CN105907019B - Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for wire and cable - Google Patents
Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for wire and cable Download PDFInfo
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- CN105907019B CN105907019B CN201610280131.9A CN201610280131A CN105907019B CN 105907019 B CN105907019 B CN 105907019B CN 201610280131 A CN201610280131 A CN 201610280131A CN 105907019 B CN105907019 B CN 105907019B
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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
- C08L53/00—Compositions 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
- C08L53/02—Compositions 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
- C08L53/025—Compositions 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of halogen-free flame retardant thermoplastic elastomer materials for wire and cable, its raw material includes by weight, 20-40 parts of SEBS, 5-15 parts of thermoplastic vulcanizates elastomer, 2-5 parts of aromatic monomer resin, 15-35 parts of halogen-free flame retardants, 15-30 parts of polyphenylene oxide, 1-3 parts of compatilizer, 2-15 parts of inorganic filler, 8-15 parts of oil of filling, 0.1-0.5 parts of antioxidant；Wherein, the halogen-free flame retardants is made of the melamine polyphosphate of the organophosphorus ester of 55-65% and 35-45% by weight percentage.Thermoplastic elastic material high temperature resistant of the present invention and satisfactory mechanical property, processability is good, while there is good flame-retardance energy, Halogen, and low toxicity, environmental protection.
Description
Technical field
The present invention relates to electric wire and cable material technical field, in particular to a kind of halogen-free flameproof thermoplastic for wire and cable
Property elastomeric material and preparation method thereof.
Background technique
As problem of environmental pollution is more and more prominent, nowadays people's gradually attaching importance to environmental protection, wires and cables industry is no exception,
Necessarily face the requirement to environmental protection.The environmental protection of wires and cables industry is mainly exactly cable material environmental protection, produces wire and cable at present
Largely using macromolecule chemical industries materials such as rubber, polyvinyl chloride, polyethylene, a large amount of poisonous and harmful gas are generated in process of production
Body.Furthermore rubber material processing is complicated, and leftover pieces cannot recycle and be easy to cause secondary pollution.Wherein, it is the advantages of polyvinyl chloride resin
With cost advantage, however easy tacky, loss of properties on aging and non-under easy to crack, high temperature under the cable low temperature that is processed into of this material
Environmental protection；Mechanical property, the environmental stress cracking resistance, resistance toization that the cable product that cross-linking polyethylene materials are processed into has imparted
Learn moral character can and the comprehensive performances such as electrical property, the problem is that anti-weather-aging property is poor, processing performance deficiency etc.；Therefore,
Other than considering the feature performance benefit of material, active development ep-type material is also wanted, produces environment-friendly type wire and cable.
Thermoplastic elastomer (TPE) achieves significant progress in recent years, is proposed a plurality of types of thermoplastic elastics in the market
Body, but various problems are still remained applied to the thermoplastic elastic material in terms of wire and cable, the application of polyphenylene oxide provides
Good fire-retardant and electrical insulation capability, but polyphenylene oxide is due to the disadvantages of viscosity is big, poor processability, insufficient color inhibition, limitation
Its application in wires and cables industry.Patent publication No. is that CN102414274A Chinese patent application is disclosed based on thermoplasticity
The elastomer and method for adding polyphenylene oxide and fire retardant is prepared for a kind of wire cable material, this method can obtain superior resistance
Performance is fired, but but has considerable restraint for preparing fire proofing more resistant to high temperature；Patent publication No. is in CN102414274A
The method that state's patent application publication prepares halogen-free flame-retardant wire CABLE MATERIALS, although also joined polyphenylene oxide improves flame retardant effect,
It is to be difficult to disperse in whole system due to joined the EP rubbers of crosslinking, high temperature resistant and mechanical performance etc. are also difficult
Reach requirement.
Summary of the invention
The problem of based on background technique, the invention proposes a kind of halogen-free combustion-proof thermoplastics for wire and cable
Elastomeric material and preparation method thereof, the thermoplastic elastic material high temperature resistant and satisfactory mechanical property, processability is good, tool
While having good flame-retardance energy, Halogen, low toxicity, environmental protection.
A kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable proposed by the present invention, raw material is by weight
It include: its raw material by weight include: 20-40 parts of SEBS, 5-15 parts of thermoplastic vulcanizates elastomer, aromatic monomer resin 2-5
Part, 15-35 parts of halogen-free flame retardants, 15-30 parts of polyphenylene oxide, 1-3 parts of compatilizer, 2-15 parts of inorganic filler, 8-15 parts of oil is filled, is resisted
0.1-0.5 parts of oxygen agent；
Wherein, the halogen-free flame retardants is the trimerization of the organophosphorus ester and 35-45% by 55-65% by weight percentage
Cyanamide Quadrafos composition；And the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly,
It is stirred to react 10-12h at 120-140 DEG C, dries, it is spare to obtain acidification intercalated graphite for grinding；By phosphorus oxychloride, pentaerythrite
It is added in anhydrous acetonitrile and stirs evenly, under conditions of nitrogen protection, be warming up to 50-60 DEG C, stir 0.5-1h, be added anhydrous
After alchlor, it is continuously heating to 90-100 DEG C, stirs 1-2h, after solvent is distilled off, is washed, it is dry, obtain pentaerythrite
Spirocyclization phosphate diacid chloride；The pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, the acidification intercalation is added
Graphite is stirred to react 5-10h at 80-100 DEG C, cooling, filters, and washing obtains the organophosphorus ester after dry.
In a specific embodiment, the parts by weight of SEBS can be 22,24,27,29,31,33,34,36,38；Thermoplasticity
The parts by weight of vulcanized elastomer can be 6,7,8,9,10,11,12,13,14；The parts by weight of aromatic monomer resin can be
2.2,2.6,2.8,3.1,3.3,3.7,4.2,4.5,4.7；The parts by weight of halogen-free flame retardants can for 16,18,19,22,26,
27,29,31,33,34；The parts by weight of polyphenylene oxide can be 16,17,18,19,21,23,25,27,28,29；The weight of compatilizer
Part can be 1.2,1.4,1.6,1.7,2.1,2.3,2.6,2.8；The parts by weight of inorganic filler can for 3,4,5,6,8,10,
11,12,13,14；The parts by weight for filling oil can be 8.7,9.3,9.8,10.1,11.5,12.6,13.7,14.8；Antioxidant
Parts by weight can be 0.12,0.15,0.17,0.22,0.23,0.25,0.28,0.32,0.36,0.38,0.42,0.45,0.47.
Preferably, the weight proportion of graphite powder, phosphorus oxychloride, pentaerythrite, alchlor are as follows: 1:0.5-1.5:0.2-
0.6:0.01-0.03。
Preferably, the SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, described
The weight average molecular weight of high molecular weight SEBS is 160000-240000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 100000-
The weight average molecular weight of 150000, low molecular weight SEBS are 50000-95000；Preferably, high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS
And the weight proportion of low molecular weight SEBS is 1:3-5:1-3.
Preferably, the thermoplastic vulcanizates elastomer is the polyolefin resin and 65- by 20-35% by weight percentage
80% olefinic rubber is generated through dynamic vulcanization；Preferably, the polyolefin resin is acrylic resin or polyvinyl resin, institute
Stating olefinic rubber is ethylene propylene diene rubber or Ethylene-octene rubber.
Preferably, the aromatic monomer resin is one of CS801, M-80, Endex160 and AMS130 or a variety of
Combination.
Preferably, the intrinsic viscosity of the polyphenylene oxide is 0.1-0.5dl/g；Preferably, the polyphenylene oxide is poly- (2,6- bis-
Methyl-1,4- phenylene) ether.
Preferably, the compatilizer is Hydrogenated thermoplastic's butadiene-styrene rubber-maleic anhydride grafts, Hydrogenated thermoplastic butylbenzene rubber
Glue-methyl methacrylate-grafted object, thermoplastic styrene butadiene rubber-maleic anhydride grafts, Hydrogenated thermoplastic's butadiene-styrene rubber-thermoplastic
One of property polyurethane copolymer, thermoplastic styrene butadiene rubber-methyl methacrylate-grafted object or a variety of combinations；The nothing
Machine filler is one of Paris white, talcum powder, wollastonite in powder or a variety of combinations.
Preferably, the filling oil is saturated straight chain alkane or naphthenic oil；The antioxidant is irgasfos 168 and antioxygen
Agent 1010.
It preferably, further include light stabilizer, colorant in the halogen-free flame retardant thermoplastic elastomer material, in lubricant
One or more kinds of combinations；
Preferably, the light stabilizer is benzotriazole stabilizer, Hinered phenols stabilizer, phosphorous acid esters are stablized
One of agent, hindered amines stabilizer or a variety of combinations；The colorant be oxidized black, iron oxide red, iron oxide yellow,
The combination of one or more of the green blue, chrome green of titanium；The lubricant is fatty acid, fatty acid amide, silicone, stearic acid
The combination of one or more of zinc, dimethicone.
A kind of preparation method of the halogen-free flame retardant thermoplastic elastomer material for wire and cable, comprising: by SEBS, filling
Oil is added in high-speed mixer, mixes 5-10min under the revolving speed of 400-500rpm, obtains oil-filled type Block copolymer SEBS；
By the oil-filled type Block copolymer SEBS, thermoplastic vulcanizates elastomer, aromatic monomer resin, compatilizer, inorganic filler, resist
Oxygen agent is added in high mixer, mixes 15-25min under the revolving speed of 350-450rpm, obtains masterbatch；The masterbatch and Halogen are hindered
Combustion agent, polyphenylene oxide add twin-screw extrude, and are 55-64, screw speed 300-500rpm in screw slenderness ratio, plasticate and add
Work temperature is plasticated under conditions of being 180-240 DEG C, then through tie rod, cooling, after pelletizing, is obtained described for wire and cable
Halogen-free flame retardant thermoplastic elastomer material.
In thermoplastic elastic material of the present invention, selection is added and is made of SEBS and thermoplastic vulcanizates elastomer first
Major ingredient, wherein main body substrate of the SEBS of specified molecular weight range as the elastomeric material, not only comprehensive performance is preferable,
The Miscibility with polyphenylene oxide can also be increased, it, will not be right while performance polyphenylene oxide effectively improves material high temperature resistance
The mechanical mechanics property and processing performance of thermoplastic elastic material have an impact；Also made by the way that thermoplastic vulcanizates elastomer is added
For major ingredient, has and significantly improve the elastic properties of materials, reduce the effect of hardness；
At the same time, the flame retardant property that the material is further increased in the present invention, in above-mentioned thermoplastic elastomer (TPE)
Major ingredient on the basis of, be additionally added the highly efficiency compositional flame retardant system being made of organophosphorus ester and melamine polyphosphate,
Middle organophosphorus ester is by the way that by tiny graphite powder, after peracetic acid intercalation, molecular acid is entered inside graphite, by stone
The inside interlamellar spacing of ink widens, and since interplanar distance increases, destroys graphite flakes shape structure, from
And increase the spacing of graphite platelet structure, make that graphite internal structure becomes loose and volume expands, then by thereon
Condensation reaction is carried out between phosphate diacid chloride after hydroxyl and pentaerythrite spirocyclization, obtains a kind of collecting fire-retardant and synergistic in one
The fire retardant of the efficient organophosphorus ester of body；Here since pentaerythrite spirane structure is as carbon forming agent, carbon content is simultaneously insufficient
To meet the needs of forming burning carbon-coating, therefore by introducing graphite in the structure of the fire retardant, can greatly improve
The phosphorus content of carbon-coating, the layer of charcoal can effectively absorb heat, and heat is hindered to transmit to material inner layer, and interior polymer cracking subtracts
Slow, system flame retardant property is improved, while also having good dispersion efficiency by the graphite powder of Phosphation, makes institute
Stating organophosphorus ester can effectively be scattered in matrix, can not only play flame-retarded efficiency, but also can play the work of skeletal support
With advantageously forming fine and close, efficient layer of charcoal to serve as solid phase charcoal core；Furthermore in addition to containing organophosphorus ester in the fire retardant
Outside, also selection addition melamine polyphosphate is compounded, and the latter is pyrolyzed deamination during heating, generates noninflammability
Gaseous product ammonia alleviate the thermal oxidation of thermoplastic elastomer (TPE) so that the oxygen concentration in ambient enviroment declines；Cause
This, organophosphorus ester and melamine polyphosphate described herein compounding are used as fire retardant, form a kind of collection acid source, charcoal
Source it is gentle derived from one natural polymer subbase expansion type flame retardant, by this fire retardant can effectively in conjunction with matrix,
Precipitation problem will not be brought, the advantage protruded meets the environmental requirement of today's society, and will not be to thermoplastic elastomer (TPE)
The mechanical mechanics property and processing performance of material have an impact；
In addition, being also added into the aromatic monomer resin of specific proportion in the present invention, the application institute can be obviously improved
State the toughness and other mechanical performances of thermoplastic elastomehc material；Saturated straight chain alkane or naphthenic oil are better than as oil is promoted
Traditional paraffin oil systems, so that the thermal stability of the system is best and mechanical property is best；The addition of inorganic filler, so that
There is different degrees of raising in the hardness of system, tensile strength, elongation at break, stretching strength, obtain good body with this
It is mechanical property；The selection of plasticizer, antioxidant and the processing aid of certain content etc., then make thermoplastic elastic material
With good processing performance and anti-aging property.
Specific embodiment
The technical scheme of the invention is described in detail through specific implementation examples.
Embodiment 1
A kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable, raw material include: SEBS 20 by weight
Part, 15 parts of thermoplastic vulcanizates elastomer, 2 parts of CS801 resin, 35 parts of halogen-free flame retardants, 15 parts of polyphenylene oxide, Hydrogenated thermoplastic's butylbenzene
3 parts of rubber-maleic anhydride grafts, 2 parts of Paris white, 15 parts of saturated straight chain alkane, 0.1 part of irgasfos 168；
Wherein, the halogen-free flame retardants is gathered by 55% organophosphorus ester and 45% melamine by weight percentage
Phosphate composition；And the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly, at 120 DEG C
Under be stirred to react 12h, dry, grinding, obtain acidification intercalated graphite it is spare；Phosphorus oxychloride, pentaerythrite are added to anhydrous second
It is stirred evenly in nitrile, under conditions of nitrogen protection, is warming up to 50 DEG C, stirs 1h, after aluminum trichloride (anhydrous) is added, continue to heat up
To 90 DEG C, 2h is stirred, after solvent is distilled off, is washed, it is dry, obtain pentaerythrite spirocyclization phosphate diacid chloride；It will be described
Pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, adds the acidification intercalated graphite, is stirred to react 10h at 80 DEG C,
It is cooling, it filters, washing obtains the organophosphorus ester after dry；Graphite powder, phosphorus oxychloride, pentaerythrite, alchlor
Weight proportion is 1:0.5:0.6:0.01；
The SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, the macromolecule
The weight average molecular weight for measuring SEBS is 160000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 100000, the weight of low molecular weight SEBS
Average molecular weight is 50000, and the weight proportion of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS are 1:3:3；
The thermoplastic vulcanizates elastomer is by 20% polyolefin resin and 80% olefinic rubber by weight percentage
It is generated through dynamic vulcanization, and the polyolefin resin is acrylic resin, the olefinic rubber is ethylene propylene diene rubber；It is described poly-
The intrinsic viscosity of phenylate is 0.1dl/g；Further include in the halogen-free flame retardant thermoplastic elastomer material light stabilizer, colorant and
Lubricant, and the light stabilizer is benzotriazole stabilizer；The colorant is oxidized black；The lubricant is fat
Acid.
Embodiment 2
A kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable, raw material include: SEBS 40 by weight
Part, 5 parts of thermoplastic vulcanizates elastomer, 5 parts of M-80 resin, 15 parts of halogen-free flame retardants, poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene) ether
30 parts, Hydrogenated thermoplastic's butadiene-styrene rubber -1 part of methyl methacrylate-grafted object, 15 parts of talcum powder, 8 parts of naphthenic oil, antioxidant
1010 0.5 parts；
Wherein, the halogen-free flame retardants is gathered by 65% organophosphorus ester and 35% melamine by weight percentage
Phosphate composition, and the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly, at 140 DEG C
Under be stirred to react 10h, dry, grinding, obtain acidification intercalated graphite it is spare；Phosphorus oxychloride, pentaerythrite are added to anhydrous second
It is stirred evenly in nitrile, under conditions of nitrogen protection, is warming up to 60 DEG C, stirs 0.5h, after aluminum trichloride (anhydrous) is added, after of continuing rising
Temperature stirs 1h to 100 DEG C, after solvent is distilled off, washs, dry, obtains pentaerythrite spirocyclization phosphate diacid chloride；By institute
It states pentaerythrite spirocyclization phosphate to be added in methanesulfonic acid, adds the acidification intercalated graphite, be stirred to react at 100 DEG C
5h, it is cooling, it filters, washing obtains the organophosphorus ester after dry；Graphite powder, phosphorus oxychloride, pentaerythrite, alchlor
Weight proportion be 1:1.5:0.2:0.03；
The SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, the macromolecule
The weight average molecular weight for measuring SEBS is 240000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 150000, the weight of low molecular weight SEBS
Average molecular weight is 95000, and the weight proportion of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS are 1:5:1；
The thermoplastic vulcanizates elastomer is by 35% polyolefin resin and 65% olefinic rubber by weight percentage
It is generated through dynamic vulcanization, and the polyolefin resin is polyvinyl resin, the olefinic rubber is Ethylene-octene rubber；Poly- (2,
6- dimethyl-Isosorbide-5-Nitrae-phenylene) ether intrinsic viscosity be 0.5dl/g；It is also wrapped in the halogen-free flame retardant thermoplastic elastomer material
Light stabilizer, colorant and lubricant are included, and the light stabilizer is Hinered phenols stabilizer, the colorant is iron oxide
Red, the lubricant is fatty acid amide.
Embodiment 3
A kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable, raw material include: SEBS 30 by weight
Part, 10 parts of thermoplastic vulcanizates elastomer, 3 parts of Endex160 resin, 25 parts of halogen-free flame retardants, poly- (2,6- dimethyl-Isosorbide-5-Nitrae-Asia benzene
Base) 22 parts of ether, 2 parts of compatilizer, 9 parts of wollastonite in powder, 11 parts of saturated straight chain alkane, 0.3 part of irgasfos 168；
Wherein, the halogen-free flame retardants is gathered by 60% organophosphorus ester and 40% melamine by weight percentage
Phosphate composition, and the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly, at 130 DEG C
Under be stirred to react 11h, dry, grinding, obtain acidification intercalated graphite it is spare；Phosphorus oxychloride, pentaerythrite are added to anhydrous second
It is stirred evenly in nitrile, under conditions of nitrogen protection, is warming up to 55 DEG C, stirs 0.7h, after aluminum trichloride (anhydrous) is added, after of continuing rising
Temperature stirs 1.5h to 95 DEG C, after solvent is distilled off, washs, dry, obtains pentaerythrite spirocyclization phosphate diacid chloride；It will
The pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, adds the acidification intercalated graphite, is stirred to react at 90 DEG C
7h, it is cooling, it filters, washing obtains the organophosphorus ester, graphite powder, phosphorus oxychloride, pentaerythrite, alchlor after dry
Weight proportion be 1:0.7:0.4:0.02；
The SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, the macromolecule
The weight average molecular weight for measuring SEBS is 200000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 120000, the weight of low molecular weight SEBS
Average molecular weight is 70000, and the weight proportion of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS are 1:4:2；
The thermoplastic vulcanizates elastomer is by 27% polyolefin resin and 73% olefinic rubber by weight percentage
It is generated through dynamic vulcanization, the polyolefin resin is acrylic resin, and the olefinic rubber is Ethylene-octene rubber；Poly- (2,6-
Dimethyl-Isosorbide-5-Nitrae-phenylene) ether intrinsic viscosity be 0.3dl/g；The compatilizer is Hydrogenated thermoplastic's butadiene-styrene rubber-methyl-prop
E pioic acid methyl ester graft, two kinds of thermoplastic styrene butadiene rubber-maleic anhydride grafts combinations；The halogen-free combustion-proof thermoplastic elasticity
It further include light stabilizer and colorant in body material, the light stabilizer is phosphite-type stabilisers, hindered amines stabilizer
Two kinds combination；The colorant is iron oxide yellow, green blue, chrome green the three kinds of combinations of titanium.
Embodiment 4
A kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable, raw material include: SEBS 35 by weight
Part, 8 parts of thermoplastic vulcanizates elastomer, 4 parts of aromatic monomer resin, 20 parts of halogen-free flame retardants, 20 parts of polyphenylene oxide, Hydrogenated thermoplastic
2 parts of butadiene-styrene rubber-thermoplastic polyurethane copolymer, 8 parts of inorganic filler, 10 parts of naphthenic oil, 0.2 part of antioxidant 1010；
Wherein, the halogen-free flame retardants is gathered by 60% organophosphorus ester and 40% melamine by weight percentage
Phosphate composition；And the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly, at 125 DEG C
Under be stirred to react 11h, dry, grinding, obtain acidification intercalated graphite it is spare；Phosphorus oxychloride, pentaerythrite are added to anhydrous second
It is stirred evenly in nitrile, under conditions of nitrogen protection, is warming up to 56 DEG C, stirs 0.8h, after aluminum trichloride (anhydrous) is added, after of continuing rising
Temperature stirs 1.3h to 98 DEG C, after solvent is distilled off, washs, dry, obtains pentaerythrite spirocyclization phosphate diacid chloride；It will
The pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, adds the acidification intercalated graphite, is stirred to react at 95 DEG C
8h, it is cooling, it filters, washing obtains the organophosphorus ester, graphite powder, phosphorus oxychloride, pentaerythrite, alchlor after dry
Weight proportion be 1:0.8:0.3:0.02；
The SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, the macromolecule
The weight average molecular weight for measuring SEBS is 210000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 130000, the weight of low molecular weight SEBS
Average molecular weight is 60000, and the weight proportion of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS are 1:4:1；
The thermoplastic vulcanizates elastomer is by 28% polyolefin resin and 72% olefinic rubber by weight percentage
It is generated through dynamic vulcanization, the polyolefin resin is polyvinyl resin, and the olefinic rubber is ethylene propylene diene rubber；The fragrance
Race's monomer resin is two kinds of combinations of M-80, AMS130；The intrinsic viscosity of the polyphenylene oxide is 0.4dl/g；The inorganic filler
For three kinds of combinations of Paris white, talcum powder, wollastonite in powder；It further include lubrication in the halogen-free flame retardant thermoplastic elastomer material
Agent, the lubricant are silicone, zinc stearate, three kinds of dimethicone of combination.
Preparation method described in above-described embodiment 1-4 for the halogen-free flame retardant thermoplastic elastomer material of wire and cable, packet
It includes: SEBS, filling oil being added in high-speed mixer, 5-10min is mixed under the revolving speed of 400-500rpm, it is embedding to obtain oil-filled type
Section copolymer SEBS；By the oil-filled type Block copolymer SEBS, thermoplastic vulcanizates elastomer, aromatic monomer resin, compatible
Agent, inorganic filler, antioxidant are added in high mixer, mix 15-25min under the revolving speed of 350-450rpm, obtain masterbatch；By institute
It states masterbatch and halogen-free flame retardants, polyphenylene oxide adds twin-screw extrude, be 55-64 in screw slenderness ratio, screw speed is
300-500rpm, processing temperature of plasticating are plasticated under conditions of being 180-240 DEG C, then through tie rod, cooling after pelletizing, is obtained
The halogen-free flame retardant thermoplastic elastomer material for wire and cable.
The halogen-free flame retardant thermoplastic elastomer material that wire and cable is used for described in above-described embodiment 1-4 is subjected to performance survey
Examination, as a result as shown in the table:
According to upper table analysis it is found that the halogen-free combustion-proof thermoplastic elasticity that the scheme of 1-4 can obtain through the foregoing embodiment
Body material stretching strength retentivity after 136 DEG C of * 168h hot air agings is greater than greater than 95% with elongation at break conservation rate
The fire-retardant UL94 standard VO grade of 90%, 1.6mm thickness burning, and UL1581VW-1 testing vertical flammability can be passed through；
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (12)
1. a kind of halogen-free flame retardant thermoplastic elastomer material for wire and cable, which is characterized in that its raw material wraps by weight
It includes: 20-40 parts of SEBS, 5-15 parts of thermoplastic vulcanizates elastomer, 2-5 parts of aromatic monomer resin, 15-35 parts of halogen-free flame retardants,
15-30 parts of polyphenylene oxide, 1-3 parts of compatilizer, 2-15 parts of inorganic filler, 8-15 parts of oil of filling, 0.1-0.5 parts of antioxidant；
Wherein, the halogen-free flame retardants is the melamine of the organophosphorus ester and 35-45% by 55-65% by weight percentage
Quadrafos composition；And the preparation process of the organophosphorus ester includes: that graphite powder is added in acetic acid to stir evenly, in 120-
It is stirred to react 10-12h at 140 DEG C, dries, it is spare to obtain acidification intercalated graphite for grinding；Phosphorus oxychloride, pentaerythrite are added
It is stirred evenly into anhydrous acetonitrile, under conditions of nitrogen protection, is warming up to 50-60 DEG C, stirs 0.5-1h, anhydrous trichlorine is added
After changing aluminium, it is continuously heating to 90-100 DEG C, stirs 1-2h, after solvent is distilled off, is washed, it is dry, obtain pentaerythrite loop coil
Change phosphate diacid chloride；The pentaerythrite spirocyclization phosphate diacid chloride is added in methanesulfonic acid, the acidification is added and inserts
Layer graphite, is stirred to react 5-10h at 80-100 DEG C, cooling, filters, and washing obtains the organophosphorus ester after dry；
The SEBS is the mixture of high molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS, the high molecular weight
The weight average molecular weight of SEBS is 160000-240000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is 100000-150000, low point
The weight average molecular weight of son amount SEBS is 50000-95000；
The filling oil is saturated straight chain alkane or naphthenic oil；The antioxidant is irgasfos 168 or antioxidant 1010.
2. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 for wire and cable, which is characterized in that stone
Ink powder, phosphorus oxychloride, pentaerythrite, alchlor weight proportion be 1:0.5-1.5:0.2-0.6:0.01-0.03.
3. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 for wire and cable, which is characterized in that high
The weight proportion of molecular weight SEBS, middle-molecular-weihydroxyethyl SEBS and low molecular weight SEBS are 1:3-5:1-3.
4. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In the thermoplastic vulcanizates elastomer is the olefinic rubber of the polyolefin resin and 65-80% by 20-35% by weight percentage
It is generated through dynamic vulcanization.
5. the halogen-free flame retardant thermoplastic elastomer material according to claim 4 for wire and cable, which is characterized in that institute
Stating polyolefin resin is acrylic resin or polyvinyl resin, and the olefinic rubber is ethylene propylene diene rubber or ethylene-octene rubber
Glue.
6. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In the aromatic monomer resin is one of CS801, M-80, Endex160, AMS130 or a variety of combinations.
7. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In the intrinsic viscosity of the polyphenylene oxide is 0.1-0.5dl/g.
8. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In the polyphenylene oxide is poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene) ether.
9. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In the compatilizer is Hydrogenated thermoplastic's butadiene-styrene rubber-maleic anhydride grafts, Hydrogenated thermoplastic's butadiene-styrene rubber-metering system
Sour methyl esters graft, thermoplastic styrene butadiene rubber-maleic anhydride grafts, Hydrogenated thermoplastic's butadiene-styrene rubber-thermoplastic polyurethane are total
One of polymers, thermoplastic styrene butadiene rubber-methyl methacrylate-grafted object or a variety of combinations；The inorganic filler is carbon
One of sour calcium powder, talcum powder, wollastonite in powder or a variety of combinations.
10. the halogen-free flame retardant thermoplastic elastomer material according to claim 1 or 2 for wire and cable, feature exist
In further including one or more of light stabilizer, colorant, lubricant in the halogen-free flame retardant thermoplastic elastomer material
Combination.
11. the halogen-free flame retardant thermoplastic elastomer material according to claim 10 for wire and cable, which is characterized in that
The light stabilizer is benzotriazole stabilizer, Hinered phenols stabilizer, phosphite-type stabilisers, hindered amines stabilizer
One of or a variety of combinations；The colorant be oxidized black, iron oxide red, iron oxide yellow, titanium be green blue, one in chrome green
Kind or a variety of combinations；The lubricant is fatty acid, in fatty acid amide, silicone, zinc stearate, dimethicone
One or more kinds of combinations.
12. a kind of -11 described in any item halogen-free flame retardant thermoplastic elastomer materials for wire and cable according to claim 1
Preparation method characterized by comprising by SEBS, filling oil be added high-speed mixer in, under the revolving speed of 400-500rpm
5-10min is mixed, oil-filled type Block copolymer SEBS is obtained；By the oil-filled type Block copolymer SEBS, thermoplastic vulcanizates bullet
Property body, aromatic monomer resin, compatilizer, inorganic filler, antioxidant be added high mixer in, under the revolving speed of 350-450rpm mix
15-25min is closed, masterbatch is obtained；The masterbatch and halogen-free flame retardants, polyphenylene oxide are added twin-screw extrude, it is long in screw rod
Diameter ratio is 55-64, and screw speed 300-500rpm, processing temperature of plasticating is plasticated under conditions of being 180-240 DEG C, then is passed through
Tie rod, it is cooling, after pelletizing, obtain the halogen-free flame retardant thermoplastic elastomer material for being used for wire and cable.
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