CN107857932B - Chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- 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
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- 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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- C08L2203/00—Applications
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- C08L2312/00—Crosslinking
Abstract
A chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof are characterized in that 80 parts of base resin, 10-30 parts of compatilizer, 100-145 parts of inorganic flame retardant, 3-10 parts of flame-retardant synergist, 1.5-3.5 parts of crosslinking agent, 1.0-2.0 parts of crosslinking sensitizer, 0.1-1 part of stabilizer, 2-4 parts of lubricant and 2.0-5.5 parts of antioxidant are weighed according to parts by weight and are put into a high-speed mixer, the mixture is stirred at normal temperature and then placed into an internal mixer for internal mixing, then the material is fed into a single-screw extruder in a forced conical feeding mode, and after being extruded by the single-screw extruder, the material is sequentially cut into particles, cooled and packaged to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material, wherein the base resin is composed of the following raw materials according to the parts by: 40-70 parts of ethylene copolymer and 10-40 parts of polyolefin elastomer. The temperature resistance grade is improved, and pre-crosslinking is avoided; simple process and high preparation efficiency.
Description
Technical Field
The invention belongs to the technical field of insulating high polymer materials, and particularly relates to a chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof.
Background
The crosslinked polyolefin is prepared by changing polyolefin molecules from linear molecular structure to three-dimensional network structure by physical and chemical methods, and changing thermoplastic material to thermosetting material, thereby improving heat resistance and mechanical properties of the crosslinked polyolefin and expanding the application range of the crosslinked polyolefin.
At present, the cross-linking type low-smoke halogen-free flame-retardant polyolefin material for the electric wires and cables mainly takes irradiation cross-linking in China, however, the irradiation cross-linking is limited by irradiation intensity, angle and material thickness, and is generally only suitable for the electric wires and cables with thin thickness and regular structure, most cable plants do not have irradiation equipment, the process needs to be entrusted to complete, and the irradiation quality cannot be completely guaranteed and controlled.
In order to overcome the above defects, many material manufacturers begin to adopt a silane crosslinking mode to crosslink the low-smoke halogen-free flame-retardant polyolefin material, however, although the silane crosslinking production is simple and rapid, and the equipment investment is small, the crosslinking process control has certain instability, such as easy pre-crosslinking, narrow processing temperature range, and easy combination of steam required by crosslinking and hydrophilic flame retardant in the material to cause the reduction of the electrical property and the mechanical property.
The chemical crosslinking method commonly used for the medium-high voltage cable crosslinked polyethylene insulation is characterized in that extrusion molding and crosslinking are continuously carried out, high-temperature initiation materials are adopted for crosslinking, the method is not limited by the morphological structure of the cable, and the crosslinking process is stable and controllable.
Therefore, the use temperature of the low-smoke halogen-free flame-retardant polyolefin material is improved by adopting a chemical crosslinking mode, and the prepared chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material can greatly improve the production efficiency of cable manufacturers and meet the quality controllability requirement. The method is tried by 'a flexible chemical crosslinking low-smoke halogen-free flame-retardant polyolefin sheath material and a preparation method' recommended by Chinese patent CN105367882A, however, the production process of the cable material needs to firstly mix the first part of the material by an internal mixer (internal mixing, the same applies below), then add the second part of the material for mixing, then thin pass the cable material by an open mill, roll out the cable material by a three-roll calender, and then add the last part of the material to repeat the above processes. The production process is complicated, the efficiency is low, the cost is high, and DCP is adopted as a crosslinking initiator, so that pre-crosslinking is easy to occur in the process of carrying out banburying and open mixing for several times in the production steps and the cable extrusion process. Therefore, the possibility of practical industrial production and use thereof is low.
Although the preparation and use method of the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin composite material provided by the publication No. CN105885188A firstly prepares the master batch without the crosslinking agent, the defect of pre-crosslinking caused by high banburying temperature is overcome, the problem of pre-crosslinking caused by decomposition of the crosslinking agent DCP in the extrusion molding process of the cable material also exists, and the production process is complicated because part of the materials are firstly banburied and then extruded by a single screw to prepare the master batch, and then extruded by a double screw and simultaneously dripped with the crosslinking agent.
Based on the prior art, it is of positive significance to explore a more concise production process to improve production efficiency and to use a more efficient material combination to overcome pre-crosslinking defects during material production and use, and the technical solutions to be described below are made in this context.
Disclosure of Invention
The invention provides a chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material which is beneficial to improving temperature resistance level and avoiding pre-crosslinking.
The invention also provides a preparation method of the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material, which has the advantages of simple preparation process and high preparation efficiency, and can ensure that the obtained cable material has ideal temperature resistance grade and avoid pre-crosslinking.
The invention is primarily aimed at completing the task, and the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is composed of the following raw materials in parts by weight:
the base resin is prepared from the following raw materials in parts by weight: 40-70 parts of ethylene copolymer and 10-40 parts of polyolefin elastomer.
In a specific embodiment of the present invention, the ethylene copolymer is an ethylene-vinyl acetate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, or an ethylene-butyl acrylate copolymer; the ethylene copolymer has a comonomer content of 18% by mass or more and a DSC melting point of less than 85 ℃.
In another particular embodiment of the invention, the polyolefin elastomer is an ethylene-octene copolymer, an ethylene-butene copolymer or an ethylene-hexene copolymer having a DSC melting point of less than 85 ℃.
In yet another specific embodiment of the present invention, the compatibilizer is a maleic anhydride grafted ethylene-butene copolymer, a maleic anhydride grafted ethylene-octene copolymer, a maleic anhydride grafted ethylene-methyl acrylate copolymer, a maleic anhydride grafted ethylene-ethyl acrylate copolymer, or a maleic anhydride grafted ethylene-propylene rubber.
In another specific embodiment of the present invention, the inorganic flame retardant is a mixture of magnesium hydroxide and calcium magnesium carbonate; the flame-retardant synergist is aluminum hypophosphite, zinc borate or carbon nano tubes.
In yet another specific embodiment of the present invention, the crosslinking agent is 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne; the crosslinking sensitizer is triallyl isocyanurate.
In a more specific embodiment of the present invention, the stabilizer is 2, 2-diphenyl-1-trinitrophenylhydrazine (DPPH), p-benzoquinone, tetramethylbenzoquinone, 2-methyl-2-nitrosomethane, or phenyl-N-tert-butylnitrone.
In a further specific embodiment of the present invention, the lubricant is one or a combination of several of polyhydroxy magnesium stearate, silicone and long chain alcohol polyester.
In yet a more specific embodiment of the present invention, the antioxidant is a combination of two or three of tetrakis [ β - (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-t-butylphenyl) phosphite, bis (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 4' -thiobis (6-t-butyl-3-methylphenol) and 1,3,5, tris (3, 5-di-t-butyl, 4-hydroxybenzyl) s-triazine.
The other task of the invention is to accomplish the preparation method of the chemical crosslinking low-smoke halogen-free flame retardant polyolefin cable material, which comprises the steps of firstly putting 80 parts by weight of base resin, 10-30 parts by weight of compatilizer, 100-145 parts by weight of inorganic flame retardant, 3-10 parts by weight of flame retardant synergist, 1.5-3.5 parts by weight of crosslinking agent, 1.0-2.0 parts by weight of crosslinking sensitizer, 0.1-1 part by weight of stabilizer, 2-4 parts by weight of lubricant and 2.0-5.5 parts by weight of antioxidant into a high-speed mixer, stirring for 2-5min at normal temperature, then putting the materials into an internal mixer, carrying out internal mixing for 8-15 min at the temperature of 110-120 ℃, then feeding the materials into a single-screw extruder in a forced conical feeding manner, wherein the extrusion temperature of the single-screw extruder is 95-110 ℃, carrying out extrusion by the single-screw extruder, then carrying out grain cutting, cooling and packaging in turn to obtain the chemical crosslinking low-smoke halogen-free flame, wherein: the base resin is prepared from the following raw materials in parts by weight: 40-70 parts of ethylene copolymer and 10-40 parts of polyolefin elastomer.
The technical scheme provided by the invention has the beneficial effects that the chemical crosslinking mode is adopted to improve the temperature resistance grade of the low-smoke halogen-free flame-retardant polyolefin cable material, the defects that irradiation crosslinking is limited by irradiation intensity, angle and material thickness, and is generally only suitable for wires and cables with thin thickness and regular structure and requires entrusted processing irradiation are overcome, and the defects that pre-crosslinking is easy to occur in a silane crosslinking mode, the processing temperature range is narrow, and steam required by crosslinking is easy to combine with hydrophilic flame retardant in the material, so that the electrical property and the mechanical property of the cable material are reduced are overcome; and secondly, the components adopt a cross-linking agent with the decomposition temperature higher than that of the cross-linking agent used by the common cross-linked cable material, and a stabilizing agent is added, so that the pre-crosslinking problem of the material in the processing and cable extrusion processes is successfully solved. The adopted flame retardant and the flame retardant synergist have higher decomposition temperature, can not be decomposed in a high-temperature crosslinking vulcanization pipeline, and meet the requirements of industrial production and use.
Detailed Description
The formula is as follows:
60 parts of ethylene-vinyl acetate copolymer with the content of vinyl acetate monomer of 33 percent by mass and the DSC melting point of less than 85 ℃, 60 parts of ethylene-octene copolymer elastomer with the DSC melting point of less than 85 ℃,10 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer, 100 parts of magnesium hydroxide, 40 parts of calcium magnesium carbonate, 10 parts of aluminum hypophosphite, 1.8 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 1.0 part of triallylisocyanurate, 0.8 part of 2, 2-diphenyl-1-trinitrophenylhydrazine, 1 part of polyhydroxy magnesium stearate, 2.5 parts of silicone, 2.0 parts of tetra [ beta- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of tris (2, 4-di-tert-butylphenyl) phosphite, 1 part of 4,4' -thiobis (6-tert-butyl-3-methylphenol).
The preparation method comprises the following steps: and putting the weighed materials into a high-speed mixer, stirring at a high speed for fully mixing for 3min, putting the mixed materials into an internal mixer, fully mixing at 110 ℃ for 10min, putting the materials into a single-screw extruder in a forced conical feeding mode for melting and extruding, wherein the processing temperature is 95-110 ℃, and carrying out granulation, cooling and packaging to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material.
The granular chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is mixed for 1min in an open mill with the temperature set to be 110 ℃, and is pressed into a test piece under the vulcanization condition of 15min × 200 × 15MPa, and the performance test is shown in table 1.
TABLE 1 Performance test of the rubber materials after compression vulcanization
Extruding the prepared chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material in a cable extruder, setting the extrusion temperature (first to fifth zones, a machine head and a mold) to be 90 ℃,105 ℃,110 ℃,115 ℃,115 ℃,115 ℃,110 ℃, 1.0mm in thickness of an extrusion insulation layer, 20m/min in linear velocity, directly feeding the extrusion cable into a vulcanization pipeline for vulcanization, setting the temperature of the vulcanization pipeline to be 240-285 ℃, setting the pressure in the pipeline to be 3-5 MPa in nitrogen atmosphere, and then feeding the extrusion cable into a water tank for cooling. And 4h, continuously extruding the cable insulating layer, wherein the cable surface is smooth and uniform, pre-crosslinked particles and rigid blocks do not appear, and the section of the sheath is free of air holes.
The cable was taken for testing and the test results are shown in table 2.
TABLE 2 Cable Performance test of the finished product
Example 2
The formula is as follows:
40 parts of ethylene-methyl acrylate copolymer with the content of methyl acrylate monomer of 24 percent by mass and the DSC melting point of less than 85 ℃, 40 parts of ethylene-butene copolymer elastomer with the DSC melting point of less than 85 ℃, 20 parts of maleic anhydride grafted ethylene-octene copolymer elastomer, 90 parts of magnesium hydroxide, 10 parts of calcium magnesium carbonate, 3 parts of zinc borate, 3.5 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 1.5 parts of triallyl isocyanurate, 1 part of p-benzoquinone, 3 parts of silicone, 1 part of long-chain alcohol polyester, 1.5 parts of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2 parts of 1,3,5, tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine and 2 parts of bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
The preparation method comprises the following steps: and putting the weighed materials into a high-speed mixer, stirring at a high speed for fully mixing for 2min, putting the mixed materials into an internal mixer, fully mixing at 120 ℃ for 10min, putting the materials into a single-screw extruder in a forced conical feeding mode for melting and extruding, wherein the processing temperature is 95-110 ℃, and carrying out granulation, cooling and packaging to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material.
The granular chemical crosslinking low smoke zero halogen flame retardant polyolefin cable material is mixed for 1min in an open mill with the temperature set as 110 ℃, and is pressed into test pieces under the vulcanization condition of 15min × 200 ℃ and 15MPa, and the performance test is shown in table 3.
Example 3
The formula is as follows:
70 parts of ethylene-ethyl acrylate copolymer with the content of ethyl acrylate monomer of 35 percent by mass and the DSC melting point of less than 85 ℃,10 parts of ethylene-hexene copolymer elastomer with the DSC melting point of less than 85 ℃, 30 parts of maleic anhydride grafted ethylene-methyl acrylate copolymer, 110 parts of magnesium hydroxide, 35 parts of calcium magnesium carbonate, 5 parts of carbon nano tube, 1.5 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 2 parts of triallyl isocyanurate, 0.1 part of tetramethylbenzoquinone, 1 part of long-chain alcohol polyester, 3 parts of polyhydroxy magnesium stearate, 1 part of 4,4 '-thiobis (6-tert-butyl-3-methylphenol), 1 part of tetra [ beta- (3', 5 '-di-tert-butyl-4' -hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine.
The preparation method comprises the following steps: and putting the weighed materials into a high-speed mixer, stirring at a high speed for fully mixing for 5min, putting the mixed materials into an internal mixer, fully mixing at 115 ℃ for 13min, putting the materials into a single-screw extruder through forced conical feeding for melting and extruding, wherein the processing temperature is 95-110 ℃, and granulating, cooling and packaging to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material.
The granular chemical crosslinking low smoke zero halogen flame retardant polyolefin cable material is mixed for 1min in an open mill with the temperature set as 110 ℃, and is pressed into test pieces under the vulcanization condition of 15min × 200 ℃ and 15Mpa, and the performance test is shown in table 3.
Example 4
The formula is as follows:
60 parts of ethylene-butyl acrylate copolymer with the content of butyl acrylate monomer by mass percent being 30% and the DSC melting point being less than 85 ℃, 20 parts of ethylene-butene copolymer elastomer with the DSC melting point being less than 85 ℃, 15 parts of maleic anhydride grafted ethylene propylene rubber, 75 parts of magnesium hydroxide, 50 parts of calcium magnesium carbonate, 8 parts of aluminum hypophosphite, 3.5 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 1.5 parts of triallyl isocyanurate, 0.8 part of 2-methyl-2-nitrosomethane, 2 parts of silicone, 1 part of long-chain alcohol polyester, 2 parts of tris (2, 4-di-tert-butylphenyl) phosphite, 1 part of 1,3,5 parts of tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine and 2.3 parts of tetra [ beta- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method comprises the following steps: and putting the weighed materials into a high-speed mixer, stirring at a high speed for fully mixing for 4min, putting the mixed materials into an internal mixer, fully mixing for 14min at 118 ℃, putting the materials into a single-screw extruder through forced conical feeding for melt extrusion, and granulating, cooling and packaging at the processing temperature of 95-110 ℃ to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material.
The granular chemical crosslinking low smoke zero halogen flame retardant polyolefin cable material is mixed for 1min in an open mill with the temperature set as 110 ℃, and is pressed into test pieces under the vulcanization condition of 15min × 200 ℃ and 15MPa, and the performance test is shown in table 3.
Example 5
The formula is as follows:
70 parts of ethylene-methyl acrylate copolymer with the content of methyl acrylate monomer of 18 percent by mass and the DSC melting point of less than 85 ℃,10 parts of ethylene-hexene copolymer elastomer with the DSC melting point of less than 85 ℃,10 parts of maleic anhydride grafted ethylene-methyl acrylate copolymer, 80 parts of magnesium hydroxide, 60 parts of calcium magnesium carbonate, 5 parts of zinc borate, 2.8 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, 0.5 part of triallyl isocyanurate, 0.5 part of phenyl-N-tert-butylnitrone, 1 part of silicone, 2.5 parts of long-chain alcohol polyester, 1 part of 4,4 '-thiobis (6-tert-butyl-3-methylphenol), 1 part of tetra [ beta- (3', 5 '-di-tert-butyl-4' -hydroxyphenyl) propionic acid ] pentaerythritol ester, 2.8 parts of 1,3,5, tri (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine.
The preparation method comprises the following steps: and putting the weighed materials into a high-speed mixer, stirring at a high speed for fully mixing for 3min, putting the mixed materials into an internal mixer, fully mixing for 11min at 114 ℃, putting the materials into a single-screw extruder through forced conical feeding for melting and extruding, wherein the processing temperature is 95-110 ℃, and granulating, cooling and packaging to obtain the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material.
The granular chemical crosslinking low smoke zero halogen flame retardant polyolefin cable material is mixed for 1min in an open mill with the temperature set as 110 ℃, and is pressed into test pieces under the vulcanization condition of 15min × 200 ℃ and 15MPa, and the performance test is shown in table 3.
Table 3 shows the test results of the chemically crosslinked LSOH flame retardant polyolefin cable material obtained in examples 2-5
Claims (5)
1. A chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is characterized by comprising the following raw materials in parts by weight:
80 parts of base resin;
10-30 parts of a compatilizer;
100 portions and 145 portions of inorganic flame retardant;
3-10 parts of a flame-retardant synergist;
1.5-3.5 parts of a cross-linking agent;
1-2 parts of a crosslinking sensitizer;
0.1-1 part of a stabilizer;
2-4 parts of a lubricant;
2-5.5 parts of an antioxidant;
the base resin is prepared from the following raw materials in parts by weight: 40-70 parts of ethylene copolymer and 10-40 parts of polyolefin elastomer; the cross-linking agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne; the crosslinking sensitizer is triallyl isocyanurate; the stabilizer is 2, 2-diphenyl-1-trinitrophenylhydrazine, p-benzoquinone, tetramethylbenzoquinone, 2-methyl-2-nitrosomethane or phenyl-N-tert-butyl nitrone; the ethylene copolymer is an ethylene-vinyl acetate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer or an ethylene-butyl acrylate copolymer; the ethylene copolymer contains 18% or more of comonomer by mass and has a DSC melting point of less than 85 ℃; the polyolefin elastomer is an ethylene-octene copolymer, an ethylene-butene copolymer or an ethylene-hexene copolymer with a DSC melting point of less than 85 ℃;
the preparation method of the chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following steps: firstly, weighing 80 parts by weight of base resin, 10-30 parts by weight of compatilizer, 100-145 parts by weight of inorganic flame retardant, 3-10 parts by weight of flame-retardant synergist, 1.5-3.5 parts by weight of cross-linking agent, 1.0-2.0 parts by weight of cross-linking sensitizer, 0.1-1 part by weight of stabilizer, 2-4 parts by weight of lubricant and 2.0-5.5 parts by weight of antioxidant, putting the mixture into a high-speed mixer, stirring for 2-5min at normal temperature, then putting the mixture into an internal mixer, internally mixing for 8-15 min at the temperature of 110-120 ℃, then feeding the mixture into a single-screw extruder in a forced conical feeding manner, wherein the extrusion temperature of the single-screw extruder is 95-110 ℃, and then carrying out extrusion by the single-screw extruder, sequentially carrying out grain cutting, cooling and packaging to obtain the chemical cross-linking low-smoke.
2. The chemically crosslinked low smoke zero halogen flame retardant polyolefin cable material according to claim 1, wherein the compatibilizer is maleic anhydride grafted ethylene-butene copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-ethyl acrylate copolymer or maleic anhydride grafted ethylene-propylene rubber.
3. The chemical crosslinking low-smoke halogen-free flame retardant polyolefin cable material according to claim 1, characterized in that the inorganic flame retardant is a mixture of magnesium hydroxide and calcium magnesium carbonate; the flame-retardant synergist is aluminum hypophosphite, zinc borate or carbon nano tubes.
4. The chemical crosslinking low smoke zero halogen flame retardant polyolefin cable material according to claim 1, characterized in that the lubricant is one or a combination of several of polyhydroxy magnesium stearate, silicone, long chain alcohol polyester.
5. The chemically crosslinked, low-smoke, halogen-free, flame retardant polyolefin cable material according to claim 1, wherein the antioxidant is a combination of two or three of tetrakis [ β - (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-t-butylphenyl) phosphite, bis (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 4' -thiobis (6-t-butyl-3-methylphenol), and 1,3,5, tris (3, 5-di-t-butyl, 4-hydroxybenzyl) s-triazine.
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| CN108624258B (en) * | 2018-06-01 | 2023-10-17 | 广东环境保护工程职业学院 | Hot melt adhesive film for crosslinked polyolefin wall cloth and preparation method thereof |
| CN110746683A (en) * | 2019-11-28 | 2020-02-04 | 江苏上上电缆集团新材料有限公司 | Ultraviolet-crosslinked high-flame-retardant low-smoke halogen-free polyolefin cable material and preparation method thereof |
| CN111253698B (en) * | 2020-04-07 | 2022-06-03 | 安徽弘宜新材料科技发展有限公司 | Multifunctional PVC (polyvinyl chloride) crosslinked cable sheath material and processing technology thereof |
| CN111621081A (en) * | 2020-04-21 | 2020-09-04 | 广东聚石化学股份有限公司 | Antibacterial environment-friendly flame-retardant elastomer material and preparation method and application thereof |
| CN111718533B (en) * | 2020-06-01 | 2023-01-17 | 广东聚石化学股份有限公司 | Ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material and preparation method and application thereof |
| CN111662497A (en) * | 2020-07-23 | 2020-09-15 | 上海方之德新材料有限公司 | Cross-linked low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN112029188A (en) * | 2020-09-21 | 2020-12-04 | 恒飞电缆股份有限公司 | High-insulation low-smoke halogen-free flame-retardant cable material and preparation method thereof |
| CN112574539A (en) * | 2020-12-21 | 2021-03-30 | 青岛润兴塑料新材料有限公司 | High-dispersion high-carbon-black-content black master batch for completely biodegradable garbage bag |
| CN115637007A (en) * | 2022-11-01 | 2023-01-24 | 湖北航天化学技术研究所 | Investable packaging material for ethylene propylene diene monomer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012940A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material |
| CN103289162A (en) * | 2013-03-28 | 2013-09-11 | 西安交通大学 | A water tree-resistant polyolefin cable material and a preparation method thereof |
| CN105367882A (en) * | 2015-09-18 | 2016-03-02 | 特变电工山东鲁能泰山电缆有限公司 | Flexible chemical crosslinking low-smoke zero-halogen flame-retardant polyolefin sheathing material and preparation method |
| CN106867090A (en) * | 2017-03-13 | 2017-06-20 | 常熟市中联光电新材料有限责任公司 | High temperature resistant soft thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095638A (en) * | 2008-10-17 | 2010-04-30 | Hitachi Cable Ltd | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire |
| CN103937087A (en) * | 2014-04-30 | 2014-07-23 | 沈阳三普高分子材料有限公司 | Low-hardness freezing-resistant irradiation crosslinking low-smoke halogen-free flame-retardant material |
| CN106543517A (en) * | 2016-10-14 | 2017-03-29 | 无锡杰科塑业有限公司 | A kind of cable material of polyolefin and preparation method thereof |
-
2017
- 2017-11-23 CN CN201711178000.0A patent/CN107857932B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012940A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material |
| CN103289162A (en) * | 2013-03-28 | 2013-09-11 | 西安交通大学 | A water tree-resistant polyolefin cable material and a preparation method thereof |
| CN105367882A (en) * | 2015-09-18 | 2016-03-02 | 特变电工山东鲁能泰山电缆有限公司 | Flexible chemical crosslinking low-smoke zero-halogen flame-retardant polyolefin sheathing material and preparation method |
| CN106867090A (en) * | 2017-03-13 | 2017-06-20 | 常熟市中联光电新材料有限责任公司 | High temperature resistant soft thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS |
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