CN112266555B - Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof - Google Patents

Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof Download PDF

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CN112266555B
CN112266555B CN202011197692.5A CN202011197692A CN112266555B CN 112266555 B CN112266555 B CN 112266555B CN 202011197692 A CN202011197692 A CN 202011197692A CN 112266555 B CN112266555 B CN 112266555B
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red mud
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graphene
foaming agent
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陈苏焕
严立万
梁璋富
黄义山
林晓超
黄晓丹
黄书琴
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FUJIAN HOSHING PLASTICS CO LTD
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Abstract

The invention discloses a red mud reinforced micro-foaming PVC composite material and a preparation method of a power protection sleeve thereof, and compared with the prior art, the red mud reinforced micro-foaming PVC composite material has the following beneficial effects: the invention provides SiO 2 Graphene double-shell hollow microsphere loaded OBSH composite foaming agent, and PVC electric power protective sleeve prepared by using the foaming agent, compared with traditional electric power protective sleeve, the prepared PVC electric power protective sleeve has uniform and dense pores, and SiO is prepared and utilized 2 The special property of the graphene double-shell hollow microsphere loaded OBSH composite foaming agent material can reduce the density of the material and improve the mechanical property and quality of the PVC electric power sheath pipe.

Description

Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof
Technical Field
The invention belongs to the field of composite materials for power protective sleeves and preparation methods of pipes thereof, and particularly relates to a red mud reinforced micro-foamed PVC composite material and a preparation method of a power protective sleeve thereof.
Background
Although the micro-foaming PVC electric power protective sleeve can reduce the weight and the cost, the strength of the pipe is reduced more or less, and the micro-foaming PVC composite material filled with the active red mud has the advantages of reinforcement and ageing resistanceFlame retardance, environmental protection and cost saving: the red mud is rich in CaO and SiO 2 、Al 2 O 3 、Fe 2 O 3 Inorganic matters such as PVC filling reinforcing modifier can not only improve the adverse effect of pipe strength reduction caused by micro-foaming, but also the filled PVC product has better ageing resistance, flame retardance and the like; the red mud is solid residue obtained after alumina is extracted from bauxite by alkali, has influence on the environment and is harmful to human bodies, and the comprehensive utilization technology of the red mud must be actively developed; compared with light calcium carbonate filled hard polyvinyl chloride, the total cost is reduced by more than 10% under the same quality condition, and the cost of the material is reduced by improving the filling amount of red mud and reducing the using amount of high-cost anti-aging agents, flame retardants and other auxiliaries on the basis of meeting performance indexes.
Disclosure of Invention
In view of the above situation, the invention aims to provide a red mud reinforced micro-foamed PVC composite material, the composite material is used for preparing a PVC power sheath pipe, and the prepared PVC power sheath pipe has uniform and dense pores compared with the traditional power sheath pipe, and the mechanical property of the PVC power sheath pipe can be improved while the material density is reduced.
The invention is realized by the following technical scheme:
the red mud reinforced micro-foaming PVC composite material is composed of the following raw materials in percentage by mass: 45% of polyvinyl chloride, 26-40% of active red mud, 6-20% of Chlorinated Polyethylene (CPE), 5% of a composite foaming agent, 2% of a heat stabilizer, 1% of a lubricant and 1% of an antioxidant;
the red mud reinforced micro-foaming PVC electric power sheath pipe is prepared by high-speed mixing, plasticizing granulation and pipe molding, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, activated red mud and a toughening agent into a high-speed mixer, mixing at a high speed for 10-30 min at a material temperature of 80-100 ℃, sequentially adding a composite foaming agent, a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 20-30 min, and discharging for later use;
(2) plasticizing and granulating: melting and extruding the blending material obtained in the step (1) through a double-screw extruder for granulation, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 100-120 ℃, the temperature of the second zone is 110-130 ℃, the temperature of the third zone is 130-150 ℃, the temperature of the fourth zone is 150-170 ℃, the temperature of the fifth zone is 160-180 ℃, the temperature of the die head is 140-160 ℃, the feeding speed is 100-200 r/min, the rotating speed of the screw is 200-400 r/min, and the red mud reinforced micro-foaming PVC composite material is obtained through extrusion granulation;
(3) forming a pipe: extruding and molding the red mud reinforced micro-foaming PVC composite material prepared in the step (2) through a pipe extruder, and controlling the technological parameters of the pipe extruder as follows: the temperature of a cylinder 1 area is 100-120 ℃, the temperature of a cylinder 2 area is 110-130 ℃, the temperature of a cylinder 3 area is 130-150 ℃, the temperature of a cylinder 4 area is 150-170 ℃, the temperature of a cylinder 5 area is 160-180 ℃, the temperature of a machine head 1 area is 160-180 ℃, the temperature of a machine head 2 area is 170-190 ℃, the temperature of a machine head 3 area is 150-170 ℃, and the extrusion molding speed is 0.5 m/min;
in a further improvement scheme of the invention, the composite foaming agent is SiO 2 The graphene double-shell hollow microsphere carries the OBSH composite foaming agent, the gas forming amount of the composite foaming agent is 100-150 ml/g, the thermal stability is good at 100-180 ℃, the decomposition percentage is less than 2%, and the preparation method comprises the following steps:
(1) depositing a graphene oxide layer on the surface of the polystyrene microsphere through the surface electrostatic adsorption effect to prepare the graphene oxide/polystyrene core-shell structure microsphere; reducing the graphene oxide by adopting a hydrothermal reduction reaction method to generate graphene/polystyrene core-shell structure microspheres;
(2) preparing 20% by mass of ethanol dispersion liquid from the graphene/polystyrene core-shell structure microspheres prepared in the step (1), taking 10-20 ml of dispersion liquid, adding 0.2-1.0 g of sodium dodecyl benzene sulfonate surfactant, 3-6 ml of concentrated ammonia water and 60-100 ml of ethanol aqueous solution, carrying out ultrasonic treatment for 60-100 min, dropwise adding 2-10 ml of ethyl orthosilicate, keeping magnetic stirring for 48 hours at room temperature, alternately washing with ethanol and water, filtering, drying, calcining, and dissolving and corroding to obtain SiO 2 Graphene double-shell hollow microspheres;
(3) taking 1g of SiO prepared in the step (2) 2 Soaking the graphene double-shell hollow microspheres in a foaming agent 4, 4' -oxo- (benzenesulfonyl hydrazide) (OBSH) solution with the concentration of 0.2-0.6 mol/L, performing magnetic stirring for 20-40 min, performing ultrasonic treatment for 10-20 min, standing for 12-24 h, performing suction filtration, alternately washing with ethanol and deionized water, and drying at 60 ℃ to obtain SiO 2 The graphene double-shell hollow microspheres carry the OBSH composite foaming agent;
the hydrothermal reduction reaction method in the step (1) comprises the following steps: adopting hydrazine hydrate for the hydrothermal reduction treatment of graphene oxide, wherein the concentration range of the hydrazine hydrate is 10-40 mg/mL, the hydrothermal reaction temperature is 200-240 ℃, and the reaction time is 1-3 h;
the dissolution corrosion reaction method in the step (2): the obtained SiO 2 Dispersing the/graphene/polystyrene core-shell structure microspheres in tetrahydrofuran solvent and continuously stirring, wherein SiO is 2 The mass ratio of the graphene/polystyrene microspheres to the tetrahydrofuran solvent is 100-150: 1, and the reaction time is 24-48 h;
the invention further improves the scheme that the particle size of the activated red mud is 2000-3000 meshes, and the preparation steps are as follows: adding the refined red mud powder into a high-speed mixer, heating to 80-100 ℃, stirring at a rotating speed of 80-100 r/min for 1-2 h, adding a long-chain alkyl trimethoxy silane coupling agent accounting for 1% of the red mud powder in percentage by mass, stirring at a rotating speed of 400-500 r/min for 0.5-1 h, and cooling to normal temperature;
the further improvement scheme of the invention is that the heat stabilizer is composed of calcium stearate and barium stearate according to the mass ratio of 1-3: 1; the invention has the further improvement scheme that the lubricant is composed of polyethylene wax and paraffin wax according to the mass ratio of 1: 1;
the further improvement scheme of the invention is that the antioxidant is composed of AT-1010 and AT-168 according to the mass ratio of 1: 1.
Compared with the prior art, the invention has the following advantages:
firstly, use SiO 2 The graphene double-shell hollow microsphere loaded OBSH composite foaming agent can effectively form a uniform and stable cell structure while reducing the material density, and overcomes the defect that the traditional foaming agent is directly added to causeThe collapse and hole breaking phenomena are generated, and SiO is utilized simultaneously 2 The graphene double-shell structure improves the strength of the material while foaming, and keeps the original mechanical properties of the material;
secondly, the adoption of the activated red mud can not only improve the adverse effect of pipe strength reduction caused by micro-foaming, but also ensure that the filled PVC product has better ageing resistance and slow down the degradation speed of the micro-foaming PVC pipe in the sun.
Drawings
FIG. 1 shows SiO prepared by the present invention 2 A structural schematic diagram of an OBSH composite foaming agent supported by graphene double-shell hollow microspheres, wherein (1) is a graphene inner shell layer of the hollow microspheres, and (2) is SiO of the hollow microspheres 2 The shell layer (3) is an OBSH foaming agent supported by hollow microspheres;
FIG. 2A is a sectional electron microscope image of a red mud-reinforced micro-foamed PVC electric power sheath tube prepared in example 1 of the present invention;
fig. 2B is a sectional electron microscope image of a red mud-reinforced micro-foamed PVC power sheathing tube prepared in comparative example 2 of the present invention.
Detailed Description
Example 1
The red mud reinforced micro-foaming PVC composite material is composed of the following raw materials in percentage by mass: 45% of polyvinyl chloride, 26-40% of active red mud, 6-20% of Chlorinated Polyethylene (CPE), 5% of a composite foaming agent, 2% of a heat stabilizer, 1% of a lubricant and 1% of an antioxidant;
the red mud reinforced micro-foaming PVC electric power sheath pipe is prepared by high-speed mixing, plasticizing granulation and pipe molding, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, active red mud and a toughening agent into a high-speed mixer, mixing at a high speed for 20min at a material temperature of 90 ℃, sequentially adding a composite foaming agent, a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 25min, and discharging for later use;
(2) plasticizing and granulating: melting, extruding and granulating the blending material obtained in the step (1) through a double-screw extruder, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 110 ℃, the temperature of the second zone is 120 ℃, the temperature of the third zone is 140 ℃, the temperature of the fourth zone is 160 ℃, the temperature of the fifth zone is 170 ℃, the temperature of the die head is 150 ℃, the feeding speed is 150r/min, the rotating speed of the screw is 300r/min, and the red mud reinforced micro-foaming PVC composite material is obtained through extrusion granulation;
(3) pipe forming: extruding and molding the red mud reinforced micro-foaming PVC composite material prepared in the step (2) through a pipe extruder, and controlling the technological parameters of the pipe extruder as follows: the temperature of the cylinder 1 zone is 110 ℃, the temperature of the cylinder 2 zone is 120 ℃, the temperature of the cylinder 3 zone is 140 ℃, the temperature of the cylinder 4 zone is 160 ℃, the temperature of the cylinder 5 zone is 170 ℃, the temperature of the head 1 zone is 170 ℃, the temperature of the head 2 zone is 180 ℃, the temperature of the head 3 zone is 160 ℃, and the extrusion molding speed is 0.5 m/min.
The composite foaming agent is SiO 2 The structure of the graphene double-shell hollow microsphere loaded OBSH composite foaming agent is shown in figure 1, and the preparation method comprises the following steps:
(1) depositing a graphene oxide layer on the surface of the polystyrene microsphere through the surface electrostatic adsorption effect to prepare the graphene oxide/polystyrene core-shell structure microsphere; reducing the graphene oxide by adopting a hydrothermal reduction reaction method to generate graphene/polystyrene core-shell structure microspheres;
(2) preparing 20 mass percent ethanol dispersion liquid from the graphene/polystyrene core-shell structure microspheres prepared in the step (1), taking 15ml of dispersion liquid, adding 0.6g of sodium dodecyl benzene sulfonate surfactant, 4ml of strong ammonia water and 80ml of ethanol aqueous solution, performing ultrasonic treatment for 80min, then dropwise adding 6ml of tetraethoxysilane, keeping magnetic stirring for 48 hours at room temperature, alternately washing with ethanol and water, filtering, drying, calcining, and then dissolving and corroding to obtain SiO by a method to obtain the product 2 Graphene double-shell hollow microspheres; (3) taking 1g of SiO prepared in the step (2) 2 Soaking the graphene double-shell hollow microspheres in a foaming agent 4, 4' -oxo- (benzenesulfonylhydrazide) (OBSH) solution with the concentration of 0.4mol/L, magnetically stirring for 30min, performing ultrasonic treatment for 30min, standing for 18h, performing suction filtration, alternately washing with ethanol and deionized water, and drying at 60 ℃ to obtain SiO 2 The graphene double-shell hollow microspheres carry OBSH composite foaming agent;
the hydrothermal reduction reaction method in the step (1) comprises the following steps: hydrazine hydrate is adopted for the hydrothermal reduction treatment of graphene oxide, the concentration range of the hydrazine hydrate is 25mg/mL, the hydrothermal reaction temperature is 220 ℃, and the reaction time is 2 hours;
the dissolution corrosion reaction method in the step (2): the obtained SiO 2 Dispersing the graphene/polystyrene core-shell structure microspheres in tetrahydrofuran solvent and continuously stirring, and then preparing the SiO 2 The mass ratio of the graphene/polystyrene microspheres to the tetrahydrofuran solvent is 125:1, and the reaction time is 36 h.
The particle size of the active red mud is 2500 meshes, and the preparation steps are as follows: adding the refined red mud powder into a high-speed mixer, heating to 90 ℃, stirring at the rotating speed of 90r/min for 1.5h, adding a long-chain alkyl trimethoxy silane coupling agent accounting for 1% of the red mud powder in percentage by mass, stirring at the rotating speed of 450r/min for 0.75h, and cooling to the normal temperature;
the heat stabilizer is composed of calcium stearate and barium stearate in a mass ratio of 2: 1;
the lubricant is composed of polyethylene wax and paraffin wax in a mass ratio of 1: 1;
the antioxidant is composed of AT-1010 and AT-168 according to the mass ratio of 1: 1.
SiO produced in this example 2 The graphene double-shell hollow microsphere loaded OBSH composite foaming agent is tested: the gas forming amount of the composite foaming agent is 130ml/g, the thermal stability is good at 100-180 ℃, and the decomposition percentage is 1.2%;
the cross-sectional electron microscope image of the prepared red mud reinforced micro-foamed PVC electric power sheath tube is shown in FIG. 2A, and can be seen from the electron microscope image: the micro-foamed PVC electric power sheath pipe has uniform bubble size, the bubbles are closed and do not collapse, and the red mud reinforced micro-foamed PVC electric power sheath pipe has the following properties: the density was 1.2g/cm 3 Compared with the prior art, the ring stiffness is reduced by 22 percent, and the ring stiffness (nominal inner diameter is 100mm, and the wall thickness is 5mm) is 11.5 kPa.
Comparative example 1
The red mud reinforced PVC composite material is composed of the following raw materials in percentage by mass: 47% of polyvinyl chloride, 35% of active red mud, 14% of Chlorinated Polyethylene (CPE), 2% of heat stabilizer (comprising calcium stearate and barium stearate in a mass ratio of 2: 1), 1% of lubricant (comprising polyethylene wax and paraffin in a mass ratio of 1: 1) and 1% of antioxidant (comprising AT-1010 and AT-168 in a mass ratio of 1: 1);
the red mud reinforced PVC electric power protective sleeve is prepared by high-speed mixing, plasticizing and granulating and pipe forming, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, activated red mud and a toughening agent into a high-speed mixer, mixing at a high speed for 20min at a material temperature of 90 ℃, sequentially adding a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 25min, and discharging for later use;
(2) plasticizing and granulating: melting, extruding and granulating the blending material obtained in the step (1) through a double-screw extruder, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 110 ℃, the temperature of the second zone is 120 ℃, the temperature of the third zone is 140 ℃, the temperature of the fourth zone is 160 ℃, the temperature of the fifth zone is 170 ℃, the temperature of a die head is 150 ℃, the feeding speed is 150r/min, the rotating speed of a screw is 300r/min, and the red mud reinforced micro-foaming PVC composite material is obtained through extrusion granulation;
(3) pipe forming: extruding and molding the red mud reinforced PVC composite material prepared in the step (2) through a pipe extruder, and controlling the technological parameters of the pipe extruder as follows: the temperature of the cylinder 1 zone is 110 ℃, the temperature of the cylinder 2 zone is 120 ℃, the temperature of the cylinder 3 zone is 140 ℃, the temperature of the cylinder 4 zone is 160 ℃, the temperature of the cylinder 5 zone is 170 ℃, the temperature of the head 1 zone is 170 ℃, the temperature of the head 2 zone is 180 ℃, the temperature of the head 3 zone is 160 ℃, and the extrusion molding speed is 0.5 m/min.
The properties of the pipe produced were as follows: the density was 1.5g/cm 3 And the ring stiffness (nominal inner diameter 100mm, wall thickness 5mm) is 12.5 kPa.
Comparative example 2
The red mud reinforced OBSH foamed PVC composite material is composed of the following raw materials in percentage by mass: 67% of polyvinyl chloride, 7% of a composite foaming agent (OBSH composite foaming agent), 20% of Chlorinated Polyethylene (CPE), 3% of a heat stabilizer (comprising calcium stearate and barium stearate in a mass ratio of 2: 1), 1.5% of a lubricant (comprising polyethylene wax and paraffin in a mass ratio of 1: 1) and 1.5% of an antioxidant (comprising AT-1010 and AT-168 in a mass ratio of 1: 1);
the red mud-enhanced OBSH foamed PVC electric power sheath pipe is prepared by high-speed mixing, plasticizing granulation and pipe molding, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, active red mud and a toughening agent into a high-speed mixer, mixing at a high speed for 20min at a material temperature of 90 ℃, sequentially adding a composite foaming agent, a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 25min, and discharging for later use;
(2) plasticizing and granulating: melting, extruding and granulating the blending material obtained in the step (1) through a double-screw extruder, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 110 ℃, the temperature of the second zone is 120 ℃, the temperature of the third zone is 140 ℃, the temperature of the fourth zone is 160 ℃, the temperature of the fifth zone is 170 ℃, the temperature of the die head is 150 ℃, the feeding speed is 150r/min, the rotating speed of the screw is 300r/min, and the red mud reinforced OBSH foamed PVC composite material is obtained through extrusion granulation;
(3) pipe forming: extruding and molding the red mud reinforced OBSH foamed PVC composite material prepared in the step (2) through a pipe extruder, and controlling the technological parameters of the pipe extruder as follows: the temperature of the cylinder 1 zone is 110 ℃, the temperature of the cylinder 2 zone is 120 ℃, the temperature of the cylinder 3 zone is 140 ℃, the temperature of the cylinder 4 zone is 160 ℃, the temperature of the cylinder 5 zone is 170 ℃, the temperature of the head 1 zone is 170 ℃, the temperature of the head 2 zone is 180 ℃, the temperature of the head 3 zone is 160 ℃, and the extrusion molding speed is 0.5 m/min.
The cross-sectional electron micrograph of the prepared red mud-reinforced OBSH foamed PVC power sheath tube is shown in FIG. 2B, and can be seen from the electron micrograph: the red mud reinforced OBSH foamed PVC electric power sheath pipe has the advantages that the sizes of the foam holes are uneven, through holes and collapse phenomena exist, and the prepared pipe has the following performances: the density was 1.07g/cm 3 Ring stiffness (nominal inner diameter 100mm, wall thickness 5mm)9.8 kPa.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, and all technical solutions that belong to the idea of the present invention belong to the scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (2)

1. A preparation method of a red mud reinforced micro-foaming PVC composite material is characterized by comprising the following steps: the red mud reinforced micro-foaming PVC composite material is composed of the following raw materials in percentage by mass: 45% of polyvinyl chloride, 26-40% of active red mud, 6-20% of Chlorinated Polyethylene (CPE), 5% of a composite foaming agent, 2% of a heat stabilizer, 1% of a lubricant and 1% of an antioxidant;
the composite foaming agent is SiO 2 The graphene double-shell hollow microsphere carries the OBSH composite foaming agent, the gas forming amount of the composite foaming agent is 100-150 ml/g, the thermal stability is good at 100-180 ℃, the decomposition percentage is less than 2%, and the preparation method comprises the following steps:
(1) depositing a graphene oxide layer on the surface of the polystyrene microsphere through the surface electrostatic adsorption effect to prepare the graphene oxide/polystyrene core-shell structure microsphere; reducing the graphene oxide by adopting a hydrothermal reduction reaction method to generate graphene/polystyrene core-shell structure microspheres;
(2) preparing 20% by mass of ethanol dispersion liquid from the graphene/polystyrene core-shell structure microspheres prepared in the step (1); taking 10-20 ml of dispersion liquid, and adding 0.2-1.0 g of sodium dodecyl benzene sulfonate surfactant, 3-6 ml of concentrated ammonia water and 60-100 ml of ethanol aqueous solution; after ultrasonic treatment is carried out for 60-100 min, 2-10 ml of tetraethoxysilane is dripped; keeping magnetic stirring for 48 hours at room temperature; washing with ethanol and water alternately, filtering, drying, calcining, dissolving and corroding to obtain SiO 2 Graphene double-shell hollow microspheres;
(3) taking 1g of SiO prepared in the step (2) 2 Soaking the graphene double-shell hollow microspheres in a foaming agent 4, 4' -oxo- (benzenesulfonyl hydrazide) (OBSH) solution with the concentration of 0.2-0.6 mol/L, performing magnetic stirring for 20-40 min, performing ultrasonic treatment for 10-20 min, standing for 12-24 h, performing suction filtration, alternately washing with ethanol and deionized water, and drying at 60 ℃ to obtain SiO 2 The graphene double-shell hollow microspheres carry OBSH composite foaming agent;
the hydrothermal reduction reaction method in the step (1) comprises the following steps: adopting hydrazine hydrate for the hydrothermal reduction treatment of graphene oxide, wherein the concentration range of the hydrazine hydrate is 10-40 mg/mL, the hydrothermal reaction temperature is 200-240 ℃, and the reaction time is 1-3 h;
the dissolution corrosion reaction method in the step (2): the obtained SiO 2 Dispersing the/graphene/polystyrene core-shell structure microspheres in tetrahydrofuran solvent and continuously stirring, wherein SiO is 2 The mass ratio of the graphene/polystyrene microspheres to the tetrahydrofuran solvent is 100-150: 1, and the reaction time is 24-48 h;
the particle size of the activated red mud is 2000-3000 meshes, and the preparation steps are as follows: adding the refined red mud powder into a high-speed mixer, heating to 80-100 ℃, stirring at a rotating speed of 80-100 r/min for 1-2 h, adding a long-chain alkyl trimethoxy silane coupling agent accounting for 1% of the red mud powder in percentage by mass, stirring at a rotating speed of 400-500 r/min for 0.5-1 h, and cooling to normal temperature;
the heat stabilizer is composed of calcium stearate and barium stearate in a mass ratio of 1-3: 1;
the lubricant is composed of polyethylene wax and paraffin wax in a mass ratio of 1: 1;
the antioxidant is composed of AT-1010 and AT-168 according to the mass ratio of 1: 1;
the red mud reinforced micro-foaming PVC composite material is prepared by high-speed mixing, plasticizing and granulating the materials, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, active red mud and Chlorinated Polyethylene (CPE) into a high-speed mixer, mixing at a high speed for 10-30 min at a material temperature of 80-100 ℃, sequentially adding a composite foaming agent, a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 20-30 min, and discharging for later use;
(2) plasticizing and granulating: melting and extruding the blending material obtained in the step (1) through a double-screw extruder for granulation, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 100-120 ℃, the temperature of the second zone is 110-130 ℃, the temperature of the third zone is 130-150 ℃, the temperature of the fourth zone is 150-170 ℃, the temperature of the fifth zone is 160-180 ℃, the temperature of the die head is 140-160 ℃, the feeding speed is 100-200 r/min, the rotating speed of the screw is 200-400 r/min, and the red mud reinforced micro-foaming PVC composite material is obtained through extrusion granulation.
2. A preparation method of a red mud reinforced micro-foamed PVC electric power protective sleeve is characterized by comprising the following steps: the red mud reinforced micro-foaming PVC composite material is composed of the following raw materials in percentage by mass: 45% of polyvinyl chloride, 26-40% of active red mud, 6-20% of Chlorinated Polyethylene (CPE), 5% of a composite foaming agent, 2% of a heat stabilizer, 1% of a lubricant and 1% of an antioxidant;
the composite foaming agent is SiO 2 The graphene double-shell hollow microsphere carries the OBSH composite foaming agent, the gas forming amount of the composite foaming agent is 100-150 ml/g, the thermal stability is good at 100-180 ℃, the decomposition percentage is less than 2%, and the preparation method comprises the following steps:
(1) depositing a graphene oxide layer on the surface of the polystyrene microsphere through the surface electrostatic adsorption effect to prepare a graphene oxide/polystyrene core-shell structure microsphere; reducing the graphene oxide by adopting a hydrothermal reduction reaction method to generate graphene/polystyrene core-shell structure microspheres;
(2) preparing 20% by mass of ethanol dispersion liquid from the graphene/polystyrene core-shell structure microspheres prepared in the step (1); taking 10-20 ml of dispersion liquid, and adding 0.2-1.0 g of sodium dodecyl benzene sulfonate surfactant, 3-6 ml of concentrated ammonia water and 60-100 ml of ethanol aqueous solution; after ultrasonic treatment is carried out for 60-100 min, 2-10 ml of tetraethoxysilane is dripped; keeping magnetic stirring for 48 hours at room temperature; washing with ethanol and water alternately, filtering, drying, calcining, dissolving and corroding to obtain SiO 2 Graphene double-shell hollow microspheres;
(3) taking 1g of SiO prepared in the step (2) 2 Soaking the graphene double-shell hollow microspheres in a foaming agent 4, 4' -oxo- (benzenesulfonyl hydrazide) (OBSH) solution with the concentration of 0.2-0.6 mol/L, performing magnetic stirring for 20-40 min, performing ultrasonic treatment for 10-20 min, standing for 12-24 h, performing suction filtration, alternately washing with ethanol and deionized water, and drying at 60 ℃ to obtain SiO 2 The graphene double-shell hollow microspheres carry the OBSH composite foaming agent;
the hydrothermal reduction reaction method in the step (1) comprises the following steps: adopting hydrazine hydrate for hydrothermal reduction treatment of graphene oxide, wherein the concentration range of the hydrazine hydrate is 10-40 mg/mL, the hydrothermal reaction temperature is 200-240 ℃, and the reaction time is 1-3 h;
the dissolution corrosion reaction method in the step (2): the obtained SiO 2 Dispersing the/graphene/polystyrene core-shell structure microspheres in tetrahydrofuran solvent and continuously stirring, wherein SiO is 2 The mass ratio of the graphene/polystyrene microspheres to the tetrahydrofuran solvent is 100-150: 1, and the reaction time is 24-48 h;
the particle size of the activated red mud is 2000-3000 meshes, and the preparation method comprises the following steps: adding the refined red mud powder into a high-speed mixer, heating to 80-100 ℃, stirring at a rotating speed of 80-100 r/min for 1-2 h, adding a long-chain alkyl trimethoxy silane coupling agent accounting for 1% of the red mud powder in percentage by mass, stirring at a rotating speed of 400-500 r/min for 0.5-1 h, and cooling to normal temperature;
the heat stabilizer is composed of calcium stearate and barium stearate in a mass ratio of 1-3: 1;
the lubricant is composed of polyethylene wax and paraffin wax in a mass ratio of 1: 1;
the antioxidant is composed of AT-1010 and AT-168 according to the mass ratio of 1: 1;
the red mud reinforced micro-foamed PVC electric power protective sleeve is prepared by high-speed mixing, plasticizing and granulating and pipeline forming of the materials, and the preparation method comprises the following steps:
(1) high-speed mixing: adding polyvinyl chloride, activated red mud and Chlorinated Polyethylene (CPE) into a high-speed mixer, mixing at a high speed for 10-30 min at a material temperature of 80-100 ℃, sequentially adding a composite foaming agent, a heat stabilizer, a lubricant and an antioxidant, mixing at a high speed for 20-30 min, and discharging for later use;
(2) plasticizing and granulating: melting and extruding the blending material obtained in the step (1) through a double-screw extruder for granulation, and controlling the process parameters of the double-screw extruder as follows: the temperature of the first zone is 100-120 ℃, the temperature of the second zone is 110-130 ℃, the temperature of the third zone is 130-150 ℃, the temperature of the fourth zone is 150-170 ℃, the temperature of the fifth zone is 160-180 ℃, the temperature of the die head is 140-160 ℃, the feeding speed is 100-200 r/min, the rotating speed of the screw is 200-400 r/min, and the red mud reinforced micro-foaming PVC composite material is obtained through extrusion granulation;
(3) pipe forming: extruding and molding the red mud reinforced micro-foaming PVC composite material prepared in the step (2) through a pipe extruder, and controlling the technological parameters of the pipe extruder as follows: the temperature of the machine barrel 1 zone is 100-120 ℃, the temperature of the machine barrel 2 zone is 110-130 ℃, the temperature of the machine barrel 3 zone is 130-150 ℃, the temperature of the machine barrel 4 zone is 150-170 ℃, the temperature of the machine barrel 5 zone is 160-180 ℃, the temperature of the machine head 1 zone is 160-180 ℃, the temperature of the machine head 2 zone is 170-190 ℃, the temperature of the machine head 3 zone is 150-170 ℃, and the extrusion molding speed is 0.5 m/min.
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