CN108456429A - A kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide - Google Patents
A kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide Download PDFInfo
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Abstract
The present invention relates to thermoplastic elastomer (TPE) technical fields, and in particular to a kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide, the thermoplastic elastomer (TPE) include the raw material of following parts by weight：20 40 parts of SEBS, 30 50 parts of OBC, 30 50 parts of PP, 40 60 parts of oil, 10 30 parts of fire retardant, 0.5 1.5 parts of antioxidant.The thermoplastic elastomer (TPE) use temperature range of the present invention is wide, can be used for a long time at 55 DEG C to 125 DEG C, improve 40 DEG C than general TPE products temperature in use, and flame retardant effect is excellent, and halogen-free environmental, weather resistance is excellent, and intensity is high, excellent combination property.
Description
Technical field
The present invention relates to thermoplastic elastomer (TPE) technical fields, and in particular to a kind of thermoplastic elastic that Applicable temperature range is wide
Body and its preparation method and application.
Background technology
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.
Currently, the material of cable is all extrusion molding, material mostly uses greatly three kinds, one is traditional PVC material, it
Have a wide range of application, simple production process, annual demand are all increasing substantially, but be used for a long time temperature range at 80 DEG C
Within, and lower temperature resistance is poor, easy to crack, and case hardness changes greatly when low temperature, and when burning generates toxic gas, it is made to apply model
It encloses and is restricted；One is fire-retardant PE or EVA material, for use temperature range within 80 DEG C, intensity is relatively low, and elasticity is very poor,
Not bend-resistance, it is not low temperature resistant；Another kind is general TPE material, which can be used for a long time at -40 DEG C to 80 DEG C, good weatherability,
It is environment-protecting and non-poisonous, but use temperature range is relatively narrow, inflammable, low strength.
Therefore, it is necessary to research and develop a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of Applicable temperature models
Wide thermoplastic elastomer (TPE) is enclosed, the thermoplastic elastomer (TPE) use temperature range is wide, can be used for a long time at -55 DEG C to 125 DEG C, than logical
40 DEG C are improved with TPE product temperature in use, and flame retardant effect is excellent, halogen-free environmental, weather resistance is excellent, and intensity is high, comprehensive
It has excellent performance.
It is another object of the present invention to provide a kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide,
The preparation method step is simple, convenient operation and control, stable quality, and production efficiency is high, and production cost is low, can heavy industrialization
Production.
The present invention's further an object is that provide a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide fire-resistant wire,
The application of cable and optical cable.
The purpose of the invention is achieved by the following technical solution：A kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide, institute
State the raw material that thermoplastic elastomer (TPE) includes following parts by weight：
Preferably, the SEBS includes modified SEBS, and the modified SEBS is the benzene second of modified by maleic acid anhydride graft processing
Alkene-ethylene-butylene, Styrene block copolymer.More preferably, the SEBS is by SEBS and modified SEBS with weight ratio 1-
10:The mixture of 10-1 compositions.
The present invention is modified processing by using maleic anhydride to SEBS, and can improve SEBS and resin has preferably
Compatibility, and modified SEBS have it is good low temperature resistant, it is weather-proof, it is and other the advantages that resistance to ozone oxidation, thermal stability is good
Resin alloy can greatly improve the impact strength and lower temperature resistance of engineering plastics.
More preferably, the preparation method of the modified SEBS includes the following steps：SEBS 40- are weighed by weight ratio
0.1-0.3 parts of 80 parts, 1-3 parts of maleic anhydride, 1-3 parts of styrene monomer, 0.1-0.5 parts of lubricant and initiator are uniformly mixed,
Obtain blend；By blend by double screw extruder extruding pelletization, the modified SEBS is made；Wherein, the twin-screw
The extruder temperature of extruder is 120-220 DEG C, screw speed 100-300r/min.
The preparation side of the styrene-ethylene-butylene-styrene block copolymer of the maleic anhydride grafted modification of the present invention
Method is simple for process, raw material environmental protection, while ensure that material has higher grafting rate, also has grafting rate high, product is different
The advantages that taste is small, and color is whiter.
The lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio
1.5-2.5：0.8-1.2：The mixture of 1 composition.
The present invention can be such that material improves in process by strictly controlling the type, compounding and proportioning of lubricant
The mobility of material and the release property of product can reduce difficulty of processing, save energy consumption.
The initiator is identical as initiator described below, and details are not described herein.
Preferably, the OBC is ethylene-octene block copolymer of the vinyl monomer weight content in 40%-60%.
OBC has the block structure of SEBS, while having the resistance to ag(e)ing of POE, and more constancy, resilience, wearability,
And fusing point ratio POE high about 30-70 degree, there is higher temperature in use.The present invention exists by using vinyl monomer weight content
The ethylene-octene block copolymer of 40%-60%, thermoplastic elastomer (TPE) use temperature range obtained are wide.
The PP is the isotactic polypropylene of metallocene catalysis.
Isotactic polypropylene 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 isotactic polypropylene, 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.
Preferably, the oil is at least one of white oil, naphthenic oil and White Mineral Oil.The present invention by using above-mentioned oil,
The mobility that SEBS can be improved improves the processing performance of thermoplastic elastomer (TPE).
Preferably, the fire retardant be ammonium phosphate, ammonium polyphosphate, ammonium polyphosphate modifying, hypo-aluminum orthophosphate, melamine and its
Compound, zinc borate, montmorillonite, clay, metal hydroxides, organophosphorus compounds, organic hypophosphites compound and
At least one of 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 fire retardant be by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite 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 fire retardant, safe to use to greatly improve its
Property, further, since fire retardant is not halogen, therefore have the characteristics that environment-protecting and non-poisonous.
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, the thermoplastic elastomer (TPE) further includes 1-3 parts of 1-10 parts of functionalized monomer and initiator, the functionalization
Monomer be styrene monomer, acrylonitrile monomer, acrylic ester monomer, methacrylate-based monomer, alkenyl class monomer,
At least one of unsaturated carboxylic acid class monomer and maleimide monomer.
The present invention polymerize by using above-mentioned functionalized monomer with SEBS, can improve thermoplastic elastomer (TPE) flexibility,
Elasticity and heat resistance.Preferably, the functionalized monomer is styrene monomer, acrylonitrile monomer, acrylic ester monomer
At least one of with methacrylate-based monomer.
The styrene monomer is styrene, α-methylstyrene, α-ethyl styrene, p-methylstyrene and adjacent uncle
At least one of butylstyrene；The acrylonitrile monomer is acrylonitrile and/or methacrylonitrile；The esters of acrylic acid
Monomer be methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid n-pentyl ester, acrylic acid just oneself
At least one of ester, 2-EHA and lauryl acrylate；The methacrylate-based monomer is methyl-prop
E pioic acid methyl ester, ethyl methacrylate, propyl methacrylate, n-BMA, n-amylmethacrylate, methyl
In the just own ester of acrylic acid, 2-Ethylhexyl Methacrylate, isobornyl methacrylate and lauryl methacrylate extremely
Few one kind；The alkenyl class monomer is ethylene, propylene, butadiene, isoprene and 5- vinyl -2- norbornene, acryloyl
Amine, N methacrylamide, vinyl imidazole, vinyl acetate, vinyl alkyl ethers, vinyl furan, N- vinyl carbazoles,
Vinylpyridine, ethenyl pyrrolidone, vinyl acetate, vinyl alkyl ethers, allyl methacrylate, three allyl of cyanuric acid
Ester, triallyl isocyanurate, ethylene glycol dimethacrylate, diallyl maleate, vinylacetate, phthalic acid
At least one of diallyl and 1,3-BDO dimethylacrylate；The unsaturated carboxylic acid class monomer be acrylic acid,
At least one of methacrylic acid, maleic acid, fumaric acid and itaconic acid；The maleimide monomer is maleimide
Amine, N- methylmaleimidos, N-phenylmaleimide, N- (2- aminomethyl phenyls) maleimide, N- (4- hydroxy phenyls)
At least one of maleimide and N- N-cyclohexylmaleimides.
The present invention is by using above-mentioned styrene monomer, acrylonitrile monomer, acrylic ester monomer, methacrylic acid
Esters monomer, alkenyl class monomer, unsaturated carboxylic acid class monomer and maleimide monomer, polymerize with SEBS, can improve heat
Flexibility, elasticity and the heat resistance of thermoplastic elastic.
More preferably, the functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate
With weight ratio 1：0.4-0.8：1.5-2.5：The mixture of 2-4 compositions.
The initiator is organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator and oxidation
Restore at least one of initiator.
For the present invention by using above-mentioned initiator, initiation effect is good, can cause free radical polymerization and copolymerization,
The rate of polymerization of SEBS and functionalized monomer can be improved.Preferably, the initiator is organic peroxide evocating agent and/or nothing
Machine peroxide initiator.
The organic peroxide evocating agent is benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tertiary fourth
Base hydrogen peroxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, the tertiary fourth of peroxidating trimethylacetic acid
In base ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate
It is at least one；The inorganic peroxide initiator is at least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；It is described
Azo-initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl and the bis- (2,4- of 2,2'- azos
At least one of methyl pentane nitrile)；The redox initiator be benzoyl peroxide/sucrose, tert-butyl hydroperoxide/
Rongalite, tert-butyl hydroperoxide/sodium pyrosulfite, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, peroxide
Change hydrogen/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide/
N,N-Dimethylaniline, benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/
Silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/chlorination
At least one of aziridine of ferrous and isopropyl benzene hydroperoxide/tetra-.
The present invention is by using above-mentioned organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator
And redox initiator, initiation effect is good, can cause free radical polymerization and copolymerization, improves SEBS and functionalization
The rate of polymerization of monomer.
More preferably, the initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 1.5-
2.5：1：The mixture of 0.8-1.2 compositions.
The present invention is functionalized SEBS, can improve heat by the way that functionalized monomer and initiator are added in SEBS
Thermoplastic elastic flexibility, elasticity and comprehensive performance.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 180-240 DEG C, screw speed 200-600r/min.
A kind of application of the thermoplastic elastomer (TPE) that Applicable temperature range is wide in fire-resistant wire, cable and optical cable.
The beneficial effects of the present invention are：The thermoplastic elastomer (TPE) use temperature range of the present invention is wide, can be can be at -55 DEG C
It is used for a long time to 125 DEG C, improves 40 DEG C than general TPE products temperature in use, and flame retardant effect is excellent, halogen-free environmental, it is weather-proof
Function admirable, intensity is high, excellent combination property.
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.
Application of the wide thermoplastic elastomer (TPE) of Applicable temperature range of the invention in fire-resistant wire, cable and optical cable.
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 thermoplastic elastomer (TPE) that Applicable temperature range is wide, the thermoplastic elastomer (TPE) include the original of following parts by weight
Material：
The SEBS includes modified SEBS, and the modified SEBS is the styrene-ethylene-of modified by maleic acid anhydride graft processing
Butylene-styrene block copolymer.
The preparation method of the modified SEBS includes the following steps：40 parts of SEBS, maleic anhydride 1 are weighed by weight ratio
Part, 1 part of styrene monomer, 0.1 part of lubricant and 0.1 part of initiator are uniformly mixed, and obtain blend；Blend is passed through into double spiral shells
The modified SEBS is made in bar extruder extruding pelletization；Wherein, the extruder temperature of the double screw extruder is 120 DEG C, screw rod
Rotating speed is 100r/min.
The OBC is ethylene-octene block copolymer of the vinyl monomer weight content 40%；The PP urges for metallocene
The isotactic polypropylene of change.
The oil is white oil.
The fire retardant is ammonium phosphate, ammonium polyphosphate or ammonium polyphosphate modifying.
The antioxidant is four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters.
The thermoplastic elastomer (TPE) further includes 1 part of 1 part of functionalized monomer and initiator, and the functionalized monomer is styrene
Class monomer；The initiator is organic peroxide evocating agent.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 180 DEG C, screw speed 200r/min.
A kind of application of the thermoplastic elastomer (TPE) that Applicable temperature range is wide in fire-resistant wire, cable and optical cable.
Embodiment 2
The present embodiment and above-described embodiment 1 the difference is that：The thermoplastic elastomer (TPE) includes following parts by weight
Raw material：
The preparation method of the modified SEBS includes the following steps：50 parts of SEBS, maleic anhydride are weighed by weight ratio
0.2 part of 1.5 parts, 15 parts of styrene monomer, 0.2 part of lubricant and initiator are uniformly mixed, and obtain blend；Blend is passed through
The modified SEBS is made in double screw extruder extruding pelletization；Wherein, the extruder temperature of the double screw extruder is 150 DEG C,
Screw speed is 150r/min.
The OBC is ethylene-octene block copolymer of the vinyl monomer weight content 45%；The PP urges for metallocene
The isotactic polypropylene of change.
The oil is naphthenic oil.
The fire retardant is hypo-aluminum orthophosphate or melamine and its compound.
The antioxidant is N, bis- [[3- (3,5)--4 hydroxy phenyl of the di-t-butyl] propiono] hexamethylene diamines of N ' -.
The thermoplastic elastomer (TPE) further includes 1.5 parts of 3 parts of functionalized monomer and initiator, and the functionalized monomer is propylene
Nitrile monomer；The initiator is inorganic peroxide initiator.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 200 DEG C, screw speed 300r/min.
Embodiment 3
The present embodiment and above-described embodiment 1 the difference is that：The thermoplastic elastomer (TPE) includes following parts by weight
Raw material：
The preparation method of the modified SEBS includes the following steps：60 parts of SEBS, maleic anhydride 2 are weighed by weight ratio
Part, 2 parts of styrene monomer, 0.3 part of lubricant and 0.2 part of initiator are uniformly mixed, and obtain blend；Blend is passed through into double spiral shells
The modified SEBS is made in bar extruder extruding pelletization；Wherein, the extruder temperature of the double screw extruder is 170 DEG C, screw rod
Rotating speed is 200r/min.
The OBC is ethylene-octene block copolymer of the vinyl monomer weight content 50%；The PP urges for metallocene
The isotactic polypropylene of change.
The oil is White Mineral Oil.
The fire retardant is zinc borate, montmorillonite or clay.
The antioxidant is three [2,4- di-tert-butyl-phenyls] phosphite esters.
The thermoplastic elastomer (TPE) further includes 2 parts of 5 parts of functionalized monomer and initiator, and the functionalized monomer is acrylic acid
Esters monomer；The initiator be azo-initiator and.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 210 DEG C, screw speed 300r/min.
Embodiment 4
The present embodiment and above-described embodiment 1 the difference is that：The thermoplastic elastomer (TPE) includes following parts by weight
Raw material：
The preparation method of the modified SEBS includes the following steps：70 parts of SEBS, maleic anhydride are weighed by weight ratio
0.25 part of 2.5 parts, 2.5 parts of styrene monomer, 0.4 part of lubricant and initiator are uniformly mixed, and obtain blend；Blend is led to
Double screw extruder extruding pelletization is crossed, the modified SEBS is made；Wherein, the extruder temperature of the double screw extruder is 190
DEG C, screw speed 250r/min.
The OBC is ethylene-octene block copolymer of the vinyl monomer weight content 55%；The PP urges for metallocene
The isotactic polypropylene of change.
The oil is white oil.
The fire retardant is metal hydroxides or organophosphorus compounds.
The antioxidant is diphosphorous acid pentaerythrite tristearin alcohol ester.
The thermoplastic elastomer (TPE) further includes 2.5 parts of 8 parts of functionalized monomer and initiator, and the functionalized monomer is methyl
Acrylic ester monomer；The initiator is redox initiator.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 220 DEG C, screw speed 500r/min.
Embodiment 5
The present embodiment and above-described embodiment 1 the difference is that：The thermoplastic elastomer (TPE) includes following parts by weight
Raw material：
The preparation method of the modified SEBS includes the following steps：80 parts of SEBS, maleic anhydride 3 are weighed by weight ratio
Part, 3 parts of styrene monomer, 0.5 part of lubricant and 0.3 part of initiator are uniformly mixed, and obtain blend；Blend is passed through into double spiral shells
The modified SEBS is made in bar extruder extruding pelletization；Wherein, the extruder temperature of the double screw extruder is 220 DEG C, screw rod
Rotating speed is 300r/min.
The OBC is ethylene-octene block copolymer of the vinyl monomer weight content 60%；The PP urges for metallocene
The isotactic polypropylene of change.
The oil is naphthenic oil.
The fire retardant is organic hypophosphites compound or polyalcohol.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester.
The thermoplastic elastomer (TPE) further includes 3 parts of 10 parts of functionalized monomer and initiator, and the functionalized monomer is alkenyl
Class monomer, unsaturated carboxylic acid class monomer or maleimide monomer；The initiator is organic peroxide evocating agent.
A kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide, includes 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
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 lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio
1.5：0.8：The mixture of 1 composition.
The fire retardant 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 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 functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with weight ratio 1：
0.4：1.5：The mixture of 2 compositions.
The initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 1.5：1：0.8 composition
Mixture.
Embodiment 7
The present embodiment and above-described embodiment 2 the difference is that：
The lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio
1.8：0.9：The mixture of 1 composition.
The fire retardant is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite with weight ratio 1.2:
0.9:1: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 1:0.3:The mixture of 0.5 composition.
The functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with weight ratio 1：
0.5：1.8：The mixture of 2.5 compositions.
The initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 1.8：1：0.9 composition
Mixture.
Embodiment 8
The present embodiment and above-described embodiment 3 the difference is that：
The lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio 2：
1：The mixture of 1 composition.
The fire retardant 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 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 functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with weight ratio 1：
0.6：2：The mixture of 3 compositions.
The initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 2：1：The mixing of 1 composition
Object.
Embodiment 9
The present embodiment and above-described embodiment 4 the difference is that：
The lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio
2.2：1.1：The mixture of 1 composition.
The fire retardant is by poly cyanamid cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite with weight ratio 1.8:
1.1:1:The mixture of 0.7 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 1:0.5:The mixture of 0.7 composition.
The functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with weight ratio 1：
0.7：2.2：The mixture of 3.5 compositions.
The initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 2.2：1：1.1 compositions
Mixture.
Embodiment 10
The present embodiment and above-described embodiment 5 the difference is that：
The lubricant is by oxidized polyethylene wax, ethylene bis stearic acid amide and glycerin monostearate with weight ratio
2.5：1.2：The mixture of 1 composition.
The fire retardant 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 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 functionalized monomer is by styrene, acrylonitrile, methyl acrylate and methyl methacrylate with weight ratio 1：
0.8：2.5：The mixture of 4 compositions.
The initiator is by benzoyl peroxide, potassium peroxydisulfate and ammonium persulfate with weight ratio 2.5：1：1.2 compositions
Mixture.
Thermoplastic elastomer (TPE) made from embodiment 1-10 is tested, test result is as follows shown in table：
As can be seen from the above table, thermoplastic elastomer (TPE) use temperature range produced by the present invention is wide, can be arrived at -50 DEG C
120 DEG C of long-time services, improve 40 DEG C, and flame retardant effect is excellent, halogen-free environmental, weatherability than general TPE products temperature in use
Can be excellent, intensity is high, excellent combination property.
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 thermoplastic elastomer (TPE) that Applicable temperature range is wide, it is characterised in that：The thermoplastic elastomer (TPE) includes following weight
Measure the raw material of part：
2. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：The SEBS
Including modified SEBS, the modified SEBS is the styrene-ethylene-butylene-styrene block of modified by maleic acid anhydride graft processing
Copolymer.
3. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 2, it is characterised in that：The modification
The preparation method of SEBS includes the following steps：40-80 parts of SEBS, 1-3 parts of maleic anhydride, styrene list are weighed by weight ratio
0.1-0.3 parts of 1-3 parts of body, 0.1-0.5 parts of lubricant and initiator are uniformly mixed, and obtain blend；Blend is passed through into double spiral shells
The modified SEBS is made in bar extruder extruding pelletization；Wherein, the extruder temperature of the double screw extruder is 120-220 DEG C,
Screw speed is 100-300r/min.
4. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：The OBC
For vinyl monomer weight content 40%-60% ethylene-octene block copolymer；The PP is that the isotactic of metallocene catalysis is poly-
Propylene.
5. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：The oil is
At least one of white oil, naphthenic oil and White Mineral Oil.
6. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：It is described fire-retardant
Agent is ammonium phosphate, ammonium polyphosphate, ammonium polyphosphate modifying, hypo-aluminum orthophosphate, melamine and its compound, zinc borate, montmorillonite, glues
At least one of soil, metal hydroxides, organophosphorus compounds, organic hypophosphites compound and polyalcohol.
7. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：The antioxygen
Agent is four [methylene -3,5- (di-t-butyl -4- hydroxy-phenies) propionic ester] pentaerythritol esters, N, the bis- [[3- (3,5)-two of N ' -
- 4 hydroxy phenyl of tertiary butyl] propiono] hexamethylene diamine, three [2,4- di-tert-butyl-phenyls] phosphite esters, diphosphorous acid pentaerythrite
At least one of stearic alcohol ester and β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester.
8. a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide according to claim 1, it is characterised in that：The thermoplastic
Property elastomer further include 1-3 part of 1-10 parts of functionalized monomer and initiator, the functionalized monomer is styrene monomer, propylene
Nitrile monomer, acrylic ester monomer, methacrylate-based monomer, alkenyl class monomer, unsaturated carboxylic acid class monomer and Malaysia
At least one of acid imide monomer；The initiator is organic peroxide evocating agent, inorganic peroxide initiator, idol
At least one of nitrogen class initiator and redox initiator.
9. such as a kind of process for preparation of thermoplastic elastomer that Applicable temperature range is wide of claim 1-8 any one of them,
It is characterized 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) thermoplastic elastomer (TPE) is made by double screw extruder extruding pelletization in mixture；
Wherein, the extruder temperature of the double screw extruder is 180-240 DEG C, screw speed 200-600r/min.
10. if a kind of thermoplastic elastomer (TPE) that Applicable temperature range is wide of claim 1-8 any one of them is in fire-resistant wire, electricity
The application of cable and optical cable.
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| CN113603960A (en) * | 2021-09-14 | 2021-11-05 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant material and preparation method and application thereof |
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