CN113667239A - Basalt fiber reinforced PVC-iron tailing antibacterial composite material and preparation method thereof - Google Patents

Basalt fiber reinforced PVC-iron tailing antibacterial composite material and preparation method thereof Download PDF

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CN113667239A
CN113667239A CN202110954448.7A CN202110954448A CN113667239A CN 113667239 A CN113667239 A CN 113667239A CN 202110954448 A CN202110954448 A CN 202110954448A CN 113667239 A CN113667239 A CN 113667239A
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parts
composite material
antibacterial
pvc
iron
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张以河
张娜
张有鹏
邸祥云
李益
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K7/00—Use of ingredients characterised by shape
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Abstract

The invention provides a basalt fiber reinforced PVC-iron tailing antibacterial composite material and a preparation method thereof, belonging to the technical field of composite materials and comprising the following steps: 100 parts of PVC resin, 25-100 parts of iron tailings, 0.2-1.0 part of coupling agent, 4-16 parts of processing aid, 2-12 parts of heat stabilizer, 0.5-4 parts of plasticizer, 0.4-2 parts of lubricant, 6-18 parts of chlorinated polyethylene, 5-30 parts of basalt fiber and 5-15 parts of antibacterial master batch. The invention utilizes the component characteristics of the iron tailings, realizes the application of the solid waste recycling high additive, controls the dosage of each component, realizes the synergistic effect of each component, and further improves the mechanical property of the composite material. The results of the examples show that the composite material provided by the invention has a tensile strength of 64MPa, a bending strength of 67MPa and a notched impact strength of 7kJ/m2And the sterilization rate is 97%.

Description

Basalt fiber reinforced PVC-iron tailing antibacterial composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a basalt fiber reinforced PVC-iron tailing antibacterial composite material and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is a polymer resin material with wide application, and with the increasing shortage of resources, the PVC manufacturing industry also carries out product improvement, the PVC composite material filled with inorganic mineral powder is converted from a single PVC material, and the inorganic mineral powder is used as a filler, so that the consumption of the polymer material can be effectively reduced, and the consumption of petroleum energy is saved; meanwhile, the waste inorganic mineral powder can be fully utilized, waste materials are changed into valuable materials, and the cost is reduced.
At present, most of inorganic mineral powder used for filling PVC composite material is marble powder, for example, marble powder is added in the invention patent with publication number CN112708227A to improve the mechanical property of PVC, however, the improvement of the mechanical property of PVC by the method is limited, and the bending strength of the composite material is only 55MPa at most.
Therefore, it is highly desirable to provide a PVC composite with higher mechanical properties.
Disclosure of Invention
The invention aims to provide a basalt fiber reinforced PVC-iron tailing antibacterial composite material and a preparation method thereof. The composite material provided by the invention has excellent mechanical properties, and simultaneously, because the iron tailings are added, the solid waste is recycled, and the production cost is reduced.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a basalt fiber reinforced PVC-iron tailing antibacterial composite material which comprises the following components in parts by weight: 100 parts of PVC resin, 25-100 parts of iron tailings, 0.2-1.0 part of coupling agent, 4-16 parts of processing aid, 2-12 parts of heat stabilizer, 0.5-4 parts of plasticizer, 0.4-2 parts of lubricant, 6-18 parts of chlorinated polyethylene, 5-30 parts of basalt fiber and 5-15 parts of antibacterial master batch.
Preferably, the particle size of the iron tailings is less than 12 μm.
Preferably, the processing aid comprises an impact modifier ACR.
Preferably, the heat stabilizer comprises a calcium zinc stabilizer, a lead-based composite stabilizer or an organotin stabilizer.
Preferably, the plasticizer comprises epoxidized soybean oil, dioctyl adipate, dioctyl phthalate, chlorinated paraffin, diisodecyl adipate or tricresyl phosphate.
Preferably, the lubricant comprises one or more of stearic acid, polyethylene wax and oxidized polyethylene.
Preferably, the length of the basalt fiber is less than or equal to 5 mm.
Preferably, the antibacterial master batch is prepared by melting and granulating polypropylene and an antibacterial agent.
Preferably, the mass ratio of the polypropylene to the antibacterial agent is (3-6): 1.
the invention also provides a preparation method of the composite material in the technical scheme, which comprises the following steps:
(1) respectively mixing the iron tailings and the basalt fibers with a coupling agent to obtain pretreated iron tailings and pretreated basalt fibers;
(2) and (2) mixing the pretreated iron tailings and the pretreated basalt fibers obtained in the step (1) with PVC resin, a processing aid, a heat stabilizer, a plasticizer, a lubricant, chlorinated polyethylene and an antibacterial master batch, and then extruding to obtain the basalt fiber reinforced PVC-iron tailings antibacterial composite material.
The invention provides a basalt fiber reinforcementThe strong PVC-iron tailing antibacterial composite material comprises the following components in parts by weight: 100 parts of PVC resin, 25-100 parts of iron tailings, 0.2-1.0 part of coupling agent, 4-16 parts of processing aid, 2-12 parts of heat stabilizer, 0.5-4 parts of plasticizer, 0.4-2 parts of lubricant, 6-18 parts of chlorinated polyethylene, 5-30 parts of basalt fiber and 5-15 parts of antibacterial master batch. The invention utilizes the component characteristics of the iron tailings, realizes the application of the solid waste recycling high additive, reduces the production cost, improves the mechanical property, the hardness and the like of the composite material, and simultaneously improves the antibacterial property of the composite material by the synergistic effect of copper ions and silver ions contained in the iron tailings and the antibacterial master batch; adding a coupling agent to improve the compatibility of each component with resin; the antibacterial master batch is added, so that the antibacterial performance is improved, and the production safety is improved; the chlorinated polyethylene is utilized to improve the connection strength of the PVC and the antibacterial master batch; basalt fibers are added to improve the mechanical property of the composite material; the dosage of each component is controlled, and the components act synergistically to further improve the mechanical property of the composite material. The results of the examples show that the composite material provided by the invention has the Shore hardness of 76.8D, the tensile strength of 64MPa, the bending strength of 67MPa and the notch impact strength of 7kJ/m2And the sterilization rate is 97%.
Detailed Description
The invention provides a basalt fiber reinforced PVC-iron tailing antibacterial composite material which comprises the following components in parts by weight: 100 parts of PVC resin, 25-100 parts of iron tailings, 0.2-1.0 part of coupling agent, 4-16 parts of processing aid, 2-12 parts of heat stabilizer, 0.5-4 parts of plasticizer, 0.4-2 parts of lubricant, 6-18 parts of chlorinated polyethylene, 5-30 parts of basalt fiber and 5-15 parts of antibacterial master batch.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises 100 parts by weight of PVC resin. In the present invention, the PVC resin serves as a base material of the composite material.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass, 100 parts of PVC resin, 25-100 parts of iron tailings, preferably 30-90 parts of iron tailings, more preferably 40-80 parts of iron tailings, and most preferably 50-70 parts of iron tailings. In the invention, the iron tailings contain various metal and nonmetal oxides, the contained titanium dioxide can effectively improve the weather resistance of the composite material, the magnesium oxide can improve the thermal stability of the composite material to a certain extent, the silicon dioxide can improve the acid and alkali resistance, the processing fluidity and the photo-thermal stability of the composite material, and the iron oxide can improve the hardness of the composite material; meanwhile, the iron tailings are large in storage amount and convenient to obtain, the utilization rate of solid waste can be improved, the resource utilization of the solid waste is realized, waste is changed into valuable, and the production cost is reduced; and the antibacterial masterbatch has a synergistic effect, so that the antibacterial performance of the composite material can be improved. The invention limits the use amount of the iron tailings in the range, can improve the comprehensive performance of the composite material by using the effective components in the iron tailings, can be uniformly dispersed in the composite material, and avoids the performance reduction of the composite material caused by agglomeration.
In the invention, the particle size of the iron tailings is preferably less than 12 μm. The particle size of the iron tailings is limited within the range, so that the iron tailings can be fully wrapped by the PVC long chain and can be more uniformly dispersed in the composite material, agglomeration is avoided, the particle size is smaller, the contact area with PVC is increased, and the mechanical property of the composite material is further improved. When the particle size of the iron tailings is not within the above range, the present invention preferably grinds the iron tailings. The invention has no special limitation on the grinding equipment and time, and can ensure that the particle size of the iron tailings is less than 12 mu m.
In the present invention, the iron tailings are preferably subjected to a drying treatment before use. In the invention, the drying temperature is preferably 50-120 ℃, and more preferably 80 ℃; the drying time is preferably 0.5-1.5 h, and more preferably 1 h. In the present invention, the drying can avoid the adverse effect of moisture on the properties of the composite material.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass of 100 parts of PVC resin, 0.2-1.0 part of coupling agent, preferably 0.3-0.7 part, more preferably 0.4-0.6 part, and most preferably 0.5 part. The invention limits the dosage of the coupling agent in the range, can improve the compatibility of inorganic-organic interfaces, and further improves the mechanical property and the thermal property of the composite material.
In the present invention, the coupling agent is preferably a titanate coupling agent. In the invention, the titanate coupling agent can be used for dry modification, the process is simpler, and the industrial production is facilitated.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass, 100 parts of PVC resin, 4-16 parts of a processing aid, preferably 5-15 parts, more preferably 7-12 parts, and most preferably 10 parts. The invention limits the dosage of the processing aid in the range, can ensure that the matrix has proper viscosity and fluidity, and improves the impact resistance of the composite material.
In the present invention, the processing aid preferably comprises an impact modifier ACR. The origin of the impact modifier ACR is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In an embodiment of the present invention, the impact modifier ACR is preferably HL-50 manufactured by Shandong Nikko chemical Co., Ltd.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass, 100 parts of PVC resin, 2-12 parts of a heat stabilizer, preferably 5-10 parts of the heat stabilizer, and more preferably 7-8 parts of the heat stabilizer. The invention limits the dosage of the heat stabilizer within the range, and can further improve the heat stability of the composite material.
In the present invention, the heat stabilizer preferably includes a calcium zinc stabilizer, a lead-based composite stabilizer or an organotin stabilizer, and more preferably a calcium zinc stabilizer. In the invention, the calcium zinc stabilizer does not contain toxic elements and is low in price.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises 0.5-4 parts of plasticizer, preferably 2-3 parts, by mass of 100 parts of PVC resin. The invention limits the dosage of the plasticizer within the range, can reduce the glass transition temperature and viscosity of the matrix, and can increase the plasticity of the composite material.
In the present invention, the plasticizer preferably includes epoxidized soybean oil, dioctyl adipate, dioctyl phthalate, chlorinated paraffin, diisodecyl adipate or tricresyl phosphate, and more preferably epoxidized soybean oil.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass of 100 parts of PVC resin, 0.4-2 parts of a lubricant, preferably 0.6-1.8 parts, more preferably 0.8-1.6 parts, and most preferably 1.0-1.3 parts. The invention limits the dosage of the lubricant within the range, can improve the mobility of the PVC chain segment and the lubricity between the composite material melt and equipment, and improves the performance and the processing performance of the composite material.
In the present invention, the lubricant preferably includes one or more of stearic acid, polyethylene wax, and oxidized polyethylene, and more preferably includes stearic acid, polyethylene wax, and oxidized polyethylene. In the invention, stearic acid is used as an internal lubricant, and small molecules can penetrate into PVC chains to improve the mobility of the chain segments; the polyethylene wax serving as an external lubricant can be separated out to the surface of the melt, so that the lubricity between the melt and equipment is improved, and the processing of the composite material is facilitated; the oxidized polyethylene has the functions of an internal lubricant and an external lubricant; the three are mutually matched, so that the performance and the processability of the composite material are further improved.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises 6-18 parts of chlorinated polyethylene, preferably 8-15 parts of chlorinated polyethylene, and more preferably 10-12 parts of chlorinated polyethylene, wherein the mass of the PVC resin is 100 parts. In the invention, the chlorinated polyethylene can play a role in crosslinking, so that the connection strength between the matrix and the antibacterial master batch is improved. The invention limits the dosage of the chlorinated polyethylene in the range, and can further improve the mechanical property of the composite material.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises, by mass, 100 parts of PVC resin, 5-30 parts of basalt fiber, preferably 10-25 parts of basalt fiber, and more preferably 15-20 parts of basalt fiber. In the invention, the basalt fiber can play a role in drawing and anchoring in the matrix, thereby improving the mechanical property of the composite material, and simultaneously, the basalt fiber is matched with other components to improve the use temperature range of the composite material. The invention limits the dosage of the basalt fiber within the range, can ensure that the basalt fiber is fully and uniformly dispersed in the composite material, avoids agglomeration, and further improves the mechanical property of the composite material.
In the present invention, the length of the basalt fiber is preferably 5mm or less. The invention limits the length of the basalt fiber within the range, can ensure that the basalt fiber has better fluidity in the matrix, avoids the product defects and the influence on the appearance caused by the surface of the matrix emerging in the processing process, can be better dispersed in the matrix, and is beneficial to processing. When the length of the basalt fiber is not within the above range, the present invention preferably cuts the basalt fiber.
The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises 5-15 parts of antibacterial master batch, preferably 7-12 parts of antibacterial master batch, and more preferably 9-11 parts of antibacterial master batch by mass of 100 parts of PVC resin. The invention limits the dosage of the antibacterial master batch within the range, so that the composite material has better antibacterial performance.
In the invention, the antibacterial master batch is preferably prepared by melting and granulating polypropylene and an antibacterial agent.
In the present invention, the antibacterial agent preferably includes an inorganic antibacterial agent, an organic antibacterial agent or a natural antibacterial agent. The specific type of the antibacterial agent is not particularly limited in the present invention, and any antibacterial agent known to those skilled in the art may be used.
In the invention, the mass ratio of the polypropylene to the antibacterial agent is preferably (3-6): 1, and more preferably (4-5): 1.
In the present invention, the temperature of the melt granulation is preferably 150 to 200 ℃, and more preferably 160 to 180 ℃.
The preparation method of the antibacterial master batch is not particularly limited, and the preparation method of the master batch known by the technical personnel in the field can be adopted.
The antibacterial agent is preferably added into the composite material in the form of antibacterial master batches, so that the influence of the toxicity of the antibacterial agent in the processing process can be avoided, the production safety is improved, and the processing and the production are convenient.
The invention utilizes the component characteristics of the iron tailings, realizes the application of the solid waste recycling high additive, reduces the production cost, improves the mechanical property, the hardness and the like of the composite material, and simultaneously improves the antibacterial property of the composite material by the synergistic effect of copper ions and silver ions contained in the iron tailings and the antibacterial master batch; adding a coupling agent to improve the compatibility of each component with resin; the antibacterial master batch is added, so that the antibacterial performance is improved, and the production safety is improved; the chlorinated polyethylene is utilized to improve the connection strength of the PVC and the antibacterial master batch; basalt fibers are added to improve the mechanical property of the composite material; the dosage of each component is controlled, and the components act synergistically to further improve the mechanical property of the composite material.
The invention also provides a preparation method of the composite material in the technical scheme, which comprises the following steps:
(1) respectively mixing the iron tailings and the basalt fibers with a coupling agent to obtain pretreated iron tailings and pretreated basalt fibers;
(2) and (2) mixing the pretreated iron tailings and the pretreated basalt fibers obtained in the step (1) with PVC resin, a processing aid, a heat stabilizer, a plasticizer, a lubricant, chlorinated polyethylene and an antibacterial master batch, and then extruding to obtain the basalt fiber reinforced PVC-iron tailings antibacterial composite material.
The invention mixes the iron tailings and the coupling agent to obtain the pretreated iron tailings.
In the invention, the mass ratio of the coupling agent to the iron tailings is preferably 0.8: 100.
In the present invention, the mixing of the iron tailings and the coupling agent is preferably performed in a high-speed mixer. In the invention, the rotating speed of the high-speed mixer is preferably 750-1500 r/min. The iron tailings are preferably added into a high-speed mixer, then the temperature is raised to 60 ℃, the coupling agent is added, and then the temperature is raised to 90 ℃ for mixing. In the invention, the mixing time is preferably 10-60 min. According to the invention, the iron tailings are treated by the coupling agent, so that the iron tailings can react with the coupling agent more fully, the iron tailings are dispersed in the composite material more uniformly, and the performance of the composite material is further improved.
The invention mixes basalt fiber with coupling agent to obtain pretreated basalt fiber.
In the present invention, the mass ratio of the coupling agent to basalt fibers is preferably 0.8: 100.
In the present invention, the mixing of the basalt fiber with the coupling agent is preferably performed in a high-speed mixer. In the invention, the rotating speed of the high-speed mixer is preferably 750-1500 r/min. The basalt fiber is preferably added into a high-speed mixer, then the temperature is raised to 60 ℃, the coupling agent is added, and then the temperature is raised to 90 ℃ for mixing. In the invention, the mixing time is preferably 10-60 min. According to the invention, the basalt fiber is treated by the coupling agent, so that the basalt fiber can be more fully reacted with the coupling agent, and is more uniformly dispersed in the composite material, and the performance of the composite material is further improved.
After the pretreated iron tailings and the pretreated basalt fibers are obtained, the pretreated iron tailings and the pretreated basalt fibers are mixed with PVC resin, a processing aid, a heat stabilizer, a plasticizer, a lubricant, chlorinated polyethylene and an antibacterial master batch and then extruded to obtain the basalt fiber reinforced PVC-iron tailings antibacterial composite material.
In the invention, the mixing of the pretreated iron tailings and the pretreated basalt fiber with the PVC resin, the processing aid, the heat stabilizer, the plasticizer, the lubricant, the chlorinated polyethylene and the antibacterial masterbatch is preferably performed first in a high-speed mixer and then in a low-speed mixer.
In the invention, the rotation speed of the high-speed mixer is preferably 750-1500 r/min, the mixing time of the high-speed mixer is preferably 10-30 min, and the mixing temperature of the high-speed mixer is preferably raised from room temperature to 90 ℃. The invention has no special limit on the temperature rising rate when the temperature rises from room temperature to 90 ℃, and the mixing time is ensured to be within the range.
In the invention, the rotation speed of the low-speed mixer is preferably 50-100 r/min, the mixing time of the low-speed mixer is preferably 10-30 min, and the mixing temperature of the low-speed mixer is preferably reduced from 90 ℃ to room temperature. The invention has no special limit on the cooling rate when the temperature is reduced from 90 ℃ to room temperature, and the mixing time is ensured to be within the range.
In the present invention, the extrusion is preferably carried out in a twin-screw extruder; the extrusion temperature is preferably 1160-170 ℃ for the material cylinder, 2160-170 ℃ for the material cylinder, 3160-170 ℃ for the material cylinder, 1170-180 ℃ for the head, 2170-180 ℃ for the head, 3190-200 ℃ for the head, 4190-200 ℃ for the head, and 160-180 ℃ for the confluence core.
By adopting the preparation method, the components can be mixed more uniformly, and the mechanical property of the composite material is further improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The components of this embodiment are: 100 parts of PVC resin, 50 parts of iron tailings, 0.44 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 6 parts of chlorinated polyethylene, 5 parts of basalt fiber and 5 parts of antibacterial master batch;
the iron tailings comprise the following components: na (Na)2O 0.501％、MgO 3.17％、Al2O3 4.24％、SiO2 54.5％、K2O 0.956％、CaO 5.38％、TiO2 0.106％、Fe3O429.9% and the balance impurities;
the preparation method comprises the following steps: (1) mixing and melting 4.17kg of polypropylene and 0.83kg of silver ion antibacterial agent at 160 ℃ by using a single-screw extruder, extruding by a die head, cooling by water for 1min, cutting and granulating by a granulator, and air-drying by a high-speed blower for 2min to obtain 5kg of antibacterial master batch;
(2) grinding the iron tailings to 1250 meshes (11.86 mu m) by using an air mill, and then drying the iron tailings in an oven at 80 ℃ for 1h to obtain the iron tailings;
(3) cutting basalt fibers to be below 5 mm;
(4) putting 50kg of iron tailing powder into a high-speed mixer, heating to 60 ℃, adding 0.4g of titanate coupling agent KTTO, heating to 90 ℃, and mixing for 30min to obtain pretreated iron tailing powder;
(5) putting 5kg of basalt fiber into a high-speed mixer, heating to 60 ℃, adding 0.04g of titanate coupling agent KTTO, heating to 90 ℃, and mixing for 30min to obtain pretreated basalt fiber;
(6) the method comprises the steps of mixing pretreated iron tailing powder, pretreated basalt fiber and 100kg of PVC resin, an impact modifier ACR 8kg, a calcium-zinc stabilizer 6kg, epoxidized soybean oil 1.5kg, stearic acid 0.2kg, polyethylene wax 0.3kg, oxidized polyethylene 0.4kg, chlorinated polyethylene 6kg and an antibacterial master batch 5kg in a high-speed mixer at 1500r/min from room temperature to 90 ℃ for 20min, then transferring the mixture into a low-speed mixer at 100r/min from 90 ℃ to room temperature for mixing for 20min, and extruding the mixture by using a double-screw extruder at the processing temperature of a charging barrel 1170 ℃, a charging barrel 2165 ℃, a charging barrel 3170 ℃, a head 1180 ℃, a head 2180 ℃, a head 3190 ℃, a head 4190 ℃ and a confluence core 175 ℃ to obtain the basalt fiber reinforced PVC-iron tailing antibacterial composite material.
Example 2
The components of this embodiment are: 100 parts of PVC resin, 50 parts of iron tailings, 0.52 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 6 parts of chlorinated polyethylene, 15 parts of basalt fiber and 5 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Example 3
The components of this embodiment are: 100 parts of PVC resin, 50 parts of iron tailings, 0.64 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 6 parts of chlorinated polyethylene, 30 parts of basalt fiber and 5 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Example 4
The components of this embodiment are: 100 parts of PVC resin, 25 parts of iron tailings, 0.32 part of titanate coupling agent KTTO, 4 parts of impact modifier ACR, 3 parts of calcium-zinc stabilizer, 0.75 part of epoxy soybean oil, 0.45 part of lubricant (0.1 part of stearic acid, 0.15 part of polyethylene wax and 0.2 part of oxidized polyethylene), 6 parts of chlorinated polyethylene, 15 parts of basalt fiber and 5 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Example 5
The components of this embodiment are: 100 parts of PVC resin, 100 parts of iron tailings, 0.92 part of titanate coupling agent KTTO, 16 parts of impact modifier ACR, 12 parts of calcium-zinc stabilizer, 3 parts of epoxidized soybean oil, 1.8 parts of lubricant (0.4 part of stearic acid, 0.6 part of polyethylene wax and 0.8 part of oxidized polyethylene), 6 parts of chlorinated polyethylene, 15 parts of basalt fiber and 5 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Example 6
The components of this embodiment are: 100 parts of PVC resin, 50 parts of iron tailings, 0.52 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 12 parts of chlorinated polyethylene, 15 parts of basalt fiber and 10 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Example 7
The components of this embodiment are: 100 parts of PVC resin, 50 parts of iron tailings, 0.52 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 18 parts of chlorinated polyethylene, 15 parts of basalt fiber and 15 parts of antibacterial master batch.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Comparative example 1
The comparative example had the following composition: 100 parts of PVC resin, 50 parts of iron tailings, 0.4 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene) and 12 parts of chlorinated polyethylene.
The preparation method is the same as that of the example 1, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Comparative example 2
The comparative example had the following composition: 100 parts of PVC resin, 50 parts of iron tailings, 0.4 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 12 parts of chlorinated polyethylene and 10 parts of antibacterial master batch.
The preparation method is the same as that of the example 1, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
Comparative example 3
The comparative example had the following composition: 100 parts of PVC resin, 50 parts of iron tailings, 0.52 part of titanate coupling agent KTTO, 8 parts of impact modifier ACR, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.9 part of lubricant (0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene), 12 parts of chlorinated polyethylene and 15 parts of basalt fiber.
The preparation method is the same as that of the embodiment 1, the mass ratio of the titanate coupling agent to the basalt fiber is 0.8:100, and the mass ratio of the titanate coupling agent to the iron tailing powder is 0.8: 100.
The composite materials prepared in examples 1 to 7 and comparative examples 1 to 3 were tested for shore hardness, tensile strength, bending strength, notched izod impact strength and sterilization rate, and the results are listed in table 1.
TABLE 1 Properties of composites prepared in examples 1-7 and comparative examples 1-3
Figure BDA0003219908120000111
The results of examples 1-3 and comparative examples 1-2 in Table 1 show that the mechanical property of the composite material can be improved by adding the basalt fiber; the results of examples 2, 4 and 5 show that the mechanical property and hardness of the composite material can be improved by increasing the using amount of the iron tailings; the results of the examples 2, 6 and 7 show that the antibacterial master batch has small influence on the mechanical property of the composite material, mainly focuses on the influence on the antibacterial property, and can improve the antibacterial property of the composite material along with the increase of the using amount of the antibacterial master batch, and the results of the example 5, the comparative example 1 and the comparative example 3 show that the iron tailings and the antibacterial master batch have a synergistic effect, so that the antibacterial property of the composite material is further improved.
In conclusion, the composite material provided by the invention has excellent mechanical property, hardness and antibacterial property.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The basalt fiber reinforced PVC-iron tailing antibacterial composite material comprises the following components in parts by weight: 100 parts of PVC resin, 25-100 parts of iron tailings, 0.2-1.0 part of coupling agent, 4-16 parts of processing aid, 2-12 parts of heat stabilizer, 0.5-4 parts of plasticizer, 0.4-2 parts of lubricant, 6-18 parts of chlorinated polyethylene, 5-30 parts of basalt fiber and 5-15 parts of antibacterial master batch.
2. The PVC-iron tailing antibacterial composite material as claimed in claim 1, wherein the particle size of the iron tailing is less than 12 μm.
3. The PVC-iron tailings antimicrobial composite material of claim 1, wherein the processing aid comprises an impact modifier ACR.
4. The PVC-iron tailings antibacterial composite material of claim 1, wherein the heat stabilizer comprises a calcium zinc stabilizer, a lead-based composite stabilizer or an organic tin stabilizer.
5. The PVC-iron tailings antimicrobial composite material according to claim 1, wherein the plasticizer comprises epoxidized soybean oil, dioctyl adipate, dioctyl phthalate, chlorinated paraffin, diisodecyl adipate or tricresyl phosphate.
6. The PVC-iron tailings antimicrobial composite material of claim 1, wherein the lubricant comprises one or more of stearic acid, polyethylene wax and oxidized polyethylene.
7. The PVC-iron tailing antibacterial composite material of claim 1, wherein the length of the basalt fiber is less than or equal to 5 mm.
8. The PVC-iron tailing antibacterial composite material as claimed in claim 1, wherein the antibacterial masterbatch is prepared from polypropylene and an antibacterial agent by melting and granulating.
9. The PVC-iron tailing antibacterial composite material as claimed in claim 8, wherein the mass ratio of the polypropylene to the antibacterial agent is (3-6): 1.
10. the preparation method of the PVC-iron tailing antibacterial composite material of any one of claims 1 to 9, which comprises the following steps:
(1) respectively mixing the iron tailings and the basalt fibers with a coupling agent to obtain pretreated iron tailings and pretreated basalt fibers;
(2) and (2) mixing the pretreated iron tailings and the pretreated basalt fibers obtained in the step (1) with PVC resin, a processing aid, a heat stabilizer, a plasticizer, a lubricant, chlorinated polyethylene and an antibacterial master batch, and then extruding to obtain the basalt fiber reinforced PVC-iron tailings antibacterial composite material.
CN202110954448.7A 2021-08-19 2021-08-19 Basalt fiber reinforced PVC-iron tailing antibacterial composite material and preparation method thereof Pending CN113667239A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559279A (en) * 2015-02-03 2015-04-29 张以河 Novel wood-plastic composite material
CN108410090A (en) * 2018-04-04 2018-08-17 佛山市利丰日用品有限公司 A kind of degradable environmentally-friendly plastic and preparation method thereof
CN112126171A (en) * 2020-08-28 2020-12-25 山东新迪丹环保科技有限公司 Red mud hollow plastic section bar and preparation method thereof
CN112708227A (en) * 2021-01-12 2021-04-27 中国地质大学（北京） Basalt fiber reinforced PVC marble tailing composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559279A (en) * 2015-02-03 2015-04-29 张以河 Novel wood-plastic composite material
CN108410090A (en) * 2018-04-04 2018-08-17 佛山市利丰日用品有限公司 A kind of degradable environmentally-friendly plastic and preparation method thereof
CN112126171A (en) * 2020-08-28 2020-12-25 山东新迪丹环保科技有限公司 Red mud hollow plastic section bar and preparation method thereof
CN112708227A (en) * 2021-01-12 2021-04-27 中国地质大学（北京） Basalt fiber reinforced PVC marble tailing composite material and preparation method thereof

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