CN115678153A - Thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- CN115678153A CN115678153A CN202211405388.4A CN202211405388A CN115678153A CN 115678153 A CN115678153 A CN 115678153A CN 202211405388 A CN202211405388 A CN 202211405388A CN 115678153 A CN115678153 A CN 115678153A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000000779 smoke Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 title claims abstract description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 35
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 34
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 5
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005057 refrigeration Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Insulated Conductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a thermoplastic flexible low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof. The composite material is prepared by using ethylene-vinyl acetate copolymer, ethylene-butylene copolymer, ethylene propylene diene monomer and modified polyolefin resin as base materials, using aluminum hydroxide as a flame-retardant filler, adding self-made antioxidant master batches, silicone master batches and polyethylene wax as processing aids, plasticizing and mixing the mixture by a mixer and a double-stage extruder unit, and then granulating the mixture. The antioxidant master batch takes metallocene polyethylene as a base material, improves the combination degree of the antioxidant and a cable material to a certain extent, can meet the temperature resistance requirement of the flame-retardant polyolefin cable material at 105 ℃, and can be applied to wire and cable sheath layers with higher requirements on product flexibility, such as wind energy cables, photoelectric composite cables, elevator cables, internal wires of refrigeration equipment, and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a thermoplastic flexible low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof.
Background
The low-smoke halogen-free electric wire is an insulating layer material halogen substance of the electric wire, does not release halogen-containing gas under the condition of combustion, has low smoke concentration and is JB/T10491-2004 as a reference standard.
The conventional thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material is prepared by taking EVA (ethylene-vinyl acetate copolymer), POE (polyolefin thermoplastic elastomer), PE (polyethylene) and modified polyolefin resin as base materials, adding inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and the like, and then adding auxiliary agents such as silicone master batch, PE wax, antioxidant, black master batch and the like, and carrying out plasticizing, mixing and granulation.
In the conventional PVC (polyvinyl chloride) electric wire, when a fire occurs, a PVC mixture is easily decomposed after being heated to release a large amount of highly toxic and corrosive HCl (hydrogen chloride) gas, and a large amount of highly toxic and dense smoke is generated, causing significant life and property loss, and causing great difficulty in rescue work (such as a fire in a korean subway). In order to avoid and reduce fire and secondary damage caused by the fire as much as possible, people find that the problem can be effectively solved by changing the outer layer material and the process used by the product through a great deal of research for more than ten years.
The halogen-free low-smoke flame-retardant wire and cable is mainly characterized in that all materials do not contain halogen, and the smoke quantity released during combustion is small. The toxicity of the halogen-containing cable released in a fire is dire. If the toxicity of the gas concentration at which human death occurs at 30min is judged to be 1, the toxicity index of polyvinyl chloride is 15.01, and the toxicity index of the halogen-free polymer is 0.79. In a fire, the intense and diffuse smoke causes the victim to be disoriented, thereby prolonging the residence time in the fire. According to the data, the light transmittance is 70%, and the naked eye of human can only distinguish the object image 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 a person in the smoke of the dense smoke is only about 2 m. The dense smoke has another characteristic of abnormally rapid propagation along with hot airflow, and the speed can reach more than 20 m/min. Therefore, the adoption of the halogen-free low-smoke wire and cable is crucial to ensuring safety, and the low-smoke halogen-free flame-retardant wire is already adopted in a large number in airports, subways, large buildings and government projects.
It has solved PVC fitment electric wire shortcoming well, does not have steamed, low cigarette, fire-retardant possess good short circuit load ability simultaneously, is the choice of wisdom when fitment, along with people's living condition improves, and is more and more important healthy, safe, the environmental protection, and the day that novel high performance environment-friendly cloth electric wire comprehensively replaced traditional PVC electric wire is forthcoming.
The problems existing in the prior art are as follows: the heat-resistant grade of the conventional thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material is 70 ℃ and 90 ℃, the temperature-resistant requirement of 105 ℃ is difficult to meet, and the products which reach the temperature-resistant grade of 105 ℃ and above are all cross-linked products, such as products of irradiation cross-linking, silane cross-linking, chemical cross-linking, ultraviolet cross-linking and the like. Furthermore, the hardness of the conventional thermoplastic halogen-free flame-retardant polyolefin cable material is above 95A, and the lower the hardness, the poorer the heat resistance, so that the thermoplastic low-smoke halogen-free flame-retardant polyolefin sheath material with the hardness of Shore 92 +/-3A and the heat resistance grade of 105 ℃ has high technical requirements and a technical bottleneck.
Disclosure of Invention
In order to solve the technical problems, the invention provides a thermoplastic flexible low-smoke halogen-free flame-retardant polyolefin cable material which comprises the following components in parts by weight:
the content of vinyl acetate in the first ethylene-vinyl acetate copolymer is 27-29wt%, and the content of Vinyl Acetate (VA) in the second ethylene-vinyl acetate copolymer is 44-46wt%;
the antioxidant master batch comprises the following components in parts by weight:
preferably, the metallocene polyethylene has a melt index of not less than 2g/10min.
The antioxidant master batch takes metallocene polyethylene as a base material, so that the combination degree of the antioxidant and the cable material is improved to a certain extent, and the temperature resistance requirement of the flame-retardant polyolefin cable material at 105 ℃ can be met.
Preferably, the ethylene-butene copolymer has a melt index of 0.3 to 0.7g/10min and a Vicat softening point of not more than 55 ℃.
Preferably, the Mooney viscosity of the ethylene propylene diene monomer is 15-25MU, and the ethylene content is 69.5-71.5wt%.
Preferably, the modified polyolefin resin is a maleic anhydride grafted ethylene-butene copolymer and/or maleic anhydride grafted EVA.
Further, the maleic anhydride grafting rate of the maleic anhydride grafted ethylene-butylene copolymer and the maleic anhydride grafted EVA is not less than 0.8%.
Preferably, the particle diameter D50 of the aluminum hydroxide is 1.6-2.2 μm, and the particle diameter D97 is not more than 7 μm.
Preferably, the polyethylene wax has a softening point of not less than 105 ℃.
Preferably, the content of the carbon black in the black master batch is 43-47wt%.
The invention also provides a preparation method of the thermoplastic flexible low-smoke halogen-free flame-retardant polyolefin cable material, which comprises the following steps: all the components are mixed and plasticized, and are subjected to single-screw extrusion granulation after double-screw extrusion processing to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the design idea of the product is to search for a thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material with the heat resistance grade of 105 ℃ by adopting soft polyolefin resin and adding self-made antioxidant master batches.
The product of the patent technology is thermoplastic, has a temperature resistance level of 105 ℃ and a hardness of 92 +/-3A, meets the technical requirements, and can be applied to wire and cable sheath layers with high requirements on product flexibility, such as wind energy cables, photoelectric composite cables, elevator cables, internal wires of refrigeration equipment and the like.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1
A thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight:
the antioxidant master batch comprises the following components in parts by weight:
all the components are mixed and plasticized, and are subjected to single-screw extrusion granulation after double-screw extrusion processing to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
Example 2
A thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight:
the antioxidant master batch comprises the following components in parts by weight:
all the components are mixed and plasticized, and are extruded and processed by double screws and then are extruded and granulated by single screws to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
Example 3
A thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight:
the antioxidant master batch comprises the following components in parts by weight:
all the components are mixed and plasticized, and are extruded and processed by double screws and then are extruded and granulated by single screws to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
Comparative example 1
A thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight:
the antioxidant master batch comprises the following components in parts by weight:
all the components are mixed and plasticized, and are extruded and processed by double screws and then are extruded and granulated by single screws to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
Effect evaluation 1
The thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material obtained by mixing, plasticizing, extruding and processing by double screws and then extruding and granulating by single screws in the embodiment is subjected to performance test.
TABLE 1 mechanical and thermal Properties test data sheet for the examples
As can be seen from Table 1, the elongation at break of the cable prepared by the invention is higher than that of the cable adopting linear low density polyethylene, and the cable can still keep higher elongation at break after aging and has excellent mechanical properties.
Meanwhile, the product of the technology disclosed by the patent is thermoplastic, has a temperature resistance level of 105 ℃ and a hardness of Shore 92 +/-3A, meets the technical requirements, and can be applied to wire and cable sheath layers with high requirements on product flexibility, such as wind energy cables, photoelectric composite cables, elevator cables, internal wires of refrigeration equipment and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A thermoplastic flexible low-smoke halogen-free flame-retardant polyolefin cable material is characterized by comprising the following components in parts by weight:
the content of vinyl acetate in the first ethylene-vinyl acetate copolymer is 27-29wt%, and the content of vinyl acetate in the second ethylene-vinyl acetate copolymer is 44-46wt%;
the antioxidant master batch comprises the following components in parts by weight:
2. the thermoplastic flexible low smoke zero halogen flame retardant polyolefin cable material of claim 1, wherein the melt index of the metallocene polyethylene is not less than 2g/10min.
3. A thermoplastic flexible low smoke zero halogen flame retardant polyolefin cable material as claimed in claim 1, wherein said ethylene-butene copolymer has a melt index of 0.3-0.7g/10min.
4. The thermoplastic flexible low smoke zero halogen flame retardant polyolefin cable material of claim 1, wherein the ethylene propylene diene monomer has an ethylene content of 69.5-71.5wt%.
5. The thermoplastic flexible low-smoke zero-halogen flame-retardant polyolefin cable material according to claim 1, wherein the modified polyolefin resin is maleic anhydride grafted ethylene-butylene copolymer and/or maleic anhydride grafted EVA.
6. The thermoplastic flexible low-smoke zero-halogen flame-retardant polyolefin cable material according to claim 5, wherein the maleic anhydride grafting ratio of the maleic anhydride grafted ethylene-butene copolymer and the maleic anhydride grafted EVA is not less than 0.8%.
7. The thermoplastic flexible low-smoke zero-halogen flame-retardant polyolefin cable material according to claim 1, wherein the particle diameter D50 of the aluminum hydroxide is 1.6-2.2 μm, and the particle diameter D97 is not more than 7 μm.
8. A thermoplastic flexible low smoke zero halogen flame retardant polyolefin cable material as claimed in claim 1, wherein said polyethylene wax has a softening point of not less than 105 ℃.
9. The thermoplastic flexible low-smoke zero-halogen flame-retardant polyolefin cable material as claimed in claim 1, wherein the content of carbon black in the black masterbatch is 43-47wt%.
10. A method for preparing the thermoplastic flexible low-smoke halogen-free flame retardant polyolefin cable material according to any one of claims 1 to 9, which is characterized by comprising the following steps: all the components are mixed and plasticized, and are subjected to single-screw extrusion granulation after double-screw extrusion processing to obtain the thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211405388.4A CN115678153A (en) | 2022-11-10 | 2022-11-10 | Thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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| CN202211405388.4A CN115678153A (en) | 2022-11-10 | 2022-11-10 | Thermoplastic soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285082A (en) * | 2023-03-22 | 2023-06-23 | 江苏益帆高分子材料有限公司 | Low-smoke halogen-free cable material with rubber improving irradiation crosslinking physical property and preparation method thereof |
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