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

Info

Publication number
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
Authority
CN
China
Prior art keywords
temperature
red mud
zone
graphene
foaming agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011197692.5A
Other languages
Chinese (zh)
Other versions
CN112266555A (en
Inventor
陈苏焕
严立万
梁璋富
黄义山
林晓超
黄晓丹
黄书琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FUJIAN HOSHING PLASTICS CO LTD
Original Assignee
FUJIAN HOSHING PLASTICS CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FUJIAN HOSHING PLASTICS CO LTD filed Critical FUJIAN HOSHING PLASTICS CO LTD
Priority to CN202011197692.5A priority Critical patent/CN112266555B/en
Publication of CN112266555A publication Critical patent/CN112266555A/en
Application granted granted Critical
Publication of CN112266555B publication Critical patent/CN112266555B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2327/04—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 containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Carbon And Carbon Compounds (AREA)

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.
CN202011197692.5A 2020-10-30 2020-10-30 Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof Active CN112266555B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011197692.5A CN112266555B (en) 2020-10-30 2020-10-30 Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011197692.5A CN112266555B (en) 2020-10-30 2020-10-30 Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof

Publications (2)

Publication Number Publication Date
CN112266555A CN112266555A (en) 2021-01-26
CN112266555B true CN112266555B (en) 2022-09-06

Family

ID=74345470

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011197692.5A Active CN112266555B (en) 2020-10-30 2020-10-30 Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof

Country Status (1)

Country Link
CN (1) CN112266555B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133672A (en) * 2021-12-17 2022-03-04 杭州人通管业有限公司 MPP cable protection pipe with high strength and high pressure resistance
CN116041771B (en) * 2023-02-09 2024-05-17 福州市福塑科学技术研究所有限公司 Preparation method of flame-retardant anti-aging micro-foaming PVC composite material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105743C (en) * 2000-10-26 2003-04-16 张双全 Foamed hard polyvinyl chloride plastic pipe and preparation process thereof
DE102006010354B4 (en) * 2006-03-07 2011-02-17 MöllerTech GmbH A method for producing a starting material for a foaming process in the form of a plastic granulate and method for producing a foamed article
CN104387701A (en) * 2014-11-19 2015-03-04 杨兵 Composite red-mud high-molecular synthetic material for building decoration and preparation method thereof
CN107022102B (en) * 2017-04-27 2022-12-13 北京化工大学 Preparation method of monodisperse mesoporous silica, nano composite foaming agent, preparation method and application

Also Published As

Publication number Publication date
CN112266555A (en) 2021-01-26

Similar Documents

Publication Publication Date Title
CN112266555B (en) Red mud reinforced micro-foaming PVC composite material and preparation method of power protective sleeve thereof
US11685683B2 (en) High-strength geopolymer hollow microsphere, preparation method thereof and phase change energy storage microsphere
CN109133975A (en) A kind of high-strength light foamed ceramic plate and preparation method thereof
CN108727824A (en) Height rebound closed pore flame-proof silicon rubber foamed material and preparation method thereof
CN111411250B (en) Expandable microsphere foaming agent, preparation method thereof and foaming material
JP2007100176A (en) Method for producing foamed aluminum
CN112062515B (en) High-strength geopolymer closed-cell foam material prepared from silicon carbide and preparation method thereof
CN113582714A (en) Heat insulation ceramic with high closed porosity and preparation method and application thereof
CN112375392A (en) Preparation method of graphene heat-conducting interface material
CN106588116A (en) Nano silicon dioxide/lauryl alcohol modified compound foaming agent and preparation method
CN106117741A (en) A kind of polyethylene composite foam material and preparation method thereof
CN111704440A (en) Lightweight porous aggregate and preparation process thereof
CN113443901A (en) High-strength alumina foamed ceramic and preparation method thereof
CN108083698A (en) A kind of inorganic non-metallic solid buoyant material of low-density grade and preparation method thereof
CN106756188B (en) A kind of uniform foamed aluminium preparation method of pore structure
CN105568032B (en) A kind of injection molding through-hole foamed metal and preparation method thereof
CN116573950A (en) Foamed ceramic synthesized by utilizing fly ash and lithium slag and preparation method thereof
CN112300527B (en) PP composite material and preparation method of power protective sleeve thereof
CN106670465A (en) Preparation method of closed-cell foamed aluminum material
Zoude et al. Combination of chemical foaming and direct ink writing for lightweight geopolymers
CN110590328A (en) Foamed ceramic and preparation method thereof
CN110590329A (en) Foamed ceramic and preparation method thereof
CN113773063B (en) Preparation method of porous ceramic
KR20030046564A (en) A fine-grained lightweight aggregate by use of the waste glass and the method for producing it
CN112194115A (en) Preparation method of hollow carbon nanospheres and hollow carbon nanospheres

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant