CN110818997A - Flame-retardant polyethylene cable material and preparation method thereof - Google Patents
Flame-retardant polyethylene cable material and preparation method thereof Download PDFInfo
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- CN110818997A CN110818997A CN201911267013.4A CN201911267013A CN110818997A CN 110818997 A CN110818997 A CN 110818997A CN 201911267013 A CN201911267013 A CN 201911267013A CN 110818997 A CN110818997 A CN 110818997A
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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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
Abstract
The invention discloses a flame-retardant polyethylene cable material which is prepared from the following raw materials in parts by weight: 50-70 parts of polyethylene resin, 10-30 parts of propylene-ethylene copolymer, 10-20 parts of compatilizer, 5-6 parts of carbon black master batch, 50-60 parts of flame retardant, 10-25 parts of flame retardant synergist, 5-10 parts of shell forming agent, 0.8-1.5 parts of antioxidant and 1-2 parts of lubricant, and provides a preparation method of the material. Compared with the traditional flame-retardant polyethylene cable material, the invention has the advantages that the addition of the shell forming agent can enable the surface of the cable to form a shell during combustion, the flame-retardant property of the polyethylene is greatly improved, the addition amount of the flame retardant is reduced, the prepared flame-retardant polyethylene has good mechanical property, the extrusion surface is smooth, and the extrusion speed is higher.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a flame-retardant polyethylene cable material capable of being burnt into carbon.
Background
Polyethylene (PE) has excellent electrical insulation, low temperature resistance, easy processing and molding, excellent chemical stability and dielectric constant, and is widely used in the fields of films, daily necessities, pipes, and electric wires and cables. With the improvement of the requirements of people on the performance of plastic products, the research and application of flame-retardant polyethylene are rapidly developed. In the early research on flame-retardant polyethylene, halogen flame retardants are mostly adopted, and have the advantages of good flame-retardant effect and low addition amount, but toxic and corrosive hydrogen halide gas is released during combustion, so that secondary disasters are easily caused. With the improvement of fire-fighting and safety environmental protection concepts, research on low-smoke and low-toxicity flame-retardant polyethylene is started at home and abroad, so that the halogen-free flame retardant is paid attention again, such as common red phosphorus and phosphorus nitrogen series intumescent flame retardants, inorganic hydroxide flame retardants and the like.
At present, the research on the domestic and foreign halogen-free flame-retardant polyethylene generally adopts Al (OH)3、Mg(OH)2As flame retardants, Al (OH)3、Mg(OH)2The flame retardant is a currently recognized flame retardant with three functions of flame retardance, smoke suppression and filling, and has low price and wide source. However, a large amount of filling is required, which results in a decrease in the mechanical properties of the cable material and poor processability. From the current research situation of the flame-retardant polyethylene at home and abroad, Al (OH) is singly used3、Mg(OH)2The flame retardant property and the mechanical property of the flame retardant coating are difficult to meet the requirements of products at the same time, so Al (OH) must be added3、Mg(OH)2A synergistic flame retardant with a synergistic flame retardant effect. The common flame retardant synergist is red phosphorus and phosphorus-nitrogen compound, but the effect is not obvious in the using process.
Therefore, the problem to be solved by those skilled in the art is how to provide a flame retardant polyethylene cable material capable of burning carbon, which has flame retardant, mechanical properties and processability.
Disclosure of Invention
In view of the above, the invention provides a flame-retardant polyethylene cable material capable of being burned into carbon and a preparation method thereof, and effectively solves the problem that the cable material in the prior art cannot have flame retardance, mechanical properties and processability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant polyethylene cable material comprises the following components in parts by weight:
preferably, in the flame-retardant polyethylene cable material, the polyethylene resin is linear low-density polyethylene, the melt index is (2-5) g/10min at 190 ℃ and 2.16kg, the melting point is 120-130 ℃, and the tensile breaking strength is more than or equal to 30 MPa.
The beneficial effects of the above technical scheme are: the limitation of the polyethylene resin can ensure good processing flow property and mechanical property of the material.
Preferably, in the flame-retardant polyethylene cable material, the propylene-ethylene copolymer is polymerized by taking propylene as a main chain and ethylene as a branch chain, the melt index at 190 ℃ and 2.16kg is (5-10) g/10min, and the tensile breaking strength is not less than 12 MPa.
The beneficial effects of the above technical scheme are: the limitation of the propylene-ethylene copolymer can ensure excellent mechanical properties of the material.
Preferably, in the flame-retardant polyethylene cable material, the compatilizer is propylene-ethylene copolymer grafted maleic anhydride, wherein the melt index of the propylene-ethylene copolymer at 190 ℃ and 2.16kg is (2-5) g/10min, and the tensile breaking elongation is more than or equal to 800%.
The beneficial effects of the above technical scheme are: the compatibility between the flame retardant and the resin is improved, and the cracking resistance of the material is improved.
Preferably, in one of the flame retardant polyethylene cable materials, the carbon black master batch comprises 40-50% of carbon black and 50-60% of a carrier by weight percent;
the carrier is polyethylene resin, the melt index is (18-25) g/10min at 190 ℃ and 2.16kg, the melting point is 120-130 ℃, and the tensile breaking strength is more than or equal to 12 Mpa.
The beneficial effects of the above technical scheme are: the carbon black master batch prepared from the carbon black and the carrier in parts by weight has good carbon black dispersibility and is not agglomerated.
Preferably, in the above flame-retardant polyethylene cable material, the flame retardant is an inorganic flame retardant, and the inorganic flame retardant is any one of magnesium hydroxide or aluminum hydroxide or a mixture of two of the magnesium hydroxide and the aluminum hydroxide.
The beneficial effects of the above technical scheme are: the addition of the inorganic flame retardant can ensure that the material has basic flame retardant performance.
Preferably, in the flame-retardant polyethylene cable material, the flame-retardant synergist is any one or a mixture of several of red phosphorus, ammonium polyphosphate and melamine cyanurate.
The beneficial effects of the above technical scheme are: the flame-retardant synergist can improve the self-extinguishing performance, the shell forming effect and the flame-retardant effect of the material.
Preferably, in the flame-retardant polyethylene cable material, the shell-forming agent is any one or a mixture of two of modified nano montmorillonite and white carbon black.
The beneficial effects of the above technical scheme are: the shell forming agent can ensure that the material has basic shell forming performance.
Preferably, in the flame-retardant polyethylene cable material, the antioxidant is prepared from the following components in a weight ratio of 1: 1: (0.2-0.5) dilauryl thiodipropionate, polyhydric hindered phenol and tris (2, 4-di-tert-butyl) phenyl phosphite.
The beneficial effects of the above technical scheme are: the thermal aging performance of the material is ensured on the premise of ensuring that the antioxidant is not precipitated.
Preferably, in one of the above flame retardant polyethylene cable materials, the lubricant is selected from one or a combination of calcium stearate and polyethylene wax.
The beneficial effects of the above technical scheme are: the addition of a lubricant can improve the extrusion speed and surface gloss of the material.
The invention also discloses a preparation method of the flame-retardant polyethylene cable material, which comprises the following steps:
(1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing to obtain a mixture, wherein the mixing temperature is 55-75 ℃;
(2) putting the mixture obtained in the step 1) into a double-screw extruder to extrude, granulate and dry to obtain the composite material.
Preferably, in the preparation method of the flame retardant polyethylene cable material, in the step (1), the rotating speed of the high-speed mixer is 200rpm to 1500rpm, and the mixing time is 8min to 10 min. Further preferably, the rotation speed of the high-speed mixing is 600rpm to 1200 rpm.
The beneficial effects of the above technical scheme are: can ensure that various materials are dispersed more uniformly.
Preferably, in the preparation method of the flame-retardant polyethylene cable material, the twin-screw extruder in the step (2) is a feeding, extruding, granulating and mixing type twin-screw extruding granulator, and the extruding temperature of the twin-screw extruder is 145-190 ℃;
the drying temperature is 70-85 ℃, and the drying time is 1-2 hours.
The beneficial effects of the above technical scheme are: so that the material is dried more thoroughly and is not caked.
Preferably, in the above preparation method of the flame retardant polyethylene cable material, the temperature of the twin-screw extruder is set as follows: the charging section is 145-150 ℃, the mixing section is 155-175 ℃, the extrusion granulation section is 180-190 ℃, and the head part is 170-180 ℃.
The beneficial effects of the above technical scheme are: the material extruded by stages has good plasticization and stable performance.
And an application of the flame-retardant polyethylene cable material in a control cable, a medium-low voltage cable and an extra-high voltage cable protective material.
According to the technical scheme, compared with the prior art, the invention discloses the flame-retardant polyethylene cable material and the preparation method thereof, the addition of the shell forming agent can enable the surface of the cable to form a shell during combustion, the flame retardant property of the polyethylene is greatly improved, the addition amount of the flame retardant is reduced, the prepared flame-retardant polyethylene has good mechanical property, the extrusion surface is smooth, and the extrusion speed is higher; the prepared cable material has good flame retardant property, and also has good mechanical property and processability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The flame-retardant polyethylene cable material capable of being burnt into carbon comprises the following raw material components in parts by weight:
wherein the polyethylene resin is linear low density polyethylene, the melt index is 2g/10min at 190 deg.C and 2.16kg, the melting point is 130 deg.C, and the tensile breaking strength is not less than 30 Mpa.
The propylene-ethylene copolymer takes propylene as a main chain and ethylene as a branched chain, the melt index is 6g/10min at 190 ℃ and 2.16kg, and the tensile breaking strength is more than or equal to 20 Mpa.
The polyethylene resin carrier is polyethylene resin, and has a melt index of 20g/10min at 190 deg.C and 2.16kg, a melting point of 126 deg.C, and a tensile breaking strength of 12MPa or more.
The preparation method of the flame-retardant polyethylene cable material for the cable comprises the following steps:
1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing at the mixing temperature of 55 ℃ for 10min at the rotating speed of 800 rpm;
2) putting the material obtained in the step 1) into a feeding extrusion granulation mixing type double-screw extrusion granulator, extruding granulation and drying, wherein the feeding section is 150 ℃, the mixing section is 165 ℃, the extrusion granulation section is 180 ℃, the machine head section is 180 ℃, the drying temperature is 70 ℃, and the drying time is 2 hours.
Example 2
The flame-retardant polyethylene cable material capable of being burnt into carbon comprises the following raw material components in parts by weight:
wherein the polyethylene resin is linear low density polyethylene, the melt index is 5g/10min at 190 deg.C and 2.16kg, the melting point is 125 deg.C, and the tensile breaking strength is not less than 30 Mpa.
The propylene-ethylene copolymer takes propylene as a main chain and ethylene as a branched chain, the melt index is 8g/10min at 190 ℃ and 2.16kg, and the tensile breaking strength is more than or equal to 12 MPa.
The polyethylene resin carrier is polyethylene resin, and has a melt index of 25g/10min at 190 deg.C and 2.16kg, a melting point of 126 deg.C, and a tensile breaking strength of 12MPa or more.
The preparation method of the flame-retardant polyethylene cable material for the cable comprises the following steps:
1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing at the mixing temperature of 55 ℃ for 8min at the rotating speed of 1000 rpm;
2) putting the material obtained in the step 1) into a feeding, extruding, granulating and mixing type double-screw extruding granulator, extruding, granulating and drying, wherein the feeding section is 145 ℃, the mixing section is 155 ℃, the extruding and granulating section is 180 ℃, the machine head section is 170 ℃, the drying temperature is 80 ℃, and the drying time is 2 hours.
Example 3
The flame-retardant polyethylene cable material capable of being burnt into carbon comprises the following raw material components in parts by weight:
wherein the polyethylene resin is linear low density polyethylene, the melt index is 5g/10min at 190 deg.C and 2.16kg, the melting point is 128 deg.C, and the tensile breaking strength is not less than 30 Mpa.
The propylene-ethylene copolymer takes propylene as a main chain and ethylene as a branched chain, the melt index is 6g/10min at 190 ℃ and 2.16kg, and the tensile breaking strength is more than or equal to 12 MPa.
The polyethylene resin carrier is polyethylene resin, the melt index is 25g/10min at 190 ℃ and 2.16kg, the melting point is 123 ℃, and the tensile breaking strength is more than or equal to 12 Mpa.
The preparation method of the flame-retardant polyethylene cable material for the cable comprises the following steps:
1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing at the mixing temperature of 55 ℃ for 10min at the rotating speed of 1200 rpm;
2) putting the material obtained in the step 1) into a feeding, extruding, granulating and mixing type double-screw extruding granulator, extruding, granulating and drying, wherein the feeding section is 150 ℃, the mixing section is 160 ℃, the extruding and granulating section is 190 ℃, the machine head section is 170 ℃, the drying temperature is 85 ℃, and the drying time is 1.5 hours.
Example 4
The flame-retardant polyethylene cable material for the cable comprises the following raw material components in parts by weight:
wherein the polyethylene resin is linear low density polyethylene, the melt index is 5g/10min at 190 deg.C and 2.16kg, the melting point is 122 deg.C, and the tensile breaking strength is not less than 30 Mpa.
The propylene-ethylene copolymer takes propylene as a main chain and ethylene as a branched chain, the melt index is 9g/10min at 190 ℃ and 2.16kg, and the tensile breaking strength is more than or equal to 12 MPa.
The polyethylene resin carrier is polyethylene resin, and has a melt index of 18g/10min at 190 deg.C and 2.16kg, a melting point of 126 deg.C, and a tensile breaking strength of 12MPa or more.
The preparation method of the flame-retardant polyethylene cable material for the cable comprises the following steps:
1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing at the mixing temperature of 55 ℃ for 10min at the rotating speed of 1200 rpm;
2) putting the material obtained in the step 1) into a feeding extrusion granulation mixing type double-screw extrusion granulator, extruding granulation and drying, wherein the feeding section is 150 ℃, the mixing section is 170 ℃, the extrusion granulation section is 190 ℃, the machine head section is 180 ℃, the drying temperature is 75 ℃, and the drying time is 2 hours.
The cable materials prepared in examples 1 to 4 were subjected to performance tests according to the relevant national standards, respectively, and the relevant performance results are shown in table 1.
TABLE 1
As can be seen from Table 1, the cable materials prepared in the above examples pass through the bundled type A combustion test, the sheath on the cable surface does not fall off after being burned, and the extrusion speed is over 30m/min, which is much higher than that of the products on the current market.
In conclusion, the invention effectively overcomes various defects in the prior art and has higher industrial utilization value.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The flame-retardant polyethylene cable material is characterized by comprising the following components in parts by weight:
2. the flame-retardant polyethylene cable material according to claim 1, wherein the polyethylene resin is linear low density polyethylene, the melt index at 190 ℃ and 2.16kg is (2-5) g/10min, the melting point is 120-130 ℃, and the tensile breaking strength is not less than 30 Mpa;
the propylene-ethylene copolymer is polymerized by taking propylene as a main chain and ethylene as a branched chain, the melt index is (5-10) g/10min at 190 ℃ and 2.16kg, and the tensile breaking strength is more than or equal to 12 MPa.
3. The flame-retardant polyethylene cable material as claimed in claim 1, wherein the compatibilizer is a propylene-ethylene copolymer grafted maleic anhydride, wherein the propylene-ethylene copolymer has a melt index of (2-5) g/10min at 190 ℃ and 2.16kg, and a tensile elongation at break of not less than 800%;
the antioxidant is prepared from the following components in percentage by weight of 1: 1: (0.2-0.5) dilauryl thiodipropionate, polyhydric hindered phenol and tris (2, 4-di-tert-butyl) phenyl phosphite.
4. The flame retardant polyethylene cable material according to claim 1, wherein the carbon black masterbatch comprises, in weight percent, 50-60% of carbon black and 40-50% of a carrier;
wherein the carrier is polyethylene resin, the melt index is (18-25) g/10min at 190 ℃ and 2.16kg, the melting point is 120-130 ℃, and the tensile breaking strength is more than or equal to 12 MPa.
5. The flame-retardant polyethylene cable material according to claim 1, wherein the flame retardant is an inorganic flame retardant, and the inorganic flame retardant is any one or a mixture of two of magnesium hydroxide or aluminum hydroxide;
the flame-retardant synergist is any one or a mixture of more of red phosphorus, ammonium polyphosphate and melamine cyanurate;
the shell forming agent is any one or a mixture of two of modified nano montmorillonite and white carbon black;
the lubricant is selected from one or a combination of calcium stearate and polyethylene wax.
6. A method for preparing the flame-retardant polyethylene cable material according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) putting the components into a high-speed mixer according to the proportion, and uniformly mixing to obtain a mixture, wherein the mixing temperature is 55-75 ℃;
(2) putting the mixture obtained in the step 1) into a double-screw extruder to extrude, granulate and dry to obtain the composite material.
7. The preparation method of the flame retardant polyethylene cable material according to claim 6, wherein in the step (1), the rotation speed of the high speed mixer is 200rpm to 1500rpm, and the mixing time is 8min to 10 min.
8. The preparation method of the flame-retardant polyethylene cable material according to claim 6, wherein the twin-screw extruder in the step (2) is a feeding, extruding, granulating and mixing type twin-screw extruding granulator, and the extruding temperature of the twin-screw extruder is 145-190 ℃;
the drying temperature is 70-85 ℃, and the drying time is 1-2 hours.
9. The method for preparing the flame-retardant polyethylene cable material according to claim 8, wherein the temperature of the twin-screw extruder is set as follows: the charging section is 145-150 ℃, the mixing section is 155-175 ℃, the extrusion granulation section is 180-190 ℃, and the head part is 170-180 ℃.
10. Use of the flame retardant polyethylene cable material according to any one of claims 1 to 5 in protective materials for control cables, medium and low voltage cables and extra high voltage cables.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911267013.4A CN110818997A (en) | 2019-12-11 | 2019-12-11 | Flame-retardant polyethylene cable material and preparation method thereof |
| PCT/CN2020/113247 WO2021114752A1 (en) | 2019-12-11 | 2020-09-03 | Flame-retardant polyethylene cable material and preparation method therefor |
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| CN201911267013.4A CN110818997A (en) | 2019-12-11 | 2019-12-11 | Flame-retardant polyethylene cable material and preparation method thereof |
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| CN116199959A (en) * | 2022-12-02 | 2023-06-02 | 中广核拓普（湖北）新材料有限公司 | Flame-retardant polyethylene sheath material and preparation method thereof |
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| CN112210161A (en) * | 2020-10-28 | 2021-01-12 | 上海凯波电缆特材股份有限公司 | Halogen-free oxygen-barrier layer cable material and preparation method and application thereof |
| CN112210161B (en) * | 2020-10-28 | 2022-12-27 | 上海凯波电缆特材股份有限公司 | Halogen-free oxygen-barrier layer cable material and preparation method and application thereof |
| CN116199959A (en) * | 2022-12-02 | 2023-06-02 | 中广核拓普（湖北）新材料有限公司 | Flame-retardant polyethylene sheath material and preparation method thereof |
| CN115926289A (en) * | 2022-12-13 | 2023-04-07 | 上海凯波电缆特材股份有限公司 | Anti-wrinkle flame-retardant polyethylene sheath material for smooth aluminum high-voltage cable and preparation method thereof |
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| WO2021114752A1 (en) | 2021-06-17 |
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