CN104177695A - Crosslinked halogen-free flame-retardant cable material - Google Patents

Crosslinked halogen-free flame-retardant cable material Download PDF

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Publication number
CN104177695A
CN104177695A CN201410476858.5A CN201410476858A CN104177695A CN 104177695 A CN104177695 A CN 104177695A CN 201410476858 A CN201410476858 A CN 201410476858A CN 104177695 A CN104177695 A CN 104177695A
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free flame
retardant cable
cable materials
crosslinked halogen
retardant
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CN201410476858.5A
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朱忠良
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a crosslinked halogen-free flame-retardant cable material which comprises linear low density polyethylene, ethylene-vinyl acetate copolymer, an inorganic flame retardant, a flame-retardant synergist, maleic anhydride grafted ethylene-vinyl acetate copolymer and a crosslinking agent. The crosslinked halogen-free flame-retardant cable material has the advantages of higher oxygen index during combustion, excellent workability, excellent mechanical properties and excellent flame retardancy.

Description

A kind of crosslinked halogen-free flame-retardant CABLE MATERIALS
Technical field
The present invention relates to a kind of CABLE MATERIALS, be specifically related to a kind of crosslinked halogen-free flame-retardant CABLE MATERIALS.
Background technology
Electric wire Chang Yin self-heating or outside fire and cause burning in electric energy transmitting.In order to improve the flame retardant resistance of electric wire, the initial fire retardant that contains halogen that adds, this type of electric wire discharges a large amount of smog and hydrogen halide in combustion processes, easily makes people be choked to death in fire, simultaneously larger to plant and instrument corrosion.Therefore, the development and application of low cigarette, low halogen and bittern-free flame-proof material has been the developing direction in domestic and international cable and other field.
Crosslinked non-halogen flame-retardant cable can improve its environmental stress resistance performance and resistance toheat significantly, and also improve its temperature classification work-ing life that can extending wire cable.Yet it is fire retardant that current non-halogen flame-retardant cable often be take the hydrate of the inorganic oxides such as aluminium hydroxide, magnesium hydroxide, its shortcoming is that loading level is large, and the interface compatibility between matrix resin is poor and cause the physical deterioration of material and processing characteristics to become bad.
Summary of the invention
The object of the invention is to propose a kind of crosslinked halogen-free flame-retardant CABLE MATERIALS; This crosslinked halogen-free flame-retardant CABLE MATERIALS has higher oxygen index when burning, and has good processing characteristics, mechanical property and flame retardant properties.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of crosslinked halogen-free flame-retardant CABLE MATERIALS, comprising: linear low density polyethylene (LLDPE), ethylene vinyl acetate (EVA), inorganic combustion inhibitor, retardant synergist, ethylene-vinylacetate grafting maleic anhydride copolymer and linking agent.
As preferably, the weight ratio of described linear low density polyethylene and ethylene vinyl acetate is 1:(3～5), be preferably 1:4.
As preferably, described inorganic combustion inhibitor is aluminium hydroxide and/or magnesium hydroxide;
Preferably, by weight percentage, the content of described inorganic combustion inhibitor in described crosslinked halogen-free flame-retardant CABLE MATERIALS is 45%～55%, is preferably 50%.
As preferably, described retardant synergist is organosilicon.
Contriver finds by test of many times, and along with the increase of organosilicon consumption, the mechanical property that can exchange non-halogen flame-retardant cable slightly declines, and oxygen index increases substantially along with the increase of organosilicon consumption.Compare with the system that a large amount of filling inorganic combustion inhibitors improve oxygen index, mechanical property loss of energy is almost negligible.As can be seen here, organosilicon is the good fire retarding synergist of inorganic combustion inhibitor, uses a small amount of organosilicon can effectively improve the flame retardant properties of co-mixing system.In addition, can also observe inorganic combustion inhibitor the organosilyl co-mixing system of interpolation be uniformly dispersed from combustion phenomena, crystal water is easily separated out, and burning evenly and without drip phenomenon, combustionresidue is the inorganics of vitreous state, plays the effect of isolated airborne oxygen.And add when organosilyl co-mixing system burns, can not produce " explosion " phenomenon, and have combustionresidue and white powder drippage.
Preferably, the content of described organosilicon in crosslinked halogen-free flame-retardant CABLE MATERIALS is 2%-4%, is preferably 3%-4%.
The present invention is usingd maleic anhydride grafted ethene-vinyl-acetic ester as compatilizer, the macromolecular chain of compatilizer can tangle mutually with the macromolecular chain of matrix resin, maleic anhydride reacts with inorganic combustion inhibitor and mortise, thereby obviously improved the interface affinity of matrix resin and inorganic combustion inhibitor, inorganic combustion inhibitor has been realized in matrix material dispersed; In the course of processing, along with the increase of maleic anhydride grafted ethene-vinyl-acetic ester, the de-glutinous phenomenon of interface flexible layer clearly, makes the deteriorated situation of composite materials property thereby can improve because filling in a large number inorganic combustion inhibitors.
As preferably, by weight percentage, the content of described ethylene-vinylacetate grafting maleic anhydride copolymer in crosslinked halogen-free flame-retardant CABLE MATERIALS is 6%～12%, is preferably 8%～10%.
As preferably, described linking agent is Dinonylphthalate;
Preferably, by weight percentage, the content of described linking agent in crosslinked halogen-free flame-retardant CABLE MATERIALS is 0.8%～1.2%, is preferably 1%.
Most preferably, crosslinked halogen-free flame-retardant CABLE MATERIALS of the present invention comprises:
Second aspect, the invention provides the complete processing of the high crosslinked halogen-free flame-retardant CABLE MATERIALS as described in first aspect, by each raw materials melt blend of described weight part, then this blend composition is hot-forming on vulcanizing press.
The present invention is usingd organosilicon as retardant synergist, can improve the dispersiveness of inorganic combustion inhibitor in matrix resin, can promote again the formation of the inorganic carbide layer of vitreous state oxygen barrier film when burning, can effectively improve the oxygen index of blend; Take ethylene-vinylacetate grafting maleic anhydride copolymer as compatilizer, can improve mechanical property and the flame retardant properties of CABLE MATERIALS.
To sum up, the present invention, by selecting suitable matrix resin, be take inorganic combustion inhibitor as main flame retardant, and organosilicon is retardant synergist, and Dinonylphthalate is linking agent, can prepare the crosslinked halogen-free flame-retardant CABLE MATERIALS of high comprehensive performance.Prepared crosslinked halogen-free flame-retardant CABLE MATERIALS has higher oxygen index when burning, and has good processing characteristics, mechanical property and flame retardant properties.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.Should be appreciated that enforcement of the present invention is not limited to following examples, those skilled in the art can carry out various improvement based on this, and these also all fall into protection scope of the present invention.
Embodiment 1
By following formula, all raw materials are carried out to melt blending:
Particularly, matrix resin, inorganic combustion inhibitor, retardant synergist, compatilizer and linking agent etc. are taken in proportion, after mixing, add two roller mill melting mixings, melting temperature is controlled at below 125 ℃, mixing time 5min, and slice is standby.
Get above-mentioned blend mold pressing and vulcanize 15min, sample preparation in flakes and in 180 ℃; Finally, by mechanical property, the oxygen index of national standard test gained finished product, result is as shown in table 1:
The performance data of table 1, embodiment 1 made CABLE MATERIALS
Performance Testing method Test result
Tensile strength/MPa GB/T1040-1992 11.2
Elongation at break/% GB/T1040-1992 350
Oxygen index GB/T2406-1993 32
Embodiment 2
By following formula, all raw materials are carried out to melt blending:
Particularly, matrix resin, inorganic combustion inhibitor, retardant synergist, compatilizer and linking agent etc. are taken in proportion, after mixing, add two roller mill melting mixings, melting temperature is controlled at below 125 ℃, mixing time 5min, and slice is standby.
Get above-mentioned blend mold pressing and vulcanize 15min, sample preparation in flakes and in 180 ℃; Finally, by mechanical property, the oxygen index of national standard test gained finished product, result is as shown in table 2:
The performance data of table 2, embodiment 2 made CABLE MATERIALS
Performance Testing method Test result
Tensile strength/MPa GB/T1040-1992 12
Elongation at break/% GB/T1040-1992 360
Oxygen index GB/T2406-1993 36
Embodiment 3
By following formula, all raw materials are carried out to melt blending:
Particularly, matrix resin, inorganic combustion inhibitor, retardant synergist, compatilizer and linking agent etc. are taken in proportion, after mixing, add two roller mill melting mixings, melting temperature is controlled at below 125 ℃, mixing time 5min, and slice is standby.
Get above-mentioned blend mold pressing and vulcanize 15min, sample preparation in flakes and in 180 ℃; Finally, by mechanical property, the oxygen index of national standard test gained finished product, result is as shown in table 3:
The performance data of table 3, embodiment 3 made CABLE MATERIALS
Performance Testing method Test result
Tensile strength/MPa GB/T1040-1992 11.8
Elongation at break/% GB/T1040-1992 356
Oxygen index GB/T2406-1993 33
Applicant statement, the present invention illustrates the present invention by above-described embodiment, but that the present invention is not limited to is above-mentioned, does not mean that the present invention must rely on above-mentioned could enforcement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of the selected raw material of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (8)

1. a crosslinked halogen-free flame-retardant CABLE MATERIALS, is characterized in that, comprising: linear low density polyethylene, ethylene vinyl acetate, inorganic combustion inhibitor, retardant synergist, ethylene-vinylacetate grafting maleic anhydride copolymer and linking agent.
2. crosslinked halogen-free flame-retardant CABLE MATERIALS according to claim 1, is characterized in that, the weight ratio of described linear low density polyethylene and ethylene vinyl acetate is 1:(3～5), be preferably 1:4.
3. crosslinked halogen-free flame-retardant CABLE MATERIALS according to claim 1 and 2, is characterized in that, described inorganic combustion inhibitor is aluminium hydroxide and/or magnesium hydroxide;
Preferably, by weight percentage, the content of described inorganic combustion inhibitor in described crosslinked halogen-free flame-retardant CABLE MATERIALS is 45%～55%, is preferably 50%.
4. according to the crosslinked halogen-free flame-retardant CABLE MATERIALS described in claim 1-3 any one, it is characterized in that, described retardant synergist is organosilicon;
Preferably, the content of described organosilicon in crosslinked halogen-free flame-retardant CABLE MATERIALS is 2%-4%, is preferably 3%-4%.
5. according to the crosslinked halogen-free flame-retardant CABLE MATERIALS described in claim 1-4 any one, it is characterized in that, by weight percentage, the content of described ethylene-vinylacetate grafting maleic anhydride copolymer in crosslinked halogen-free flame-retardant CABLE MATERIALS is 6%～12%, is preferably 8%～10%.
6. according to the crosslinked halogen-free flame-retardant CABLE MATERIALS described in claim 1-5 any one, it is characterized in that, described linking agent is Dinonylphthalate;
Preferably, by weight percentage, the content of described linking agent in crosslinked halogen-free flame-retardant CABLE MATERIALS is 0.8%～1.2%, is preferably 1%.
7. according to the crosslinked halogen-free flame-retardant CABLE MATERIALS described in claim 1-6 any one, it is characterized in that, comprising:
。
8. the complete processing of the high crosslinked halogen-free flame-retardant CABLE MATERIALS as described in claim 1-7 any one, is characterized in that, by each raw materials melt blend of described weight part, then this blend composition is hot-forming on vulcanizing press.
CN201410476858.5A 2014-09-17 2014-09-17 Crosslinked halogen-free flame-retardant cable material Pending CN104177695A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104893088A (en) * 2015-06-17 2015-09-09 上海至正道化高分子材料股份有限公司 Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof
CN105646998A (en) * 2016-04-07 2016-06-08 杭州科佳新材料股份有限公司 Ultraviolet resistant, rat-and-ant-resistant, low-temperature-resistant and environment-friendly polyolefin material and preparation method
CN106009194A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Silane crosslinked polyethylene insulation material black wire cable and preparation method thereof
CN106009225A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Black organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106009224A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Method for preparing silane crosslinking polyethylene insulating material for 10 kV or below black wires and cables through one step
CN106009227A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and preparation method thereof
CN106009230A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Soft flame-retardant halogen-free low-smoke power line insulating material and preparation method thereof
CN106009229A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Black aerial insulated cable and preparing method thereof
CN106009228A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Method for preparing organosilane-crosslinked-polyethylene insulation material for black electric wire of 10 kV or below with double-step method
CN106009231A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Silver gray organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106009226A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106084412A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 Two step method prepares the method for silver gray electric wire organosilane crosslinked polyethylene insulation material
CN106084439A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 10kV and following black electric wire organosilane crosslinked polyethylene insulation material and preparation method thereof
CN106084410A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 One-step method prepares the method for black electric wire organosilane crosslinked polyethylene insulation material
CN106117738A (en) * 2016-07-08 2016-11-16 浙江太湖远大新材料股份有限公司 Electric wire organosilane crosslinked polyethylene insulation material and preparation method thereof
CN106397943A (en) * 2015-07-31 2017-02-15 杭州科佳塑化有限公司 Low-smoke halogen-free flame-retardant cable material and preparation method thereof
CN114815109A (en) * 2022-05-25 2022-07-29 江苏亨通光电股份有限公司 B2 ca-grade large-core multi-layer stranded flame-retardant air-blowing micro cable and preparation method thereof
CN115433400A (en) * 2022-07-25 2022-12-06 广东金阳光电缆实业有限公司 Process for producing halogen-free flame-retardant cable

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104893088A (en) * 2015-06-17 2015-09-09 上海至正道化高分子材料股份有限公司 Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof
CN104893088B (en) * 2015-06-17 2017-05-10 上海至正道化高分子材料股份有限公司 Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof
CN106397943A (en) * 2015-07-31 2017-02-15 杭州科佳塑化有限公司 Low-smoke halogen-free flame-retardant cable material and preparation method thereof
CN105646998A (en) * 2016-04-07 2016-06-08 杭州科佳新材料股份有限公司 Ultraviolet resistant, rat-and-ant-resistant, low-temperature-resistant and environment-friendly polyolefin material and preparation method
CN106009228A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Method for preparing organosilane-crosslinked-polyethylene insulation material for black electric wire of 10 kV or below with double-step method
CN106084412A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 Two step method prepares the method for silver gray electric wire organosilane crosslinked polyethylene insulation material
CN106009230A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Soft flame-retardant halogen-free low-smoke power line insulating material and preparation method thereof
CN106009229A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Black aerial insulated cable and preparing method thereof
CN106009224A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Method for preparing silane crosslinking polyethylene insulating material for 10 kV or below black wires and cables through one step
CN106009231A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Silver gray organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106009226A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106009227A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Halogen-free low-smoke flame-retardant oxygen insulation layer insulating material and preparation method thereof
CN106084439A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 10kV and following black electric wire organosilane crosslinked polyethylene insulation material and preparation method thereof
CN106084410A (en) * 2016-07-08 2016-11-09 浙江太湖远大新材料股份有限公司 One-step method prepares the method for black electric wire organosilane crosslinked polyethylene insulation material
CN106117738A (en) * 2016-07-08 2016-11-16 浙江太湖远大新材料股份有限公司 Electric wire organosilane crosslinked polyethylene insulation material and preparation method thereof
CN106009225A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Black organosilane crosslinked polyethylene wires and cables of 10 kV or below and preparation method thereof
CN106009194A (en) * 2016-07-08 2016-10-12 浙江太湖远大新材料股份有限公司 Silane crosslinked polyethylene insulation material black wire cable and preparation method thereof
CN114815109A (en) * 2022-05-25 2022-07-29 江苏亨通光电股份有限公司 B2 ca-grade large-core multi-layer stranded flame-retardant air-blowing micro cable and preparation method thereof
CN115433400A (en) * 2022-07-25 2022-12-06 广东金阳光电缆实业有限公司 Process for producing halogen-free flame-retardant cable

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Application publication date: 20141203