CN111621085A - B1-grade special high-flame-retardant low-smoke halogen-free cable material and preparation method thereof - Google Patents
B1-grade special high-flame-retardant low-smoke halogen-free cable material and preparation method thereof Download PDFInfo
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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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08L2201/22—Halogen free composition
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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
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- 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
Abstract
The invention discloses a B1-grade special high-flame-retardant low-smoke halogen-free cable material and a preparation method thereof, and relates to the technical field of wires and cables. The technical key points are as follows: a B1-grade special high-flame-retardant low-smoke halogen-free cable material comprises the following components in parts by weight: linear low density polyethylene: 25-50 parts; ethylene-vinyl acetate copolymer: 50-100 parts; aluminum hydroxide: 100-150 parts; modified nano-silica: 10-25 parts; montmorillonite: 5-10 parts; antioxidant: 1-5 parts; a compatilizer: 5-10 parts; lubricant: 5-10 parts; the preparation method of the modified nano silicon dioxide comprises the following steps: adding the nano silicon dioxide into absolute ethyl alcohol, stirring and dispersing uniformly, then adding a silane coupling agent, heating to react for 3-4h, and drying and grinding the nano silicon dioxide after the reaction is finished to obtain the modified nano silicon dioxide. The low-smoke halogen-free cable material obtained by the invention has the advantages of reaching B1-grade flame retardant standard, high mechanical property and excellent processing property.
Description
Technical Field
The invention relates to the technical field of wires and cables, in particular to a B1-grade special high-flame-retardant low-smoke halogen-free cable material and a preparation method thereof.
Background
In the electrical fire in China, most of the electrical fire is caused by aging and overload use of the electric wire and the electric wire, and meanwhile, combustible insulating and sheath materials in the electric wire and the electric wire are ignited in the fire, so that the fire accident is further expanded. The toxic gases emitted by the burning of the wire and cable insulation and sheathing materials can cause a great deal of casualties and prevent fire fighting by fire fighters. The main characteristics of low-smoke halogen-free flame retardance are that all materials do not contain halogen, and the smoke quantity released during combustion is small. The concentration of the gas which can cause death of people and is emitted by the polyvinyl chloride material in 30min is 15 times of the concentration of the lethal gas, the concentration of the gas which can cause death of people and is emitted by the halogen-free polyolefin is only 5 percent of that of the polyvinyl chloride material, and when the light transmittance is 70 percent, the object image distinguishing capability of naked eyes of people is only about 5 m. The light transmittance of the smoke emitted by the burning of the polyvinyl chloride is below 15 percent, namely the naked visual distance of people in the smoke with the concentration is only about 2 m. Therefore, the popularization and the use of the flame-retardant cable and the optical cable have important significance for the fireproof safety of buildings.
Based on the background, the flame retardant and fire resistant performance of cables in various large cable plants is required, but the problems of the combustion smoke generation amount and the heat generation amount in the aspect of the low-smoke halogen-free insulated cable material still need to be solved. Therefore, a new solution is needed to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a B1-grade special high-flame-retardant low-smoke halogen-free cable material which has the advantages of reaching B1-grade flame-retardant standard, high mechanical property and excellent processing property.
The invention aims to provide a preparation method of a B1-grade special high-flame-retardant low-smoke halogen-free cable material, which has the advantages of simple preparation method and suitability for large-scale production.
In order to achieve the first purpose, the invention provides the following technical scheme:
a B1-grade special high-flame-retardant low-smoke halogen-free cable material comprises the following components in parts by weight:
linear low density polyethylene: 25-50 parts;
ethylene-vinyl acetate copolymer: 50-100 parts;
aluminum hydroxide: 100-150 parts;
modified nano-silica: 10-25 parts;
montmorillonite: 5-10 parts;
antioxidant: 1-5 parts;
a compatilizer: 5-10 parts;
lubricant: 5-10 parts;
the preparation method of the modified nano silicon dioxide comprises the following steps: adding the nano silicon dioxide into absolute ethyl alcohol, stirring and dispersing uniformly, then adding a silane coupling agent, heating to react for 3-4h, and drying and grinding the nano silicon dioxide after the reaction is finished to obtain the modified nano silicon dioxide.
By adopting the technical scheme, the nano silicon dioxide is not an effective flame retardant, flame retardance is realized by only depending on the extremely small using amount of the nano silicon dioxide, and the practical requirement is difficult to achieve. Montmorillonite is a layered mineral composed of particles and fine hydrous aluminosilicate, also called as montmorillonite and microcrystalline kaolinite, and is the main component of bentonite formed by the alteration of igneous rocks such as volcanic concretion rocks and the like in an alkaline environment. By adding a certain amount of modified nano silicon dioxide and montmorillonite to replace a part of aluminum hydroxide, the flame retardant effect of the cable material is improved, and the cable material has high physical-mechanical properties, meets the use requirements and has good processability.
More preferably, the linear low density polyethylene has a melt index of 0.5 to 20 g/min.
By adopting the technical scheme, the low-density polyethylene with the melt index can ensure that the product has better heat resistance and mechanical property.
More preferably, the ethylene-vinyl acetate copolymer has a melt index of 2 to 10g/10min and a vinyl acetate monomer content of 18 to 33 wt%.
By adopting the technical scheme, the mechanical properties such as strength and the like of the product can be improved, the heat resistance of the product is improved, and cracking is avoided.
More preferably, the antioxidant is the combination of dilauryl thiodipropionate and tris (2, 4-di-tert-butyl-4-hydroxyphenyl) phosphite ester according to the weight ratio of 1 (1-1.5).
By adopting the technical scheme, the antioxidant can inhibit or prolong the oxidation reaction of the polymer, and the principle is that the antioxidant can eliminate peroxide free radicals generated in the oxidation reaction, reduce alkoxy or hydroxyl free radicals and decompose peroxides, so that the oxidation chain reaction is stopped, and the aim of preventing the polymer from being oxidized is fulfilled.
More preferably, the compatibilizer is maleic anhydride grafted polyethylene.
By adopting the technical scheme, the addition of the maleic anhydride grafted polyethylene can improve the compatibility among resins and indirectly increase the macroscopic properties of materials such as mechanics and the like.
Further preferably, the lubricant is zinc stearate, silicone oil or PE wax.
By adopting the technical scheme, the lubricant can reduce the friction between raw materials and between the raw materials and the surface of processing equipment, thereby reducing the flow resistance of the melt, reducing the viscosity of the melt, improving the fluidity of the melt, avoiding the adhesion of the melt and the equipment, improving the smoothness of the surface of a product and the like.
More preferably, the particle size of the aluminum hydroxide is 80-100nm, and the surface of the aluminum hydroxide is treated by a silane coupling agent.
By adopting the technical scheme, the silane coupling agent is adopted to modify the surface of the aluminum hydroxide, so that the aluminum hydroxide has good affinity with polyolefin, the dispersion of aluminum hydroxide particles in raw material components is solved under the condition of ensuring the flame retardant property, the interface action between the aluminum hydroxide particles and the polyolefin is enhanced, and the mechanical property of the cable material is improved.
In order to achieve the second purpose, the invention provides the following technical scheme:
a preparation method of a B1-grade special high-flame-retardant low-smoke halogen-free cable material comprises the following steps:
s1, adding linear low-density polyethylene, ethylene-vinyl acetate copolymer, aluminum hydroxide, modified nano-silica and montmorillonite into a high-speed mixer, and stirring at high speed for 3-5min to obtain a mixture A;
s2, adding an antioxidant, a compatilizer and a lubricant into the mixture A, and stirring and mixing at a high speed for 3-5min to obtain a mixture B;
s3, kneading the mixture B in a kneading machine, and then extruding and granulating by a double-screw extruder, wherein the discharge temperature of the kneading machine is 140-165 ℃, the kneading time is 12-15min, and the temperature of the double-screw extruder is 110-145 ℃.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, through modification treatment on the nano silicon dioxide, the dispersibility of the nano silicon dioxide in raw material components is improved, and montmorillonite is compounded and used, so that part of aluminum hydroxide is replaced, the flame retardant effect of the cable material is improved, and the cable material has higher physical-mechanical properties, meets the use requirements and has good processing performance;
(2) the aluminum hydroxide adopted by the invention is in a nanometer level, and the surface of the aluminum hydroxide is modified by the silane coupling agent, so that the aluminum hydroxide has good affinity with polyolefin, the dispersion of aluminum hydroxide particles in raw material components is solved under the condition of ensuring the flame retardant property, the interface action between the aluminum hydroxide particles and the polyolefin is enhanced, and the mechanical property of the cable material is improved.
Drawings
FIG. 1 is a flow chart of a preparation process of a B1-grade special high-flame-retardant low-smoke halogen-free cable material.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
In the invention, the melt index of the linear low-density polyethylene is 0.5-20 g/min; the ethylene-vinyl acetate copolymer has a melt index of 2-10g/10min and a vinyl acetate monomer content of 18-33 wt%.
The silane coupling agent is silane coupling agent KH570, and is purchased from Shanghai Yanghua chemical plants.
The compatibilizer was maleic anhydride grafted polyethylene and was purchased from Nanjing plastitai polymer science and technology, Inc.
Montmorillonite was purchased from Bengtze, Bentoniaceae, Inc., of Nenggumincheng Tianyu.
Other raw material components are all commonly purchased in the market.
Example 1: the B1-grade special high-flame-retardant low-smoke halogen-free cable material comprises the following components in parts by weight as shown in Table 1 and shown in figure 1, and is prepared by the following steps:
s1, adding linear low-density polyethylene, ethylene-vinyl acetate copolymer, aluminum hydroxide, modified nano-silica and montmorillonite into a high-speed mixer, and stirring at the rotating speed of 600rpm for 5min to obtain a mixture A;
s2, adding an antioxidant, a compatilizer and a lubricant into the mixture A, and stirring at the rotating speed of 600rpm for 5min to obtain a mixture B;
s3, kneading the mixture B in a kneading machine, and then extruding and granulating by a double-screw extruder, wherein the discharging temperature of the kneading machine is 165 ℃, the kneading time is 12min, the set temperature of each section of the double-screw is 110 ℃, 120 ℃, 1350 ℃, 135 ℃ and 145 ℃, and the screw rotating speed in the extrusion process is 200 rpm.
In this embodiment, the preparation method of the modified nano-silica comprises: adding 10 parts of nano silicon dioxide with the average particle size of 25nm into 100 parts of absolute ethyl alcohol, adding 50 parts of silane coupling agent, heating to 50 ℃ for reaction for 3 hours, drying the nano silicon dioxide at the temperature of 110 ℃ after the reaction is finished, and then grinding to obtain the modified nano silicon dioxide.
In this example, the particle size of aluminum hydroxide was 80nm and the surface was treated with a silane coupling agent.
The antioxidant is prepared by combining dilauryl thiodipropionate and tris (2, 4-di-tert-butyl-4-hydroxyphenyl) phosphite ester according to the weight ratio of 1:1.
The lubricant is zinc stearate.
Examples 2 to 6: a B1 grade special high flame-retardant low-smoke halogen-free cable material is different from the embodiment 1 in that the components and the corresponding parts by weight are shown in Table 1.
TABLE 1 Components and parts by weight of examples 1-6
Example 7: a B1-grade special high-flame-retardant low-smoke halogen-free cable material is different from that of example 1 in that the cable material is prepared by the following steps:
s1, adding linear low-density polyethylene, ethylene-vinyl acetate copolymer, aluminum hydroxide, modified nano-silica and montmorillonite into a high-speed mixer, and stirring at the rotating speed of 800rpm for 3min to obtain a mixture A;
s2, adding an antioxidant, a compatilizer and a lubricant into the mixture A, and stirring at the rotating speed of 800rpm for 3min to obtain a mixture B;
s3, kneading the mixture B in a kneading machine, and then extruding and granulating by a double-screw extruder, wherein the discharging temperature of the kneading machine is 140 ℃, the kneading time is 15min, the set temperature of each section of the double-screw is 110 ℃, 120 ℃, 1350 ℃, 135 ℃ and 145 ℃, and the screw rotating speed in the extrusion process is 200 rpm.
Example 8: a B1 grade special high flame-retardant low-smoke halogen-free cable material is different from the embodiment 1 in that:
in this example, the particle size of aluminum hydroxide was 90nm and the surface was treated with a silane coupling agent.
The antioxidant is prepared by combining dilauryl thiodipropionate and tris (2, 4-di-tert-butyl-4-hydroxyphenyl) phosphite ester according to the weight ratio of 1: 1.3.
The lubricant is silicone oil.
Example 9: a B1 grade special high flame-retardant low-smoke halogen-free cable material is different from the embodiment 1 in that:
in this example, the particle size of aluminum hydroxide was 100nm and the surface was treated with a silane coupling agent.
The antioxidant is prepared by combining dilauryl thiodipropionate and tris (2, 4-di-tert-butyl-4-hydroxyphenyl) phosphite ester according to the weight ratio of 1: 1.5.
The lubricant is PE wax.
Comparative example 1: a cable material different from example 1 in that the nano silica has an average particle size of 25nm and is not modified.
Comparative example 2: a cable material, which is different from the cable material in example 1 in that modified nano-silica is not added to the cable material.
Comparative example 3: a cable material which differs from example 1 in that montmorillonite is not added to the cable material.
Comparative example 4: a cable material different from example 1 in that aluminum hydroxide had an average particle diameter of 80nm and had not been subjected to surface modification treatment with a silane coupling agent.
Comparative example 5: a cable material, which is different from that of example 1 in that aluminum hydroxide is not added to the cable material.
Performance testing
The cable materials obtained in examples 1 to 9 and comparative examples 1 to 5 were subjected to performance tests, and the test results are shown in Table 2.
As can be seen from the test data in Table 2, the cable material of the present invention has mechanical strength, thermal aging resistance and flame retardancy all completely meet the national standards. Comparative examples 2, 3 and 5 were the worst comparative example, because modified nano silica, montmorillonite and aluminum hydroxide were not added, respectively, and the combustion tests were all passed, and the oxygen index was lower, and other mechanical properties were also lower. In conclusion, the modified nano silicon dioxide compounded with a small amount of montmorillonite is adopted to replace part of the aluminum hydroxide flame retardant, so that the obtained cable material still has good flame retardance and improved mechanical properties.
Table 2 results of performance testing
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A B1-grade special high-flame-retardant low-smoke halogen-free cable material is characterized by comprising the following components in parts by weight:
linear low density polyethylene: 25-50 parts;
ethylene-vinyl acetate copolymer: 50-100 parts;
aluminum hydroxide: 100-150 parts;
modified nano-silica: 10-25 parts;
montmorillonite: 5-10 parts;
antioxidant: 1-5 parts;
a compatilizer: 5-10 parts;
lubricant: 5-10 parts;
the preparation method of the modified nano silicon dioxide comprises the following steps: adding the nano silicon dioxide into absolute ethyl alcohol, stirring and dispersing uniformly, then adding a silane coupling agent, heating to react for 3-4h, and drying and grinding the nano silicon dioxide after the reaction is finished to obtain the modified nano silicon dioxide.
2. The B1 grade special use high flame retardant low smoke zero halogen cable material according to claim 1, wherein the linear low density polyethylene has a melt index of 0.5-20 g/min.
3. The B1 grade special use high flame retardant low smoke zero halogen cable material according to claim 1, wherein the ethylene-vinyl acetate copolymer has a melt index of 2-10g/10min, and the ethylene-vinyl acetate copolymer has a vinyl acetate monomer content of 18-33 wt%.
4. The B1-grade special high-flame-retardant low-smoke halogen-free cable material as claimed in claim 1, wherein the antioxidant is a combination of dilauryl thiodipropionate and tris (2, 4-di-tert-butyl-4-hydroxyphenyl) phosphite in a weight ratio of 1 (1-1.5).
5. The B1 grade special use high flame retardant low smoke zero halogen cable material according to claim 1, wherein the compatibilizer is maleic anhydride grafted polyethylene.
6. The B1 grade special use high flame retardant low smoke zero halogen cable material as claimed in claim 1, wherein the lubricant is zinc stearate, silicone oil or PE wax.
7. The B1 grade special use high flame retardant low smoke zero halogen cable material according to claim 1, wherein the particle size of the aluminum hydroxide is 80-100nm, and the surface is treated with a silane coupling agent.
8. The preparation method of the B1-grade special high-flame-retardant low-smoke halogen-free cable material according to any one of claims 1-7, characterized by comprising the following steps:
s1, adding linear low-density polyethylene, ethylene-vinyl acetate copolymer, aluminum hydroxide, modified nano-silica and montmorillonite into a high-speed mixer, and stirring at high speed for 3-5min to obtain a mixture A;
s2, adding an antioxidant, a compatilizer and a lubricant into the mixture A, and stirring and mixing at a high speed for 3-5min to obtain a mixture B;
s3, kneading the mixture B in a kneading machine, and then extruding and granulating by a double-screw extruder, wherein the discharge temperature of the kneading machine is 140-165 ℃, the kneading time is 12-15min, and the temperature of the double-screw extruder is 110-145 ℃.
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| CN112662042A (en) * | 2020-12-21 | 2021-04-16 | 常州市沃科科技有限公司 | B1-grade low-smoke halogen-free cable sheath material and preparation method thereof |
| CN112679837A (en) * | 2020-12-21 | 2021-04-20 | 常州市沃科科技有限公司 | B1-grade low-smoke halogen-free cable oxygen insulation material and preparation method thereof |
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| CN113527799A (en) * | 2021-06-21 | 2021-10-22 | 杭州永通新材料有限公司 | Special halogen-free low-smoke oxygen-insulating layer material for B1-grade cable |
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| CN112662042A (en) * | 2020-12-21 | 2021-04-16 | 常州市沃科科技有限公司 | B1-grade low-smoke halogen-free cable sheath material and preparation method thereof |
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Application publication date: 20200904 |