CN112500625A - Flame-retardant antistatic polyolefin for underground coal mine, and preparation method and application thereof - Google Patents
Flame-retardant antistatic polyolefin for underground coal mine, and preparation method and application thereof Download PDFInfo
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- CN112500625A CN112500625A CN202011353041.0A CN202011353041A CN112500625A CN 112500625 A CN112500625 A CN 112500625A CN 202011353041 A CN202011353041 A CN 202011353041A CN 112500625 A CN112500625 A CN 112500625A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention provides a flame-retardant antistatic polyolefin for underground coal mines, which comprises polyethylene, polypropylene, POE, a silicon-boron-phosphorus composite flame retardant, a composite antistatic agent, a lubricant and the like. The invention takes POE (ethylene-octene copolymer) as an interface melting agent, is beneficial to the organic combination of Polyethylene (PE) and polypropylene (PP), adopts the silicon-boron-phosphorus composite flame retardant and graphene and other composite antistatic agents to prepare the flame-retardant antistatic polyolefin, and meets the comprehensive performances of the pipeline used under the coal mine such as physical machinery, antistatic property and the like of the modified material.
Description
Technical Field
The invention relates to the field of polymer chemistry, in particular to flame-retardant antistatic polyolefin for underground coal mines and a preparation method and application thereof.
Background
China has been the first coal producing country and the first consuming country in the world for many years, the production and consumption amount accounts for about half of the world at present, and the coal is mainly used for the heavy industry of electric power, metallurgy, building materials and the like. Coal is used as important basic energy and industrial raw materials in China, the economic and social development is effectively supported, the yield of coal in China is 38.7 hundred million tons in 2014, and the coal provides inexhaustible power for continuous and rapid forward of economic trains in China.
The underground pipe for coal mine is used as metal pipeline for pumping water, draining water, exhausting gas, etc. Metal pipes are susceptible to corrosion by other chemical agents. Corrosion is one of the major factors causing pipe breakage, and the maintenance and anti-corrosion painting of metal pipes is carried out annually at a high cost and is expensive. Statistics of british gas company data show that corrosion accounts for 40% of the accident causes of pipeline failure. Pipelines with corrosion defects may cause collapse of mines, flood hazards and the like in the operation process.
The recent development of plastic tubing for underground coal mines, produced from modified High Density Polyethylene (HDPE) as the basic raw material, partially solves the above-mentioned problems. The modified polyethylene material for the underground coal mine has good flame-retardant antistatic performance, and due to the good low-temperature resistance of the polyethylene material, the modified polyethylene material for the underground coal mine is endowed with good low-temperature resistance and low-temperature impact strength. However, the installation requirements of the coal mine pipeline require that the pipeline has higher span bending strength. The modified polyethylene pipeline is easy to bend and deform, the span bending strength is small, and the pipeline after installation and operation deforms seriously.
The coal mine underground pipe produced by the flame-retardant antistatic modified polypropylene on the market at present overcomes part of defects of a modified polyethylene pipeline, greatly improves the span bending strength of the coal mine underground pipe, and also improves the service temperature of the pipeline. However, the flame retardant antistatic performance of the pipeline made of the modified polypropylene material is obviously reduced along with the prolonging of time; meanwhile, the material has poor low temperature resistance, and when the environmental temperature is lower than 0 ℃, the product shows fine low-temperature brittleness and low impact strength, and a pipeline is easy to crack; moreover, the material has low melt strength, is sensitive to temperature and has low hot-melt bonding strength, thereby bringing great difficulty to the production of composite pipelines in particular and bringing great use risk to the transportation and use of the product.
Disclosure of Invention
The invention aims to provide flame-retardant antistatic polyolefin for underground coal mines and a preparation method and application thereof. The invention takes POE (ethylene-octene copolymer) as an interface melting agent, is beneficial to the organic combination of Polyethylene (PE) and polypropylene (PP), adopts the silicon-boron-phosphorus composite flame retardant and graphene and other composite antistatic agents to prepare the flame-retardant antistatic polyolefin, and meets the comprehensive performances of the pipeline used under the coal mine such as physical machinery, antistatic property and the like of the modified material.
The invention mainly aims to provide a flame-retardant antistatic polyolefin for underground coal mines, which comprises the following components in percentage by weight:
according to some embodiments of the invention, the flame retardant antistatic polyolefin comprises at least one or both of polyethylene or polypropylene.
According to some embodiments of the invention, the silicon boron phosphorus-based composite flame retardant comprises one or more of POSS, zinc borate, red phosphorus.
According to some embodiments of the present invention, the silicon boron phosphorus-based composite flame retardant comprises the following components by weight:
POSS 0～2％
0 to 8 percent of zinc borate
0-10% of red phosphorus.
According to some embodiments of the invention, the composite antistatic agent comprises one or more of graphene, carbon nanotubes, carbon black.
According to some embodiments of the invention, the composite antistatic agent comprises the following components by weight:
0 to 6 percent of graphene
0 to 6 percent of carbon nano tube
0-6% of carbon black.
Another object of the present invention is to provide a method for preparing the flame retardant antistatic polyolefin, comprising the following steps:
1) pretreating each component of the flame-retardant antistatic polyolefin;
2) pre-blending of polyethylene/POE or polypropylene/POE: mixing the pretreated polyethylene or polypropylene with POE, and then performing pre-blending treatment in a plastic extruder of a double-screw extruder to uniformly mix the POE with the polyethylene or polypropylene;
3) the components are mixed and stirred according to the proportion, added into a plastic extruder, and subjected to blending extrusion, granulation and drying to obtain the flame-retardant antistatic modified polyolefin.
According to some embodiments of the invention, the pre-treatment comprises drying the individual components. In some more specific embodiments of the invention, the drying of the polyethylene, polypropylene and POE comprises vacuum drying; in some more specific embodiments of the invention, the vacuum drying comprises vacuum drying at a temperature of 70-80 ℃ for a period of 3-4 hours.
According to some embodiments of the present invention, the pretreatment comprises adding a surfactant and a grafted polyolefin to red phosphorus for activation and coating, so as to achieve the purpose of mixing with other raw materials for direct use; or mixing the pretreated red phosphorus with polyethylene or polypropylene, and granulating to obtain the red phosphorus master batch.
According to some embodiments of the present invention, the pre-blending of polyethylene/POE or polypropylene/POE comprises pre-blending the pre-treated polyethylene or polypropylene and POE in a twin-screw extruder plastic extruder after mixing the polyethylene or polypropylene and POE with a lower content of components, so as to uniformly mix the POE and the polyethylene or polypropylene.
According to some embodiments of the invention, the step 3) plastic extruder comprises a twin screw extruder; preferably, the extrusion temperature of the double-screw extruder is 180 ℃ and 240 ℃, and the extrusion speed is 10-40 r/min.
The invention also aims to provide application of the flame-retardant antistatic polyolefin in underground coal mine pipelines or lines.
Compared with the prior art, the flame-retardant antistatic polyolefin has the following advantages:
1) the inventor finds that: the preparation of the modified polyolefin material of the invention preferably ensures the drying of various raw materials to avoid affecting the properties of various materials, especially reducing the strength of the modified material. In addition, the inventors found that excessive moisture generates water vapor under high temperature conditions, thereby foaming the product, and directly affecting the quality and appearance of the product. Unnecessary moisture in the polyolefin material can be removed by a method such as vacuum drying, and performance deterioration caused by generation of steam due to high temperature can be avoided in the moisture dehumidification process. And materials other than the polyolefin and red phosphorus, such as zinc borate, graphene, carbon nanotubes, carbon black, etc., may be dried using a conventional method. Secondly, in addition to the pre-treatment drying, the material is preferably kept dry during the polymerization and preparation of the flame-retardant antistatic polyolefin.
2) Compared with the common flame-retardant antistatic polyethylene or polypropylene material, the flame-retardant antistatic polyolefin for the underground coal mine avoids the defects of the flame-retardant antistatic polyethylene and polypropylene modified material, fully utilizes the complementary advantages and performances of the materials, and overcomes the defects of low span bending strength of the polyethylene material, poor low-temperature resistance performance of the polypropylene material and low impact strength; the characteristics of excellent low temperature resistance and impact resistance of the polyethylene material and high strength, high rigidity and high span bending strength of the polypropylene material are effectively utilized. The invention achieves the organic combination of the two materials through the interaction of the phase-melting agent; meanwhile, the modified polyolefin material of the invention also reduces the sensitivity of the modified polypropylene material to temperature, improves the melt strength and effectively avoids the risk of the bonding and sealing separation of the composite pipeline.
3) The flame-retardant antistatic polyolefin for the underground coal mine also fully utilizes the advantages of materials such as coal chemical industry polyethylene, polypropylene and the like, so that the requirements of the flame-retardant antistatic polyolefin pipeline for the underground coal mine on the physical and mechanical properties and the price of a modified material are met.
4) More importantly, the flame-retardant antistatic polyolefin for the underground coal mine disclosed by the invention takes single components or combination of POSS, zinc borate and red phosphorus as flame retardants, so that lasting and excellent flame retardant property is provided for materials; the single component or the combination of the graphene, the carbon nano tube and the carbon black is used as an antistatic agent, so that stable antistatic performance which is not influenced by external deformation is provided for the modified polyolefin material.
The flame-retardant antistatic polyolefin for the underground coal mine has no solvent, no pollution, no toxicity and no smell, and belongs to an environment-friendly chemical product. The preparation method of the flame-retardant antistatic polyolefin for the underground coal mine is simple, the reaction process is easy to control, the operation is simple, and the large-scale production is easy, so that the preparation method has a good application prospect.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as being without limitation.
In the following examples of the present invention, "%" means weight percent unless otherwise specified.
The performance detection indexes of the flame-retardant antistatic polyolefin for the underground coal mine in the following embodiments of the invention are as follows: the requirements of the raw materials are as follows
(1) Dehumidification and drying of raw materials
For PE (polyethylene), PP (polypropylene) or POE (ethylene-octene copolymer) particles, vacuum dehumidification is used, the temperature is 70-80 ℃, and the time is 3-4 hours; in addition to red phosphorus, other materials may be dehumidified using a hot oven.
(2) Raw material weighing and proportioning
The raw materials were accurately weighed for use according to the formulation listed in table 1 below. It is worth noting that the various raw materials weighed out need to be kept dry.
(3) Pretreatment of part of the raw material
a. Pretreatment of red phosphorus
The red phosphorus is pretreated according to the method already described herein.
Preblending PE/POE or PP/POE
The method is characterized in that one of PE or PP with less dosage in the formula is mixed with POE material and then pre-blended in a double-screw extruder, so that POE and PE or PP are uniformly mixed, the PE or PP material is fully coated by the POE material, and conditions are created for better fusion of the premix and more PP or PE materials in the formula in the later period.
If the mass portion of the materials in the formula of table 1 is 0, pre-blending is not needed.
(4) Stirring, mixing, granulating and drying of flame-retardant and antistatic polyolefin for underground coal mine
a. Compounding of raw materials
The pretreated raw materials and other various materials are weighed and placed in a stirring container according to the requirements of mass parts (mass parts required to be converted and calculated for the pretreated materials) in the formula of table 1, and are uniformly stirred in a mixer for later use. The raw materials are carefully protected from moisture in the stirring process, and the materials are uniformly stirred at normal temperature.
b. Preparation process of flame-retardant antistatic polyolefin for underground coal mine
The evenly stirred mixed materials are added into a double-screw extruder, and the preparation process of the flame-retardant antistatic modified polyolefin material is realized through the shearing, blending extrusion, cooling, grain cutting, drying and the like of the double-screw extruder under the conditions of certain extrusion temperature (180 ℃ plus 240 ℃) and extrusion speed (screw rotating speed: 10-40 r/min).
Examples of the invention
The specific formulations of examples 1-6 and the performance indexes of the prepared products are shown in the following table
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A flame-retardant antistatic polyolefin comprises the following components in percentage by weight:
0 to 85 percent of polyethylene
0 to 75 percent of polypropylene
POE 2％～10％
8 to 10 percent of silicon-boron-phosphorus composite flame retardant
1 to 6 percent of composite antistatic agent
0.2 to 1 percent of lubricant
The other 0.2%.
2. Flame retardant antistatic polyolefin according to claim 1 characterized in that the components comprise at least one or both of polyethylene or polypropylene.
3. The flame-retardant antistatic polyolefin as claimed in claim 1 or 2, wherein the silicon-boron-phosphorus composite flame retardant comprises one or more of POSS, zinc borate and red phosphorus.
4. The flame-retardant antistatic polyolefin as claimed in claim 3, wherein the silicon-boron-phosphorus-based composite flame retardant comprises the following components by weight:
POSS 0～2％
0 to 8 percent of zinc borate
0-10% of red phosphorus.
5. The flame-retardant antistatic polyolefin as claimed in claim 1 or 2, wherein the composite antistatic agent comprises one or more of graphene, carbon nanotubes and carbon black.
6. Flame-retardant antistatic polyolefin according to claim 5, characterized in that the composite antistatic agent comprises the following components by weight:
0 to 6 percent of graphene
0 to 6 percent of carbon nano tube
0-6% of carbon black.
7. A process for the preparation of a flame-retardant, antistatic polyolefin according to any of claims 1 to 6, comprising the following steps:
1) pretreating each component of the flame-retardant antistatic polyolefin;
2) pre-blending of polyethylene/POE or polypropylene/POE: mixing the pretreated polyethylene or polypropylene with POE, and then performing pre-blending treatment in a plastic extruder to uniformly mix the POE with the polyethylene or polypropylene;
3) the components are mixed and stirred according to the proportion, added into a plastic extruder, and subjected to blending extrusion, granulation and drying to obtain the flame-retardant antistatic modified polyolefin.
8. The method of claim 7, wherein the pre-treating comprises drying the individual components; and/or the drying of the polyethylene, polypropylene and POE comprises vacuum drying, preferably comprises vacuum drying at a temperature of 70-80 ℃ for 3-4 hours.
9. The method of claim 7, wherein the step 3) plastic extruder comprises a twin screw extruder; preferably, the extrusion temperature of the double-screw extruder is 180 ℃ and 240 ℃, and the extrusion speed is 10-40 r/min.
10. Use of the flame retardant antistatic polyolefin according to any one of claims 1 to 6 in underground coal mine pipes or lines.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011353041.0A CN112500625A (en) | 2020-11-26 | 2020-11-26 | Flame-retardant antistatic polyolefin for underground coal mine, and preparation method and application thereof |
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| CN202011353041.0A CN112500625A (en) | 2020-11-26 | 2020-11-26 | Flame-retardant antistatic polyolefin for underground coal mine, and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340717A (en) * | 2022-08-19 | 2022-11-15 | 神华科技发展有限责任公司 | Natural-color polyolefin material for underground coal mine and preparation method thereof |
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| WO2017083996A1 (en) * | 2015-11-16 | 2017-05-26 | 陈达兵 | Flame resistant antistatic material |
| CN107805335A (en) * | 2017-11-16 | 2018-03-16 | 李君� | A kind of Antimicrobial preservative degredation plastic and preparation method thereof |
| CN109705401A (en) * | 2018-12-11 | 2019-05-03 | 苏州鼎烯聚材纳米科技有限公司 | A kind of composite anti-static plastics concentration masterbatch and preparation method thereof |
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2020
- 2020-11-26 CN CN202011353041.0A patent/CN112500625A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304992A (en) * | 2013-06-14 | 2013-09-18 | 慈溪金岛塑化有限公司 | High-glow-wire initiation temperature flame-retardant nylon composition |
| WO2017083996A1 (en) * | 2015-11-16 | 2017-05-26 | 陈达兵 | Flame resistant antistatic material |
| CN107805335A (en) * | 2017-11-16 | 2018-03-16 | 李君� | A kind of Antimicrobial preservative degredation plastic and preparation method thereof |
| CN109705401A (en) * | 2018-12-11 | 2019-05-03 | 苏州鼎烯聚材纳米科技有限公司 | A kind of composite anti-static plastics concentration masterbatch and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340717A (en) * | 2022-08-19 | 2022-11-15 | 神华科技发展有限责任公司 | Natural-color polyolefin material for underground coal mine and preparation method thereof |
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