CN109627567A - A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material and preparation method thereof - Google Patents
A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention discloses a kind of B1 grades fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable materials and preparation method thereof.The mass fraction of each component in the CABLE MATERIALS are as follows: ethylene-vinyl acetate copolymer (EVA) 5-30%, ethylene-octene copolymer (POE) 1-20%, polyethylene (PE) 1-20%, ethylene-ethyl methacrylate copolymer (EMA) 1-10%, silane 1-5%, compatilizer 1-10%, fire retardant 40-70%, antioxidant 1-5%, other auxiliary agents 0-5%, inert filler 10-40%.CABLE MATERIALS of the invention can satisfy B1 grades of flame-retardancy requirements, and have good mechanical performance and processing performance.
Description
Technical field
The present invention relates to cable material technical fields, and in particular to a kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated electro
Cable material and preparation method thereof.
Background technique
In the electrical fire that China occurs, it is most of be as caused by the aging and overload use of wire and cable, meanwhile, fire
Ignite flammable insulation and sheath material in wire and cable when calamity, causes fire incident further expansion.Wire cable insulating and shield
The toxic gas that the burning of cover material gives out will cause a large amount of casualties, and hinder the fire extinguishing of fire fighter.Low cigarette without
Halogen it is fire-retardant be mainly characterized by being halogen-free in all materials, and the amount of smoke that discharges is seldom in burning.Polyvinyl chloride material
Expect 30min issue can the gas concentration of causing death be 15 times of lethal gas concentration, and what halogen-free polyolefin distributed makes
The lethal gas concentration of people is only the 5% of pvc material.When light transmittance is 70%, the naked view of people differentiates the ability of image only
There is 5m or so.The light transmittance of cigarette that polyvinyl chloride is issued when burning 15% hereinafter, i.e. people is in the cigarette of this concentration, naked view
Distance only 2m or so.Therefore it promotes the use of flame retardant cable and optical cable is of great significance safely to building fire protection.
Based on the above background, major cable factory all improves requirement to cable flame-retardant performance now, however irradiates and hand over
Still have in terms of connection low smoke and zero halogen insulated cable material about the problem of burning fuming amount and calorific value to be solved.Therefore, this field needs
The irradiated crosslinking low-smoke and halogen-free insulated cable material for wanting a kind of fire-retardant rank to reach B1 grades.
Summary of the invention
One of the objects of the present invention is to provide a kind of B1 grades fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable materials, have
Can by B1 grades of flame-retardant standards, mechanical performance height, processing performance is excellent the features such as.
The second object of the present invention is to provide the preparation of above-mentioned B1 grades fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material
Method.
Specifically, the present invention provides a kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material, which is characterized in that
Based on mass fraction, the CABLE MATERIALS includes:
In one or more embodiments, the CABLE MATERIALS has following one or more features:
The mass fraction of ethylene-vinyl acetate copolymer is 5-15%；
The mass fraction of ethylene-octene copolymer is 5-15%；
The mass fraction of polyethylene is 1-5%；
The mass fraction of ethylene-ethyl methacrylate copolymer is 1-5%；
The mass fraction of silane coupling agent is 1-3%；
The mass fraction of compatilizer is 2-8%；
The mass fraction of fire retardant is 40-55%；
The mass fraction of antioxidant is 2-5%；
The mass fraction of other auxiliary agents is 2-5%；With
The mass fraction of inert filler is 10-25%.
In one or more embodiments, the ethylene-ethyl methacrylate copolymer has to be formed with ethylene
Branched structure is formed for backbone structure and with methacrylate；Preferably, the ethylene-ethyl methacrylate copolymer
Melting temperature is 140-160 DEG C, and melt flow rate (MFR) is in 1-10g/10min (190 DEG C, 2.16kg) range.
In one or more embodiments, the fire retardant is aluminium hydroxide, magnesium hydroxide, hypo-aluminum orthophosphate and melamine
One of amine cyanurate or any two or more combination, preferably aluminium hydroxide, magnesium hydroxide and melamine cyanurea
The combination of hydrochlorate.
In one or more embodiments, the inert filler include calcium carbonate, talcum powder, titanium dioxide, montmorillonite or
One of white carbon black is a variety of；Preferably, the inert filler is calcium carbonate.
In one or more embodiments, the CABLE MATERIALS has following one or more features:
The Vinyl Acetate Monomer content of the ethylene-vinyl acetate copolymer is in the range of 20-30wt%, preferably
In the range of 25-28wt%；Preferably, the melt index of the ethylene-vinyl acetate copolymer is in 3-8g/10min
In the range of (190 DEG C, 2.16kg)；
The melt flow rate (MFR) of the ethylene-octene copolymer is in the range of 1-10g/10min (190 DEG C, 2.16kg)；
Preferably, the tensile strength of the ethylene-octene copolymer is greater than 5Mpa, elongation at break is greater than 900%；
The polyethylene is high density polyethylene (HDPE)；
The silane coupling agent is the three of triethoxysilicane alkane derivatives, preferably flash-point >=90 DEG C and molecular weight >=200
Ethoxysilane derivative；
The ethylene-octene copolymer of the polyolefin that the compatilizer is grafted for maleic anhydride, preferably maleic anhydride grafting,
The polyethylene or combinations thereof of maleic anhydride grafting；Preferably, the compatilizer is random ethylene-acrylate-maleic anhydride three
Membered copolymer and/or the polyethylene of maleic anhydride grafting；
The antioxidant compounds for Hinered phenols antioxidant with phosphite ester antioxidant or sulphur ester antioxidant resulting
Composite antioxidant；Preferably, the antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters,
N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, bis- [β-(the 3- tert-butyls-of triethylene-glycol
4- hydroxy-5-methyl base phenyl) propionic ester] and β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester in one
Kind or a variety of combinations compound resulting multiple with three (2,4- di-tert-butyl-phenyl) phosphite esters or the double lauryls of thio-2 acid
Close antioxidant；With
Other described auxiliary agents include one of lubricant, anti-dripping agent, color masterbatch or a variety of；Preferably, the lubrication
Agent is one of polyethylene wax, zinc stearate, erucyl amide and silicone master batch or a variety of combinations and/or the anti-dripping melt
Agent is polytetrafluoroethylene (PTFE).
In one or more embodiments, the CABLE MATERIALS includes:
Mass fraction be 5-15% Vinyl Acetate Monomer content is in the range of 25-28wt% and melt index is in 3-
Ethylene-vinyl acetate copolymer in the range of 8g/10min (190 DEG C, 2.16kg)；
Mass fraction is that the melt flow rate (MFR) of 5-15% in the range of 1-10g/10min (190 DEG C, 2.16kg) and is drawn
Stretch the ethylene-octene copolymer that intensity is greater than 900% greater than 5MPa, elongation at break；
Mass fraction is the high density polyethylene (HDPE) of 1-10%；
Mass fraction is the ethylene-ethyl methacrylate copolymer of 1-5%；
Mass fraction is flash-point >=90 DEG C of 1-3% and the triethoxysilicane alkane derivatives of molecular weight >=200；
Mass fraction is the maleic anhydride grafted polyethylene of 2-8%；
Mass fraction is the aluminium hydroxide of 20-30%；
Mass fraction is the magnesium hydroxide of 5-12%；
Mass fraction is the melamine cyanurate of 5-15%；
Mass fraction is the antioxidant 1010 of 0.1-1%；
Mass fraction is the irgasfos 168 of 1-2%；
Mass fraction is the antioxidant 1098 of 0.1-1%；
Mass fraction is the polytetrafluoroethylene (PTFE) of 0.1-1%；
Mass fraction is the polyethylene wax of 0.5-4%；With
Mass fraction is the calcium carbonate of 10-25%.
B1 described in any embodiment herein grades of fire-retardant irradiated crosslinking low-smoke and halogen-free is prepared the present invention also provides a kind of
The method of insulated cable material, which is characterized in that the described method includes:
(1) each raw material are provided according to weight ratio；
(2) all raw material is put into mixing in mixer；
(3) material after mixing is put into double screw extruder and is sheared, is mediated；With
(4) material being plasticized through double screw extruder is put into single screw extrusion machine and is squeezed out, is granulated；
Thus the CABLE MATERIALS is made.
In one or more embodiments, the method has following one or more features:
Until mixer material temperature reaches 140-160 DEG C, material is poured out from mixer, is put into double screw extruder；
Material after mixing is put into double screw extruder by connecting conveyor track；
Twin-screw temperature is 145-190 DEG C, revolving speed 100-400rpm；With
Single screw rod temperature is 110-160 DEG C, revolving speed 10-50rpm.
The present invention also provides the fire-retardant irradiation of B1 grade being prepared using method described in any one of this paper embodiment
Cross-linking low-smoke halogen-free insulated cable material.
The present invention also provides a kind of electric wire or cable, the sheath of the electric wire or cable is by any embodiment institute herein
The fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of B1 grade stated is prepared；Or the sheath of the electric wire or cable is by containing this
The CABLE MATERIALS of B1 described in any embodiment grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material is prepared in text.
The present invention also provides ethylene-ethyl methacrylate copolymer, magnalium flame retardant, calcium carbonate and optional phosphorus
Nitrogenated flame retardant is preparing its flame retardant property up to B1 grade and is having improved processing performance, mechanical strength, heat-resistant aging and exhausted
Application in the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of edge.
Specific embodiment
To make those skilled in the art can be appreciated that the features of the present invention and effect, below sincerely with regard to specification and claims
In the term that refers to and term carry out general explanation and definition.Unless otherwise specified, otherwise all technologies used herein
And scientific words, it is that those skilled in the art answer the ordinary meaning of the invention understood when there is collision scenario
It is subject to the definition of this specification.
Theory or mechanism described and disclosed herein, either right or wrong, should not in any way limit of the invention
Range, i.e. the content of present invention can be implemented in the case where not limited by any specific theoretical or mechanism.
Herein, all features defined in the form of numberical range or percentage range such as numerical value, quantity, content and concentration
Merely to succinctly and conveniently.Accordingly, the description of numberical range or percentage range should be regarded as having covered and specifically disclose all
Individual number (including integer and score) in possible subranges and range.
Herein, unless otherwise noted, all percentage is mass percent.
It herein, for simplicity of description, can not to all of each technical characteristic in each embodiment or embodiment
The combination of energy is all described.Therefore, as long as there is no contradiction in the combination of these technical features, each embodiment or embodiment
In each technical characteristic can be combined arbitrarily, it is all possible combination be all considered to be this specification record model
It encloses.
Herein, term " containing ", " include " or " contain " indicate that various composition can be applied to mixing of the invention together
In object or composition.Therefore, term " mainly by ... form " and " by ... form " be included in term " containing ", " comprising " or
In "comprising".
Herein, term " B1 grades " refers to that the fire-retardant rank of material, in particular to the burning behavior class of cable reach GB/
The B1 grade of T31247-2014 " cable and optical cable classification system for fire performance " defined.
The present inventor is by a large amount of experiment discovery ethylene-ethyl methacrylate copolymer (EMA) and magnalium
There is flame retardant synergism between flame retardant and inert filler especially calcium carbonate, while successfully improving flame retardant property,
Keep the cost of entire product lower and is provided with superior processing performance.A small amount of phosphorus-nitrogen containing flame retardant is further added, can be made
Product reaches the B1 grade flame retardant property of requirements at the higher level.
Being suitable for the invention ethylene-ethyl methacrylate copolymer (EMA) preferably has using ethylene as main chain, introduces
Methacrylate is the structure of branch.Preferably, it is suitable for the invention the melting of ethylene-ethyl methacrylate copolymer
Temperature is 140-160 DEG C, such as 150 DEG C；Melt flow rate (MFR) is in the range of 1-10g/10min (190 DEG C, 2.16kg).At certain
In a little embodiments, 24MA 02 that the ethylene-ethyl methacrylate copolymer that the present invention uses is France A Kema and/or
The 1209AC of Dupont.
In general, ethylene-ethyl methacrylate copolymer accounts for the fire-retardant irradiated crosslinking low-smoke and halogen-free insulation of B1 grade of the invention
The mass fraction of CABLE MATERIALS raw material can be 1-10%, such as 1-8%, 1-5%, 2-7%, 2-5% etc..
Being suitable for the invention fire retardant can be the fire retardant commonly used in the art in CABLE MATERIALS.Preferably, it is suitable for this
The fire retardant of invention is compounding for magnalium fire retardant and nitrogenated flame retardant, optionally may also include phosphorus flame retardant, such as secondary phosphorus
Sour aluminium etc..Both magnalium fire retardant can be aluminium hydroxide, magnesium hydroxide or combinations thereof, preferably.Magnesium hydroxide and/or hydrogen-oxygen
The average grain diameter for changing aluminium can be in the range of 0.8-3 μm.In certain embodiments, magnesium hydroxide and/or aluminium hydroxide be through
Cross surface modification treatment.For example, being silane coupling agent for the modifying agent of magnesium hydroxide and/or Modified by Aluminum Hydroxide, lead to
Formula is RSiX3, R, which is represented, in formula has the active function groups of affinity or respond (such as: oxygroup, vinyl, ammonia third with macromolecule
Base etc.)；X represents the group (such as halogen, alkoxy, acyloxy) that can be hydrolyzed.Being suitable for the invention nitrogenated flame retardant can
Think melamine cyanurate.Being suitable for the invention aluminium hydroxide can be BASF200 and/or nation forever
Zirconium industry h-wf-1.It is suitable for the invention magnesium hydroxide Ke Yi Wei Ai Teke Aitemag10 and/or Aitemag12.Suitable for this
The melamine cyanurate of invention can be domestic MCA-152.In certain embodiments, the present invention using aluminium hydroxide,
Magnesium hydroxide and the mixture of melamine cyanurate are as fire retardant；In this kind of embodiment, aluminium hydroxide, hydroxide
The weight ratio of magnesium and melamine cyanurate can be 3:(0.5-2): (0.2-2), preferably 3:1:(1-2).
In general, fire retardant accounts for the mass fraction of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
It can be 30-70%, such as 35-55%.In certain embodiments, the present invention uses aluminium hydroxide, magnesium hydroxide and trimerization
The mixture of cyanamide cyanurate is as fire retardant；In this kind of embodiment, with the total restatement of CABLE MATERIALS, the content of aluminium hydroxide
For 20-30%, the content of magnesium hydroxide is 5-12%, and the content of melamine cyanurate is 5-15%.
Being suitable for the invention inert filler can be the inert filler commonly used in the art in CABLE MATERIALS, including but not limited to
One of calcium carbonate, talcum powder, white carbon black, montmorillonite (such as organo montmorillonite) and titanium dioxide or any two kinds of combination, it is excellent
It is selected as calcium carbonate.Preferably, the partial size of inert filler is suitable for the invention between 10-1300 mesh.
In general, inert filler accounts for the quality point of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
Number can be 10-40%, such as 10-30% or 10-25% etc..
In addition to ethylene-ethyl methacrylate copolymer (EMA), fire retardant and inert filler especially calcium carbonate, this hair
Ethylene-vinyl acetate copolymer (EVA), the pungent dilute copolymer (POE) of ethylene-, polyethylene can also be contained in bright CABLE MATERIALS
(PE), silane coupling agent, compatilizer and antioxidant.
Be suitable for the invention ethylene-vinyl acetate copolymer (EVA) can be it is commonly used in the art in CABLE MATERIALS
EVA.In general, 20% can be more than or equal to by being suitable for the invention the content of the Vinyl Acetate Monomer (VA) of EVA, for example,
20-30%.In certain embodiments, the VA content of EVA is suitable for the invention in the range of 25-28%.Suitable for this
The melt index (melt flow rate (MFR)) of the EVA of invention can be in the range of 3-8g/10min (190 DEG C, 2.16kg).At certain
In a little embodiments, the present invention is using VA content is in the range of 25-28% and melt index is in the range of 3-8g/10min
EVA, such as Yangtze BASF 6110MC and/or Taiwan plastic cement 7470M.
In general, the mass fraction that EVA accounts for the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention can
Think 5-30%, such as 5-20%, 5-15%, 5-10%, 8-15% etc..
Being suitable for the invention ethylene-octene copolymer (POE) can be the POE commonly used in the art in CABLE MATERIALS.In general,
The melt index of POE is suitable for the invention in the range of 1-10g/10min (190 DEG C, 2.16kg).Preferably, it is suitable for
POE tensile strength of the invention is greater than 5MPa and/or elongation at break is greater than 900%.In certain embodiments, the present invention makes
With melt index in the range of 1-10g/min (190 DEG C, 2.16kg), tensile strength is greater than 5MPa and elongation at break and is greater than
900% POE, for example, Mitsui chemistry DF840 and/or Dow POE8480.
In general, the mass fraction that POE accounts for the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention can
Think 1-20%, such as 5-20%, 5-15%, 8-15%, 8-12% etc..
Being suitable for the invention polyethylene can be the polyethylene commonly used in the art in CABLE MATERIALS, preferably high-density polyethylene
Alkene.High density polyethylene (HDPE) has good heat resistance and cold resistance, and chemical stability is good；Rigidity and toughness also with higher,
Mechanical strength is good；Dielectric properties, environmental stress crack resistance are also preferable；Hardness, tensile strength and creep properties are poly- better than low-density
Ethylene；Wearability, electrical insulating property, toughness and cold resistance are preferable.In certain embodiments, the polyethylene that the present invention uses is
The 722 of 7300 and/or Japanese Japan of Japanese Japan.
In general, polyethylene accounts for the mass fraction of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
It can be 1-20%, such as 1-15%, 1-10%, 2-10%, 2-8%, 2-5% etc..
Being suitable for the invention silane coupling agent can be the silane coupling agent commonly used in the art in CABLE MATERIALS, such as can be with
For triethoxysilicane alkane derivatives.Herein, triethoxysilicane alkane derivatives refer on the si-h bond in triethoxysilane
Product obtained from hydrogen is replaced by organic substituent, general formula are RSi (OC2H5)3, R represents organic substituent in formula, preferably
There are the active function groups (such as: oxygroup, vinyl, aminopropyl) of affinity or respond with macromolecule.It is a discovery of the invention that silicon
The addition of alkane coupling agent can significantly improve the oxygen index (OI) numerical value of CABLE MATERIALS.Preferably, being suitable for the invention silane coupling agent can
To be the triethoxysilicane alkane derivatives (such as gamma-aminopropyl-triethoxy-silane) of flash-point >=90 DEG C and molecular weight >=200.At certain
In a little embodiments, being suitable for the invention silane coupling agent is γ-aminopropyl triethylsilane, such as middle illuminate irrigates the KH- of person of outstanding talent
550。
In general, silane coupling agent accounts for the quality of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
Score can be 1-5%, such as 1-4%, 2-4%, 2-3%, 1-3% etc..
Being suitable for the invention compatilizer can be the compatilizer commonly used in the art in CABLE MATERIALS, such as can be maleic acid
The polyolefin of acid anhydride grafting.Be suitable for the invention maleic anhydride stem grafting polyolefin compatilizer can selected from maleic anhydride grafting POE,
Maleic anhydride is grafted ethylene acrylate copolymer (such as random ethylene-acrylate-maleic anhydride of PE, maleic anhydride grafting
Terpolymer), maleic anhydride inoculated polypropylene etc., the preferably PE and/or random ethylene-acrylic acid of maleic anhydride grafting
Ester-maleic anhydride terpolymer.In certain embodiments, the compatilizer that the present invention uses is the PE of maleic anhydride grafting,
Such as the LS-102L of the bright Sheng of A1068 and/or Nanjing of magnificent all scientific and technological HD900E, Shenzhen Paasche spy.
In general, compatilizer accounts for the mass fraction of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
It can be 1-10%, such as 2-10%, 2-8%, 3-8% etc..
Being suitable for the invention antioxidant can be the antioxidant commonly used in the art in CABLE MATERIALS, include but is not limited to be obstructed
Phenolic antioxidant, suffocated amine antioxidant, sulphur ester antioxidant, phosphite ester antioxidant or combinations thereof.In certain embodiment party
In case, being suitable for the invention antioxidant is that Hinered phenols antioxidant is compounded with sulphur ester antioxidant or phosphite ester antioxidant
Gained composite antioxidant.Preferably, being suitable for the invention antioxidant is antioxidant 1010 (four [β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] pentaerythritol ester), (N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl of antioxidant 1098
Base) hexamethylene diamine), it is antioxidant 245 (triethylene-glycol is bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester]), anti-
Oxygen agent 1076 (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester), irgasfos 168 (three (the tertiary fourths of 2,4- bis-
Base phenyl) phosphite ester), the two or more compoundings in anti-oxidant DLTP (thio-2 acid double lauryls).It is highly preferred that suitable
It for antioxidant of the invention is one of antioxidant 1010, antioxidant 1098, antioxidant 245 and antioxidant 1076 or a variety of
Combination compound resulting composite antioxidant with irgasfos 168 or anti-oxidant DLTP.It is particularly preferred that being suitable for the invention anti-
Oxygen agent is weight ratio in 0.5:(1-2): (0-5), preferably 0.5:1.5:(0-5) four [3- (3,5- di-t-butyl -4- in range
Hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2,4- DI-tert-butylphenol compounds) phosphite esters (irgasfos 168)
With N, the composite antioxidant of bis- (3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamines (antioxidant 1098) of N '-.
In general, antioxidant accounts for the mass fraction of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
It can be 1-5%, such as 2-5%, 2-4%, 2-3% etc..In certain embodiments, CABLE MATERIALS of the invention contains antioxidant
1010, irgasfos 168 and antioxidant 1098, wherein with the total restatement of CABLE MATERIALS, the content of antioxidant 1010 is 0.1-1%, antioxygen
The content of agent 168 is 1-2%, and the content of antioxidant 1098 is 0.1-1%.
May also include in CABLE MATERIALS of the invention except silane coupling agent, compatilizer, fire retardant, antioxidant, inert filler with
Other outer auxiliary agents, including commonly used in the art in one of anti-dripping agent, lubricant and color masterbatch of CABLE MATERIALS etc. or a variety of.
Being suitable for the invention anti-dripping agent can be the anti-dripping agent commonly used in the art in CABLE MATERIALS, such as PTFE.It is logical
Often, the additive amount of anti-dripping agent can be the 0-1% of CABLE MATERIALS total mass of raw material of the invention, such as 0.1~0.8%.It is suitable for
Lubricant of the invention can be the lubricant commonly used in the art in CABLE MATERIALS, including but not limited to polyethylene wax, zinc stearate,
One of erucyl amide and silicone master batch or any two or more combination, preferably silicone master batch and/or polyethylene wax.It is logical
Often, the additive amount of lubricant can be the 0.5~4% of CABLE MATERIALS total mass of raw material of the invention.
In general, other auxiliary agents account for the quality point of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material raw material of B1 grade of the invention
Number can be 0-5%, such as 1-5%, 2-5% etc..
In certain embodiments, the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of B1 of the invention grade has with next
Item or multinomial feature:
It is more than or equal to 9MPa, preferably greater than or equal to 10MPa according to the tensile strength that GB/T 2951.11 is measured；
It is more than or equal to 180%, preferably greater than or equal to 190% according to the elongation at break that GB/T 2951.11 is measured；
(135 DEG C × 168h) of the tensile strength change rate measured according to GB/T 2951.12 be less than or equal to 15%, it is preferably small
In equal to 12%；
(135 DEG C × 168h) of the elongation at break change rate measured according to GB/T 2951.12 be less than or equal to 15%, preferably
Less than or equal to 10%；
It is more than or equal to 30%, preferably greater than or equal to 35% according to the oxygen index (OI) that GB/T 2406.2 is measured；
It is more than or equal to 1.0 × 10 according to the volume resistivity that GB/T 1410 is measured13Ω·m；
The burning of the wire and cable single vertical made of CABLE MATERIALS of the invention is measured according to GB/T 19666-2005 to pass through
Anti-flammability test；
It is more than or equal to 60 according to the smoke density that GB/T17651.2 is measured；
It is less than or equal to 1.2m according to the propagation of flame that GB/T31248-2014 is measured；
It is less than or equal to 30kW according to the heat release rate peak value that GB/T31248-2014 is measured；
It is less than or equal to 15MJ by the hot total volume in fiery 1200s according to what GB/T31248-2014 was measured；
It is less than or equal to 150W/s according to the fire growth rate index that GB/T31248-2014 is measured；
It is less than or equal to 0.25m according to the production cigarette rate peak value that GB/T31248-2014 is measured2/s；
It is less than or equal to 50m by the production cigarette total amount in fire 1200 according to what GB/T31248-2014 was measured2；With
The Vertical Flame sprawling measured according to GB/T 18380.12 is less than or equal to 425mm, is preferably smaller than equal to 60mm.
The present invention also provides a kind of preparation methods of CABLE MATERIALS, this method comprises:
Mixed phase answers each raw material of mass fraction；With
The raw material mixed is squeezed out, is granulated；
Thus the CABLE MATERIALS is made.
The mixing of this field routine can be used, extrusion, prilling process carry out in the preparation method of CABLE MATERIALS of the invention
Mixing is squeezed out, is granulated.For example, mixer can be used to mix raw material；Double screw extruder and/or single screw rod can be used
Extruder is further mixed, is sheared, is mediated, is plasticized and/or squeezed out to raw material；After squeezing out cooling, pelleter can be used
The material of extrusion is granulated.
Preferably, the preparation method of CABLE MATERIALS of the invention may comprise steps of:
(1) corresponding raw material are got out according to weight ratio；
(2) all raw material is put into mixing in mixer；
(3) material after mixing is put into double screw extruder and is sheared, is mediated；With
(4) material being plasticized through double screw extruder is put into single screw extrusion machine and is squeezed out, is granulated；
Thus the CABLE MATERIALS is made.
In general, material can be poured out from mixer, put into until mixer material temperature reaches 140-160 DEG C, such as 150 DEG C
In double screw extruder；Preferably, the material after mixer is put into subsequent double screw extruder by connection conveyor track.
Temperature, the speed of double-screw extruder screw can be temperature, the speed of the twin-screw shearing of this field routine, engagement CABLE MATERIALS
Degree.In certain embodiments, the temperature of double-screw extruder screw is 145-190 DEG C, revolving speed 100-400rpm.
The material being plasticized is put into rear single screw extrusion machine from twin-screw head after twin-screw shearing, engagement.
The single screw rod that temperature, the speed of single screw extrusion machine screw rod can be this field routine squeezes out temperature, the speed of CABLE MATERIALS.At certain
In a little embodiments, the temperature of single screw extrusion machine screw rod is 110-160 DEG C, revolving speed 10-50rpm.
In certain embodiments, the present invention is granulated using air-cooled pelleter.After granulation, the particle that can be cut is defeated
It send to vibrating screen sieving, can be prepared by B1 grades of the present invention fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material.
It can be the fire-retardant spoke of B1 grade of the invention using the CABLE MATERIALS that the preparation method of CABLE MATERIALS of the invention is prepared
According to cross-linking low-smoke halogen-free insulated cable material.
Compared with the prior art, the advantages of the present invention are as follows:
A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable materials of the present invention can fully meet standard GB/
The performance of the fire-retardant B1 grades of cables required in T31247-2014 and GB/T31248-2014.In addition, the CABLE MATERIALS processing technology is steady
Fixed, situation, expression surface is very smooth and can reach higher linear velocity to improve without being cast for die orifice in cable extrusion process
The yield of cable producer.
Therefore, the present invention also provides a kind of electric wire or cable, the sheath of the electric wire or cable is fire-retardant by B1 grade of the invention
Irradiated crosslinking low-smoke and halogen-free insulated cable material is prepared；Or the sheath of the electric wire or cable is by containing B1 grade resistance of the invention
The CABLE MATERIALS of combustion irradiated crosslinking low-smoke and halogen-free insulated cable material is prepared；Preferably, the electric wire or cable are building cotton covered wire.
The invention also includes ethylene-ethyl methacrylate copolymer, magnalium flame retardant, calcium carbonate and optional phosphorus
Nitrogenated flame retardant is preparing its flame retardant property up to B1 grade and is having improved processing performance, mechanical strength, heat-resistant aging and exhausted
Application in the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of edge.
CABLE MATERIALS and preparation method thereof of the invention is described in further detail below in conjunction with specific embodiment.Ying Li
Solution, these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.For institute in this paper and embodiment
Reagent, method, condition etc., unless otherwise stated, being conventional reagent, method and condition.In the following example
Test method without specific conditions usually measures according to national standards.If without corresponding national standard, according to general
International standard, normal condition or carry out according to the normal condition proposed by manufacturer.
The weight percent proportion of each raw material of the CABLE MATERIALS of embodiment 1-5 and comparative example 1-2 is as shown in table 1 below.
Table 1: the CABLE MATERIALS raw material weight per distribution ratio (wt%) of comparative example 1-2 and embodiment 1-5
The CABLE MATERIALS of embodiment 1-5 and comparative example 1-2 are prepared according to the following steps:
(1) corresponding raw material is got out according to weight percent proportion；
It (2) is in the mixer of 55L by all raw materials investment volume, depression bolt starts mixing；
(3) until mixer material temperature reaches 150 DEG C, material is poured out from mixer, it will be after mixing by connection conveyor track
Material put into subsequent double screw extruder；
(3) material being plasticized rear single screw rod is put into from twin-screw head after twin-screw shearing, kneading to squeeze out
Machine, 145-90 DEG C of twin-screw temperature, revolving speed 100-400rpm, 110-160 DEG C of single screw rod temperature, revolving speed 10-50rpm；
(4) head of single screw rod is granulated using air-cooled pelleter, after the particle cut is delivered to vibrating screen later
Corresponding CABLE MATERIALS is made.
Above-described embodiment 1-5 CABLE MATERIALS being prepared is tested for the property, each performance test project, test method and
Test result is as shown in table 2.
Table 2: the performance test results of the CABLE MATERIALS of embodiment 1-5
It can be seen that the fire-retardant irradiated crosslinking low-smoke and halogen-free of B1 grade of the invention from the properties of the Examples 1 to 5 of table 2
The performances such as mechanical strength, heat-resistant aging, anti-flammability, the insulating properties of insulated cable material comply fully with national standard, other rowers
And foreign standard.
According to standard GB/T31247-2014 " cable and optical cable classification system for fire performance " and GB/T31248-2014 " cable
And optical cable under the conditions of by fire propagation of flame heat release and produce cigarette characteristic test method " for testing of materials smoke density, combustion
It burns the rate of fire travel, heat release rate peak value, the hot total volume by fiery 1200s, burn rate growth indices, produce cigarette speed
Rate peak value, by fiery 1200s produce cigarette total amount, Vertical Flame sprawling etc. performances requirement, to embodiment 1-5 and comparative example 1-2
CABLE MATERIALS carry out life test, corresponding test method and test result are as shown in table 3.
Table 3: the life test results of comparative example 1,2 and the CABLE MATERIALS of embodiment 1-5 comparison
As seen from Table 3, the CABLE MATERIALS of comparative example 1,2, which only has partial properties, can satisfy GB/T31247-2014 and GB/
The requirement of T31248-2014 standard, and the properties of the CABLE MATERIALS of experimental example 1-5 can meet the requirement of above-mentioned standard.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or surmounts the range that the appended claims define.
Claims (10)
1. a kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material, which is characterized in that based on mass fraction, the cable
Material includes:
2. B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material as described in claim 1, which is characterized in that the cable
Material has following one or more features:
The mass fraction of ethylene-vinyl acetate copolymer is 5-15%；
The mass fraction of ethylene-octene copolymer is 5-15%；
The mass fraction of polyethylene is 1-5%；
The mass fraction of ethylene-ethyl methacrylate copolymer is 1-5%；
The mass fraction of silane coupling agent is 1-3%；
The mass fraction of compatilizer is 2-8%；
The mass fraction of fire retardant is 40-55%；
The mass fraction of antioxidant is 2-5%；
The mass fraction of other auxiliary agents is 2-5%；With
The mass fraction of inert filler is 10-25%.
3. B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material as claimed in claim 1 or 2, which is characterized in that
It is backbone structure and with methacrylate shape that the ethylene-ethyl methacrylate copolymer, which has with ethylene formation,
At branched structure；Preferably, the melting temperature of the ethylene-ethyl methacrylate copolymer is 140-160 DEG C, melt flows
Rate is in 1-10g/10min (190 DEG C, 2.16kg) range；
The fire retardant is one of aluminium hydroxide, magnesium hydroxide, hypo-aluminum orthophosphate and melamine cyanurate or any two
Kind or more combination, the preferably combination of aluminium hydroxide, magnesium hydroxide and melamine cyanurate；With
The inert filler includes one of calcium carbonate, talcum powder, titanium dioxide, montmorillonite or white carbon black or a variety of；Preferably,
The inert filler is calcium carbonate.
4. B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material as claimed in any one of claims 1-3, feature exist
In the CABLE MATERIALS has following one or more features:
The Vinyl Acetate Monomer content of the ethylene-vinyl acetate copolymer preferably exists in the range of 20-30wt%
In the range of 25-28wt%；Preferably, the melt index of the ethylene-vinyl acetate copolymer is in 3-8g/10min (190
DEG C, 2.16kg) in the range of；
The melt flow rate (MFR) of the ethylene-octene copolymer is in the range of 1-10g/10min (190 DEG C, 2.16kg)；It is preferred that
Ground, the tensile strength of the ethylene-octene copolymer is greater than 5Mpa, elongation at break is greater than 900%；
The polyethylene is high density polyethylene (HDPE)；
The silane coupling agent is triethoxysilicane alkane derivatives, preferably three ethoxies of flash-point >=90 DEG C and molecular weight >=200
Base silane derivative；
The compatilizer is the polyolefin of maleic anhydride grafting, preferably the ethylene-octene copolymer of maleic anhydride grafting, Malaysia
The polyethylene or combinations thereof of acid anhydrides grafting；Preferably, the compatilizer is total for random ethylene-acrylate-maleic anhydride ternary
Polymers and/or the polyethylene of maleic anhydride grafting；
The antioxidant compounds for Hinered phenols antioxidant with phosphite ester antioxidant or sulphur ester antioxidant resulting compound
Antioxidant；Preferably, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, N, N '-
Double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, the bis- [β-(3- tert-butyl -4- hydroxyls of triethylene-glycol
Base -5- aminomethyl phenyl) propionic ester] and one of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester or
A variety of combinations compounds resulting compound anti-with three (2,4- di-tert-butyl-phenyl) phosphite esters or the double lauryls of thio-2 acid
Oxygen agent；With
Other described auxiliary agents include one of lubricant, anti-dripping agent, color masterbatch or a variety of；Preferably, the lubricant is
One of polyethylene wax, zinc stearate, erucyl amide and silicone master batch or a variety of combinations and/or the anti-dripping agent are
Polytetrafluoroethylene (PTFE).
5. B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material as described in claim 1, which is characterized in that the cable
Material includes:
Mass fraction be 5-15% Vinyl Acetate Monomer content is in the range of 25-28wt% and melt index is in 3-8g/
Ethylene-vinyl acetate copolymer in the range of 10min (190 DEG C, 2.16kg)；
Mass fraction is the melt flow rate (MFR) of 5-15% in the range of 1-10g/10min (190 DEG C, 2.16kg) and stretches strong
Degree is greater than the ethylene-octene copolymer of 5MPa, elongation at break greater than 900%；
Mass fraction is the high density polyethylene (HDPE) of 1-10%；
Mass fraction is the ethylene-ethyl methacrylate copolymer of 1-5%；
Mass fraction is flash-point >=90 DEG C of 1-3% and the triethoxysilicane alkane derivatives of molecular weight >=200；
Mass fraction is the maleic anhydride grafted polyethylene of 2-8%；
Mass fraction is the aluminium hydroxide of 20-30%；
Mass fraction is the magnesium hydroxide of 5-12%；
Mass fraction is the melamine cyanurate of 5-15%；
Mass fraction is the antioxidant 1010 of 0.1-1%；
Mass fraction is the irgasfos 168 of 1-2%；
Mass fraction is the antioxidant 1098 of 0.1-1%；
Mass fraction is the polytetrafluoroethylene (PTFE) of 0.1-1%；
Mass fraction is the polyethylene wax of 0.5-4%；With
Mass fraction is the calcium carbonate of 10-25%.
6. a kind of prepare B1 grades according to any one of claims 1 to 5 fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material
Method, which is characterized in that the described method includes:
(1) each raw material are provided according to weight ratio；
(2) all raw material is put into mixing in mixer；
(3) material after mixing is put into double screw extruder and is sheared, is mediated；With
(4) material being plasticized through double screw extruder is put into single screw extrusion machine and is squeezed out, is granulated；
Thus the CABLE MATERIALS is made.
7. method as claimed in claim 6, which is characterized in that the method has following one or more features:
Until mixer material temperature reaches 140-160 DEG C, material is poured out from mixer, is put into double screw extruder；
Material after mixing is put into double screw extruder by connecting conveyor track；
Twin-screw temperature is 145-190 DEG C, revolving speed 100-400rpm；With
Single screw rod temperature is 110-160 DEG C, revolving speed 10-50rpm.
8. using the fire-retardant irradiated crosslinking low-smoke and halogen-free insulation of B1 grade that method described in any one of claim 6-7 is prepared
CABLE MATERIALS.
9. a kind of electric wire or cable, which is characterized in that the sheath of the electric wire or cable is by any one of claim 1-5 or 8
The fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of B1 grade is prepared；Or the sheath of the electric wire or cable is by containing
The CABLE MATERIALS of the fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material of B1 grade described in any one of claim 1-5 or 8 is prepared into
It arrives.
10. ethylene-ethyl methacrylate copolymer, magnalium flame retardant, calcium carbonate and optional phosphorus-nitrogen containing flame retardant exist
Prepare its flame retardant property up to B1 grade and have improved processing performance, mechanical strength, heat-resistant aging and insulating properties fire-retardant spoke
According to the application in cross-linking low-smoke halogen-free insulated cable material.
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