypropylene composite masterbatch by melt-blowing spinning technology. The present invention utilizes nano silver-loaded zirconium phosphate and PHMG as compound antibacterial agents, and proposes a twin-screw thread combination technology, so that the nano silver-loaded zirconium phosphate and PHMG have an inorganic-organic hybridization effect in the PP melt, thereby improving the dispersibility and compatibility of the two with the matrix, improving the molding uniformity and mechanical properties of the fiber, and forming a long-lasting synergistic antibacterial effect.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial meltblown fabrics, and in particular to an antibacterial polypropylene meltblown fabric based on inorganic-organic hybridization, and a preparation method and application thereof. Background Art

[0002] Polypropylene (PP) meltblown cloth is the core material of protective masks, protective clothing, air purifiers, air filters and other products. It is characterized by a relatively complex pore structure, with a fiber diameter of 1-5 microns and a large specific surface area, which makes the meltblown cloth have good filtering, shielding, insulation and oil absorption properties. In addition to air filtration, it can also be widely used in liquid filtration materials, isolation materials, absorption materials, thermal insulation materials, oil absorption materials and wiping cloths. However, the PP meltblown cloth on the market currently only uses physical principles to intercept and adsorb particulate matter. In the high-incidence season of influenza, rhinitis, and respiratory infections, almost all of the above application fields have put forward higher requirements for the meltblown cloth's ability to efficiently and sustainably kill bacteria and viruses. Therefore, the development of highly efficient and antibacterial PP meltblown cloth filter materials has important theoretical and practical value.

[0003] There are two main types of existing antibacterial technologies. One is to attach the antibacterial agent to the surface of the material or graft the antibacterial group onto the material through post-treatment methods. The process is long, the cost is high, the antibacterial agent destroys the original filter aperture structure, the antibacterial agent is easy to fall off, and the antibacterial effect is insufficient. The second is to melt-blend the antibacterial agent with polypropylene. However, the molecular weight of melt-blown grade PP raw materials is low and the viscosity is low. The dispersibility and compatibility of ordinary antibacterial agents after blending are insufficient. When the content of antibacterial agent is increased, the spinnability of melt-blown fibers is reduced, and the molding is difficult. The content of antibacterial agent cannot be increased, basically between 0.3% and 1.0%, and the antibacterial effect is not fully exerted, especially it is impossible to form a high-efficiency and long-lasting antibacterial property with an antibacterial rate higher than 99.9%.

[0004] In summary, the current conventional methods are prone to problems such as insufficient antibacterial effect, low content, poor molding, many defects, and decreased mechanical properties due to insufficient dispersibility and compatibility of antibacterial agents. Summary of the invention

[0005] In order to solve the problems of poor dispersibility and compatibility of antibacterial agents, unsustainable antibacterial effects, poor fiber molding, many defects, and decreased mechanical properties in the prior art, the present invention provides an antibacterial polypropylene melt-blown cloth based on inorganic-organic hybridization, and a preparation method and application thereof. The present invention uses nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride (PHMG) as compound antibacterial agents, proposes a twin-screw thread combination technology, and causes nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride (PHMG) to undergo inorganic-organic hybridization effects in the PP melt, thereby improving the dispersibility of the two and their compatibility with the matrix, improving the molding uniformity and mechanical properties of the fibers, and forming a long-lasting synergistic antibacterial effect.

[0006] In order to achieve the above object, the present invention provides the following technical solutions: a method for preparing a polypropylene composite masterbatch, wherein the composite antibacterial agent and the polypropylene resin are melt-blended and granulated to prepare the composite masterbatch;

[0007] The compound antibacterial agent is nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride.

[0008] Preferably, the mass ratio of the polyhexamethyleneguanidine hydrochloride to the polypropylene resin is 1-2:100.

[0009] Preferably, the mass ratio of the nano-silver-loaded zirconium phosphate to the polyhexamethyleneguanidine hydrochloride is 3:1.

[0010] Preferably, the preparation of the composite masterbatch by melt-blending and granulating the compound antibacterial agent and the polypropylene resin is specifically carried out by using a twin-screw extruder for melt-blending and granulation.

[0011] Preferably, the temperature configuration of the twin-screw extruder is: 135℃±5℃ in zone one, 145℃±5℃ in zone two, 155℃±5℃ in zone three, 155℃±5℃ in zone four, 160℃±5℃ in zone five; 170℃±5℃ in zone six, 170℃±5℃ in zone seven, 170℃±5℃ in zone eight, 175℃±5℃ in zone nine, and 190℃±5℃ in the head zone.

[0012] The present invention also provides a polypropylene composite masterbatch prepared by the preparation method described in the above technical solution.

[0013] The present invention also provides an antibacterial polypropylene melt-blown cloth based on inorganic-organic hybridization, which is prepared from the polypropylene composite masterbatch by melt-blowing spinning technology.

[0014] The present invention also provides a method for preparing the antibacterial polypropylene melt-blown cloth based on inorganic-organic hybridization, wherein the polypropylene composite masterbatch described in the above technical scheme is placed in a feeding bin of a melt-blown machine to prepare the antibacterial melt-blown cloth; the melt-blown machine adopts a single-screw melt extrusion, and the temperature configuration of each zone of the screw extruder is: 130°C±5°C for zone one, 150°C±5°C for zone two, and 160°C±5°C for zone three.

[0015] The present invention also provides the use of the inorganic-organic hybrid antibacterial polypropylene melt-blown cloth in the preparation of protective masks, protective clothing, air purifiers, and air filter elements.

[0016] Beneficial technical effects:

[0017] The invention discloses an antibacterial polypropylene melt-blown cloth based on inorganic-organic hybridization. PHMG and nano silver-loaded zirconium phosphate are successively added into melt-blown grade PP, and a twin-screw multi-zone high-shear granulation and melt-blown spinning technology are used to make the nano silver-loaded zirconium phosphate and PHMG produce a certain inorganic-organic hybridization reaction, thereby improving the dispersibility and compatibility, improving the molding conditions of PP, improving the mechanical properties of the fiber, increasing the content of the antibacterial agent to about 5%, fully exerting and maintaining the antibacterial property, and obtaining a long-acting antibacterial PP melt-blown cloth.

[0018] Compared with the prior art, the method for preparing the antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization of the present invention utilizes the temperature of melt extrusion and the high shear environment to produce an inorganic-organic hybridization reaction, thereby eliminating the modification process of the traditional nanoparticle pretreatment, shortening the process flow, and greatly improving the mechanical properties, antibacterial properties and service life of the PP meltblown cloth, thereby having strong market competitiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0020] Figure 1 This is a SEM-EDS image of the cross section of the polypropylene composite masterbatch prepared in Example 1;

[0021] Figure 2 This is a SEM image of the antibacterial polypropylene meltblown fabric prepared in Example 4;

[0022] Figure 3 The photos are the results of the colony counts of the blank control sample and the antibacterial polypropylene melt-blown cloth culture medium prepared in Example 4;

[0023] Figure 4This is the tensile fracture curve of the antibacterial polypropylene meltblown fabric prepared in Example 4. DETAILED DESCRIPTION

[0024] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0025] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0026] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0027] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0028] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0029] The present invention provides a method for preparing a polypropylene composite masterbatch, wherein a composite antibacterial agent and a polypropylene resin are melt-blended and granulated to prepare the composite masterbatch;

[0030] The compound antibacterial agent is nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride (PHMG).

[0031] In some embodiments, the mass ratio of the polyhexamethyleneguanidine hydrochloride to the polypropylene resin is 1-2:100.

[0032] In some embodiments, the mass ratio of the nano silver-loaded zirconium phosphate to the polyhexamethylene guanidine hydrochloride is 3: 1. When the ratio of the nano silver-loaded zirconium phosphate to the polyhexamethylene guanidine hydrochloride exceeds 3: 1, the agglomeration of the nano silver-loaded zirconium phosphate in the matrix is ​​serious, and the role of the organic antibacterial agent polyhexamethylene guanidine hydrochloride in assisting the compatibility of the nano silver-loaded zirconium phosphate with the PP matrix is ​​weakened; when the ratio of the nano silver-loaded zirconium phosphate to the polyhexamethylene guanidine hydrochloride is lower than 3: 1, the hybridization reaction sites provided by the nano silver-loaded zirconium phosphate are insufficient, resulting in reduced reaction efficiency, that is, when the ratio of the two materials is higher or lower than the above ratio, the hybridization effect of the two materials in the melt will be weakened, the synergistic antibacterial effect cannot be optimally exerted, and the antibacterial performance of the meltblown cloth is reduced.

[0033] In some embodiments, the nano silver-loaded zirconium phosphate and the polyhexamethylene guanidine hydrochloride further include a drying step before being melt-blended and granulated with the polypropylene resin; the drying step of the nano silver-loaded zirconium phosphate is: drying in a vacuum oven, heating at 60 to 80°C, vacuum degree -0.1 to 0.15MPa, drying time 7 to 8h, and the moisture content of the nano silver-loaded zirconium phosphate powder after drying is ≤0.01%; the drying step of the polyhexamethylene guanidine hydrochloride is: drying in a vacuum oven, heating at 50 to 60°C, vacuum degree -0.1 to 0.15MPa, drying time 8 to 9h, and the moisture content of the PHMG powder after drying is ≤0.01%.

[0034] In some embodiments, the nano silver-loaded zirconium phosphate is a white powder with an average particle size of 80 nm; the antibacterial agent polyhexamethylene guanidine hydrochloride (PHMG) is an amorphous powder; the polypropylene (PP) resin is a melt-blown grade polypropylene resin with a molecular weight of 50,000-80,000, a melt mass flow rate of 1500±100 g / 10 min, and the slices are granular with an average diameter of 3 mm.

[0035] In some embodiments, the preparation of the composite masterbatch by melt-blending and granulating the compounded antibacterial agent and the polypropylene resin is specifically performed by using a twin-screw extruder for melt-blending and granulation.

[0036] In some embodiments, the present invention firstly uses a high-speed mixer to fully mix the dried PHMG and PP chips, and the mass fraction ratio of PHMG to PP is 1-2:100.

[0037] In some embodiments, after the dried PHMG and PP chips are fully mixed, the present invention uses a twin-screw extruder for melt blending and granulation; the twin-screw main feed port adds the fully mixed PHMG and PP chips raw materials, and the auxiliary feed port is set in the third zone to add the dried nano silver-loaded zirconium phosphate; the mass fraction ratio of the main feed and the auxiliary feed is 100:3-6; the twin-screw extruder adopts a building block screw element combination mode, the screw element is configured with ten zones, the first and second zones are feeding and conveying zones, the third zone is initially melted, the fourth and fifth zones are fully melted, the rear end of the sixth zone is provided with a reverse screw element to establish high pressure on the melt, the front end is provided with a triangular kneading element to increase the shear stress, the seventh zone is provided with a toothed kneading element to increase the mixing and interaction frequency of nanoparticles and organic molecules in the melt, the eighth zone is provided with a conveying screw element, the ninth zone uses a small lead screw element to homogenize the melt, and the tenth zone is the head zone. Pressure sensors are respectively configured in the sixth zone and the head zone to detect the melt pressure.

[0038] In some embodiments, to avoid excessively high temperatures leading to low viscosity and decomposition reactions, the temperature configuration of the twin-screw extruder is: 135°C ± 5°C in zone 1, 145°C ± 5°C in zone 2, 155°C ± 5°C in zone 3, 155°C ± 5°C in zone 4, 160°C ± 5°C in zone 5; 170°C ± 5°C in zone 6, 170°C ± 5°C in zone 7, 170°C ± 5°C in zone 8, 175°C ± 5°C in zone 9, and 190°C ± 5°C in die zone. The melt pressures in the six zones are all controlled at 9-10 MPa, and the melt pressures in the die zone are all controlled at 8-9 MPa.

[0039] In some embodiments, after the melt is extruded through the die, the melt further includes entering a water cooling tank, cooling the strands, using a hot air blower to dry the moisture, and then cutting the strands through a pelletizer to form composite masterbatches; the cooling water temperature in the water cooling tank is maintained at 20°C ± 5°C.

[0040] The present invention also provides a polypropylene composite masterbatch prepared by the preparation method described in the above technical solution. The proportion of the compound antibacterial agent in the polypropylene composite masterbatch is 4%-6%. The present invention uses nano silver zirconium phosphate and polyhexamethylene monoguanidine hydrochloride (PHMG) as compound antibacterial agents to develop an antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization, which solves the problems of poor dispersibility of antibacterial agents and poor compatibility with the matrix, and exerts the synergistic antibacterial effect of organic antibacterial agents and inorganic antibacterial agents, so that the antibacterial rate of the meltblown cloth reaches 99.99%, and the mechanical properties are improved by about 20% compared with pure meltblown cloth, which has very important practical and theoretical significance.

[0041] The present invention also provides an antibacterial polypropylene melt-blown cloth based on inorganic-organic hybridization, which is prepared from the polypropylene composite masterbatch by melt-blowing spinning technology.

[0042] The present invention also provides a method for preparing the antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization, and the polypropylene composite masterbatch described in the above technical scheme is placed in a meltblown machine feeding bin to prepare the antibacterial meltblown cloth.

[0043] In some embodiments, before the polypropylene composite masterbatch is placed in the feed bin of the meltblown machine for preparing the antibacterial meltblown cloth, the step of drying the polypropylene composite masterbatch is also included; the drying is specifically: using a vacuum drum dryer to dry the prepared composite masterbatch, and the drying process parameters are: heating temperature 60-70°C, vacuum degree 0.08±0.01MPa, drying time 9-10h, and the moisture content of the composite masterbatch after drying is ≤0.05%.

[0044] In some embodiments, the meltblown machine adopts single-screw melt extrusion, and the temperature configuration of each zone of the screw extruder is: 130℃±5℃ in zone 1, 150℃±5℃ in zone 2, and 160℃±5℃ in zone 3. In addition, in order to stabilize, homogenize and remove impurities from the melt, a melt filter and a long neck tube need to be configured after the screw zone. The melt enters the spinneret after being accurately measured by a metering pump, and the ejected fibers are stretched and pulled by high-pressure hot air, and the antibacterial meltblown cloth is collected by a roller curtain. The diameter of the die spinneret hole is 0.35mm, the hot air temperature is 110℃±5℃, and the receiving distance is 40cm±5cm.

[0045] The present invention also provides the use of the inorganic-organic hybrid antibacterial polypropylene melt-blown cloth in the preparation of protective masks, protective clothing, air purifiers, and air filter elements.

[0046] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0047] Unless otherwise specified, the raw materials used in the examples can be obtained from commercial channels.

[0048] In the embodiment, the nano silver-loaded zirconium phosphate used is a white powder with an average particle size of 80 nm; the antibacterial agent polyhexamethylene guanidine hydrochloride (PHMG) is an amorphous powder; the polypropylene (PP) resin is a melt-blown grade polypropylene resin with a molecular weight of 50,000-80,000, a melt mass flow rate of 1500±100 g / 10 min, and the slices are granular with an average diameter of 3 mm.

[0049] The present invention adopts the following test method, and the corresponding results obtained are shown in the accompanying drawings:

[0050] The morphology of the composite masterbatch cross section was observed using a TESCAN MIRALMS scanning electron microscope. The accelerating voltage was set to 3 kV. The EDS spectrometer (model Xplore) equipped with the equipment was used to perform point scanning on the nanoparticles exposed on the masterbatch cross section. The SEM image and EDS element scanning spectrum results are shown in the attached Figure 1 .

[0051] The morphology of the meltblown fabric fibers was observed using a JSM-6510LA scanning electron microscope at an electron acceleration voltage of 10 kV. The surface of the meltblown fabric was treated with gold spraying. The SEM image of the fibers is shown in the attached figure. Figure 2 .

[0052] The antibacterial performance of meltblown fabric was tested in accordance with the national standard GB / T20944.3-2008. The sterilized samples were placed in a 5 The concentration of Escherichia coli and Staphylococcus aureus was shaken for 18 hours, the shaken test solution was aspirated, diluted by 10 times dilution method and then coated on the plate, placed in a constant temperature and humidity incubator for 24 hours, and the colonies were counted after being taken out. The calculation formula of antibacterial rate is as follows:

[0053]

[0054] Where, Y is the antibacterial rate of the sample, W t is the average value of the viable bacterial concentration in the flask (CFU / mL) of the four control samples after 18 hours of shaking contact, Q t It is the average value (CFU / mL) of the viable bacteria concentration in the flask after 18 hours of shaking contact of 4 antibacterial fabric samples.

[0055] The results of the blank control sample and the antibacterial meltblown cloth culture medium colony count are shown in the attached Figure 3 .

[0056] The mechanical properties of the prepared meltblown fabric were tested according to the standard ISO 9073-18-2007. The meltblown fabric was made into a standard specimen with an effective size of 50mm×20mm, and its mechanical properties were tested at room temperature using a universal material testing machine with a tensile speed of 100mm / min. The results were taken as the average of 5 tests, see the attached Figure 4 .

[0057] Example 1

[0058] Preparation of polypropylene composite masterbatch:

[0059] (1) The nano-silver-loaded zirconium phosphate and PHMG were dried in a vacuum oven. The drying process parameters of the nano-silver-loaded zirconium phosphate were as follows: heating temperature 60°C, vacuum degree -0.1MPa, drying time 7h, and the moisture content of the nano-silver-loaded zirconium phosphate powder after drying was ≤0.01%. The drying process parameters of the PHMG powder were as follows: heating temperature 50°C, vacuum degree -0.1MPa, drying time 8h, and the moisture content of the PHMG powder after drying was ≤0.01%.

[0060] (2) The dried PHMG and PP chips were fully mixed using a high-speed mixer with a mass fraction ratio of 1:100.

[0061] (3) Melt blending and granulation are performed using a twin-screw extruder. The fully mixed PHMG and PP chip raw materials are added to the main feed port of the twin-screw, and the auxiliary feed port is set in the third zone to add the dried nano silver-loaded zirconium phosphate. The mass fraction ratio of the main feed and the auxiliary feed is 100:3. The twin-screw extruder adopts a building block screw element combination method. The screw element is configured with ten zones. Zones 1 and 2 are feeding and conveying zones, zone 3 is for initial melting, and zone 4 and zone 5 are for full melting. A reverse screw element is set at the rear end of zone 6 to establish high pressure on the melt. A triangular kneading element is set at the front end to increase the shear stress. A toothed kneading element is set in zone 7 to increase the mixing and interaction frequency of nanoparticles and organic molecules in the melt. A conveying screw element is set in zone 8. A small lead screw element is used in zone 9 to homogenize the melt. Zone 10 is the head zone. Pressure sensors are respectively configured in zone 6 and the head zone to detect the melt pressure.

[0062] (4) To avoid excessive temperature causing low viscosity and decomposition reaction, the temperature configuration of each zone of the twin-screw extruder is: zone 1 135℃±5℃, zone 2 145℃±5℃, zone 3 155℃±5℃, zone 4 155℃±5℃, zone 5 160℃±5℃; zone 6 170℃±5℃, zone 7 170℃±5℃, zone 8 170℃±5℃, zone 9 175℃±5℃, and die head zone 190℃±5℃;

[0063] (5) The melt pressure in the six zones is controlled at 9-10 MPa, and the melt pressure in the die head zone is controlled at 8-9 MPa.

[0064] (6) The melt is extruded through the die head and then enters the water cooling tank to cool the strands. The hot air blower dries the water and the strands are cut into composite masterbatches by a pelletizer. The cooling water temperature in the water cooling tank is maintained at 20°C ± 5°C.

[0065] Example 2

[0066] Preparation of polypropylene composite masterbatch:

[0067] (1) Same as step (1) of Example 1.

[0068] (2) The same as step (2) of Example 1, except that the mass ratio of PHMG to PP chips is 1.5:100.

[0069] (3) The same as step (3) of Example 1, except that the mass fraction ratio of the main feed and the auxiliary feed is 100:5.

[0070] (4) Same as step (4) in Example 1.

[0071] (5) Same as step (5) in Example 1.

[0072] (6) Same as step (6) of Example 1.

[0073] Example 3

[0074] Preparation of polypropylene composite masterbatch:

[0075] (1) Same as step (1) of Example 1.

[0076] (2) The same as step (2) of Example 1, except that the mass ratio of PHMG to PP slices is 2:100.

[0077] (3) The same as step (3) of Example 1, except that the mass fraction ratio of the main feed to the auxiliary feed is 100:6.

[0078] (4) Same as step (4) in Example 1.

[0079] (5) Same as step (5) in Example 1.

[0080] (6) Same as step (6) of Example 1.

[0081] Example 4

[0082] Preparation of antibacterial polypropylene meltblown fabric based on inorganic-organic hybrid:

[0083] Step 1. Use a vacuum drum dryer to dry the composite masterbatch prepared in Example 1. The drying process parameters are: heating temperature 60° C., vacuum degree 0.08±0.01 MPa, drying time 9 h, and the moisture content of the composite masterbatch after drying is ≤0.05%.

[0084] Step 2. Place the dried composite masterbatch in the feed bin of the meltblown machine to prepare the antibacterial meltblown cloth. The meltblown machine adopts single-screw melt extrusion, and the temperature configuration of each zone of the screw extruder is: 130℃±5℃ in zone 1, 150℃±5℃ in zone 2, and 160℃±5℃ in zone 3. In addition, in order to stabilize, homogenize and remove impurities from the melt, a melt filter and a long neck tube need to be configured after the screw zone. The melt enters the spinneret after being accurately metered by the metering pump, and the ejected fibers are stretched and pulled by high-pressure hot air, and the antibacterial meltblown cloth is obtained by collecting the roller curtain. The diameter of the die spinneret hole is 0.35mm, the hot air temperature is 110℃±5℃, and the receiving distance is 40cm±5cm.

[0085] Example 5

[0086] The preparation method of the antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization in this embodiment is the same as that in Example 4, except that the composite masterbatch prepared in Example 1 is replaced by the composite masterbatch prepared in Example 2.

[0087] Example 6

[0088] The preparation method of the antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization in this embodiment is the same as that in Example 4, except that the composite masterbatch prepared in Example 1 is replaced by the composite masterbatch prepared in Example 3.

[0089] The cross-sectional SEM-EDS image of the composite masterbatch prepared in Example 1 is as follows: Figure 1 As shown, nano silver zirconium phosphate and PHMG are evenly dispersed in the PP matrix without interface separation, indicating good compatibility with the PP matrix. And through the EDS spectrum, it can be seen that the Zr element, P element, Ag element of nano silver zirconium phosphate and N element and Cl element spectrum of PHMG appear at the same point, indicating that nano silver zirconium phosphate and PHMG form a hybrid whole, showing synergistic antibacterial effect in the PP matrix.

[0090] The SEM image of the antibacterial polypropylene meltblown fabric prepared in Example 4 is as follows: Figure 2 As shown, the diameter of the fibers is 2-3 μm and is evenly distributed.

[0091] Figure 3 The following are photos of the colony count results of the blank control sample (without nano-silver-loaded zirconium phosphate and PHMG) and the antibacterial polypropylene melt-blown cloth culture medium prepared in Example 4. From the colony count in the figure, it can be seen that the antibacterial property of the antibacterial melt-blown cloth can reach 99.9%, indicating that the technical effect is obvious.

[0092] Figure 4 This is the tensile fracture curve of the antibacterial polypropylene meltblown cloth prepared in Example 4. It can be seen from the figure that the meltblown cloth has excellent mechanical properties.

[0093] The present invention also verifies the antibacterial properties and mechanical properties of the antibacterial polypropylene meltblown cloth prepared in Examples 5 and 6. The results are similar to those in Example 4. The antibacterial polypropylene meltblown cloth prepared in Examples 5 and 6 of the present invention has an antibacterial property of up to 99.9%, and the strength can reach 4-5 MPa during the deformation process of 0-40 mm.

[0094] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An antibacterial polypropylene meltblown cloth based on inorganic-organic hybridization, which is prepared from polypropylene composite masterbatch by meltblowing spinning technology; the proportion of the compound antibacterial agent in the polypropylene composite masterbatch is 4%-6%; The preparation method of the polypropylene composite masterbatch is as follows: melt-blending and granulating the compound antibacterial agent and the polypropylene resin to prepare the composite masterbatch; The compound antibacterial agent is nano silver-loaded zirconium phosphate and polyhexamethylene guanidine hydrochloride; The mass ratio of the polyhexamethyleneguanidine hydrochloride to the polypropylene resin is 1-2:100; The mass ratio of the nano silver-loaded zirconium phosphate to the polyhexamethylene guanidine hydrochloride is 3:1; The preparation of the composite masterbatch by melt blending and granulating the compound antibacterial agent and the polypropylene resin is specifically carried out by using a twin-screw extruder to melt blend and granulate. The temperature configuration of the twin-screw extruder is: zone one 135℃±5℃, zone two 145℃±5℃, zone three 155℃±5℃, zone four 155℃±5℃, zone five 160℃±5℃; zone six 170℃±5℃, zone seven 170℃±5℃, zone eight 170℃±5℃, zone nine 175℃±5℃, and head zone 190℃±5℃.

2. A method for preparing an inorganic-organic hybrid antibacterial polypropylene meltblown fabric according to claim 1, characterized in that: The polypropylene composite masterbatch is placed in a melt-blown machine feeding bin to prepare the antibacterial melt-blown cloth; the melt-blown machine adopts single-screw melt extrusion, and the temperature configuration of each zone of the screw extruder is: 130℃±5℃ for zone one, 150℃±5℃ for zone two, and 160℃±5℃ for zone three.

3. An application of the inorganic-organic hybrid antibacterial polypropylene meltblown cloth according to claim 1 in the preparation of protective masks, protective clothing, air purifiers, and air filter elements.

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