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CN108456394A - A kind of fire-retardant TPE cable insulating materials or protective cover material and preparation method thereof with electro-magnetic screen function - Google Patents

A kind of fire-retardant TPE cable insulating materials or protective cover material and preparation method thereof with electro-magnetic screen function Download PDF

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Publication number
CN108456394A
CN108456394A CN201810036959.9A CN201810036959A CN108456394A CN 108456394 A CN108456394 A CN 108456394A CN 201810036959 A CN201810036959 A CN 201810036959A CN 108456394 A CN108456394 A CN 108456394A
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fire
retardant
electro
protective cover
magnetic screen
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Inventor
李同兵
黄有为
刘悦
钟荣栋
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ADVANCED THERMOPLASTIC POLYMER TECHNOLOGY Co Ltd
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ADVANCED THERMOPLASTIC POLYMER TECHNOLOGY Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/441Insulators 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/442Insulators 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 aromatic vinyl compounds
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2255Oxides; Hydroxides of metals of molybdenum
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
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    • C08K2003/2265Oxides; Hydroxides of metals of iron
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/322Ammonium phosphate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
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    • C08K2003/323Ammonium polyphosphate
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    • C08L2201/02Flame or fire retardant/resistant
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Abstract

A kind of fire-retardant TPE cable insulating materials or protective cover material and preparation method thereof with electro-magnetic screen function, the TPE cable insulating materials or protective cover material include the raw material of following parts by weight:SEBS or 40 parts of SEPS20,10 30 parts of PP, 10 30 parts of POE, 5 20 parts of PE, 20 40 parts of oil, 5 45 parts of graphene, 5 35 parts of fire retardant, 0.5 5 parts of compatilizer, 0.02 0.1 parts of antioxidant.The TPE cable insulating materials or protective cover material of the present invention has electro-magnetic screen function, its shield effectiveness SE values can reach 17 50db, and flame retardant effect is excellent, single vertical combustion testing can reach V0 grades, and intensity is high, and tensile strength can reach 17MPa or more, flexibility is good, elongation at break is high, and elongation at break can reach 470% or more, excellent in mechanical performance.

Description

A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function and its Preparation method
Technical field
The present invention relates to CABLE MATERIALS technical fields, and in particular to a kind of fire-retardant TPE cables with electro-magnetic screen function are exhausted Edge material or protective cover material and preparation method thereof.
Background technology
Currently, cable is widely used in electric system, information transmission and the fields such as instrument system, still, with traditional Covering material of cable is easy to happen catching fire in use made of high molecular material PVC, causes fire, due to PVC In chlorinity be up to 60%, will produce the smog of the toxic gases such as hydrogen halides and carbon monoxide in combustion.
TPE (Thermoplastic Elastomer) is the abbreviation of thermoplastic elastomer (TPE), is a kind of high-elastic with rubber Property, high intensity, high resilience, but with can injection molding feature material;Not only the processing performance with thermoplastic, but also Physical property with vulcanized rubber is the advantageous combination of plastics and rubber advantage.Because TPE it is environment-protecting and non-poisonous and safety, Hardness range is wide, and has excellent coloring, soft-touch, weatherability, fatigue resistance and temperature tolerance, and processing performance is superior, nothing Must vulcanization, can recycle and reduce cost, both can be with secondary injection molding, with the basis materials such as PP, PE, PC, PS, ABS Coating and bonding, can also be separately formed.TPE is the plastic material that plastic cement processer is commonly used, and feature makes it that can also answer For in electric wire industry.
But general thermoplastic elastomer (TPE) does not have anti-flammability, and with wireless communication tool, the height of radio-television industries Speed development, office computer automation all-round popularization, the rapid proliferation of electric vehicle, electromagnetic radiation be it is ubiquitous, it is non-porous Do not enter, becomes a kind of novel environmental pollution.To fetus, the influence of child is maximum, is exposed to electromagnetic radiation for a long time for electromagnetic radiation Under, cancer, leukaemia etc. can be induced, the inducement of many diseases is become.In addition, electromagnetic interference can also cause instrument, instrument Interference, causes to be unable to normal use, and especially in field of medical device, instrument precision is high, and the electromagnetic interference that cable generates is shadow The main reason for ringing instrument normal work.Therefore, it is necessary to research and develop a kind of fire-retardant TPE cable insulations with electro-magnetic screen function Material or protective cover material.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide one kind having electromagnetic screen The fire-retardant TPE cable insulating materials or protective cover material of function are covered, the TPE cable insulating materials or protective cover material have electro-magnetic screen function, and Flame retardant effect is excellent, and intensity is high, and flexibility is good, and elongation at break is high, excellent in mechanical performance.
Another object of the present invention is to provide a kind of fire-retardant TPE cable insulating materials or sheath with electro-magnetic screen function The preparation method of material, the preparation method step is simple, convenient operation and control, stable quality, and production efficiency is high, and production cost is low, It can large-scale industrial production.
The purpose of the invention is achieved by the following technical solution:A kind of fire-retardant TPE cables with electro-magnetic screen function are exhausted Edge material or protective cover material include the raw material of following parts by weight:
Preferably, the SEBS be styrene units content in 40%-60%, acetate unit content in 20%-30%, fourth Styrene-ethylene-butylene-styrene block copolymer of the alkene unit content in 20%-30%.The present invention is by using benzene second Alkene-ethylene-butylene, Styrene block copolymer, and its unit content is controlled, there is preferable UV stable, antioxidant And thermal stability, it is added to the tensile strength and flexibility that polyurethane can be improved in polyurethane.
The SEPS is for styrene units content in 40%-60%, acetate unit content in 20%-30%, propylene units Styrene ethylene-propylene-styrene type block copolymer of the content in 20%-30%.The present invention is by using styrene-second Alkene-propylene-styrene type block copolymer, and control its unit content, has a fabulous mechanical performance, good weatherability, Splendid cryogenic property, it is preferred that electric insulating quality, it is preferred that heat resistance, fabulous chemical resistance, and have with polyolefin Good compatibility.
Preferably, the PP be Rockwell hardness at a temperature of 90-120,230 DEG C melt index in the equal of 5-20g/10min At least one of poly- polypropylene, block copolymerization polypropylene and atactic copolymerized polypropene.The present invention by using above-mentioned polypropylene, So that the composite material of the present invention has good mechanical property, it is easily processed into type.More preferably, the PP is that Rockwell is hard The degree homopolypropylene of melt index in the metallocene catalysis of 5-20g/10min at a temperature of 90-120,230 DEG C.
Homopolypropylene highly crystallized due to compound with regular structure, therefore fusing point may be up to 167 DEG C, it is heat-resisting, corrosion-resistant, have Higher temperature in use.Density is small, is most light general-purpose plastics.The disadvantage is that low-temperature impact resistance is poor, it is more easy to aging, but can lead to Modification is crossed to be overcome.
The present invention carries out modification by copolymerization by using metallocene to homopolypropylene, using metallocene as catalyst, with third The modification carried out in polymerization stage based on alkene monomer can improve polyacrylic low-temperature flexibility, impact property, the transparency and processing Mobility.
The POE be hardness 70-85A, octene units content 20%-30% ethylene-octene copolymer.The present invention Have ageing-resistant, resistance to smelly in the ethylene-octene copolymer of 20%-30% in 70-85A, octene units content by using hardness The excellent properties such as oxygen, resistant to chemical media are added to the tensile strength and flexibility that polyurethane can be improved in polyurethane.
The PE be low density polyethylene (LDPE), linear low density polyethylene and metallocene linear-low density polyethylene at least It is a kind of.The present invention has higher softening temperature and melting temperature by using above-mentioned PE, there is that intensity is big, good toughness, rigidity Greatly, heat-resisting, the advantages that cold resistance is good, also has good environmental stress crack resistance, the property such as impact strength, tear-resistant intensity Energy.More preferably, the PE be melt index in 0.2-2.2g/10min, density in 0.918-0.946g/cm3It is linear low Density polyethylene.
The oil is at least one of white oil, naphthenic oil and the White Mineral Oil of flash-point >=200 DEG C.The present invention is by using upper Oil is stated, the mobility of SEBS can be improved, improves the processing performance of thermoplastic elastomer (TPE).
Preferably, the graphene is graphene of the surface through coupling agent treatment.Graphene is after coupling agent treatment, surface Containing carboxyl, carbonyl isopolarity group so that the dispersion of graphene in the composite after coupling agent treatment is more uniform, The compatibility of graphene and polyolefin can be improved.Specifically, the coupling agent is KH550 and/or KH770.
Preferably, the graphene is single-layer graphene or multi-layer graphene.The present invention by using single-layer graphene or Multi-layer graphene so that TPE cable material has electro-magnetic screen function, greatly reduces injury of the electromagnetic radiation to human body.More Preferably, the number of plies of the multi-layer graphene is 2-100 layers.
Preferably, the fire retardant is halogen-free flame retardants, and dosage is 10-35 parts;The halogen-free flame retardants be ammonium phosphate, Ammonium polyphosphate, ammonium polyphosphate modifying, hypo-aluminum orthophosphate, melamine and its compound, zinc borate, montmorillonite, clay, metal hydrogen-oxygen At least one of compound, organophosphorus compounds, organic hypophosphites compound and polyalcohol.
Wherein, the ammonium polyphosphate modifying is piperazine ammonium polyphosphate modifying, ethylenediamine ammonium polyphosphate modifying, diethylenetriamine At least one of ammonium polyphosphate modifying and hydroxyethyl ethylenediamine ammonium polyphosphate modifying.
The melamine and its compound are melamine, melamine phosphate, melamine polyphosphate, trimerization Pyrophosphate, melamine hypophosphite, melamine phosphite, melamine cyanurate and 2- carboxyethyl phenyls At least one of phosphinic acids melamine salt.
The metal hydroxides is aluminium hydroxide and/magnesium hydroxide.
The organophosphorus compounds is trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, phosphorus Sour three (2- ethylhexyls) esters, tricresyl phosphate (2- chloroethyls) ester, tricresyl phosphate (2,3- bis- chloropropyl) ester, tricresyl phosphate (2,3- dibromos Propyl) in ester, tricresyl phosphate-diphenyl ester, tricresyl phosphate, triphenyl phosphate and phosphoric acid (2- ethylhexyls)-diphenyl ester It is at least one.
The organic hypophosphites compound is hypophosphorous acid trimethyl, hypophosphorous acid triethyl, three propyl ester of hypophosphorous acid and secondary phosphorus At least one of sour tributyl.
The polyalcohol is at least one of polyester polyol, polyether polyol and phosphorus-containing polyol.
More preferably, the halogen-free flame retardants is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and Meng Tuo Soil is with weight ratio 1-2:0.8-1.2:1:The mixture of 0.4-0.8 compositions.
The present invention can improve the anti-flammability of material by using above-mentioned halogen-free flame retardants, to greatly improve its use Safety further, since fire retardant is not halogen, therefore has the characteristics that environment-protecting and non-poisonous.
Another preferred, the fire retardant is by halogen containing flame-retardant and synergistic flame retardant with weight ratio 4-8:1-2 compositions Mixture, dosage are 10-20 parts;The halogen containing flame-retardant is 2,6- dibromobenzene aethers, tetrabromobisphenol A, hexabromocyclododecane, eight Bromo-ether, decabromodiphenylethane, poly- phenyl-pentabromide phenolic group acrylate, brominated polycarbonate, brominated epoxy resin and brominated polyphenylene second At least one of alkene;The synergistic flame retardant is antimony oxide, bismuth oxide, molybdenum trioxide, di-iron trioxide, oxidation At least one of tin, zinc oxide, zinc borate and zinc sulfate.More preferably, the fire retardant be by decabromodiphenylethane and Antimony oxide is with weight ratio 4-8:The mixture of 1-2 compositions.
The present invention is used in compounding by using above-mentioned halogen containing flame-retardant and synergistic flame retardant, has excellent flame retardant property, And it is cheap, stability is good, additive amount is few, good with the compatibility of synthetic resin material, and the original reason of material can be kept Change performance.
The present invention is used in compounding by using halogen containing flame-retardant and synergistic flame retardant, can greatly reduce inorganic combustion inhibitor Usage amount will not be to the processability of composite material to there is too big harmful effect to the mechanical property of composite material It can cause harmful effect.
Preferably, the compatilizer is polypropylene grafted maleic anhydride, styrene-ethylene-butadiene-styrene copolymer Grafted maleic anhydride, atactic styrene-maleic anhydride copolymer, ethylene-vinyl acetate grafted maleic anhydride and ethylene-octene At least one of copolymer elastomer grafted maleic anhydride.More preferably, the compatilizer is by polypropylene grafted Malaysia Acid anhydrides and styrene-ethylene-butadiene-styrene copolymer grafted maleic anhydride are with weight ratio 1-2:0.5-1.5 compositions mix Close object.
The present invention can improve inorganic filler and organic resin compatibility by using above-mentioned compatilizer, improve composite material Tensile strength and tearing strength, improve rheological performance, improve surface smoothness, it is scratch resistant white.
Preferably, the antioxidant is four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] Ji Wusi Alcohol ester, N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -, three [2,4- di-tert-butyl-phenyls] are sub- Phosphate, diphosphorous acid pentaerythrite tristearin alcohol ester and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester At least one of.More preferably, the antioxidant is by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) third Acid esters] pentaerythritol ester, three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid Positive octadecanol ester is with weight ratio 1:0.2-0.6:The mixture of 0.4-0.8 compositions.
The present invention can delay or inhibit the progress of material oxidation process, to prevent material by using above-mentioned antioxidant The aging of material simultaneously extends its service life.
Preferably, further include 1-10 parts of smoke suppressant;The smoke suppressant is molybdenum compound, iron compound, metal oxide, magnesium At least one of zinc complexes and zinc compound.
Wherein, the molybdenum compound is molybdenum trioxide and/or ammonium octamolybdate.The iron compound is ferrocene.The gold Category oxide is at least one of magnesia, zinc oxide, nickel oxide, zirconium oxide, antimony trioxide and antimony pentoxide.The magnesium Zinc complexes are magnesia and zinc oxide composites.The zinc compound is at least one in zinc borate, zinc aluminate and zinc stannate Kind.
More preferably, the smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 0.5-1.5: 1.5-2.5:The mixture of 1 composition.
For the present invention by using above-mentioned smoke suppressant, smoke suppressing effect is good, can reduce thermoplastic polyurethane and be produced in burning Raw toxic gas and smog.
Preferably, further include 0.5-1.5 parts of 0.2-1.0 parts of UV resistant agent and lubricant.
The UV resistant agent is phenyl salicylate, Ultraviolet Absorber UV-P, ultra-violet absorber UV-O, ultraviolet light suction Receive agent UV-9, ultraviolet absorbent UV-531, ultra-violet absorber UVP-327, ultra-violet absorber RMB, light stabilizer AM- 101, at least one of light stabilizer 744, light stabilizer HPT and 2,4,6- tri- (2 ' n-butoxyphenyl) -1,3,5- triazines. More preferably, the ultra-violet absorber is by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with weight ratio 0.8-1.2:0.5-1.5:The mixture of 1 composition.
The present invention is by using above-mentioned UV resistant agent, with excellent when can absorb ultraviolet light strongly, and be used in compounding Synergistic effect.
The lubricant is atoleine, solid paraffin, natural paraffin wax, microcrystalline wax, chlorinated paraffin, polyethylene wax, oxygen It is hard to change polyethylene wax, aliphatic acid, butyl stearate, glycerin monostearate, ethylene bis stearamide, oleamide, pentaerythrite Resin acid ester, N, N- ethylenebis Stearyl Amine, N, in N- ethylenebis ricinoleic acids acid amide, silicone and fluoropolymer at least It is a kind of.More preferably, the lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 2-4: 0.5-1.5:The mixture of 1 composition.
For the present invention by using above-mentioned lubricant, can make material in process improves the mobility and product of material Release property, improve the processing performance of material.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 180-240 DEG C, screw speed 200-600r/min.
The beneficial effects of the present invention are:The TPE cable insulating materials or protective cover material of the present invention has electro-magnetic screen function, and Flame retardant effect is excellent, and intensity is high, and flexibility is good, and elongation at break is high, excellent in mechanical performance.
The preparation method step of the present invention is simple, convenient operation and control, stable quality, and production efficiency is high, and production cost is low, It can large-scale industrial production.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, include the raw material of following parts by weight:
The SEBS be styrene units content in 40%, acetate unit content in 30%, butene units content 30% Styrene-ethylene-butylene-styrene block copolymer.
The PP is the Rockwell hardness homopolypropylene of melt index in 5g/10min at a temperature of 90,230 DEG C;It is described POE is ethylene-octene copolymer of the hardness in 70A, octene units content 20%;The PE is low density polyethylene (LDPE);It is described Oil is white oil of the flash-point at 200 DEG C.
The graphene is graphene of the surface through coupling agent treatment.
The graphene is single-layer graphene.
The fire retardant is halogen-free flame retardants;The halogen-free flame retardants be ammonium phosphate, ammonium polyphosphate, ammonium polyphosphate modifying, Hypo-aluminum orthophosphate or melamine and its compound.
The compatilizer is polypropylene grafted maleic anhydride.
The antioxidant is four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters.
It further include 1 part of smoke suppressant;The smoke suppressant is molybdenum compound.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 180 DEG C, screw speed 200r/min.
Embodiment 2
A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, include the raw material of following parts by weight:
The SEPS be styrene units content in 40%, acetate unit content in 30%, propylene units content 30% Styrene ethylene-propylene-styrene type block copolymer.
The PP is the Rockwell hardness block copolymerization polypropylene of melt index in 8g/10min at a temperature of 100,230 DEG C; The POE is ethylene-octene copolymer of the hardness in 75A, octene units content 22%;The PE is linear low density polyethylene Alkene;The oil is naphthenic oil of the flash-point at 220 DEG C.
The graphene is graphene of the surface through coupling agent treatment.
The graphene is multi-layer graphene, and the number of plies of the multi-layer graphene is 2 layers.
The fire retardant is by halogen containing flame-retardant and synergistic flame retardant with weight ratio 4:The mixture of 1 composition;It is described halogen Fire retardant is 2,6- dibromobenzene aethers, tetrabromobisphenol A, hexabromocyclododecane, eight bromo ether, decabromodiphenylethane or poly- phenyl-pentabromide phenolic group Acrylate;The synergistic flame retardant is antimony oxide, bismuth oxide, molybdenum trioxide or di-iron trioxide.
The compatilizer is styrene-ethylene-butadiene-styrene copolymer grafted maleic anhydride.
The antioxidant is N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -.
It further include 3 parts of smoke suppressant;The smoke suppressant is iron compound.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 200 DEG C, screw speed 300r/min.
Embodiment 3
A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, include the raw material of following parts by weight:
The SEBS be styrene units content in 50%, acetate unit content in 25%, butene units content 25% Styrene-ethylene-butylene-styrene block copolymer.
The PP is the Rockwell hardness atactic copolymerized polypropene of melt index in 12g/10min at a temperature of 105,230 DEG C; The POE is ethylene-octene copolymer of the hardness in 78A, octene units content 25%;The PE is that metallocene linear is low close Spend polyethylene;The oil is White Mineral Oil of the flash-point at 250 DEG C.
The graphene is graphene of the surface through coupling agent treatment.
The graphene is multi-layer graphene, and the number of plies of the multi-layer graphene is 10 layers.
The fire retardant is halogen-free flame retardants;The halogen-free flame retardants is zinc borate, montmorillonite, clay or metal hydroxide Object.
The compatilizer is atactic styrene-maleic anhydride copolymer.
The antioxidant is three [2,4- di-tert-butyl-phenyls] phosphite esters.
It further include 5 parts of smoke suppressant;The smoke suppressant is metal oxide.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 210 DEG C, screw speed 400r/min.
Embodiment 4
A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, include the raw material of following parts by weight:
The SEPS be styrene units content in 50%, acetate unit content in 25%, propylene units content 25% Styrene ethylene-propylene-styrene type block copolymer.
The PP be Rockwell hardness at a temperature of 110,230 DEG C melt index 16g/10min metallocene catalysis it is equal Poly- polypropylene;The POE is ethylene-octene copolymer of the hardness in 80A, octene units content 28%;The PE is low close Spend polyethylene;The oil is white oil of the flash-point at 280 DEG C.
The graphene is graphene of the surface through coupling agent treatment.
The graphene is multi-layer graphene, and the number of plies of the multi-layer graphene is 50 layers.
The fire retardant is by halogen containing flame-retardant and synergistic flame retardant with weight ratio 8:The mixture of 2 compositions;It is described halogen Fire retardant is brominated polycarbonate, brominated epoxy resin or brominated Polystyrene;The synergistic flame retardant is tin oxide, oxidation Zinc, zinc borate or zinc sulfate.
The compatilizer is ethylene-vinyl acetate grafted maleic anhydride.
The antioxidant is diphosphorous acid pentaerythrite tristearin alcohol ester.
It further include 8 parts of smoke suppressant;The smoke suppressant is magnesium zinc complexes.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 220 DEG C, screw speed 500r/min.
Embodiment 5
A kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, include the raw material of following parts by weight:
The SEBS be styrene units content in 60%, acetate unit content in 20%, butene units content 20% Styrene-ethylene-butylene-styrene block copolymer.
The PP is the Rockwell hardness block copolymerization polypropylene of melt index in 20g/10min at a temperature of 120,230 DEG C; The POE is ethylene-octene copolymer of the hardness in 85A, octene units content 30%;The PE is that melt index exists 1.2g/10min, density is in 0.932g/cm3Linear low density polyethylene;The oil is naphthenic oil of the flash-point at 300 DEG C.
The graphene is graphene of the surface through coupling agent treatment.
The graphene is multi-layer graphene, and the number of plies of the multi-layer graphene is 100 layers.
The fire retardant is halogen-free flame retardants;The halogen-free flame retardants is organophosphorus compounds, organic hypophosphites Compound or polyalcohol.
The compatilizer is ethylene-octene copolymer elastomer graft maleic anhydride.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester.
It further include 10 parts of smoke suppressant;The smoke suppressant is zinc compound.
A kind of preparation method of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, including walk as follows Suddenly:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE with electro-magnetic screen function is made by double screw extruder extruding pelletization in mixture Cable insulating material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 240 DEG C, screw speed 600r/min.
Embodiment 6
The present embodiment and above-described embodiment 1 the difference is that:
The halogen-free flame retardants is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite with weight ratio 1:0.8:1:The mixture of 0.4 composition.
The compatilizer is grafted by polypropylene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer Maleic anhydride is with weight ratio 1:The mixture of 0.5 composition.
The antioxidant be by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, Three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters are with weight Measure ratio 1:0.2:The mixture of 0.4 composition.
The smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 0.5:1.5:The mixture of 1 composition.
Further include 0.5 part of 0.2 part of UV resistant agent and lubricant.
The ultra-violet absorber be by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with Weight ratio 0.8:0.5:The mixture of 1 composition.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 2:0.5:1 composition Mixture.
Embodiment 7
The present embodiment and above-described embodiment 2 the difference is that:
The fire retardant is by decabromodiphenylethane and antimony oxide with weight ratio 4:The mixture of 1 composition.
The compatilizer is grafted by polypropylene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer Maleic anhydride is with weight ratio 1.2:The mixture of 0.8 composition.
The antioxidant be by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, Three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters are with weight Measure ratio 1:0.3:The mixture of 0.5 composition.
The smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 0.8:1.8:The mixture of 1 composition.
Further include 0.8 part of 0.4 part of UV resistant agent and lubricant.
The ultra-violet absorber be by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with Weight ratio 0.9:0.8:The mixture of 1 composition.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 2.5:0.8:1 group At mixture.
Embodiment 8
The present embodiment and above-described embodiment 3 the difference is that:
The halogen-free flame retardants is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite with weight ratio 1.5:1:1:The mixture of 0.6 composition.
The compatilizer is grafted by polypropylene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer Maleic anhydride is with weight ratio 1.5:The mixture of 1 composition.
The antioxidant be by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, Three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters are with weight Measure ratio 1:0.4:The mixture of 0.6 composition.
The smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 1:2:The mixture of 1 composition.
Further include 1 part of 0.6 part of UV resistant agent and lubricant.
The ultra-violet absorber be by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with Weight ratio 1:1:The mixture of 1 composition.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 3:1:1 composition Mixture.
Embodiment 9
The present embodiment and above-described embodiment 4 the difference is that:
The fire retardant is by decabromodiphenylethane and antimony oxide with weight ratio 8:The mixture of 2 compositions.
The compatilizer is grafted by polypropylene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer Maleic anhydride is with weight ratio 1.8:The mixture of 1.2 compositions.
The antioxidant be by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, Three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters are with weight Measure ratio 1:0.5:The mixture of 0.7 composition.
The smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 1.2:2.2:The mixture of 1 composition.
Further include 1.2 parts of 0.8 part of UV resistant agent and lubricant.
The ultra-violet absorber be by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with Weight ratio 1.1:1.2:The mixture of 1 composition.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 3.5:1.2:1 group At mixture.
Embodiment 10
The present embodiment and above-described embodiment 5 the difference is that:
The halogen-free flame retardants is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite with weight ratio 2:1.2:1:The mixture of 0.8 composition.
The compatilizer is grafted by polypropylene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer Maleic anhydride is with weight ratio 2:The mixture of 1.5 compositions.
The antioxidant be by four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, Three [2,4- di-tert-butyl-phenyls] phosphite esters and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters are with weight Measure ratio 1:0.6:The mixture of 0.8 composition.
The smoke suppressant is by ferrocene, antimony oxide and zinc borate with weight ratio 1.5:2.5:The mixture of 1 composition.
Further include 1.5 parts of 1.0 parts of UV resistant agent and lubricant.
The ultra-violet absorber be by ultraviolet absorbent UV-531, ultra-violet absorber RMB and light stabilizer 744 with Weight ratio 1.2:1.5:The mixture of 1 composition.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and silicone with weight ratio 4:1.5:1 composition Mixture.
TPE cable insulating materials or protective cover material produced by the present invention have electro-magnetic screen function, shield effectiveness SE values can be with Reach 17-50db, and flame retardant effect is excellent, single vertical combustion testing can reach V0 grades, and intensity is high, and tensile strength can reach To 17MPa or more, flexibility is good, and elongation at break is high, and elongation at break can reach 470% or more, excellent in mechanical performance.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner, Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.

Claims (10)

1. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function, it is characterised in that:Including following weight The raw material of part:
Wherein, the graphene is graphene of the surface through coupling agent treatment.
2. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The SEBS is that styrene units content contains in 40%-60%, acetate unit content in 20%-30%, butene units Measure the styrene-ethylene-butylene-styrene block copolymer in 20%-30%;The SEPS is that styrene units content exists 40%-60%, acetate unit content 20%-30%, propylene units content 20%-30% styrene ethylene-propylene- Styrene type block copolymer.
3. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The PP be Rockwell hardness at a temperature of 90-120,230 DEG C melt index 5-20g/10min homopolypropylene, At least one of block copolymerization polypropylene and atactic copolymerized polypropene;The POE is hardness in 70-85A, octene units content In the ethylene-octene copolymer of 20%-30%.
4. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The PE be low density polyethylene (LDPE), linear low density polyethylene and metallocene linear-low density polyethylene at least It is a kind of;The oil is at least one of white oil, naphthenic oil and the White Mineral Oil of flash-point >=200 DEG C.
5. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The graphene is single-layer graphene or multi-layer graphene, and the number of plies of the multi-layer graphene is 2-100 layers.
6. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The fire retardant is halogen-free flame retardants, and dosage is 10-35 parts;The halogen-free flame retardants is ammonium phosphate, polyphosphoric acid Ammonium, ammonium polyphosphate modifying, hypo-aluminum orthophosphate, melamine and its compound, zinc borate, montmorillonite, clay, metal hydroxides, At least one of organophosphorus compounds, organic hypophosphites compound and polyalcohol.
7. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The fire retardant is by halogen containing flame-retardant and synergistic flame retardant with weight ratio 4-8:The mixture of 1-2 compositions, dosage It is 10-20 parts;The halogen containing flame-retardant is 2,6- dibromobenzene aethers, tetrabromobisphenol A, hexabromocyclododecane, eight bromo ether, decabrominated dipheny At least one in ethane, poly- phenyl-pentabromide phenolic group acrylate, brominated polycarbonate, brominated epoxy resin and brominated Polystyrene Kind;The synergistic flame retardant is antimony oxide, bismuth oxide, molybdenum trioxide, di-iron trioxide, tin oxide, zinc oxide, boron At least one of sour zinc and zinc sulfate.
8. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The compatilizer is polypropylene grafted maleic anhydride, styrene-ethylene-butadiene-styrene copolymer grafting Malaysia Acid anhydrides, atactic styrene-maleic anhydride copolymer, ethylene-vinyl acetate grafted maleic anhydride and ethylene-octene copolymer bullet At least one of property body grafted maleic anhydride.
9. a kind of fire-retardant TPE cable insulating materials or protective cover material with electro-magnetic screen function according to claim 1, special Sign is:The antioxidant be four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, N, Bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -, three [2,4- di-tert-butyl-phenyls] phosphite esters, In diphosphorous acid pentaerythrite tristearin alcohol ester and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester at least It is a kind of.
10. such as claim 1-9 any one of them a kind of fire-retardant TPE cable insulating materials or sheath with electro-magnetic screen function The preparation method of material, it is characterised in that:Include the following steps:
(1) above-mentioned raw materials mixing is weighed by weight ratio, is put into high speed blender and is uniformly mixed, obtains mixture;
(2) the fire-retardant TPE cables with electro-magnetic screen function are made by double screw extruder extruding pelletization in mixture Insulation Material or protective cover material;
Wherein, the extruder temperature of the double screw extruder is 180-240 DEG C, screw speed 200-600r/min.
CN201810036959.9A 2018-01-15 2018-01-15 A kind of fire-retardant TPE cable insulating materials or protective cover material and preparation method thereof with electro-magnetic screen function Withdrawn CN108456394A (en)

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CN109777027A (en) * 2019-01-10 2019-05-21 宁波市青湖弹性体科技有限公司 A kind of halogen-free flame-retardant conductive elastomer and preparation method thereof for data line electromagnetic shielding
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CN116554631A (en) * 2023-06-13 2023-08-08 广州恒星传导科技股份有限公司 Flexible wear-resistant power line outer sheath and power line
CN117844087A (en) * 2023-11-23 2024-04-09 四川安费尔高分子材料科技有限公司 Polyethylene material with efficient flame retardant property and preparation method thereof

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CN109233100A (en) * 2018-09-07 2019-01-18 安徽华网电缆有限公司 A kind of special plastic substitution shielding material and its manufacturing method
CN109777027B (en) * 2019-01-10 2021-06-08 宁波市青湖弹性体科技有限公司 Halogen-free flame-retardant conductive elastomer for data line electromagnetic shielding and preparation method thereof
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CN110951204A (en) * 2019-12-11 2020-04-03 上海凯波特种电缆料厂有限公司 Flame-retardant TPE sheath material and preparation method and application thereof
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CN113121946A (en) * 2021-04-21 2021-07-16 宁波怡顺佳新材料科技有限公司 TPE material applied to fire hose
CN113621249A (en) * 2021-08-24 2021-11-09 浙江鼎富橡塑科技有限公司 Abnormal sound prevention TPE dustproof sleeve and production process thereof
CN113621249B (en) * 2021-08-24 2022-07-26 浙江鼎富橡塑科技有限公司 Abnormal sound prevention TPE dustproof sleeve and production process thereof
CN113956602A (en) * 2021-10-08 2022-01-21 广州敬信高聚物科技有限公司 Oil-resistant and heat-resistant insulating material and preparation method and application thereof
CN116554631A (en) * 2023-06-13 2023-08-08 广州恒星传导科技股份有限公司 Flexible wear-resistant power line outer sheath and power line
CN116554631B (en) * 2023-06-13 2023-11-07 广州恒星传导科技股份有限公司 Flexible wear-resistant power line outer sheath and power line
CN117844087A (en) * 2023-11-23 2024-04-09 四川安费尔高分子材料科技有限公司 Polyethylene material with efficient flame retardant property and preparation method thereof

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