CN113045839B - Composite material for reinforcing thermoplastic polymer resin and preparation method thereof - Google Patents

Composite material for reinforcing thermoplastic polymer resin and preparation method thereof Download PDF

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CN113045839B
CN113045839B CN202110232967.2A CN202110232967A CN113045839B CN 113045839 B CN113045839 B CN 113045839B CN 202110232967 A CN202110232967 A CN 202110232967A CN 113045839 B CN113045839 B CN 113045839B
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coal gangue
powder
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coupling agent
thermoplastic polymer
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CN113045839A (en
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张以河
丁冲
张娜
张有鹏
邸祥云
李益
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China University of Geosciences Beijing
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention discloses a composite material of reinforced thermoplastic polymer resin and a preparation method thereof, and the composite material comprises the following steps: crushing, grinding, drying, modifying by a coupling agent, coating by a toughening agent, and granulating the coal gangue to obtain coal gangue particles; mixing and stirring thermoplastic polymer resin powder, basalt fibers, coal gangue particles and auxiliary materials; extruding by a double-screw extruder to obtain a finished product. According to the invention, the coal gangue powder is modified by the coupling agent, coated by the toughening agent, extruded and granulated, and then mixed with the thermoplastic resin powder, the basalt fiber and the auxiliary material, so that the compatibility of the coal gangue powder and a thermoplastic polymer matrix composite material can be greatly improved, the problem of toughness and strength reduction caused by coal gangue filling is weakened, and the defects of high processing viscosity, poor fluidity and low processing fusion with polar mineral coal gangue powder of the thermoplastic polymer, which cause reduction of mechanical property and thermal stability of the material, are improved.

Description

Composite material for reinforcing thermoplastic polymer resin and preparation method thereof
Technical Field
The invention relates to the field of thermoplastic polymer composite materials, in particular to a composite material for reinforcing thermoplastic polymer resin and a preparation method thereof.
Background
The coal gangue is produced in the course of mining operation and mineral dressing operation in coal industryA bulk industrial solid waste mainly containing SiO2、Al2O3CaO, MgO, etc., the minerals mainly comprise kaolinite, quartz, mica, dolomite, etc., and the physical and chemical properties are stable. China is a large country for coal production and consumption, and the yield of coal gangue is huge and accounts for 10-15 wt% of the coal industry. But because of various coal types, the coal gangue types are also various, the composition and mineral texture are very complex, and the utilization rate is low. At present, the method is only greatly utilized in the fields of concrete and mineral filling, and a large amount of coal gangue is naturally stacked near coal mines to form a huge gangue dump, so that great harm is caused to the nearby ecological environment, including soil pollution, water pollution and atmospheric pollution.
The thermoplastic polymer resin comprises polyethylene, polyvinyl chloride and polypropylene, has large yield and wide application, and has various applications in the fields of industry, agriculture, building materials and the like, such as doors and windows, pipelines, wallboards, household appliances, packaging, film products, fishing gear, fibers for weaving, hollow products of various sizes and the like. However, the disadvantages of low heat resistance and low thermal stability further limit their application fields and application ranges. At present, the polymer base materials are subjected to enhanced modification mainly by adopting chemical methods (crosslinking, grafting and copolymerization) and physical methods (blending). The method adopts inorganic filler powder (RIF) for physical blending modification, has the advantages of simple process, obvious effect and low cost, and is increasingly paid attention to.
The coal gangue is a solid waste, contains quartz, aluminosilicate kaolin, mica and the like with stable chemical properties, and can be used as a filler for reinforcing and modifying a thermoplastic base material after being crushed and ground. On one hand, the coal gangue has high hardness and large modulus, and the rigidity of the thermoplastic polymer composite material can be improved; on the other hand, the alumina component contained in the coal gangue can improve the flame retardant property of the polymer to a certain extent. However, in the practical application process, the inventor of the application finds that the thermoplastic polymer generally has the defects of large processing viscosity, poor fluidity and low processing fusion with polar mineral coal gangue powder, which can cause the reduction of the mechanical property and the thermal stability of the material. Therefore, how to better integrate and utilize coal gangue resources, enhance the performance of polymer composite materials, and solve the agglomeration phenomenon becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a composite material for reinforcing thermoplastic polymer resin, which is prepared by modifying a coal gangue filler through a coupling agent and a toughening agent, and then mixing thermoplastic polymer resin powder, basalt fiber and auxiliary materials to achieve the effect of reinforcing the composite material.
The second purpose is to provide a preparation method of the composite material for reinforcing the thermoplastic polymer resin, and the preparation method can improve the interface bonding strength of the coal gangue and the polymer matrix by means of coal gangue powder pretreatment and interface regulation. By pre-granulating the coal gangue filler, the coupling agent and the toughening agent and then mixing the polymer resin powder, the basalt fiber and the auxiliary materials, the compatibility of the coal gangue powder and the polymer matrix material can be greatly improved, and the problem of toughness and strength reduction caused by coal gangue filling is weakened.
In order to achieve the purpose, the invention provides a composite material of reinforced thermoplastic polymer resin and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 60-100 parts of coal gangue particles coated with a flexibilizer, 100 parts of thermoplastic polymer resin powder, 2-15 parts of basalt fiber, 4-10 parts of a stabilizer, 0.5-1 part of a lubricant, 1-6 parts of a plasticizer and 5-10 parts of a regulator.
Further, the coal gangue particles coated with the toughening agent comprise the following components: 70-100 parts of coal gangue powder, 0.5-2.5 wt% of coupling agent and 20-40 parts of toughening agent.
Further, the thermoplastic polymer resin powder is selected from one of polyethylene, polypropylene and polyvinyl chloride; the cutting length of the basalt fiber is 5-10 mm.
Further, the coupling agent is selected from one or more of a chloro-silane coupling agent, an aluminate coupling agent, a zirconate coupling agent, a borate coupling agent and an aluminum-titanium composite coupling agent;
the toughening agent is selected from one or more of ethylene-octene copolymer grafted glycidyl methacrylate, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic acid copolymer and acrylonitrile-butadiene-styrene copolymer;
the stabilizer is selected from one or more of calcium zinc stabilizer, organic tin stabilizer, lead salt stabilizer, potassium zinc stabilizer and barium zinc stabilizer;
the lubricant is selected from one or more of paraffin, stearic acid, polyethylene wax and oxidized polyethylene wax;
the plasticizer is selected from one or more of citrate, dioctyl adipate and epoxidized soybean oil;
the regulator is high-viscosity methyl methacrylate with the viscosity of 10.5 +/-0.3.
Further, a method for preparing a composite material of a reinforced thermoplastic polymer resin, comprising the steps of:
Preparing raw materials: crushing, grinding and drying the coal gangue to obtain coal gangue powder;
pretreating coal gangue powder: modifying coal gangue powder by using a coupling agent, coating the coal gangue powder by using a toughening agent, and granulating to obtain coal gangue particles;
mixing materials: stirring and mixing thermoplastic polymer resin powder, coal gangue particles, a stabilizer, a lubricant, a plasticizer and a regulator uniformly;
preparing a finished product: and processing the mixed materials by using a double-screw extruder or a single-screw extruder, and extruding to obtain a finished product.
Further, in the raw material preparation step: crushing the coal gangue, grinding to 800-1300 meshes, and drying until the water content is lower than the mass ratio of 0.5 wt% to obtain the coal gangue powder.
Further, in the step of modifying the coal gangue powder by the coupling agent: and (3) mixing the coupling agent and the modified coal gangue powder at a high speed in a mixer of 150r/min for 10 minutes, then mixing the materials at a speed of 60r/min for 5 minutes, and standing and curing for 24 hours.
Further, the method for coating the toughening agent comprises the following steps: mixing the cured coal gangue powder and the toughening agent at the speed of 150r/min for 5 minutes, and then putting the mixture into an extruder for production and extrusion.
Further, the mixing method comprises the steps of heating the mixed materials at a high speed of 150r/min to 90 ℃, and then stirring the mixed materials at a low speed of 60r/min for 20 min.
Compared with the prior art, the invention has the following beneficial effects:
1) the coal gangue is used as the thermoplastic polymer composite material filler, so that the resource utilization of the waste of the coal gangue is realized, the resource utilization efficiency is improved, and the ecological environment is protected.
2) The coal gangue serves as a reinforcing filler, and due to the characteristics of high hardness, alumina-containing components and the like, the hardness, the photo-thermal stability and the like of the polymer composite material can be improved.
3) In the preparation of the composite material, the coupling agent is used for modifying the coal gangue powder, and then the toughening agent is used for coating, so that pre-granulation is carried out. Therefore, the characteristic of poor fluidity of the coal gangue powder in the processing process of the polymer composite material is effectively solved, and the compatibility of the coal gangue filler and the polymer matrix material is further improved, so that the effect of reinforcing the polymer composite material is achieved.
4) Because, molecular chain blocks with good compatibility and entanglement capability with olefin polymer macromolecular chains exist in the molecular structure of the toughening agent. Therefore, the coal gangue powder is pretreated by the coal gangue particles coated by the toughening agent, so that the free flow of the toughening agent/coal gangue powder capsule structure in a matrix can be realized in the processing process of the polymer composite material, the agglomeration phenomenon of a reinforcement in the polymer matrix is further reduced, and the effect of improving the better compatibility of the coal gangue filler and the polymer matrix material is achieved.
5) Meanwhile, the decrease of the toughness and the strength of the polymer composite material caused by the filling of the coal gangue is further improved through the filling and the reinforcement of the basalt fibers.
Detailed Description
The embodiment of the application provides a preparation method of a composite material for reinforcing thermoplastic polymer resin, and solves the problems that in the prior art, the mechanical property and the thermal stability of the material are reduced due to the fact that the thermoplastic polymer is high in processing viscosity and poor in fluidity and has low processing fusion with polar mineral coal gangue powder. In the preparation process, the gangue filler, the coupling agent and the toughening agent are pre-granulated, and then the thermoplastic polymer resin powder, the basalt fiber and the auxiliary material are mixed, so that the compatibility of the gangue powder and the thermoplastic polymer resin material can be greatly improved, and the problem of toughness reduction caused by gangue filling is weakened.
In order to solve the above problems, the technical solution in the embodiment of the present application has the following general idea:
example 1
Preparing coal gangue powder: crushing the coal gangue, grinding the coal gangue into 1250 meshes by adopting an airflow mill, and drying the coal gangue for later use;
pretreating coal gangue powder: adding 80 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 1.0 wt% into a mixer, performing high-speed hot mixing at 150r/min for 10 minutes, then performing low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours. Adding cured coal gangue powder and 40 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, mixing at a high speed of 150r/min for 5 minutes, and then putting the mixture into a double-screw extruder for melt extrusion granulation to coat the coal gangue powder with a toughening agent, thereby forming a coal gangue/toughening agent capsule structure. The extrusion granulator conditions are shown in table 1:
TABLE 1 extruder processing parameters
Temperature zone Charging barrel 1 Charging barrel 2 Charging barrel 3 Handpiece 1 Handpiece 2 Handpiece 3 Handpiece 4 Confluence core
Temperature/. degree.C 168 170 175 180 195 195 195 195
Mixing materials: 100 parts of coal gangue particles coated by the toughening agent, 100 parts of PVC resin powder, 15 parts (8mm) of basalt fibers, 8 parts of high-viscosity methyl methacrylate with the viscosity of 10.5, 6 parts of a calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a mixer by using a high-speed mixer, and the mixture is firstly heated to 90 ℃ at a high speed at 150r/min and then stirred at a low speed of 60r/min for 20 min.
Preparing a finished product: processing the mixture by using a double-screw extruder, and extruding a finished product, wherein the set temperature of the extruder is shown in the following table 2:
TABLE 2 extruder processing parameters
Temperature zone Charging barrel 1 Charging barrel 2 Charging barrel 3 Handpiece 1 Handpiece 2 Handpiece 3 Handpiece 4 Confluence core
Temperature/. degree.C 170 165 170 180 180 190 190 175
Example 2
Pretreating coal gangue powder: adding 100 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 0.5 wt% into a mixer, performing high-speed hot mixing at 150r/min for 10 minutes, then performing low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours. Adding the cured coal gangue powder and 20 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, mixing at a high speed of 150r/min for 5 minutes, and then putting the mixture into a double-screw extruder for melt extrusion granulation to coat the coal gangue powder with a toughening agent, thereby forming a coal gangue/toughening agent capsule structure. The extrusion granulator conditions are shown in table 1;
Mixing materials: 100 parts of coal gangue particles coated by the toughening agent, 100 parts of PVC resin powder, 5 parts (8mm) of basalt fibers, 10 parts of high-viscosity methyl methacrylate with the viscosity of 10.8, 6 parts of a calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a mixer by using a high-speed mixer, and the mixture is firstly heated to 90 ℃ at a high speed at 150r/min and then stirred at a low speed of 60r/min for 20 min.
The rest of the procedure was the same as in example 1.
Example 3
Pretreating coal gangue powder: adding 60 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 2.5 wt% into a mixer, carrying out high-speed hot mixing at 150r/min for 10 minutes, then carrying out low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours. Adding cured coal gangue powder and 30 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, mixing at a high speed of 150r/min for 5 minutes, and then putting the mixture into a double-screw extruder for melt extrusion granulation to coat the coal gangue powder with a toughening agent, thereby forming a coal gangue/toughening agent capsule structure. The extrusion granulator conditions are shown in table 1;
mixing materials: 100 parts of coal gangue particles coated by the toughening agent, 100 parts of PVC resin powder, 5 parts (10mm) of basalt fibers, 5 parts of high-viscosity methyl methacrylate with the viscosity of 10.2, 10 parts of a calcium-zinc stabilizer, 6 parts of epoxidized soybean oil, 0.3 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a high-speed mixer, and the mixture is firstly heated to 90 ℃ at a high speed at 150r/min and then stirred and mixed at a low speed of 60r/min for 20 min.
The remaining procedure was the same as in example 1.
Comparative example 1
Pretreating coal gangue powder: adding 80 parts of coal gangue powder and 40 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, mixing at a high speed of 150r/min for 5 minutes, and then putting the mixture into a double-screw extruder for melt extrusion granulation to coat the coal gangue powder with the toughening agent, so as to form a coal gangue/toughening agent capsule structure. The extrusion granulator conditions are shown in table 1;
mixing materials: 100 parts of coal gangue particles coated by the toughening agent, 100 parts of PVC resin powder, 15 parts (8mm) of basalt fibers, 8 parts of high-viscosity methyl methacrylate with the viscosity of 10.5, 6 parts of a calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a mixer by using a high-speed mixer, and the mixture is firstly heated to 90 ℃ at a high speed at 150r/min and then stirred at a low speed of 60r/min for 20 min.
The remaining procedure was the same as in example 1.
Comparative example 2
Pretreating coal gangue powder: adding 80 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 1.0 wt% into a mixer, performing high-speed hot mixing at 150r/min for 10 minutes, then performing low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours. Adding cured coal gangue powder and 40 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, mixing at a high speed of 150r/min for 5 minutes, and then putting the mixture into a double-screw extruder for melt extrusion granulation to coat the coal gangue powder with a toughening agent, thereby forming a coal gangue/toughening agent capsule structure. The extrusion granulator conditions are shown in table 1:
Mixing materials: 100 parts of coal gangue particles coated by the toughening agent, 100 parts of PVC resin powder, 8 parts of high-viscosity methyl methacrylate with the viscosity of 10.5, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a high-speed mixer, the mixture is heated to 90 ℃ at a high speed of 150r/min, and then the mixture is stirred at a low speed of 60r/min for 20 min.
The rest of the procedure was the same as in example 1.
Comparative example 3
Pretreating coal gangue powder: adding 80 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 1.0 wt% into a mixer, performing high-speed hot mixing at 150r/min for 10 minutes, then performing low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours. And adding the cured coal gangue powder and 40 parts of acrylonitrile-butadiene-styrene copolymer into a mixer, and mixing at a high speed of 150r/min for 5 minutes for later use.
Mixing materials: 100 parts of the coal gangue particles and acrylonitrile-butadiene-styrene blend, 100 parts of PVC resin powder, 15 parts (8mm) of basalt fiber, 8 parts of high-viscosity methyl methacrylate with the viscosity of 10.5, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a mixer by using a high-speed mixer, the mixture is heated to 90 ℃ at a high speed of 150r/min, and then the mixture is stirred at a low speed of 60r/min for 20 min.
The remaining procedure was the same as in example 1.
Comparative example 4
Pretreating coal gangue powder: adding 100 parts of 3-chloropropyltriethoxysilane coupling agent modified coal gangue powder with the mass ratio of 1.0 wt% into a mixer, performing high-speed hot mixing at 150r/min for 10 minutes, then performing low-speed mixing at 60r/min for 5 minutes, and standing and curing the mixed coal gangue powder for 24 hours.
Mixing materials: 100 parts of coal gangue particles, 100 parts of PVC resin powder, 15 parts (8mm) of basalt fibers, 8 parts of high-viscosity methyl methacrylate with the viscosity of 10.5, 6 parts of calcium-zinc stabilizer, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.3 part of polyethylene wax and 0.4 part of oxidized polyethylene wax are added into a high-speed mixer, and the mixture is firstly heated to 90 ℃ at a high speed at 150r/min and then stirred at a low speed of 60r/min for 20 min.
The rest of the procedure was the same as in example 1.
Figure BDA0002958803370000081
Figure BDA0002958803370000091
Example comparison:
the above experimental results show that the indexes of shore hardness, tensile strength, bending strength and notched izod impact strength of examples 1-3 are all significantly stronger than those of the comparative examples.
In examples 1 to 3, the coal gangue powder is modified by a 3-chloropropyltriethoxysilane coupling agent, and then mixed with an acrylonitrile-butadiene-styrene copolymer and extruded for granulation, and the coal gangue particles and basalt fibers coated with the toughening agent can effectively prevent the toughness of the material from being reduced while the rigidity of the PVC-based composite material is increased.
In comparative example 1, the coal gangue is directly extruded and granulated with the acrylonitrile-butadiene-styrene copolymer without being modified, so that the adhesion between the coal gangue and the acrylonitrile-butadiene-styrene copolymer is poor, and the coal gangue and the acrylonitrile-butadiene-styrene copolymer are debonded due to inconsistent Poisson ratios of the coal gangue and the acrylonitrile-butadiene-styrene copolymer, so that a stress concentrator is formed, and the performance is reduced.
In comparative example 2, the basalt fiber is not added, and the toughness of the toughening agent cannot be enhanced in an auxiliary manner, so that the toughness of the PVC-based composite material added with the coal gangue particles is reduced, and the notch cantilever beam impact strength index is obviously reduced.
In comparative example 3, the coal gangue modified by the coupling agent is directly mixed with the acrylonitrile-butadiene-styrene copolymer without extrusion granulation, the capsule structure of the acrylonitrile-butadiene-styrene copolymer to the modified coal gangue particles cannot be realized, the toughening effect of the toughening agent cannot be fully exerted in the mixing process of the coal gangue and the PVC-based composite material, and the index data of the tensile strength and the bending strength are obviously lower than those of the embodiment of the application.
In comparative example 4, the coal gangue modified by the coupling agent without adding the toughening agent is directly mixed with the PVC-based composite material, and although the basalt fiber is added, the toughening agent blended with the coal gangue particles is lacked, so that the toughness of the material cannot be improved, and the notched izod impact strength index data is the lowest.
To sum up, compared with the prior art, the technical scheme of the application can effectively prevent the reduction of the toughness of the material and greatly improve the performance of the polymer composite material while improving the rigidity of the PVC-based composite material. The technical scheme that the coupling agent is used for modifying coal gangue powder, the toughening agent is used for coating, the extrusion granulation is carried out, and then the thermoplastic resin powder, the basalt fiber and the auxiliary material are mixed to form a whole is adopted, so that the compatibility of the coal gangue powder and polymer matrix materials is improved, and the problem of toughness and strength reduction caused by coal gangue filling is weakened.
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (6)

1. A composite material for reinforcing thermoplastic polymer resin, characterized in that the composite material comprises the following components in parts by weight: 60-100 parts of coal gangue particles coated with a flexibilizer, 100 parts of thermoplastic polymer resin powder, 2-15 parts of basalt fiber, 4-10 parts of a stabilizer, 0.5-1 part of a lubricant, 1-6 parts of a plasticizer and 5-10 parts of a regulator;
the coal gangue particles coated with the toughening agent comprise the following components: 70-100 parts of coal gangue powder, 0.5-2.5 wt% of coupling agent and 20-40 parts of toughening agent;
the thermoplastic polymer resin powder is selected from one of polyethylene, polypropylene and polyvinyl chloride; cutting the basalt fiber to a length of 5-10 mm;
the coupling agent is selected from one or more of a chloro-silane coupling agent, an aluminate coupling agent, a zirconate coupling agent, a borate coupling agent and an aluminum-titanium composite coupling agent;
the toughening agent is selected from one or more of ethylene-octene copolymer grafted glycidyl methacrylate, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic acid copolymer and acrylonitrile-butadiene-styrene copolymer;
the stabilizer is selected from one or more of calcium zinc stabilizer, organic tin stabilizer, lead salt stabilizer, potassium zinc stabilizer and barium zinc stabilizer;
The lubricant is selected from one or more of paraffin, stearic acid, polyethylene wax and oxidized polyethylene wax;
the plasticizer is selected from one or more of citric acid ester, dioctyl adipate and epoxidized soybean oil;
the regulator is high-viscosity methyl methacrylate with the viscosity of 10.5 +/-0.3.
2. A method of preparing a reinforced thermoplastic polymer resin composite as claimed in claim 1, comprising the steps of:
preparing raw materials: crushing, grinding and drying the coal gangue to obtain coal gangue powder;
pretreating coal gangue powder: modifying coal gangue powder by using a coupling agent, coating the coal gangue powder by using a toughening agent, and granulating to obtain coal gangue particles;
mixing materials: uniformly stirring and mixing thermoplastic polymer resin powder, coal gangue particles, basalt fibers, a stabilizer, a lubricant, a plasticizer and a regulator;
preparing a finished product: and processing the mixed materials by using a double-screw extruder or a single-screw extruder, and extruding to obtain a finished product.
3. The method of claim 2, wherein the raw material preparation step comprises: crushing the coal gangue, grinding to 800-1300 meshes, and drying until the water content is lower than the mass ratio of 0.5 wt% to obtain the coal gangue powder.
4. The preparation method of claim 2, wherein the coupling agent is used for modifying the coal gangue powder, and the preparation method comprises the following steps: the coupling agent and the modified coal gangue powder are mixed for 10 minutes at a high speed in a mixer of 150r/min, then mixed for 5 minutes at a speed of 60r/min, and then left to stand for curing for 24 hours.
5. The method of claim 2, wherein the toughening agent is encapsulated by: mixing the cured coal gangue powder and the toughening agent at the speed of 150r/min for 5 minutes, and then putting the mixture into an extruder for production and extrusion.
6. A method as claimed in claim 2, wherein the mixing is carried out by heating the mixture to 90 ℃ at a high speed of 150r/min and then stirring the mixture at a low speed of 60r/min for 20 min.
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