CN111674130A - PVC anti-static toughening modified material for underground coal mine and preparation method thereof - Google Patents

PVC anti-static toughening modified material for underground coal mine and preparation method thereof Download PDF

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Publication number
CN111674130A
CN111674130A CN202010544230.XA CN202010544230A CN111674130A CN 111674130 A CN111674130 A CN 111674130A CN 202010544230 A CN202010544230 A CN 202010544230A CN 111674130 A CN111674130 A CN 111674130A
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parts
surface layer
coupling agent
static
toughening
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Inventor
李乃朋
张�成
冯继凡
李芳�
马洁
王纲
栾晓波
高虎
赵方伟
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Shandong Lutai Holding Group Co Ltd
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Shandong Lutai Holding Group Co Ltd
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Priority to CN202010544230.XA priority Critical patent/CN111674130A/en
Publication of CN111674130A publication Critical patent/CN111674130A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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
    • C08L27/02—Compositions 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
    • C08L27/04—Compositions 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
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
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    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a PVC anti-static toughening modified material for underground coal mine and a preparation method thereof. The PVC anti-static toughening modification material is formed by a three-layer co-extrusion process and consists of an inner surface layer, an outer surface layer and a middle layer; the inner surface layer and the outer surface layer comprise polyvinyl chloride resin, an impact modifier, an antistatic agent, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent; the middle layer comprises polyvinyl chloride resin, an impact modifier, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent. The invention solves the problems of higher cost, low impact strength of the material and obvious low-temperature brittleness caused by adding a large amount of carbon black in the prior art.

Description

PVC anti-static toughening modified material for underground coal mine and preparation method thereof
Technical Field
The invention relates to the technical field of pipes for coal mines, in particular to a PVC anti-static toughening modified material for coal mines and a preparation method thereof.
Background
For a long time, the gas drainage pipes for coal mines mainly comprise metal materials, glass fiber reinforced plastic materials, high polymer materials and the like. The use of steel pipes in the coal mine industry has obvious drawbacks: the mass is large and the installation is inconvenient; in the high humidity and corrosive gas environment of coal mines, steel is easily corroded, the service life is short, the inner wall of the steel pipe is easily corroded, scales are formed, and the like, so people are always seeking for a substitute of the steel pipe. The glass fiber reinforced plastic pipe is not impact-resistant, has more joints, is easy to leak, has poor comprehensive performance and is rarely used at present. The PVC pipe has incomparable advantages such as light weight, low price, simple installation and the like compared with a metal pipe, but the PVC pipe is a good insulator, has large surface resistance, is easy to generate static electricity in the using process and has potential harm. Static electricity is accumulated to a certain degree, so that static electricity dust absorption, discharge and breakdown can be caused, fire, explosion and other conditions occur, and static electricity accumulation is easily generated under a coal mine to cause fire or gas explosion, so that the PVC pipe for the underground coal mine has good antistatic performance, which is one of the primary conditions for the underground coal mine.
According to the gas drainage pipe for the coal mine, which is prepared by three-layer co-extrusion technology, the gas drainage pipe for the coal mine has the characteristics of convenience in installation, high cost performance, corrosion resistance, flame retardance, good antistatic performance and the like by utilizing the advantages of light weight, low price, corrosion resistance, good flame retardant effect and the like of PVC resin and combining the excellent conductivity of carbon materials, and can replace products such as steel pipes, cast iron pipes and the like used in the coal mine industry on a large scale.
An impact-modified polyvinyl chloride (PVC-M) pipe for coal mines is disclosed in patent application publication No. CN 110066483A. According to the pipe, the nano-scale conductive carbon black is added into the polyvinyl chloride resin to serve as an antistatic agent, and any two or more of MBS resin, ACM composite impact modifier and EVA and ABS are selected to serve as impact modifiers, so that the antistatic capacity and the impact resistance of the pipe are improved, and the pipe is suitable for being applied to underground systems of coal mines.
The patent application with the application number of 201110187263.4 discloses a three-layer co-extrusion PVC-M pipe for coal mines, MBS is added into polyvinyl chloride resin to serve as a toughening agent, nano conductive carbon black serves as an antistatic agent, and the prepared PVC-M pipe has permanent antistatic performance and the impact resistance can be comparable to that of a polyethylene antistatic pipe through a three-layer co-extrusion process.
Patent application with publication number CN103131096A discloses a high impact PVC mining pipe and a method for making the same. Acrylic ester rubber (ACM) is selected as a high impact resistance modifier, and is respectively put into a leather layer and a core layer PVC double-screw extruder to extrude a three-layer composite structure pipe, the inner surface and the outer surface of the pipe are antistatic for a long time, and the pipe is high in impact resistance and good in low temperature resistance.
In order to ensure the antistatic performance of the PVC mining pipe in the prior art, a large amount of conductive carbon black needs to be added into a PVC formula, the cost of raw materials of the carbon black is relatively high, so that the overall material cost of the pipe for the coal mine is relatively high, the carbon black can influence the mechanical property of the material, especially the impact strength of the material is seriously reduced, the low-temperature brittleness is particularly obvious, and the application and popularization of the PVC pipe for the coal mine are not facilitated in practical use.
Disclosure of Invention
The invention provides a PVC anti-static toughening modified material for coal mine underground and a preparation method thereof aiming at the defects. The invention solves the problems of higher cost, low impact strength of the material and obvious low-temperature brittleness caused by adding a large amount of carbon black in the prior art. The invention effectively reduces the addition of the conductive carbon black and increases the filling amount of the nano inorganic filler on the premise of ensuring that the antistatic performance meets the requirements, thereby reducing the raw material cost of the PVC antistatic pipe material for the underground coal mine, improving the cold resistance of the material, improving the adaptability of the PVC pipe material for the underground coal mine, and having good impact strength, tensile strength and surface strength.
The technical scheme of the PVC anti-static toughening and modifying material for the coal mine underground and the preparation method thereof is that the PVC anti-static toughening and modifying material is formed by a three-layer co-extrusion process and consists of an inner surface layer, an outer surface layer and an intermediate layer; the inner surface layer and the outer surface layer comprise polyvinyl chloride resin, an impact modifier, an antistatic agent, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent; the middle layer comprises polyvinyl chloride resin, an impact modifier, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent.
The inner surface layer and the outer surface layer comprise the following components in parts by weight:
100 parts of polyvinyl chloride (PVC) resin,
10 to 15 parts of an impact modifier, wherein,
5-8 parts of an antistatic agent,
2-5 parts of a processing aid,
1-3 parts of a lubricating agent,
3-6 parts of a heat stabilizer, namely,
5-25 parts of a filler,
0.5-2 parts of a coupling agent.
The polyvinyl chloride (PVC) resin is SG-7 or SG-8 type suspension polyvinyl chloride resin, and the two types of resin have good fluidity and can ensure that the thickness of the surface layer is controlled in a smaller range;
the impact modifier contains at least one of Thermoplastic Polyurethane (TPU), Thermoplastic Polyurethane (TPE) and Thermoplastic Polyurethane (TPR), and also contains at least one of Chlorinated Polyethylene (CPE) and an impact modifier (ACR);
the antistatic agent is nano-scale conductive carbon black;
the processing aid is Acrylate (ACR), such as KN-120N, K175, ACR201, ACR401 and the like;
the lubricant is at least two of stearic acid, synthetic polyethylene wax (PE wax), synthetic oxidized polyethylene wax (OPE wax) and polyol fatty acid ester;
the heat stabilizer is a calcium-zinc stabilizer;
the filler is at least one of nano-grade active calcium carbonate, talcum powder, titanium dioxide and fly ash, and the nano-grade filler has good compatibility with the PVC resin matrix and can also play a toughening effect;
the coupling agent is an aluminate coupling agent or a titanate coupling agent.
The PVC anti-static toughening modification material for the underground coal mine comprises the following components in parts by weight in the middle layer: 100 parts of polyvinyl chloride (PVC) resin,
10 to 15 parts of an impact modifier, wherein,
2-5 parts of a processing aid,
1-2 parts of a lubricating agent,
3-6 parts of a heat stabilizer, namely,
10-30 parts of a filler,
0.5-2 parts of a coupling agent.
The polyvinyl chloride (PVC) resin is SG-5 type suspension polyvinyl chloride resin, and the type of resin has better mechanical property and can ensure the integral tensile strength and impact strength of the pipe;
the impact modifier contains at least one of Thermoplastic Polyurethane (TPU), Thermoplastic Polyurethane (TPE) and Thermoplastic Polyurethane (TPR), and also contains at least one of Chlorinated Polyethylene (CPE) and an impact modifier (ACR);
the processing aid is Acrylate (ACR), such as KN-120N, K175, ACR201, ACR401 and the like;
the lubricant is at least two of stearic acid, synthetic polyethylene wax (PE wax), synthetic oxidized polyethylene wax (OPE wax) and polyol fatty acid ester;
the heat stabilizer is a calcium-zinc stabilizer;
the filler is at least one of nano-grade active calcium carbonate, talcum powder, titanium dioxide and fly ash, and the nano-grade filler has good compatibility with the PVC resin matrix and can also play a toughening effect;
the coupling agent is an aluminate coupling agent or a titanate coupling agent.
The thickness ratio of the inner surface layer, the outer surface layer and the middle layer is 1:1:8-1:1:3, the thickness ratio can be controlled by adjusting the feeding amount of the components of the inner surface layer, the outer surface layer and the middle layer, and the fixed ratio of the thicknesses of the inner surface layer and the outer surface layer is 1: 1.
The preparation method of the PVC anti-static toughening modification material for the underground coal mine comprises the steps of premixing a filler, an antistatic agent, a coupling agent and an impact modifier, extruding and granulating to prepare master batches, mixing the master batches with other auxiliary agents in a formula, and carrying out secondary granulation to obtain a material for an inner surface layer or an outer surface layer;
premixing the filler, the coupling agent and the impact modifier, extruding and granulating to prepare master batches, mixing the master batches with other auxiliary agents in the formula on a high-speed mixer, and carrying out secondary granulation to obtain the special material for the middle layer;
and (3) carrying out a three-layer co-extrusion molding process on the materials for the inner surface layer and the outer surface layer and the special material for the middle layer at the temperature of 165-185 ℃ to obtain the PVC anti-static toughening and modifying material for the underground coal mine.
In the preparation process of the materials for the inner surface layer or the outer surface layer and the special material for the middle layer, the premixing process is carried out on a high-speed mixer at the rotating speed of 1000-3000r/min for 10-15 min.
The three-layer co-extrusion molding process is characterized in that the temperature of a machine head is divided into three sections: the machine head 1165 and 2170 and the machine head 3170 and 185 ℃ respectively, and the machine head 2 is opened for ethanol spray cooling every 30-50 s in the middle. As the processing temperature of the SG-5 type resin is higher than that of SG-7 and SG-8 type resins, the forming temperature of the middle layer is 5-15 ℃ higher than that of the inner and outer surface layers, the integral mechanical property of the pipe is ensured in order to reduce the occupation ratio of the inner and outer surface layers, and the combination capability of three-layer co-extrusion can be ensured by the process of setting the temperature of the machine head and adding spray cooling.
The invention has the beneficial effects that: .
(1) The filler and the impact modifier are prepared into master batches and then mixed with PVC, the dispersion of nano particles in a matrix is facilitated through a secondary granulation processing process, and the mechanical property of the same formula is superior to that of the components which are directly granulated after being mixed;
(2) thermoplastic Polyurethane (TPU) is added into the formula system, so that the cold resistance of the material can be improved, and the adaptability of the polyvinyl chloride pipe for the underground coal mine is improved;
(3) the additive amount of the conductive carbon black can be effectively reduced and the filling amount of the nano inorganic filler can be increased on the premise of ensuring that the antistatic performance meets the requirements, so that the raw material cost of the PVC antistatic pipe for the underground coal mine is reduced, and the application of the antistatic PVC pipe in mining or other fields is promoted.
(4) The filler such as nano active calcium carbonate and the like has the toughening and modifying effects on a PVC composite system, and can play a synergistic toughening effect on PVC when being used together with impact modifiers such as CPE and the like. The mechanism is as follows: the polyvinyl chloride resin is modified by adding the impact modifier, but the rigidity, heat resistance and dimensional stability of the material are reduced while toughening, and the toughened PVC with good impact strength, tensile strength and surface strength can be obtained after adding the fillers such as nano active calcium carbonate and the like.
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
The starting materials mentioned in the examples of the present invention are not specifically defined and are commercially available.
Example 1
The inner surface layer and the outer surface layer of the PVC anti-static toughening modification material for the underground coal mine comprise the following components in parts by weight: 100 parts of PVC resin (SG-7 or SG-8 type), 8 parts of impact modifier CPE and 4 parts of TPU, 5 parts of nano conductive carbon black as antistatic agent, 2 parts of Acrylate (ACR) as processing aid, 0.5 part of stearic acid, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester, 1.5 parts in total, 5 parts of heat-stable calcium-zinc stabilizer, 15 parts of nano active calcium carbonate as filler and 0.5 part of titanate coupling agent as coupling agent.
The preparation method of the antistatic composite material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the blend of the nano-scale active calcium carbonate, the nano-scale conductive carbon black, the coupling agent, CPE, TPU and ACR on a high-speed mixer; the premixing is carried out on a high-speed mixer, the rotating speed is 1000-3000r/min, and the time is 10-15 min.
(3) Extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed materials into a double-screw extruder to carry out secondary granulation to obtain the special material for the inner and outer surface layers.
The PVC anti-static toughening modification material interlayer for the coal mine comprises the following components in parts by weight: 100 parts of PVC resin (SG-5 type), 8 parts of chlorinated polyethylene CPE (135A) and 4 parts of thermoplastic polyurethane elastomer TPU (thermoplastic polyurethane elastomer), 2 parts of Acrylate (ACR) as a processing aid, 0.5 part of stearic acid as a lubricant, 0.5 part of PE wax, 0.3 part of OPE wax, 0.2 part of polyol fatty acid ester, 5 parts of calcium-zinc stabilizer as a heat stabilizer, 15 parts of nano-active calcium carbonate as a filler and 0.5 part of titanate coupling agent as a coupling agent.
The preparation method of the pipe intermediate layer material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the nano-scale active calcium carbonate, the coupling agent and the blend of CPE, TPU and ACR on a high-speed mixer; the premixing is carried out on a high-speed mixer, the rotating speed is 1000-3000r/min, and the time is 10-15 min.
(3) Extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the special material for the middle layer.
The special material for the inner and outer surface layers and the special material for the middle layer of the polyvinyl chloride pipe for the underground coal mine are subjected to three-layer co-extrusion equipment at the temperature of 165-185 ℃ to obtain the anti-static pipe for the mine.
Example 2
A toughening modification formula of an antistatic material for inner and outer surface layers of a tubular product for a coal mine underground comprises the following components in parts by weight: 100 parts of PVC resin (SG-7 type or SG-8 type), 8 parts of impact modifier CPE and 4 parts of TPU, 8 parts of antistatic agent nano conductive carbon black, 2 parts of processing aid Acrylate (ACR), 0.5 part of lubricant stearic acid, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester, 1.5 parts of heat stabilizer, 5 parts of heat stabilizer calcium zinc stabilizer, 15 parts of filler nano active calcium carbonate and 0.5 part of coupling agent titanate.
The preparation method of the antistatic composite material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the blend of the nano-scale active calcium carbonate, the nano-scale conductive carbon black, the coupling agent, CPE, TPU and ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the special material for the inner and outer surface layers.
A toughening modification formula for a middle layer of a polyvinyl chloride pipe middle layer material for underground coal mines comprises the following components in parts by weight: 100 parts of PVC resin (SG-5 type), 8 parts of impact modifier CPE, 4 parts of TPU, 2 parts of ACR as processing aid, 0.5 part of stearic acid as lubricant, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester as heat stabilizer, 5 parts of calcium-zinc stabilizer as heat stabilizer, 15 parts of nano-active calcium carbonate as filler and 0.5 part of titanate coupling agent as coupling agent.
The preparation method of the pipe intermediate layer material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the nano-scale active calcium carbonate, the coupling agent and the blend of CPE, TPU and ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the special material for the middle layer.
The special material for the inner and outer surface layers and the special material for the middle layer of the polyvinyl chloride pipe for the underground coal mine are subjected to three-layer co-extrusion equipment at the temperature of 165-185 ℃ to obtain the anti-static pipe for the mine. Wherein the temperature of the machine head is divided into three sections: the machine head is 1160 ℃, the machine head is 2180 ℃, the machine head is 3185 ℃, and the machine head 2 is opened with ethanol for spray cooling every 30s in the middle.
Comparative example 1
A toughening modification formula of an antistatic material for inner and outer surface layers of a tubular product for a coal mine underground comprises the following components in parts by weight: 100 parts of PVC resin (SG-7 type or SG-8 type), 8 parts of antistatic agent, 2 parts of Acrylate (ACR) as a processing aid, 0.5 part of stearic acid as a lubricant, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester, 1.5 parts of calcium-zinc stabilizer as a heat stabilizer, 15 parts of nano-active calcium carbonate as a filler and 0.5 part of titanate coupling agent as a coupling agent.
The preparation method of the antistatic composite material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the blend of the nano-grade active calcium carbonate, the nano-grade conductive carbon black, the coupling agent and the ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the special material for the inner and outer surface layers of the polyvinyl chloride pipe for the underground coal mine.
A toughening modification formula for a middle layer of a polyvinyl chloride pipe middle layer material for underground coal mines comprises the following components in parts by weight: 100 parts of PVC resin (SG-5 type), 2 parts of ACR (acrylate copolymer) as a processing aid, 0.5 part of stearic acid as a lubricant, 0.5 part of PE (polyethylene) wax, 0.3 part of OPE (ethylene propylene) wax and 0.2 part of polyol fatty acid ester as a lubricant, 5 parts of calcium-zinc stabilizer as a heat stabilizer and 0.5 part of titanate coupling agent as a coupling agent.
The preparation method of the pipe intermediate layer material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing a blend of nano-scale active calcium carbonate, a coupling agent and ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the material special for the middle layer of the polyvinyl chloride pipe for the underground coal mine.
The special material for the inner surface layer and the outer surface layer and the special material for the middle layer of the polyvinyl chloride pipe for the underground coal mine are subjected to three-layer co-extrusion equipment at the temperature of 165-185 ℃ to obtain the anti-static pipe for the mine, wherein the temperature of an extrusion three-section machine head is respectively as follows: the machine head is 1170 ℃, the machine head is 2180 ℃, the machine head is 3185 ℃, and the machine head 2 is opened with ethanol for spraying and cooling every 50s in the middle.
Comparative example 2
A toughening modification formula of an antistatic material for inner and outer surface layers of a tubular product for a coal mine underground comprises the following components in parts by weight: 100 parts of PVC resin (SG-7 type or SG-8 type), 8 parts of impact modifier, 4 parts of TPU, 8 parts of nano conductive carbon black as antistatic agent, 2 parts of Acrylate (ACR) as processing aid, 0.5 part of stearic acid, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester, 1.5 parts of the total, 5 parts of calcium-zinc stabilizer as heat stabilizer and 0.5 part of titanate coupling agent as coupling agent.
The preparation method of the antistatic composite material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the blend of the nano conductive carbon black, the coupling agent and the ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the special material for the inner and outer surface layers.
A toughening modification formula for a middle layer of a polyvinyl chloride pipe middle layer material for underground coal mines comprises the following components in parts by weight: 100 parts of PVC resin (SG-5 type), 8 parts of impact modifier CPE and 4 parts of TPU, 2 parts of ACR, 0.5 part of stearic acid, 0.5 part of PE wax, 0.3 part of OPE wax and 0.2 part of polyol fatty acid ester as lubricant, 5 parts of calcium zinc stabilizer as heat stabilizer and 0.5 part of titanate coupling agent as coupling agent.
The preparation method of the pipe intermediate layer material comprises the following steps:
(1) weighing the components according to the weight;
(2) premixing the coupling agent and the blend of CPE, TPU and ACR on a high-speed mixer;
(3) extruding and granulating the premix on a double-screw extruder to prepare master batches;
(4) mixing the master batch with other additives in the formula on a high-speed mixer;
(5) and adding the mixed material into a double-screw extruder to carry out secondary granulation to obtain the material special for the middle layer of the polyvinyl chloride pipe for the underground coal mine.
The special material for the inner and outer surface layers and the special material for the middle layer of the polyvinyl chloride pipe for the underground coal mine are subjected to three-layer co-extrusion equipment at the temperature of 165-185 ℃ to obtain the anti-static pipe for the mine. Wherein the temperature of the machine head is divided into three sections: the machine head is 1160 ℃, 2170 ℃ and 3180 ℃, and ethanol is started to spray and cool at the machine head 2 every 30 s.
Performance test experiments:
the obtained special material for the middle layer and the special material for the antistatic inner and outer layers are respectively split on a double roller at 180 ℃ and tabletted on a tabletting machine at 180 ℃, a sample is preheated for 5min and kept for 5min, wherein the special material for the middle layer is pressed into an intermediate sheet with the thickness of 4mm, the special material for the antistatic inner and outer layers is respectively pressed into an inner layer sheet and an outer layer sheet with the thickness of 0.5mm, the intermediate sheet is placed in the middle, the inner layer sheet and the outer layer sheet with the corresponding formulas are respectively placed on the upper surface and the lower surface of the middle layer, and then the three-layer composite sheet is molded for the second time so as to carry out performance test, wherein the test results are.
Tests show that the polyvinyl chloride pipe for the underground coal mine prepared by the invention can effectively reduce the addition of the conductive carbon black and increase the filling amount of the nano inorganic filler on the premise of ensuring that the antistatic performance meets the requirements, and the toughness is obviously improved while the cost of raw materials is effectively reduced.
TABLE 1
Figure BDA0002540118260000091
Figure BDA0002540118260000101
The pipes prepared in example 1 and example 2 were subjected to an impact resistance test with a general PVC pipe on the market, and the results are shown in table 2:
TABLE 2
Figure BDA0002540118260000102

Claims (9)

1. The PVC anti-static toughening and modifying material for the underground coal mine is characterized in that the PVC anti-static toughening and modifying material is formed by a three-layer co-extrusion process and consists of an inner surface layer, an outer surface layer and an intermediate layer; the inner surface layer and the outer surface layer comprise polyvinyl chloride resin, an impact modifier, an antistatic agent, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent; the middle layer comprises polyvinyl chloride resin, an impact modifier, a processing aid, a lubricant, a heat stabilizer, a filler and a coupling agent.
2. The PVC anti-static toughening and modifying material for the underground coal mine according to claim 1, wherein the inner surface layer and the outer surface layer comprise the following components in parts by weight:
100 parts of polyvinyl chloride resin, namely 100 parts of polyvinyl chloride resin,
10 to 15 parts of an impact modifier, wherein,
5-8 parts of an antistatic agent,
2-5 parts of a processing aid,
1-3 parts of a lubricating agent,
3-6 parts of a heat stabilizer, namely,
5-25 parts of a filler,
0.5-2 parts of a coupling agent.
3. The PVC anti-static toughening and modifying material for the underground coal mine according to claim 2, wherein the polyvinyl chloride resin is SG-7 or SG-8 type suspended polyvinyl chloride resin;
the impact modifier contains at least one of Thermoplastic Polyurethane (TPU), Thermoplastic Polyurethane (TPE) and Thermoplastic Polyurethane (TPR), and also contains at least one of Chlorinated Polyethylene (CPE) and an impact modifier (ACR);
the antistatic agent is nano-scale conductive carbon black;
the processing aid is acrylate;
the lubricant is at least two of stearic acid, synthetic polyethylene wax, synthetic oxidized polyethylene wax and polyol fatty acid ester;
the heat stabilizer is a calcium-zinc stabilizer;
the filler is at least one of nano-grade active calcium carbonate, talcum powder, titanium dioxide and fly ash;
the coupling agent is an aluminate coupling agent or a titanate coupling agent.
4. The PVC anti-static toughening and modifying material for the underground coal mine according to claim 1, wherein the middle layer comprises the following components in parts by weight:
100 parts of polyvinyl chloride resin, namely 100 parts of polyvinyl chloride resin,
10 to 15 parts of an impact modifier, wherein,
2-5 parts of a processing aid,
1-2 parts of a lubricating agent,
3-6 parts of a heat stabilizer, namely,
10-30 parts of a filler,
0.5-2 parts of a coupling agent.
5. The PVC anti-static toughening and modifying material for the underground coal mine according to claim 4, wherein the polyvinyl chloride resin is SG-5 type suspension polyvinyl chloride resin;
the impact modifier contains at least one of Thermoplastic Polyurethane (TPU), Thermoplastic Polyurethane (TPE) and Thermoplastic Polyurethane (TPR), and also contains at least one of Chlorinated Polyethylene (CPE) and an impact modifier (ACR);
the processing aid is acrylate;
the lubricant is at least two of stearic acid, synthetic polyethylene wax, synthetic oxidized polyethylene wax and polyol fatty acid ester;
the heat stabilizer is a calcium-zinc stabilizer;
the filler is at least one of nano-grade active calcium carbonate, talcum powder, titanium dioxide and fly ash;
the coupling agent is an aluminate coupling agent or a titanate coupling agent.
6. The PVC anti-static toughening and modifying material for the underground coal mine according to claim 1, wherein the thickness ratio of the inner surface layer, the outer surface layer and the middle layer is 1:1:8-1:1:3, and the fixed ratio of the thicknesses of the inner surface layer and the outer surface layer is 1: 1.
7. The preparation method of the PVC anti-static toughening and modifying material for the underground coal mine according to claim 1, wherein the filler, the antistatic agent, the coupling agent and the impact modifier are premixed, extruded and granulated to prepare master batches, the master batches are mixed with other auxiliary agents in the formula, and secondary granulation is carried out to obtain the material for the inner surface layer or the outer surface layer;
premixing the filler, the coupling agent and the impact modifier, extruding and granulating to prepare master batches, mixing the master batches with other auxiliary agents in the formula on a high-speed mixer, and carrying out secondary granulation to obtain the special material for the middle layer;
and (3) carrying out a three-layer co-extrusion molding process on the materials for the inner surface layer and the outer surface layer and the special material for the middle layer at the temperature of 165-185 ℃ to obtain the PVC anti-static toughening and modifying material for the underground coal mine.
8. The method as claimed in claim 7, wherein the pre-mixing process is performed in a high-speed mixer at a rotation speed of 1000-.
9. The preparation method of the PVC anti-static toughening and modifying material for the underground coal mine according to claim 7, wherein in the three-layer co-extrusion molding process, the temperature of a machine head is divided into three sections: the machine head 1165 and 2170 and the machine head 3170 and 185 ℃ respectively, and the machine head 2 is opened for ethanol spray cooling every 30-50 s in the middle.
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Application publication date: 20200918