CN104448519A - High-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material and preparation method thereof - Google Patents
High-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- CN104448519A CN104448519A CN201410652728.2A CN201410652728A CN104448519A CN 104448519 A CN104448519 A CN 104448519A CN 201410652728 A CN201410652728 A CN 201410652728A CN 104448519 A CN104448519 A CN 104448519A
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- cable material
- free flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a high-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material and a preparation method thereof. The high-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material is prepared from the following raw materials in parts by weight: 20-50 parts of an ethylene-octylene copolymer, 20-50 parts of an ethylene-vinyl acetate copolymer, 5-20 parts of polyethylene, 10-25 parts of a compatilizer, 150-200 parts of a flame retardant, 1-9 parts of a synthetic flame retardant, 0.5-2 parts of an antioxidant, 3-6 parts of a lubricating agent and 0.5-3 parts of a surfactant. The high-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material is excellent in mechanical property, a product is excellent in flexibility, and the thermal cracking problem is avoided.
Description
Technical field
The invention belongs to and relate to a kind of thermoplastic halogen-free flame retarding cable material of polyolefin and preparation method thereof.
Background technology
At society, along with increasing rapidly of electric wire application, the fire caused by electric wire has accounted for sizable ratio.In the market of China, polyolefinic CABLE MATERIALS is occupied an leading position, and typical representative is polyethylene kind and polyvinyl chloride.But polyvinyl chloride cable material produces halogen gas when burning, contaminate environment, and the amount of being fuming is larger.Moreover the developed country such as American-European, Japanese, prohibites and uses containing the objectionable impurities containing halogen such as heavy metal, poly-bromo biphenyl ether.Particularly to fire-resistant cable material, the requirement environmental protection that the kind of fire retardant, synergistic flame retardant are strict.Magnesium hydroxide and aluminium hydroxide are described as nuisanceless inorganic combustion inhibitor, and and many kinds of substance generation synergistic effect.In addition, it is cheap, abundance, not halogen-containing, burning time corrosion-free, not volatile, be combined with polyolefine and can reach good flame retardant effect.
The oxygen index of polyolefin resin only has about 18, very easily burns, and material is very limited in the process of application.
At present, in order to overcome above-mentioned defect, the method usually adopted is: add fire retardant to stop the burning of material.Current fire retardant used is divided into magnalium flame retardant, silicone flame retardant, nitrogenated flame retardant, halogenated flame retardant etc.Silicone flame retardant price is rather stiff; Nitrogenated flame retardant is very easily hydrolyzed; Halogenated flame retardant burning is serious to topsoil; Magnalium flame retardant is cheap, and it is fine that compactedness reaches more than 60% flame retardant properties.And adopt magnalium flame retardant to there is certain defect at present: the selection of synergistic flame retardant.Add flame retardant properties and oxygen index that a small amount of synergistic flame retardant just can improve material to a great extent.
Summary of the invention
The object of the present invention is to provide a kind of high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin and preparation method thereof, to overcome the defect that prior art exists.
Described high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin, its raw material comprises the component of following parts by weight:
Described ethylene-octene copolymer is metallocene ethylene-octene copolymer;
Described ethylene-vinyl acetate copolymer to be vinyl acetate between to for plastic weight content be 14 ~ 28% ethylene-vinyl acetate copolymer;
Described polyethylene is linear low density polyethylene;
Described compatilizer is maleated ethylene vinyl acetate copolyme, ethylene-propylene copolymer or maleic anhydride grafted linear low density polyethylene;
Described fire retardant is metal hydroxides, is preferably magnesium hydroxide, aluminium hydroxide, magnesium hydroxide and aluminium hydroxide composite anti-flaming agent one wherein;
Described synergistic flame retardant is siliceous inorganic salts, preferred kaolin, quartz sand, olive soil or glass microballon in more than one;
Described oxidation inhibitor is more than one in Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant and composite antioxidant;
Described Hinered phenols antioxidant is 2,6 di tert butyl 4 methyl phenol, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester; Described phosphite ester kind antioxidant is trisnonyl phenyl phosphite, isooctyl diphenyl phosphite; Described monothioester kind antioxidant is the two Lauryl Alcohol ester of thio-2 acid; Described composite antioxidant is B215 or B900;
Described lubricant be in fatty acid amide (as methylene bis stearic amide, stearic amide), polyethylene wax, silicone master batch more than one;
Described surface-modifying agent is silane coupling agent or titanate coupling agent, and described silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, functional polysiloxane; Titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester.
During preparation, above-mentioned each component is added melting mixing in Banbury mixer even, then move in single screw extrusion machine and melt extrude, through pelletizing, cooling, packaging, obtain high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin.
Advantage of the present invention:
Due to raw material and reasonable ratio thereof, thus there is excellent mechanical property; Owing to introducing compatilizer and surface treatment agent in formula, make product have good flexibility and avoid Thermal cracking problem.Reasonable owing to introducing synergistic flame retardant, oxidation inhibitor and nano level amount of flame-retardant agent, thus can improve oxygen index and the flame retardant properties of fire retardant material.
Embodiment
Embodiment 1 ~ 6
During preparation, above-mentioned each component is added melting mixing in Banbury mixer even, then move in single screw extrusion machine and melt extrude, through pelletizing, cooling, packaging, obtain high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin.
In embodiment 1 ~ 6, component is parts by weight.Formula is as following table.
Vinyl acetate between to for plastic percentage composition described in embodiment 1 ~ 3 is the ethylene-vinyl acetate copolymer of 28%; Vinyl acetate between to for plastic percentage composition described in embodiment 4 ~ 6 is the ethylene-vinyl acetate copolymer of 14%; Described metal hydroxides is through the aluminium hydroxide of surface treating nano level and magnesium hydroxide.
Detect embodiment 4, the numerical value obtained is as shown in the table, and the desired value in form is machinery industry standard JB/T 10707-2007.
| Title | Unit | Desired value | Representative value |
| Density | g/cm 3 | — | 1.51 |
| Tensile strength | MPa | ≥9.0 | 11.9 |
| Elongation at break | ％ | ≥150 | 188 |
| Oxygen index | ％ | ≥32 | 41 |
| Halogen gas content | mg/g | ≤5 | 0 |
| PH value | — | ≥4.3 | 6.2 |
| Specific conductivity | μS/mm | ≤10 | 0.4 |
Above-mentioned case is only limitted to the present invention, and those skilled in the art can replace, all in the claimed range of right of the present invention with other raw material.
Claims (8)
1. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin, it is characterized in that, its raw material comprises the component of following parts by weight:
2. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, it is characterized in that, described ethylene-octene copolymer is metallocene ethylene-octene copolymer.
3. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, is characterized in that, described ethylene-vinyl acetate copolymer to be vinyl acetate between to for plastic weight content be 14 ~ 28% ethylene-vinyl acetate copolymer.
4. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, it is characterized in that, described polyethylene is linear low density polyethylene.
5. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, it is characterized in that, described compatilizer is maleated ethylene vinyl acetate copolyme, ethylene-propylene copolymer or maleic anhydride grafted linear low density polyethylene.
6. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, it is characterized in that, described fire retardant is metal hydroxides, is preferably magnesium hydroxide, aluminium hydroxide, magnesium hydroxide and aluminium hydroxide composite anti-flaming agent one wherein; Described synergistic flame retardant is siliceous inorganic salts.
7. high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to claim 1, is characterized in that, described oxidation inhibitor is more than one in Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant and composite antioxidant;
Described lubricant be in fatty acid amide (as methylene bis stearic amide, stearic amide), polyethylene wax, silicone master batch more than one;
Described surface-modifying agent is silane coupling agent or titanate coupling agent, and described silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, functional polysiloxane; Titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester.
8. the preparation method of the high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin according to any one of claim 1 ~ 7, it is characterized in that, above-mentioned each component is added melting mixing in Banbury mixer even, then move in single screw extrusion machine and melt extrude, through pelletizing, cooling, namely obtain high oxygen index thermoplastic halogen-free flame retarding cable material of polyolefin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410652728.2A CN104448519A (en) | 2014-11-17 | 2014-11-17 | High-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material and preparation method thereof |
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| CN201410652728.2A CN104448519A (en) | 2014-11-17 | 2014-11-17 | High-oxygen-index thermoplastic halogen-free flame retardant polyolefin cable material and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315541A (en) * | 2015-10-23 | 2016-02-10 | 山东理工大学 | Irradiation crosslinking halogen-free flame retardant polyolefin material for locomotive wires and preparation method of irradiation crosslinking halogen-free flame retardant polyolefin material |
| CN105524324A (en) * | 2016-01-23 | 2016-04-27 | 安徽瑞昊缆业有限公司 | Formula of insulator of super flexible cable |
| CN106633284A (en) * | 2016-11-16 | 2017-05-10 | 中广核三角洲（苏州）高聚物有限公司 | Bunched high-fire-retardant polyolefin sheath layers for network cables |
| CN106750855A (en) * | 2016-11-30 | 2017-05-31 | 中广核三角洲（苏州）新材料研发有限公司 | Fire resisting expansion low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| 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 |
| CN109762236A (en) * | 2018-12-11 | 2019-05-17 | 上海至正道化高分子材料股份有限公司 | A kind of low-cost and high-performance thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS and preparation method thereof and application thereof |
| CN111234361A (en) * | 2020-03-16 | 2020-06-05 | 山东华凌电缆有限公司 | Thermoplastic halogen-free low-smoke flame-retardant polyolefin cable sheath material and preparation method thereof |
| CN112063038A (en) * | 2020-09-25 | 2020-12-11 | 宝胜科技创新股份有限公司 | Halogen-free low-smoke high-flame-retardant thermoplastic power cable sheath material and preparation method thereof |
| CN113462067A (en) * | 2021-07-12 | 2021-10-01 | 潍坊亚星化学股份有限公司 | Halogen-free flame-retardant EVA cable material composite material and preparation method thereof |
| CN114507389A (en) * | 2021-12-29 | 2022-05-17 | 中广核拓普（湖北）新材料有限公司 | Halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
| CN115651305A (en) * | 2022-11-18 | 2023-01-31 | 江苏馨德高分子材料股份有限公司 | High-strength halogen-free flame-retardant optical cable sheath material |
-
2014
- 2014-11-17 CN CN201410652728.2A patent/CN104448519A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315541A (en) * | 2015-10-23 | 2016-02-10 | 山东理工大学 | Irradiation crosslinking halogen-free flame retardant polyolefin material for locomotive wires and preparation method of irradiation crosslinking halogen-free flame retardant polyolefin material |
| CN105524324A (en) * | 2016-01-23 | 2016-04-27 | 安徽瑞昊缆业有限公司 | Formula of insulator of super flexible cable |
| CN106633284A (en) * | 2016-11-16 | 2017-05-10 | 中广核三角洲（苏州）高聚物有限公司 | Bunched high-fire-retardant polyolefin sheath layers for network cables |
| CN106750855A (en) * | 2016-11-30 | 2017-05-31 | 中广核三角洲（苏州）新材料研发有限公司 | Fire resisting expansion low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| 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 |
| CN106867090B (en) * | 2017-03-13 | 2019-11-05 | 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 |
| CN109762236A (en) * | 2018-12-11 | 2019-05-17 | 上海至正道化高分子材料股份有限公司 | A kind of low-cost and high-performance thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS and preparation method thereof and application thereof |
| CN111234361A (en) * | 2020-03-16 | 2020-06-05 | 山东华凌电缆有限公司 | Thermoplastic halogen-free low-smoke flame-retardant polyolefin cable sheath material and preparation method thereof |
| CN112063038A (en) * | 2020-09-25 | 2020-12-11 | 宝胜科技创新股份有限公司 | Halogen-free low-smoke high-flame-retardant thermoplastic power cable sheath material and preparation method thereof |
| CN113462067A (en) * | 2021-07-12 | 2021-10-01 | 潍坊亚星化学股份有限公司 | Halogen-free flame-retardant EVA cable material composite material and preparation method thereof |
| CN114507389A (en) * | 2021-12-29 | 2022-05-17 | 中广核拓普（湖北）新材料有限公司 | Halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
| CN115651305A (en) * | 2022-11-18 | 2023-01-31 | 江苏馨德高分子材料股份有限公司 | High-strength halogen-free flame-retardant optical cable sheath material |
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Application publication date: 20150325 |