CN106751028A - A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof - Google Patents
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof Download PDFInfo
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- CN106751028A CN106751028A CN201611153321.0A CN201611153321A CN106751028A CN 106751028 A CN106751028 A CN 106751028A CN 201611153321 A CN201611153321 A CN 201611153321A CN 106751028 A CN106751028 A CN 106751028A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, its raw material includes by weight：100 300 parts of EPDM, 20 80 parts of polypropylene, 40 100 parts of TPUE, 15 30 parts of SEBS, 25 40 parts of organophosphorus ester, 2 20 parts of expanded graphite, 5 15 parts of nanoclay, 1 15 parts of calcium carbonate, 5 15 parts of compatilizer, 0.2 5 parts of vulcanizing agent, active 15 parts of Zinc Oxide, 13 parts of antioxidant, 13 parts of ultra-violet absorber, 20 100 parts of processing oil, 26 parts of lubricant.The preparation-obtained thermoplastic vulcanizate material of the present invention has intensity high, and good flame resistance, durability is strong, the good advantage of toughness, meanwhile, Halogen, low toxicity, environmental protection.
Description
Technical field
The present invention relates to technical field of rubber material, more particularly to a kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material
And preparation method thereof.
Background technology
TPV has good elasticity and compression resistant morphotropism, and resistance to environment, resistance to ag(e)ing are equivalent to second third
Rubber, while its oil resistant solvent resistance is equally matched with polychloroprene rubber for general purpose.TPV body can -60 DEG C -
Used in 135 DEG C of temperature ranges, need not vulcanized when TPV body is used, directly can processed by modes such as blowings
Shaping, can shorten processing process, reduce processing cost.Increasing product uses thermoplastic vulcanizates in the market
Elastomeric material.
United States Patent (USP) US4311628/0272871A1 discloses the method for preparing TPV, described elasticity
Body is EP rubbers, and resin is polypropylene, and vulcanizing system is that Phenolic resin curative, two hydrated stannous chlorides are vulcanization accelerator
TPV is prepared using dynamic vulcanization technology, but the intensity of the vulcanized rubber, fire-retardant and flexility phase
To poor, the performance requirement of most of rubber product is not met by.
The content of the invention
Based on problem present in background technology, the present invention proposes a kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material
Material and preparation method thereof, thus preparation-obtained thermoplastic vulcanizate material has intensity high, good flame resistance, durability
By force, the good advantage of toughness, meanwhile, Halogen, low toxicity, environmental protection.
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material includes by weight：
EPDM 100-300 parts, polypropylene 20-80 parts, TPUE 40-100 parts, SEBS15-30 parts, organic phosphoric acid
Ester 25-40 parts, expanded graphite 2-20 parts, nanoclay 5-15 parts, calcium carbonate 1-15 parts, compatilizer 5-15 parts, vulcanizing agent 0.2-5
Part, active 1-5 parts, antioxidant 1-3 parts, ultra-violet absorber 1-3 parts, processing oil 20-100 parts, lubricant 2-6 parts of Zinc Oxide.
Preferably, the EPDM be by 40-60wt% Third monomer for ethenylidene ENB E type EPDMs
Rubber, the Third monomer of 10-30wt% are for the D types ethylene propylene diene rubber and the Third monomer of 20-40wt% of dicyclopentadiene
The H types ethylene propylene diene rubber composition of Isosorbide-5-Nitrae-hexadiene.
Preferably, the polypropylene is by the random polypropylene copolymerization of the HOPP and 65-80wt% of 20-35wt%
Thing is constituted；Preferably, the atactic polypropylene copolymer be by 80-95wt% propylene monomer and 5-20wt% with 2-12
Other unsaturated olefin monomer copolymerizations of individual carbon atom are formed.
Preferably, the organophosphorus ester is chitin modified phosphate, and its preparation method includes：Glycerine is polymerized
After reaction obtains polyglycerol, add POCl3 to carry out substitution reaction and obtain polyglycerol phosphate acyl chlorides, add shell and gather
Sugar obtains the chitin modified phosphate after proceeding substitution reaction.
Preferably, the preparation method of the chitin modified phosphate includes：By weight by glycerine, 10 parts are heated to
230-270 DEG C, under conditions of nitrogen protection, NaOH is added to carry out polymerisation as catalyst, it is cold after reaction 2-4h
But to room temperature, filtering, washing obtains polyglycerol；By in the polyglycerol and POCl3 25-32 parts of addition anhydrous acetonitrile
Stir, under conditions of nitrogen protection, be warming up to 50-60 DEG C, add aluminum trichloride (anhydrous) to be replaced as catalyst
Reaction, distills removal solvent after reaction 1-2h, washing is dried, and obtains polyglycerol phosphate acyl chlorides；By the polyglycerol phosphorus
Acid esters acyl chlorides is added in methanesulfonic acid, is added shitosan 8-36 parts and is stirred, and under conditions of nitrogen protection, is warming up to 40-
60 DEG C carry out substitution reaction, are filtered after reaction 2-4h, and washing is dried, and obtains the chitin modified phosphate.
Preferably, the nanoclay is montmorillonite, nontronite, bentonite, chromium-rich nontronite, hectorite, saponite, zinc
One or more combination in montmorillonite, magadiite, kenyaite, humite, vermiculite, kaolin, hydrotalcite.
Preferably, the compatilizer is maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafting
One or more combination in SEBS, maleic anhydride grafted polystyrene.
Preferably, the vulcanizing agent is made up of vulcanizing agent and vulcanization aid；Vulcanizing agent is phenolic resin or peroxide；
When using phenolic resin as vulcanizing agent, vulcanization aid is metal halide；, as vulcanizing agent, vulcanize when using peroxide
Auxiliary agent is cyanate, divinylbenzene class or esters of acrylic acid.
Preferably, the antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and/or
Three [2,4- di-tert-butyl-phenyl] phosphite esters；
Preferably, the ultra-violet absorber is 2- (2 '-hydroxyl -3 ', 5 '-bis- (a, a- dimethyl benzyl) phenyl) benzo
Triazole and/or 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorination BTAs；
Preferably, the processing oil is paraffin oil and/or naphthenic oil；
Preferably, the lubricant is silicone powder and/or vinyl bis-stearamides.
A kind of preparation method of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, including：By EPDM, thermoplastic polyurethane
Elastomer, SEBS, organophosphorus ester, expanded graphite, nanoclay, calcium carbonate, compatilizer, antioxidant, ultra-violet absorber, plus
Banburying is uniform during work oil and lubricant add banbury, is re-fed into extruding pelletization in single screw extrusion machine, obtains rubber master batch；Will
The rubber master batch and polypropylene, vulcanizing agent, active Zinc Oxide add high-speed mixer and mixing 20-30min, transfer to twin-screw
Plasticated in extruder, tie rod, cooling, pelletizing obtains the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, wherein, screw rod
Draw ratio is 55-64, and feeding rotating speed is 30-80rpm, and screw speed is 300-500rpm, and processing temperature is 160-250 DEG C.
In the present invention, the thermoplastic vulcanizate material uses E types ethylene propylene diene rubber, the D type ternarys of specific proportioning
EP rubbers and H types ethylene propylene diene rubber make its tensile strength, bending modulus all in one as the source of ethylene propylene diene rubber
Individual rational state, can obtain excellent resistance to permanent deformation, such；The addition of a high proportion of polypropylene, thermoplastic elastomer (TPE) and SEBS,
When being compounded with ethylene propylene diene rubber, elastomeric material pliability in itself can be substantially improved, and with very excellent processing
Performance performance.Additionally, the fire resistance in order to improve the material, in the present invention on the basis of vulcanized rubber, be additionally added by
The highly efficiency compositional flame retardant system of organophosphorus ester, expanded graphite and nanoclay composition, wherein, organophosphorus ester is by polymerization
After glycerine carries out substitution esterification as intermediate and POCl3, the structure of phosphoryl chloride phosphorus oxychloride present on it can be with shitosan
Reacted, substantial amounts of polar group is included on thus obtained chitin modified phosphate, can be to the nanoclay of introducing
Fine dispersion is carried out, it is good compatible using can not only be carried out to polymeric matrix after heating or illumination curing, and when combination
When thing is exposed to very high temperature environment, hyaloid protectiveness layer structure formed in situ, it makees with the expansion of expanded graphite
With synergy is produced, expanding material will form coke structure, so as to provide very effective composite flame-proof base to polymer matrix
Matter；And chitin modified phosphate is used as organic principle, stronger with rubber molecule adhesion, itself as well into charcoal
Agent, also can form carbon-coating, you can form a kind of fire-retardant and synergistic polymer-based in the efficient natural of one in material surface rapidly
Fire retardant, can effectively improve the flame retarding efficiency of elastomeric material；The vulcanizing agent system of specific proportioning is also added into the present invention, with
Organic peroxide cross-linking system can efficiently control the crosslinking degree and uniform performance of cross-linked material as vulcanizing agent, make
Ethylene propylene diene rubber realizes dynamic vulcanization in the melt blending process with polyolefin etc., so as to improve the machine of the elastomeric material
Tool mechanical property and consistency, heat-resisting, the antioxygenic property of reinforcing material；Add antioxidant, the ultraviolet radiation absorption of certain content
Agent, processing oil and lubricant then cause that the elastomeric material has good processing characteristics and thermal ageing resistant performance, the system
Not only the performance such as mechanics is fabulous for the standby elastomeric material for obtaining, but also can meet circular economy concept with recycling use.
Specific embodiment
Technical scheme is described in detail below by specific embodiment.
Embodiment 1
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, its raw material includes by weight：100 parts of EPDM, poly- third
80 parts of alkene, 40 parts of TPUE, 30 parts of SEBS, 25 parts of organophosphorus ester, 20 parts of expanded graphite, nanoclay 5
Part, 15 parts of calcium carbonate, 5 parts of compatilizer, 5 parts of vulcanizing agent, active 1 part of Zinc Oxide, 3 parts of antioxidant, 1 part of ultra-violet absorber, plus
Work oil 100 parts, 2 parts of lubricant；
Wherein, the EPDM be by 40wt% Third monomer for ethenylidene ENB E types ethylene propylene diene rubber,
The Third monomer of 30wt% is Isosorbide-5-Nitrae-hexadiene for the D types ethylene propylene diene rubber of dicyclopentadiene and the Third monomer of 30wt%
H types ethylene propylene diene rubber is constituted；The polypropylene is by the random polypropylene copolymerization of the HOPP and 80wt% of 20wt%
Thing is constituted, and the atactic polypropylene copolymer is its with 2-12 carbon atom of propylene monomer by 80wt% and 20wt%
Its unsaturated olefin monomer copolymerization is formed；
The organophosphorus ester is chitin modified phosphate, and its preparation method includes：By weight by glycerine, 10 parts add
Heat under conditions of nitrogen protection, adds NaOH to carry out polymerisation as catalyst to 230 DEG C, is cooled down after reaction 4h
To room temperature, filtering, washing obtains polyglycerol；Stirring is equal during 25 parts of the polyglycerol and POCl3 are added into anhydrous acetonitrile
It is even, under conditions of nitrogen protection, 60 DEG C are warming up to, add aluminum trichloride (anhydrous) to carry out substitution reaction as catalyst, react
Removal solvent is distilled after 1h, washing is dried, and obtains polyglycerol phosphate acyl chlorides；The polyglycerol phosphate acyl chlorides is added
Enter in methanesulfonic acid, add 36 parts of shitosan and stir, under conditions of nitrogen protection, being warming up to 40 DEG C replace instead
Should, to be filtered after reaction 4h, washing is dried, and obtains the chitin modified phosphate；
The nanoclay is montmorillonite, nontronite and bentonite；The compatilizer is maleic anhydride grafted polyethylene；Institute
Vulcanizing agent is stated to be made up of phenolic resin and metal halide；The antioxidant is four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester；The ultra-violet absorber is 2- (2 '-hydroxyl -3 ', 5 '-bis- (a, a- dimethyl benzyl) phenyl)
BTA；The processing oil is paraffin oil；The lubricant is silicone powder.
Embodiment 2
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, its raw material includes by weight：300 parts of EPDM, poly- third
20 parts of alkene, 100 parts of TPUE, 15 parts of SEBS, 40 parts of organophosphorus ester, 2 parts of expanded graphite, nanoclay
15 parts, 1 part of calcium carbonate, 15 parts of compatilizer, 0.2 part of vulcanizing agent, active 5 parts of Zinc Oxide, 1 part of antioxidant, ultra-violet absorber 3
Part, 20 parts of processing oil, 6 parts of lubricant；
Wherein, the EPDM be by 60wt% Third monomer for ethenylidene ENB E types ethylene propylene diene rubber,
The Third monomer of 10wt% is Isosorbide-5-Nitrae-hexadiene for the D types ethylene propylene diene rubber of dicyclopentadiene and the Third monomer of 30wt%
H types ethylene propylene diene rubber is constituted；The polypropylene is by the random polypropylene copolymerization of the HOPP and 65wt% of 35wt%
Thing is constituted, and the atactic polypropylene copolymer is its with 2-12 carbon atom of propylene monomer by 95wt% and 5wt%
Its unsaturated olefin monomer copolymerization is formed；
The organophosphorus ester is chitin modified phosphate, and its preparation method includes：By weight by glycerine, 10 parts add
Heat under conditions of nitrogen protection, adds NaOH to carry out polymerisation as catalyst to 270 DEG C, is cooled down after reaction 2h
To room temperature, filtering, washing obtains polyglycerol；Stirring is equal during 32 parts of the polyglycerol and POCl3 are added into anhydrous acetonitrile
It is even, under conditions of nitrogen protection, 50 DEG C are warming up to, add aluminum trichloride (anhydrous) to carry out substitution reaction as catalyst, react
Removal solvent is distilled after 2h, washing is dried, and obtains polyglycerol phosphate acyl chlorides；The polyglycerol phosphate acyl chlorides is added
Enter in methanesulfonic acid, add 8 parts of shitosan and stir, under conditions of nitrogen protection, being warming up to 60 DEG C carries out substitution reaction,
Filtered after reaction 2h, washing is dried, and obtains the chitin modified phosphate；
The nanoclay is chromium-rich nontronite, hectorite, saponite, sauconite and magadiite；It is described compatible
Agent is maleic anhydride inoculated polypropylene；The vulcanizing agent is made up of peroxide and cyanate；The antioxidant be three [2,
4- di-tert-butyl-phenyls] phosphite ester；The ultra-violet absorber is 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorine
Change BTA；The processing oil is naphthenic oil；The lubricant is vinyl bis-stearamides.
Embodiment 3
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, its raw material includes by weight：200 parts of EPDM, poly- third
50 parts of alkene, 70 parts of TPUE, 20 parts of SEBS, 30 parts of organophosphorus ester, 11 parts of expanded graphite, nanoclay
10 parts, 8 parts of calcium carbonate, 10 parts of compatilizer, 2.6 parts of vulcanizing agent, active 3 parts of Zinc Oxide, 2 parts of antioxidant, ultra-violet absorber 2
Part, 60 parts of processing oil, 4 parts of lubricant；
Wherein, the EPDM be by 50wt% Third monomer for ethenylidene ENB E types ethylene propylene diene rubber,
The Third monomer of 30wt% is Isosorbide-5-Nitrae-hexadiene for the D types ethylene propylene diene rubber of dicyclopentadiene and the Third monomer of 20wt%
H types ethylene propylene diene rubber is constituted；The polypropylene is by the random polypropylene copolymerization of the HOPP and 75wt% of 25wt%
Thing is constituted, and the atactic polypropylene copolymer is its with 2-12 carbon atom of propylene monomer by 85wt% and 15wt%
Its unsaturated olefin monomer copolymerization is formed；
The organophosphorus ester is chitin modified phosphate, and its preparation method includes：By weight by glycerine, 10 parts add
Heat under conditions of nitrogen protection, adds NaOH to carry out polymerisation as catalyst to 250 DEG C, is cooled down after reaction 3h
To room temperature, filtering, washing obtains polyglycerol；Stirring is equal during 28 parts of the polyglycerol and POCl3 are added into anhydrous acetonitrile
It is even, under conditions of nitrogen protection, 55 DEG C are warming up to, add aluminum trichloride (anhydrous) to carry out substitution reaction as catalyst, react
Removal solvent is distilled after 1.5h, washing is dried, and obtains polyglycerol phosphate acyl chlorides；By the polyglycerol phosphate acyl chlorides
Add in methanesulfonic acid, add 22 parts of shitosan and stir, under conditions of nitrogen protection, being warming up to 50 DEG C replace instead
Should, to be filtered after reaction 3h, washing is dried, and obtains the chitin modified phosphate；
The nanoclay is kenyaite and humite；The compatilizer is maleic anhydride-g-SBS；The sulphur
Agent is made up of peroxide and divinylbenzene class；The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] pentaerythritol ester and three [2,4- di-tert-butyl-phenyl] phosphite esters；The ultra-violet absorber be 2- (2 '-hydroxyl -3 ',
5 '-bis- (a, a- dimethyl benzyl) phenyl) BTA and 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorination benzos
Triazole；The processing oil is paraffin oil and naphthenic oil；The lubricant is silicone powder and vinyl bis-stearamides.
Embodiment 4
A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, its raw material includes by weight：150 parts of EPDM, poly- third
60 parts of alkene, 60 parts of TPUE, 25 parts of SEBS, 35 parts of organophosphorus ester, 15 parts of expanded graphite, nanoclay 8
Part, 10 parts of calcium carbonate, 12 parts of compatilizer, 3 parts of vulcanizing agent, active 4 parts of Zinc Oxide, 1.5 parts of antioxidant, ultra-violet absorber 2.5
Part, 80 parts of processing oil, 5 parts of lubricant；
Wherein, the EPDM be by 40wt% Third monomer for ethenylidene ENB E types ethylene propylene diene rubber,
The Third monomer of 20wt% is Isosorbide-5-Nitrae-hexadiene for the D types ethylene propylene diene rubber of dicyclopentadiene and the Third monomer of 40wt%
H types ethylene propylene diene rubber is constituted；The polypropylene is by the random polypropylene copolymerization of the HOPP and 70wt% of 30wt%
Thing is constituted, and the atactic polypropylene copolymer is its with 2-12 carbon atom of propylene monomer by 90wt% and 10wt%
Its unsaturated olefin monomer copolymerization is formed；
The organophosphorus ester is chitin modified phosphate, and its preparation method includes：By weight by glycerine, 10 parts add
Heat under conditions of nitrogen protection, adds NaOH to carry out polymerisation as catalyst to 260 DEG C, cold after reaction 2.5h
But to room temperature, filtering, washing obtains polyglycerol；Stirred during 30 parts of the polyglycerol and POCl3 are added into anhydrous acetonitrile
Uniformly, under conditions of nitrogen protection, 56 DEG C are warming up to, add aluminum trichloride (anhydrous) to carry out substitution reaction as catalyst, instead
Removal solvent is distilled after answering 1.8h, washing is dried, and obtains polyglycerol phosphate acyl chlorides；By the polyglycerol phosphate acyl
Chlorine is added in methanesulfonic acid, is added 20 parts of shitosan and is stirred, and under conditions of nitrogen protection, is warming up to 45 DEG C and is replaced
Reaction, is filtered after reaction 2.5h, and washing is dried, and obtains the chitin modified phosphate；
The nanoclay is vermiculite, kaolin and hydrotalcite；The compatilizer is maleic anhydride grafted polyethylene and horse
Maleic anhydride grafted polystyrene；The vulcanizing agent is made up of peroxide and acrylate；The antioxidant be four [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester；The ultra-violet absorber be 2- (2 '-hydroxyl -3 ', 5 '-two uncles
Butyl phenyl) -5- chlorination BTAs；The processing oil is paraffin oil；The lubricant is vinyl bis-stearamides.
The preparation method of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material described in above-described embodiment 1-4, including：Will
EPDM, TPUE, SEBS, organophosphorus ester, expanded graphite, nanoclay, calcium carbonate, compatilizer, antioxygen
Agent, ultra-violet absorber, banburying is uniform during processing oil and lubricant add banbury, is re-fed into extruding in single screw extrusion machine making
Grain, obtains rubber master batch；The rubber master batch and polypropylene, vulcanizing agent, active Zinc Oxide are added into high-speed mixer and mixing 20-
30min, transfers to and plasticate in double screw extruder, and tie rod, cooling, pelletizing obtains the high-efficiency environment friendly flame-proofed thermoplastic sulphur
Change elastomeric material, wherein, screw slenderness ratio is 55-64, and feeding rotating speed is 30-80rpm, and screw speed is 300-500rpm, plus
Work temperature is 160-250 DEG C.
High-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material described in above-described embodiment 1-4 is carried out into performance test, as a result
It is as shown in the table：
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, it is characterised in that its raw material includes by weight：EPDM
100-300 parts, polypropylene 20-80 parts, TPUE 40-100 parts, SEBS 15-30 parts, organophosphorus ester 25-
40 parts, expanded graphite 2-20 parts, nanoclay 5-15 parts, calcium carbonate 1-15 parts, compatilizer 5-15 parts, vulcanizing agent 0.2-5 parts, work
1-5 parts, antioxidant 1-3 parts, ultra-violet absorber 1-3 parts, processing oil 20-100 parts, lubricant 2-6 parts of Zinc Oxide of property.
2. high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim 1, it is characterised in that the EPDM is
By the Third monomer that the Third monomer of 40-60wt% is the E types ethylene propylene diene rubber of ethenylidene ENB, 10-30wt%
For the D types ethylene propylene diene rubber of dicyclopentadiene and the Third monomer of 20-40wt% are the H type ethylene-propylene-diene monomers of Isosorbide-5-Nitrae-hexadiene
Glue is constituted.
3. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claims 1 or 2, it is characterised in that described
Polypropylene is made up of the HOPP of 20-35wt% and the atactic polypropylene copolymer of 65-80wt%；Preferably, it is described
Atactic polypropylene copolymer be by 80-95wt% propylene monomer and 5-20wt% with 2-12 other insatiable hungers of carbon atom
Formed with olefinic monomer copolymerization.
4. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-3, it is characterised in that institute
Organophosphorus ester is stated for chitin modified phosphate, its preparation method includes：Glycerine is carried out into polymerisation and obtains polyglycerol
Afterwards, add POCl3 to carry out substitution reaction and obtain polyglycerol phosphate acyl chlorides, add shitosan and proceed substitution instead
Should after obtain the chitin modified phosphate.
5. high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim 4, it is characterised in that the shitosan
The preparation method of modified phosphate includes：By weight by glycerine, 10 parts are heated to 230-270 DEG C, in the condition of nitrogen protection
Under, add NaOH to carry out polymerisation as catalyst, room temperature is cooled to after reaction 2-4h, to filter, washing is polymerized
Glycerine；Stirred during the polyglycerol and POCl3 25-32 parts are added into anhydrous acetonitrile, in the condition of nitrogen protection
Under, 50-60 DEG C is warming up to, add aluminum trichloride (anhydrous) to carry out substitution reaction as catalyst, it is molten to distill removal after reaction 1-2h
Agent, washing is dried, and obtains polyglycerol phosphate acyl chlorides；By the polyglycerol phosphate acyl chlorides add methanesulfonic acid in, then add
Enter shitosan 8-36 parts to stir, under conditions of nitrogen protection, being warming up to 40-60 DEG C carries out substitution reaction, reacts 2-4h
After filter, wash, dry, obtain the chitin modified phosphate.
6. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-5, it is characterised in that institute
Nanoclay is stated for montmorillonite, nontronite, bentonite, chromium-rich nontronite, hectorite, saponite, sauconite, wheat hydroxyl silicon sodium
One or more combination in stone, kenyaite, humite, vermiculite, kaolin, hydrotalcite.
7. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-6, it is characterised in that institute
It is maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride-g-SBS, maleic anhydride grafting to state compatilizer
One or more combination in polystyrene.
8. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-7, it is characterised in that institute
Vulcanizing agent is stated to be made up of vulcanizing agent and vulcanization aid；Vulcanizing agent is phenolic resin or peroxide；Make when using phenolic resin
During for vulcanizing agent, vulcanization aid is metal halide；When using peroxide as vulcanizing agent, vulcanization aid be cyanate,
Divinylbenzene class or esters of acrylic acid.
9. the high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-8, it is characterised in that institute
Antioxidant is stated for four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and/or three [2,4- di-tert-butyls
Base] phosphite ester；
Preferably, the ultra-violet absorber is 2- (2 '-hydroxyl -3 ', 5 '-bis- (a, a- dimethyl benzyl) phenyl) BTA
And/or 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorination BTAs；
Preferably, the processing oil is paraffin oil and/or naphthenic oil；
Preferably, the lubricant is silicone powder and/or vinyl bis-stearamides.
10. the preparation side of a kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material according to claim any one of 1-9
Method, it is characterised in that including：EPDM, TPUE, SEBS, organophosphorus ester, expanded graphite, nanometer are glued
Banburying is uniform during soil, calcium carbonate, compatilizer, antioxidant, ultra-violet absorber, processing oil and lubricant add banbury, then send
Enter extruding pelletization in single screw extrusion machine, obtain rubber master batch；By the rubber master batch and polypropylene, vulcanizing agent, active zinc oxygen
Powder adds high-speed mixer and mixing 20-30min, transfers to and plasticate in double screw extruder, tie rod, cooling, pelletizing, obtains described
High-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material, wherein, screw slenderness ratio is 55-64, and feeding rotating speed is 30-80rpm, screw rod
Rotating speed is 300-500rpm, and processing temperature is 160-250 DEG C.
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