CN110845783A - Low-smoke halogen-free flame-retardant polyolefin wire material for B1-grade wire distribution and preparation method thereof - Google Patents
Low-smoke halogen-free flame-retardant polyolefin wire material for B1-grade wire distribution 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
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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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Abstract
The invention discloses a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight: 10-30 parts of ethylene-vinyl acetate copolymer; 10-20 parts of linear low-density polyethylene; 5-10 parts of a compatilizer; 5-6 parts of an inorganic flame retardant; 2-5 parts of a shell forming agent; 2-5 parts of a smoke suppressant; 0.1-0.5 part of antioxidant; 0.5-1 part of lubricant; the inorganic flame retardant comprises first magnesium hydroxide subjected to surface treatment by adopting an anionic surfactant and second magnesium hydroxide formed by performing surface activation on magnesium hydroxide by adopting a titanate coupling agent. The invention not only has no harmful substance, but also can absorb a great deal of harmful gas and smoke generated by burning rubber, plastic and the like while the decomposed product is flame-retardant, and the active magnesium oxide continuously absorbs the incompletely burnt melting residue, thereby eliminating smoke and preventing molten drops while stopping burning quickly; therefore, the polyolefin wire material has good flame retardant property, small combustion smoke quantity and small pollution to human bodies and air in the environment of fire.
Description
Technical Field
The invention relates to the technical field of wire materials, in particular to a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire and a preparation method thereof.
Background
With the scientific progress and the improvement of the living standard of people, the electrical and our life relationship is more and more close, and the electric wire and the electric cable are one of the products which must be matched when using electrical products, and play the roles of transmitting electric power, transmitting information and realizing electromagnetic energy conversion. The wire and cable for civil buildings are mainly divided into two categories of cables and wires, wherein the cables are of a multi-core structure, the structural design is complex, and the structure can be used for finishing the combustion grade specified by the standard. The wire is typically of single core construction, the only way to pass the standard specified fire rating is to select a suitable insulating material. The single-core wiring in the common civil construction cannot meet the requirement of B1 grade in flame retardant grade due to the structural problem, thereby influencing the wide use of the single-core wiring.
The wire material is a material for preparing the wire insulating layer, and the performance of the wire material directly influences the application safety and the service life of the wire, so that the development and research of the wire material with excellent comprehensive performance are very important. Flame retardancy is one of the most important performance indexes of electric wire materials. In recent years, more and more fires are caused by aging of wires and cables, and how to reduce the occurrence rate of the fires and the death rate of the fires, low smoke, no halogen, flame retardance and environmental protection become the development direction of the wire material industry. With the research, application and continuous improvement of decades in the industry, the low-smoke halogen-free flame-retardant polyolefin wire material and the preparation and application technology thereof tend to be mature, so that the application field of the low-smoke halogen-free flame-retardant polyolefin wire material is continuously expanded, and the market amount is increased.
At present, low-smoke halogen-free flame-retardant polyolefin wire materials produced and used at home and abroad are generally prepared by taking ethylene-vinyl acetate copolymer (EVA) as a main base material, Polyethylene (PE) and ethylene- α -olefin as auxiliary base materials, taking aluminum hydroxide or magnesium hydroxide as a main flame retardant, and then taking a lubricant, an antioxidant and the like as auxiliary materials through extrusion granulation.
The Chinese patent with application number 201610577200.2 provides a low-smoke halogen-free flame-retardant polyolefin wire material, which adopts a polyolefin base material consisting of a polyolefin elastomer, an ethylene-vinyl acetate copolymer and polyethylene; the aluminum hydroxide with the surface coated with the basic zinc stannate has excellent flame retardant and smoke suppression performances; vinyl triethoxysilane is used as a cross-linking agent, so that the dispersibility of the flame retardant is improved, and the mechanical property of the product is improved; the mixture of ammonium molybdate and aluminum hydroxide is adopted to further inhibit smoke; adopting a nylon 6/clay nano composite material as a synergistic flame retardant; the aging life of the polyolefin material is prolonged by adopting zinc borate; the wire material has excellent flame retardant and smoke suppression performances, is halogen-free, and is safe and reliable. But the raw materials such as ammonium molybdate, zinc stannate and the like are expensive, and are not suitable for large-scale commercial production.
Therefore, the development of the novel low-smoke halogen-free flame-retardant polyolefin wire material with good flame retardant property for the B1-grade wire cloth meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the wire material industry.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire cloth with good flame retardant property and a preparation method thereof, and mainly solves the problem that the flame retardance reaches B1 grade.
The invention aims to provide a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight:
the inorganic flame retardant comprises first magnesium hydroxide subjected to surface treatment by adopting an anionic surfactant and second magnesium hydroxide formed by performing surface activation on magnesium hydroxide by adopting a titanate coupling agent.
Magnesium hydroxide is decomposed and absorbs the surface heat of the combustion object to achieve the flame retardant effect when being heated (340 DEG 490 ℃); meanwhile, a large amount of moisture is released to dilute oxygen on the surface of the combustible, and active magnesium oxide generated by decomposition is attached to the surface of the combustible to further prevent the combustion from proceeding. Since magnesium hydroxide has poor compatibility with polymers, surface treatment of magnesium hydroxide is required.
The invention selects the first magnesium hydroxide which is subjected to surface treatment by adopting an anionic surfactant and the second magnesium hydroxide which is formed by adopting a titanate coupling agent to carry out surface activation on the magnesium hydroxide, the hydrophilic group and the hydrophilic group of the anionic surfactant in the first magnesium hydroxide respectively interact with the magnesium hydroxide and the polymer, thereby improving the mechanical property of the flame retardant material, the alkoxy of the titanate coupling agent in the second magnesium hydroxide can react with the magnesium hydroxide, a titanate monomolecular film is formed on the surface of the magnesium hydroxide, so that the second magnesium hydroxide obtains good dispersibility and wettability, thereby reducing the surface energy of the second magnesium hydroxide, improving the compatibility of the first magnesium hydroxide and the second magnesium hydroxide with the high molecular material, thereby playing a role in synergy and complementation, enhancing the flame-retardant effect and improving the compatibility of the inorganic flame retardant and the resin.
Preferably, the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate and sodium N-lauroyl sarcosinate.
Preferably, the titanate coupling agent is at least one of isopropyldioleacyloxy (dioctylphosphonoyl) titanate, isopropyltris (dioctylphosphonoyl) titanate, isopropyl triisostearate, bis (dioctyloxypyrophosphate) ethylene titanate.
Preferably, the ratio of the weight parts of the first magnesium hydroxide and the second magnesium hydroxide is 1 (0.8-1.2).
Preferably, the particle size of the inorganic flame retardant is 0.5 to 1.5 μm.
Preferably, the compatilizer is at least one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene; in the invention, the compatilizer is added to promote the fusion of the resin and the powder, so that the system is more uniform.
Preferably, the shell-forming agent is selected from 1,3;2, 4-dibenzylidene sorbitol and/or stearate; according to the invention, the shell forming agent is added and mixed with the inorganic compound flame retardant, so that the flame retardant property of the halogen-free flame retardant material can be improved.
Preferably, the smoke suppressant is at least one selected from the group consisting of zinc borate and molybdenum trioxide; in the invention, in order to reach the heat release standard of the material, a smoke suppressant is added, so that harmful gases and smoke generated by burning high molecular substances can be suppressed.
Preferably, the antioxidant is at least one selected from antioxidant DSTP and antioxidant 1010.
Preferably, the lubricant is at least one selected from the group consisting of silicone and PE wax.
The second purpose of the invention is to provide a preparation method of the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire, which comprises the following steps: and (2) mixing the weighed ethylene-vinyl acetate copolymer, linear low-density polyethylene, compatilizer, inorganic flame retardant, shell forming agent, smoke suppressant, antioxidant and lubricant at a high speed, uniformly mixing, heating and banburying, and performing single-screw and double-screw extrusion granulation to obtain the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-level wire distribution.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire cloth has the advantages that no harmful substance is generated in the whole flame-retardant process, the decomposed product can absorb a large amount of harmful gas and smoke generated by the burning of high polymers such as rubber and plastic while the flame is retarded, and the active magnesium oxide continuously absorbs the incompletely burnt melting residues, so that the burning is stopped quickly while the smoke is eliminated and the molten drops are prevented; therefore, the polyolefin wire material has good flame retardant property, small combustion smoke quantity and small pollution to human bodies and air in the environment of fire.
Detailed Description
The following provides a detailed description of preferred embodiments of the invention.
The invention provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight:
wherein the inorganic flame retardant comprises first magnesium hydroxide subjected to surface treatment by adopting an anionic surfactant and second magnesium hydroxide formed by performing surface activation on magnesium hydroxide by adopting a titanate coupling agent; the weight portion ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1 (0.8-1.2). Wherein the first magnesium hydroxide and the second magnesium hydroxide are both prepared in advance.
The preparation method of the first magnesium hydroxide comprises the following steps: dispersing magnesium hydroxide in ethanol, adding anionic surfactant with the mass of 2% of that of the magnesium hydroxide, stirring and reacting at 70 ℃ for 7 hours, and then removing the ethanol by rotary evaporation.
The preparation method of the second magnesium hydroxide comprises the following steps: dispersing magnesium hydroxide in ethanol, adding titanate coupling agent with the mass being 2% of that of the magnesium hydroxide, stirring and reacting for 7 hours at 70 ℃, and then removing the ethanol by rotary evaporation.
The anionic surfactant is at least one of sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate and N-lauroyl sarcosine sodium, and is purchased from Guangzhou Na-English chemical industry; the titanate coupling agent is at least one of isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl triisostearate titanate and bis (dioctyl oxide pyrophosphate) ethylene titanate, and is purchased from Nanjing warp and weft chemical industry.
The particle size of the inorganic flame retardant is 0.5-1.5 microns; the compatilizer is at least one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene. The compatibilizer of the present invention is purchased from the liter of Zhejiang days. The shell-forming agent is selected from 1,3;2, 4-dibenzylidene sorbitol and stearate. The shell forming agent is purchased from Shanghai Zhuang Jing. The smoke suppressant is at least one selected from zinc borate and molybdenum trioxide. The smoke suppressant of the invention is purchased from Zhejiang Asahi Sen. The antioxidant is one or more selected from DSTP and 1010. The antioxidant is purchased from Beijing and is very easy to be used in chemical industry. The lubricant is one or more selected from silicone and PE wax. The lubricant of the invention is purchased from Jiangyin Jiuli.
A preparation method of a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire comprises the following steps: the weighed ethylene-vinyl acetate copolymer, linear low-density polyethylene, compatilizer, inorganic flame retardant, shell forming agent, smoke suppressant, antioxidant and lubricant are mixed at high speed, evenly mixed, heated and banburied, and then extruded by single and double screws for granulation to obtain the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-level wire distribution.
The following provides a detailed description of preferred embodiments of the invention.
Example 1
Embodiment 1 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight:
wherein the inorganic flame retardant comprises first magnesium hydroxide which is subjected to surface treatment by adopting sodium dodecyl benzene sulfonate and second magnesium hydroxide which is formed by performing surface activation on magnesium hydroxide by adopting isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate; the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1:1.
The invention discloses a preparation method of a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following steps: and (2) mixing the weighed ethylene-vinyl acetate copolymer, linear low-density polyethylene, compatilizer, inorganic flame retardant, shell forming agent, smoke suppressant, antioxidant and lubricant at a high speed, uniformly mixing, heating and banburying, and performing single-screw and double-screw extrusion granulation to obtain the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-level wire distribution.
Example 2
Embodiment 2 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, the formula and the preparation method of which are basically the same as those of embodiment 1, except that the material comprises the following components in parts by weight:
example 3
Embodiment 3 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, the formula and the preparation method of which are basically the same as those of embodiment 1, except that the material comprises the following components in parts by weight:
example 4
Embodiment 4 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, and the preparation method is completely the same as that of embodiment 1, except that: 50 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 0.8).
Example 5
Embodiment 5 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, and the preparation method is completely the same as that of embodiment 1, except that: 50 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 1.2).
Example 6
Embodiment 6 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, and the preparation method is completely the same as that of embodiment 1, except that: 60 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 0.8).
Example 7
Embodiment 7 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, and the preparation method is completely the same as that of embodiment 1, except that: 60 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 1.2).
Example 8
Embodiment 8 provides a low smoke, zero halogen and flame retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as in embodiment 1, the preparation method is completely the same as in embodiment 1, and the difference is that: and 30 parts of ethylene-vinyl acetate copolymer.
Comparative example 1
Comparative example 1 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as those in example 1, and the preparation method is completely the same as that in example 1, and the difference is that: aluminum hydroxide is used as an inorganic flame retardant, and the mass fraction of the aluminum hydroxide is 55 parts.
Comparative example 2
Comparative example 2 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as those in example 1, and the preparation method is completely the same as that in example 1, except that: the first magnesium hydroxide is not added, the inorganic flame retardant is second magnesium hydroxide, and the added mass fraction is 55 parts.
Comparative example 3
Comparative example 3 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as those in example 1, and the preparation method is completely the same as that in example 1, except that: the second magnesium hydroxide is not added, the inorganic flame retardant is the first magnesium hydroxide, and the added mass fraction is 55 parts.
Comparative example 4
Comparative example 4 provides a low-smoke halogen-free flame-retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as those in example 1, and the preparation method is completely the same as that in example 1, except that: 55 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 0.6).
Comparative example 5
Comparative example 5 provides a low smoke zero halogen flame retardant polyolefin wire material for a B1-grade wire, which comprises the following components in parts by weight, the formula components are basically the same as in example 1, the preparation method is completely the same as in example 1, and the difference is that: 55 parts of inorganic flame retardant (the weight part ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1: 1.5).
In order to further illustrate the beneficial technical effects of the embodiments of the invention, the performance test of the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution prepared in each example is carried out according to the corresponding national standard, and the test results are shown in Table 1.
TABLE 1 results of the Combustion Performance test of examples 1 to 10 and comparative examples 1 to 6
As can be seen from Table 1, the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution disclosed in the embodiment of the invention has more excellent flame retardance and corrosion resistance, which are the result of the synergistic effect of the components.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A low-smoke halogen-free flame-retardant polyolefin wire material for a B1-level wire, which is characterized in that: the paint comprises the following components in parts by weight:
10-30 parts of ethylene-vinyl acetate copolymer;
10-20 parts of linear low-density polyethylene;
5-10 parts of a compatilizer;
5-6 parts of an inorganic flame retardant;
2-5 parts of a shell forming agent;
2-5 parts of a smoke suppressant;
0.1-0.5 part of antioxidant;
0.5-1 part of lubricant;
the inorganic flame retardant comprises first magnesium hydroxide subjected to surface treatment by adopting an anionic surfactant and second magnesium hydroxide formed by performing surface activation on magnesium hydroxide by adopting a titanate coupling agent.
2. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the weight portion ratio of the first magnesium hydroxide to the second magnesium hydroxide is 1 (0.8-1.2).
3. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the particle size of the inorganic flame retardant is 0.5-1.5 microns.
4. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the compatilizer is at least one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
5. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the shell forming agent is at least one selected from 1,3, 2, 4-dibenzylidene sorbitol and stearate.
6. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the smoke suppressant is at least one selected from zinc borate and molybdenum trioxide.
7. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the antioxidant is at least one selected from antioxidant DSTP and antioxidant 1010.
8. The low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade wire distribution according to claim 1, which is characterized in that: the lubricant is at least one selected from the group consisting of silicone and PE wax.
9. The preparation method of the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-grade electric wire according to any one of claims 1-8, characterized by comprising the following steps: and (2) mixing the weighed ethylene-vinyl acetate copolymer, linear low-density polyethylene, compatilizer, inorganic flame retardant, shell forming agent, smoke suppressant, antioxidant and lubricant at a high speed, uniformly mixing, heating and banburying, and performing single-screw and double-screw extrusion granulation to obtain the low-smoke halogen-free flame-retardant polyolefin wire material for the B1-level wire distribution.
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| CN113555147A (en) * | 2021-08-25 | 2021-10-26 | 金杯电工衡阳电缆有限公司 | Novel B1 electric wire |
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Application publication date: 20200228 |