CN105907019A - Halogen-free flame-retardant thermoplastic elastomer material for wires and cables and preparation method of material - Google Patents
Halogen-free flame-retardant thermoplastic elastomer material for wires and cables and preparation method of material Download PDFInfo
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- CN105907019A CN105907019A CN201610280131.9A CN201610280131A CN105907019A CN 105907019 A CN105907019 A CN 105907019A CN 201610280131 A CN201610280131 A CN 201610280131A CN 105907019 A CN105907019 A CN 105907019A
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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 halogen-free flame-retardant thermoplastic elastomer material for wires and cables. The material comprises, by weight, 20-40 parts of SEBS, 5-15 parts of thermoplastic vulcanized elastomer, 2-5 parts of aromatic monomer resin, 15-35 parts of a halogen-free flame retardant, 15-30 parts of polyphenyl ether, 1-3 parts of a compatilizer, 2-15 parts of an inorganic filler, 8-15 parts of filling oil and 0.1-0.5 part of an antioxidant, wherein the halogen-free flame retardant is composed of, by weight, 55-65% of organic phosphate and 35-45% of melamine polyphosphate. The thermoplastic elastomer material is resistant to high temperature, good in mechanical performance, high in processability, good in flame-retardant performance, halogen-free, low in toxicity and environment-friendly.
Description
Technical field
The present invention relates to electric wire and cable material technical field, hinder particularly to a kind of Halogen for electric wire
Combustion thermoplastic elastic material and preparation method thereof.
Background technology
Along with problem of environmental pollution is more and more prominent, nowadays people's gradually attaching importance to environmental protection, wires and cables industry is also
Unexceptional, necessarily face the requirement to environmental protection.The environmental protection of wires and cables industry is exactly mainly cable material environmental protection,
Produce electric wire at present and use the macromolecule chemical industry materials such as rubber, polyvinyl chloride, polyethylene in a large number, giving birth to
A large amount of toxic and harmful is produced during product.In addition elastomeric material processed complex, leftover pieces can not reclaim appearance
Easily cause secondary pollution.Wherein, the advantage of polyvinyl chloride resin is have cost advantage, but this materials processing
The most tacky, loss of properties on aging and non-environmental protection under easy to crack, high temperature under the cable low temperature become；Crosslinked polyethylene
Materials processing become cable goods impart mechanical property, environmental stress cracking resistance, chemicals-resistant
The combination property such as performance and electrical property, there is problems of poor, the processing characteristics deficiency of anti-weather-aging property etc.；
Therefore, in addition to considering the feature performance benefit of material, also want active development ep-type material, produce environment-friendly type
Electric wire.
Thermoplastic elastomer (TPE) achieves significant progress in recent years, and market is proposed polytype thermoplasticity
Elastomer, but the thermoplastic elastic material in terms of being applied to electric wire still also exists various problem, poly-
The application of phenylate provides good fire-retardant and electrical insulation capability, but polyphenylene oxide is owing to viscosity is big, processing characteristics
The shortcomings such as difference, color inhibition are not enough, limit its application at wires and cables industry.Patent publication No. is
CN102414274A Chinese patent application discloses based on thermoplastic elastomer (TPE) and adds polyphenylene oxide and fire retardant
Method is prepared for a kind of wire cable material, and this method is obtained in that superior fire resistance, but for system
Standby more resistant to elevated temperatures fire proofing but has considerable restraint；Patent publication No. is CN102414274A Chinese patent Shen
Please announce the method preparing halogen-free flame-retardant wire CABLE MATERIALS, although also add polyphenylene oxide and improve flame retardant effect,
But being difficult to dispersion owing to adding the EP rubbers of crosslinking in whole system, it is high temperature resistant and mechanical performance
Etc. aspect also be difficult to reach requirement.
Summary of the invention
Based on problem present in background technology, the present invention proposes a kind of halogen-free flameproof for electric wire
Thermoplastic elastic material and preparation method thereof, described thermoplastic elastic material is high temperature resistant and mechanical performance
Well, processability is good, while there is good flame-retardance energy, and Halogen, low toxicity, environmental protection.
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire that the present invention proposes, its raw material is pressed
Weight portion includes: its raw material includes by weight: SEBS 20-40 part, thermoplastic vulcanizates elastomer 5-15
Part, aromatic monomer resin 2-5 part, halogen-free flame retardants 15-35 part, polyphenylene oxide 15-30 part, compatilizer
1-3 part, inorganic filler 2-15 part, fill oil 8-15 part, antioxidant 0.1-0.5 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 55-65% and 35-45% by weight percentage
Melamine polyphosphate composition；And the preparation technology of described organophosphorus ester includes: graphite powder is added
Stirring in acetic acid, at 120-140 DEG C, stirring reaction 10-12h, dries, and grinds, and obtains acidifying and inserts
Layer graphite is standby；POCl3, pentaerythrite are joined in anhydrous acetonitrile and stir, protects at nitrogen
Under conditions of, it is warming up to 50-60 DEG C, stirs 0.5-1h, after adding aluminum trichloride (anhydrous), be continuously heating to
90-100 DEG C, stir 1-2h, after solvent is distilled off, washing, it is dried, obtains pentaerythrite spirocyclization phosphorus
Acid esters diacid chloride；Described pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, adds described acidifying and insert
Layer graphite, at 80-100 DEG C, stirring reaction 5-10h, cooling, suction filtration, washing, after drying, obtain institute
State organophosphorus ester.
In a specific embodiment, the weight portion of SEBS can be 22,24,27,29,31,33,34,
36、38；The weight portion of thermoplastic vulcanizates elastomer can be 6,7,8,9,10,11,12,13,14；
The weight portion 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 weight portion of halogen-free flame retardants can be 16,18,19,22,26,27,29,31,33,34；
The weight portion of polyphenylene oxide can be 16,17,18,19,21,23,25,27,28,29；Compatilizer
Weight portion can be 1.2,1.4,1.6,1.7,2.1,2.3,2.6,2.8；The weight portion of inorganic filler
Can be 3,4,5,6,8,10,11,12,13,14；The weight portion filling oil can be 8.7,9.3,
9.8、10.1、11.5、12.6、13.7、14.8；The weight portion of antioxidant 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, graphite powder, POCl3, pentaerythrite, the weight proportion of alchlor are:
1:0.5-1.5:0.2-0.6:0.01-0.03。
Preferably, described SEBS is HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS
Mixture, the weight average molecular weight of described HMW SEBS is 160000-240000, middle-molecular-weihydroxyethyl SEBS
Weight average molecular weight be 100000-150000, the weight average molecular weight of low-molecular-weight SEBS is 50000-95000；
Preferably, the weight proportion of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS is
1:3-5:1-3。
Preferably, described thermoplastic vulcanizates elastomer be by weight percentage by the vistanex of 20-35% and
The olefinic rubber of 65-80% generates through dynamic vulcanization；Preferably, described vistanex be acrylic resin or
Polyvinyl resin, described olefinic rubber is ethylene propylene diene rubber or Ethylene-octene rubber.
Preferably, described aromatic monomer resin is in CS801, M-80, Endex160 and AMS130
The combination of one or more.
Preferably, the intrinsic viscosity of described polyphenylene oxide is 0.1-0.5dl/g；Preferably, described polyphenylene oxide is
Poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether.
Preferably, described compatilizer is Hydrogenated thermoplastic's butadiene-styrene rubber-maleic anhydride grafts, Hydrogenated thermoplastic
Butadiene-styrene rubber-methyl methacrylate-grafted thing, thermoplastic styrene butadiene rubber-maleic anhydride grafts, the heat of hydrogenation
Plasticity butadiene-styrene rubber-thermoplastic polyurethane copolymer, thermoplastic styrene butadiene rubber-methyl methacrylate-grafted thing
In the combination of one or more；Described inorganic filler is in Paris white, talcum powder, wollastonite in powder
Kind or multiple combination.
Preferably, described filling oil is saturated straight chain alkane or naphthenic oil；Described antioxidant is irgasfos 168
And antioxidant 1010.
Preferably, described halogen-free flame retardant thermoplastic elastomer material also includes light stabilizer, colouring agent, profit
One or more combination in lubrication prescription；
Preferably, described light stabilizer is benzotriazole stabilizer, Hinered phenols stabilizer, phosphite ester
The combination of one or more in class stabilizer, hindered amines stabilizer；Described colouring agent be oxidized black,
One or more combination in iron oxide red, iron oxide yellow, titanium green grass or young crops orchid, chrome green；Described lubricant is
One or more group in aliphatic acid, fatty acid amide, silicone, zinc stearate, dimethicone
Close.
A kind of preparation method of the halogen-free flame retardant thermoplastic elastomer material for electric wire, including: will
SEBS, filling oil add in high-speed mixer, mix 5-10min, obtain under the rotating speed of 400-500rpm
Oil-filled type Block copolymer SEBS；By described oil-filled type Block copolymer SEBS, thermoplastic vulcanizates elastomer,
Aromatic monomer resin, compatilizer, inorganic filler, antioxidant add in high mixer, 350-450rpm's
Mix 15-25min under rotating speed, obtain masterbatch；Described masterbatch and halogen-free flame retardants, polyphenylene oxide are added double spiral shell
In bar extruder, being 55-64 at screw slenderness ratio, screw speed is 300-500rpm, processing temperature of plasticating
Plasticate under conditions of 180-240 DEG C, then through tie rod, cooling, after pelletizing, obtain described for electricity
The halogen-free flame retardant thermoplastic elastomer material of line cable.
In thermoplastic elastic material of the present invention, first select to add by SEBS and thermoplastic vulcanizates elasticity
The major ingredient of body composition, wherein the SEBS of specific molecular weight range is as the main body base material of described elastomeric material,
Not only combination property is preferable, also can increase the Miscibility with polyphenylene oxide, is effectively improved playing polyphenylene oxide
While material resistance to elevated temperatures, will not be to the mechanical mechanics property of thermoplastic elastic material and processing characteristics
Produce impact；Also by adding thermoplastic vulcanizates elastomer as major ingredient, it has and significantly improves described material
Elasticity, reduces the effect of hardness；
Meanwhile, in order to improve the fire resistance of described material further in the present invention, in above-mentioned thermoplasticity
On the basis of the major ingredient of elastomer, it is additionally added and is efficiently answered by what organophosphorus ester and melamine polyphosphate formed
Join flame retardant system, wherein organophosphorus ester by by tiny graphite powder after peracetic acid intercalation, second
Acid molecule enters into inside graphite, the interior layer spacing of graphite is widened, owing to interplanar distance increases, through height
Temperature makes graphite flakes shape structure be destroyed after processing, thus increases the spacing of graphite platelet structure, makes stone
Ink internal structure becomes loose and volume and expands, then by hydroxyl thereon and pentaerythrite spirocyclization
After phosphate diacid chloride between carry out condensation reaction, obtain a kind of integrating efficiently having of fire-retardant and synergistic
The fire retardant of machine phosphate；Here owing to pentaerythrite spirane structure is as carbon forming agent, its carbon content is the most not enough
With the satisfied demand forming burning carbon-coating, therefore by introducing graphite in the structure of described fire retardant, it can
To be greatly improved the phosphorus content of carbon-coating, described layer of charcoal can effectively absorb heat, hinders heat to material inner layer
Transmission, the cracking of interior polymeric thing slows down, and system fire resistance is improved, simultaneously through the stone of Phosphation
Ink powder also has good dispersion usefulness, and it makes described organophosphorus ester to be effectively scattered in matrix, no
Only can play flame-retarded efficiency, and the effect of skeletal support can be played, thus serve as solid phase charcoal core, have
It is beneficial to form densification, efficient layer of charcoal；In the most described fire retardant in addition to containing organophosphorus ester, also select to add
Entering melamine polyphosphate to compound, the latter is pyrolyzed deamination during heating up, and generates noninflammability
Gaseous product ammonia so that oxygen concentration in surrounding environment declines, and alleviates the heat of thermoplastic elastomer (TPE)
Oxidation；Therefore, organophosphorus ester described herein and melamine polyphosphate are compounding as fire-retardant
Agent, defines a kind of acid source, gentle natural polymer subbase expansion type flame retardant coming from one in charcoal source of collecting, logical
Crossing this fire retardant can effectively be combined with matrix, will not bring precipitation problem, its prominent advantage all accords with
Close the environmental requirement of society, and will not be to the mechanical mechanics property of thermoplastic elastic material and processing
Performance produces impact；
Further, in the present invention, being also added into the aromatic monomer resin of specific proportioning, it can be obviously improved
The toughness of herein described thermoplastic elastomehc material and other mechanical performances；Saturated straight chain alkane or naphthenic oil
As promoting oil, it is better than traditional paraffin oil system so that the heat endurance of described system is preferably and mechanics
Performance is optimal；The addition of inorganic filler so that the hardness of system, hot strength, elongation at break, stretches surely
All there is raising in various degree in intensity, obtains good system mechanical property with this；The plasticising of certain content
The selection of agent, antioxidant and processing aid etc., then make thermoplastic elastic material have good processing
Performance and ageing resistace.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight:
SEBS 20 parts, 15 parts of thermoplastic vulcanizates elastomer, CS801 resin 2 parts, halogen-free flame retardants 35 parts, poly-
Phenylate 15 parts, Hydrogenated thermoplastic's butadiene-styrene rubber-maleic anhydride grafts 3 parts, Paris white 2 parts is saturated
Linear paraffin 15 parts, irgasfos 168 0.1 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 55% and the melamine of 45% by weight percentage
Amine Quadrafos forms；And the preparation technology of described organophosphorus ester includes: graphite powder is added in acetic acid and stirs
Mixing uniformly, at 120 DEG C, stirring reaction 12h, dries, and grinds, and obtains being acidified intercalated graphite standby；By three
Chlorethoxyfos, pentaerythrite join in anhydrous acetonitrile and stir, and under conditions of nitrogen is protected, are warming up to
50 DEG C, stir 1h, after adding aluminum trichloride (anhydrous), be continuously heating to 90 DEG C, stir 2h, be distilled off
After solvent, washing, it is dried, obtains pentaerythrite spirocyclization phosphate diacid chloride；By described pentaerythrite spiral shell
Cyclisation phosphate adds in methanesulfonic acid, adds described acidifying intercalated graphite, stirring reaction 10h at 80 DEG C,
Cooling, suction filtration, washing, after drying, obtain described organophosphorus ester；Graphite powder, POCl3, season penta
Tetrol, the weight proportion of alchlor are 1:0.5:0.6:0.01；
Described SEBS is the mixture of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS,
The weight average molecular weight of described HMW SEBS is 160000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is
100000, the weight average molecular weight of low-molecular-weight SEBS is 50000, and HMW SEBS, middle-molecular-weihydroxyethyl
The weight proportion of SEBS and low-molecular-weight SEBS is 1:3:3；
Described thermoplastic vulcanizates elastomer is the vistanex by 20% and the alkene of 80% by weight percentage
Rubber generates through dynamic vulcanization, and described vistanex is acrylic resin, and described olefinic rubber is ternary
EP rubbers；The intrinsic viscosity of described polyphenylene oxide is 0.1dl/g；Described halogen-free flame-retardant thermoplastic elastomer material
Material also includes light stabilizer, colouring agent and lubricant, and described light stabilizer is benzotriazole stabilizer；
Described colouring agent is oxidized black；Described lubricant is aliphatic acid.
Embodiment 2
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight:
SEBS 40 parts, 5 parts of thermoplastic vulcanizates elastomer, M-80 resin 5 parts, halogen-free flame retardants 15 parts, poly-(2,
6-dimethyl-Isosorbide-5-Nitrae-phenylene) 30 parts of ether, Hydrogenated thermoplastic's butadiene-styrene rubber-methyl methacrylate-grafted
Thing 1 part, talcum powder 15 parts, naphthenic oil 8 parts, antioxidant 1010 0.5 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 65% and the melamine of 35% by weight percentage
Amine Quadrafos forms, and the preparation technology of described organophosphorus ester includes: is added in acetic acid by graphite powder and stirs
Mixing uniformly, at 140 DEG C, stirring reaction 10h, dries, and grinds, and obtains being acidified intercalated graphite standby；By three
Chlorethoxyfos, pentaerythrite join in anhydrous acetonitrile and stir, and under conditions of nitrogen is protected, are warming up to
60 DEG C, stirring 0.5h, after adding aluminum trichloride (anhydrous), be continuously heating to 100 DEG C, stir 1h, distillation removes
After removing solvent, washing, it is dried, obtains pentaerythrite spirocyclization phosphate diacid chloride；By described pentaerythrite
Spirocyclization phosphate adds in methanesulfonic acid, adds described acidifying intercalated graphite, stirring reaction at 100 DEG C
5h, cooling, suction filtration, washing, after drying, obtain described organophosphorus ester；Graphite powder, POCl3,
Pentaerythrite, the weight proportion of alchlor are 1:1.5:0.2:0.03；
Described SEBS is the mixture of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS,
The weight average molecular weight of described HMW SEBS is 240000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is
150000, the weight average molecular weight of low-molecular-weight SEBS is 95000, and HMW SEBS, middle-molecular-weihydroxyethyl
The weight proportion of SEBS and low-molecular-weight SEBS is 1:5:1；
Described thermoplastic vulcanizates elastomer is the vistanex by 35% and the alkene of 65% by weight percentage
Rubber generates through dynamic vulcanization, and described vistanex is polyvinyl resin, described olefinic rubber be ethene-
Octene rubber；The intrinsic viscosity of poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether is 0.5dl/g；Described nothing
Halogen flame retardant thermoplastic elastomer material also includes light stabilizer, colouring agent and lubricant, and described light is stable
Agent is Hinered phenols stabilizer, and described colouring agent is iron oxide red, and described lubricant is fatty acid amide.
Embodiment 3
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight:
SEBS 30 parts, 10 parts of thermoplastic vulcanizates elastomer, Endex160 resin 3 parts, halogen-free flame retardants 25 parts,
Poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) 22 parts of ether, compatilizer 2 parts, wollastonite in powder 9 parts is saturated
Linear paraffin 11 parts, irgasfos 168 0.3 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 60% and the melamine of 40% by weight percentage
Amine Quadrafos forms, and the preparation technology of described organophosphorus ester includes: is added in acetic acid by graphite powder and stirs
Mixing uniformly, at 130 DEG C, stirring reaction 11h, dries, and grinds, and obtains being acidified intercalated graphite standby；By three
Chlorethoxyfos, pentaerythrite join in anhydrous acetonitrile and stir, and under conditions of nitrogen is protected, are warming up to
55 DEG C, stir 0.7h, after adding aluminum trichloride (anhydrous), be continuously heating to 95 DEG C, stir 1.5h, distillation
After removing solvent, washing, it is dried, obtains pentaerythrite spirocyclization phosphate diacid chloride；By described Ji Wusi
Alcohol spirocyclization phosphate adds in methanesulfonic acid, adds described acidifying intercalated graphite, stirring reaction at 90 DEG C
7h, cooling, suction filtration, washing, after drying, obtain described organophosphorus ester, graphite powder, POCl3,
Pentaerythrite, the weight proportion of alchlor are 1:0.7:0.4:0.02；
Described SEBS is the mixture of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS,
The weight average molecular weight of described HMW SEBS is 200000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is
120000, the weight average molecular weight of low-molecular-weight SEBS is 70000, and HMW SEBS, middle-molecular-weihydroxyethyl
The weight proportion of SEBS and low-molecular-weight SEBS is 1:4:2；
Described thermoplastic vulcanizates elastomer is the vistanex by 27% and the alkene of 73% by weight percentage
Rubber through dynamic vulcanization generate, described vistanex is acrylic resin, described olefinic rubber be ethene-
Octene rubber；The intrinsic viscosity of poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether is 0.3dl/g；Described phase
Holding agent is Hydrogenated thermoplastic's butadiene-styrene rubber-methyl methacrylate-grafted thing, thermoplastic styrene butadiene rubber-maleic acid
Two kinds of combinations of acid anhydride graft；Described halogen-free flame retardant thermoplastic elastomer material also includes light stabilizer and
Toner, described light stabilizer is two kinds of combinations of phosphite-type stabilisers, hindered amines stabilizer；Described
Colouring agent is iron oxide yellow, titanium green grass or young crops orchid, three kinds of combinations of chrome green.
Embodiment 4
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight:
SEBS 35 parts, 8 parts of thermoplastic vulcanizates elastomer, aromatic monomer resin 4 parts, halogen-free flame retardants 20 parts,
Polyphenylene oxide 20 parts, Hydrogenated thermoplastic's butadiene-styrene rubber-thermoplastic polyurethane copolymer 2 parts, inorganic filler 8 parts,
Naphthenic oil 10 parts, antioxidant 1010 0.2 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 60% and the melamine of 40% by weight percentage
Amine Quadrafos forms；And the preparation technology of described organophosphorus ester includes: graphite powder is added in acetic acid and stirs
Mixing uniformly, at 125 DEG C, stirring reaction 11h, dries, and grinds, and obtains being acidified intercalated graphite standby；By three
Chlorethoxyfos, pentaerythrite join in anhydrous acetonitrile and stir, and under conditions of nitrogen is protected, are warming up to
56 DEG C, stir 0.8h, after adding aluminum trichloride (anhydrous), be continuously heating to 98 DEG C, stir 1.3h, distillation
After removing solvent, washing, it is dried, obtains pentaerythrite spirocyclization phosphate diacid chloride；By described Ji Wusi
Alcohol spirocyclization phosphate adds in methanesulfonic acid, adds described acidifying intercalated graphite, stirring reaction at 95 DEG C
8h, cooling, suction filtration, washing, after drying, obtain described organophosphorus ester, graphite powder, POCl3,
Pentaerythrite, the weight proportion of alchlor are 1:0.8:0.3:0.02；
Described SEBS is the mixture of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS,
The weight average molecular weight of described HMW SEBS is 210000, and the weight average molecular weight of middle-molecular-weihydroxyethyl SEBS is
130000, the weight average molecular weight of low-molecular-weight SEBS is 60000, HMW SEBS, middle-molecular-weihydroxyethyl SEBS
And the weight proportion of low-molecular-weight SEBS is 1:4:1；
Described thermoplastic vulcanizates elastomer is the vistanex by 28% and the alkene of 72% by weight percentage
Rubber generates through dynamic vulcanization, and described vistanex is polyvinyl resin, and described olefinic rubber is ternary second
Third rubber；Described aromatic monomer resin is two kinds of combinations of M-80, AMS130；The characteristic of described polyphenylene oxide
Viscosity number is 0.4dl/g；Described inorganic filler is three kinds of combinations of Paris white, talcum powder, wollastonite in powder；
Also including lubricant in described halogen-free flame retardant thermoplastic elastomer material, described lubricant is silicone, tristearin
Acid zinc, the combination of dimethicone three kinds.
The preparation side of the halogen-free flame retardant thermoplastic elastomer material of electric wire it is used for described in above-described embodiment 1-4
Method, including: by SEBS, fill in oil addition high-speed mixer, mix under the rotating speed of 400-500rpm
5-10min, obtains oil-filled type Block copolymer SEBS；By described oil-filled type Block copolymer SEBS, thermoplastic
Property vulcanized elastomer, aromatic monomer resin, compatilizer, inorganic filler, antioxidant add in high mixer,
Under the rotating speed of 350-450rpm, mix 15-25min, obtain masterbatch；By described masterbatch and halogen-free flame retardants,
Polyphenylene oxide adds in double screw extruder, is 55-64 at screw slenderness ratio, and screw speed is 300-500rpm,
Processing temperature of plasticating is plasticated under conditions of being 180-240 DEG C, then through tie rod, cooling, after pelletizing, obtains
To the described halogen-free flame retardant thermoplastic elastomer material for electric wire.
The halogen-free flame retardant thermoplastic elastomer material being used for electric wire described in above-described embodiment 1-4 is carried out
Performance test, result is as shown in the table:
According to upper table analysis, the halogen-free flameproof thermoplastic being obtained in that by the scheme of above-described embodiment 1-4
Property elastomeric material stretching strength retentivity after 136 DEG C of * 168h hot air agings stretch with fracture more than 95%
Long rate conservation rate is more than 90%, and 1.6mm thickness burns fire-retardant UL94 standard VO grade, and can pass through UL1581
VW-1 testing vertical flammability；
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (10)
1. the halogen-free flame retardant thermoplastic elastomer material for electric wire, it is characterised in that its raw material
Include by weight: SEBS 20-40 part, thermoplastic vulcanizates elastomer 5-15 part, aromatic monomer resin
2-5 part, halogen-free flame retardants 15-35 part, polyphenylene oxide 15-30 part, compatilizer 1-3 part, inorganic filler 2-15
Part, fill oil 8-15 part, antioxidant 0.1-0.5 part；
Wherein, described halogen-free flame retardants is the organophosphorus ester by 55-65% and 35-45% by weight percentage
Melamine polyphosphate composition；And the preparation technology of described organophosphorus ester includes: graphite powder is added
Stirring in acetic acid, at 120-140 DEG C, stirring reaction 10-12h, dries, and grinds, and obtains acidifying and inserts
Layer graphite is standby；POCl3, pentaerythrite are joined in anhydrous acetonitrile and stir, protects at nitrogen
Under conditions of, it is warming up to 50-60 DEG C, stirs 0.5-1h, after adding aluminum trichloride (anhydrous), be continuously heating to
90-100 DEG C, stir 1-2h, after solvent is distilled off, washing, it is dried, obtains pentaerythrite spirocyclization phosphorus
Acid esters diacid chloride；Described pentaerythrite spirocyclization phosphate is added in methanesulfonic acid, adds described acidifying and insert
Layer graphite, at 80-100 DEG C, stirring reaction 5-10h, cooling, suction filtration, washing, after drying, obtain institute
State organophosphorus ester.
Halogen-free flame retardant thermoplastic elastomer material for electric wire the most according to claim 1, its
Being characterised by, graphite powder, POCl3, pentaerythrite, the weight proportion of alchlor are
1:0.5-1.5:0.2-0.6:0.01-0.03。
Halogen-free flame retardant thermoplastic elastomer material for electric wire the most according to claim 1 and 2,
It is characterized in that, described SEBS is HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS
Mixture, the weight average molecular weight of described HMW SEBS is 160000-240000, middle-molecular-weihydroxyethyl SEBS
Weight average molecular weight be 100000-150000, the weight average molecular weight of low-molecular-weight SEBS is 50000-95000；
Preferably, the weight proportion of HMW SEBS, middle-molecular-weihydroxyethyl SEBS and low-molecular-weight SEBS is
1:3-5:1-3。
4. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-3
Material, it is characterised in that described thermoplastic vulcanizates elastomer is by the polyolefin of 20-35% by weight percentage
The olefinic rubber of resin and 65-80% generates through dynamic vulcanization；Preferably, described vistanex is polypropylene
Resin or polyvinyl resin, described olefinic rubber is ethylene propylene diene rubber or Ethylene-octene rubber.
5. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-4
Material, it is characterised in that described aromatic monomer resin is in CS801, M-80, Endex160, AMS130
The combination of one or more.
6. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-5
Material, it is characterised in that the intrinsic viscosity of described polyphenylene oxide is 0.1-0.5dl/g；Preferably, described poly-
Phenylate is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether.
7. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-6
Material, it is characterised in that described compatilizer is Hydrogenated thermoplastic's butadiene-styrene rubber-maleic anhydride grafts, hydrogenation
Thermoplastic styrene butadiene rubber-methyl methacrylate-grafted thing, thermoplastic styrene butadiene rubber-maleic anhydride grafts,
Hydrogenated thermoplastic's butadiene-styrene rubber-thermoplastic polyurethane copolymer, thermoplastic styrene butadiene rubber-methyl methacrylate
The combination of one or more in graft；Described inorganic filler is Paris white, talcum powder, wollastonite in powder
In the combination of one or more.
8. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-7
Material, it is characterised in that described filling oil is saturated straight chain alkane or naphthenic oil；Described antioxidant is anti-
Oxygen agent 168 or antioxidant 1010.
9. according to the halogen-free flame-retardant thermoplastic elastomer for electric wire described in any one of claim 1-8
Material, it is characterised in that also include light stabilizer, coloring in described halogen-free flame retardant thermoplastic elastomer material
One or more combination in agent, lubricant；
Preferably, described light stabilizer is benzotriazole stabilizer, Hinered phenols stabilizer, phosphite ester
The combination of one or more in class stabilizer, hindered amines stabilizer；Described colouring agent be oxidized black,
One or more combination in iron oxide red, iron oxide yellow, titanium green grass or young crops orchid, chrome green；Described lubricant is
One or more group in aliphatic acid, fatty acid amide, silicone, zinc stearate, dimethicone
Close.
10. one kind according to the halogen-free combustion-proof thermoplastic for electric wire described in any one of claim 1-9
The preparation method of elastomeric material, it is characterised in that including: by SEBS, fill oil addition high-speed mixer
In, under the rotating speed of 400-500rpm, mix 5-10min, obtain oil-filled type Block copolymer SEBS；By institute
State oil-filled type Block copolymer SEBS, thermoplastic vulcanizates elastomer, aromatic monomer resin, compatilizer, nothing
Machine filler, antioxidant add in high mixer, mix 15-25min, obtain under the rotating speed of 350-450rpm
Masterbatch；Described masterbatch and halogen-free flame retardants, polyphenylene oxide are added in double screw extruder, at screw slenderness ratio
For 55-64, screw speed is 300-500rpm, and processing temperature of plasticating is carried out under conditions of being 180-240 DEG C
Plasticate, then through tie rod, cooling, after pelletizing, obtain the described halogen-free combustion-proof thermoplastic bullet for electric wire
Elastomer material.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398087A (en) * | 2016-09-29 | 2017-02-15 | 中广核高新核材集团（东莞）祈富新材料有限公司 | Highly-flame-retardant scratch-resistant frosting TPE sheathing material |
| CN106750930A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of electric wire flame-proofed thermoplastic elastomeric material and preparation method thereof |
| CN106751028A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof |
| CN106832994A (en) * | 2016-12-14 | 2017-06-13 | 天长市康宁甘油科技有限公司 | A kind of halogen-free combustion-proof thermoplastic elastomeric pad and preparation method thereof |
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| CN109825075A (en) * | 2019-01-28 | 2019-05-31 | 苏州迈荣祥信息科技有限公司 | Halogen-free flame-retardant thermoplastic elastomer new-energy automobile cable material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294654A (en) * | 1991-08-12 | 1994-03-15 | General Electric Company | Flame-retarded, conductive compositions which include polyphenylene ether and polystyrene resins |
| CN101309970A (en) * | 2005-11-16 | 2008-11-19 | 通用电气公司 | Thermoplastic method, composition, and article |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
-
2016
- 2016-04-27 CN CN201610280131.9A patent/CN105907019B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294654A (en) * | 1991-08-12 | 1994-03-15 | General Electric Company | Flame-retarded, conductive compositions which include polyphenylene ether and polystyrene resins |
| CN101309970A (en) * | 2005-11-16 | 2008-11-19 | 通用电气公司 | Thermoplastic method, composition, and article |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
Cited By (10)
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|---|---|---|---|---|
| CN106398087A (en) * | 2016-09-29 | 2017-02-15 | 中广核高新核材集团（东莞）祈富新材料有限公司 | Highly-flame-retardant scratch-resistant frosting TPE sheathing material |
| CN106750930A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of electric wire flame-proofed thermoplastic elastomeric material and preparation method thereof |
| CN106751028A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof |
| CN106832994A (en) * | 2016-12-14 | 2017-06-13 | 天长市康宁甘油科技有限公司 | A kind of halogen-free combustion-proof thermoplastic elastomeric pad and preparation method thereof |
| CN108841059A (en) * | 2018-07-18 | 2018-11-20 | 合肥安力电力工程有限公司 | A kind of high-ductility cracking resistance CABLE MATERIALS and preparation method thereof |
| CN109825075A (en) * | 2019-01-28 | 2019-05-31 | 苏州迈荣祥信息科技有限公司 | Halogen-free flame-retardant thermoplastic elastomer new-energy automobile cable material |
| CN109825075B (en) * | 2019-01-28 | 2021-04-27 | 凯尔科美(广州)高新材料科技有限公司 | Halogen-free flame-retardant thermoplastic elastomer cable material for new energy automobile |
| CN110218459A (en) * | 2019-05-29 | 2019-09-10 | 江苏中利集团股份有限公司 | A kind of TPE insulating materials |
| CN114736481A (en) * | 2022-02-15 | 2022-07-12 | 杭州巨星科技股份有限公司 | Gasoline-resistant TPE material |
| CN115386157A (en) * | 2022-06-07 | 2022-11-25 | 博睿谷伦(武汉)科技有限公司 | Special light flame-retardant insulating coiled material for cable line cladding and preparation method and application thereof |
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