CN110283392A - Thermoplastic elastomer with high conductivity and mechanical property and preparation method thereof - Google Patents
Thermoplastic elastomer with high conductivity and mechanical property and preparation method thereof Download PDFInfo
- Publication number
- CN110283392A CN110283392A CN201910655676.7A CN201910655676A CN110283392A CN 110283392 A CN110283392 A CN 110283392A CN 201910655676 A CN201910655676 A CN 201910655676A CN 110283392 A CN110283392 A CN 110283392A
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- Prior art keywords
- parts
- rubber
- conductive
- thermoplastic elastomer
- added
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- Pending
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims abstract description 110
- 239000005060 rubber Substances 0.000 claims abstract description 77
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 35
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 23
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 78
- 230000008569 process Effects 0.000 claims description 73
- 239000003431 cross linking reagent Substances 0.000 claims description 71
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 239000000843 powder Substances 0.000 claims description 61
- -1 vinylsiloxane Chemical class 0.000 claims description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 229920002943 EPDM rubber Polymers 0.000 claims description 45
- 239000004743 Polypropylene Substances 0.000 claims description 35
- 229920001155 polypropylene Polymers 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 33
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- 229920000459 Nitrile rubber Polymers 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 19
- 239000004917 carbon fiber Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000004945 silicone rubber Substances 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 15
- DHTZCPJVIMRMBB-UHFFFAOYSA-N benzylbenzene;pyrrole-2,5-dione Chemical group O=C1NC(=O)C=C1.C=1C=CC=CC=1CC1=CC=CC=C1 DHTZCPJVIMRMBB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052740 iodine Inorganic materials 0.000 claims description 15
- 239000011630 iodine Substances 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000008236 heating water Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000013013 elastic material Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical group CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920005560 fluorosilicone rubber Polymers 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims 1
- 239000000806 elastomer Substances 0.000 abstract description 33
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 50
- 238000010438 heat treatment Methods 0.000 description 29
- 239000000178 monomer Substances 0.000 description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 24
- 239000005977 Ethylene Substances 0.000 description 24
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 23
- 239000000835 fiber Substances 0.000 description 23
- 239000000314 lubricant Substances 0.000 description 23
- 239000003381 stabilizer Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 19
- 239000010439 graphite Substances 0.000 description 19
- 235000019241 carbon black Nutrition 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 230000007423 decrease Effects 0.000 description 12
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 8
- 150000002689 maleic acids Chemical class 0.000 description 8
- 239000011231 conductive filler Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011177 media preparation Methods 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical compound CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- 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—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a thermoplastic elastomer with high conductivity and mechanics and a preparation method thereof, and the thermoplastic elastomer comprises the following components: ethylene propylene rubber, silicon rubber, polyolefin resin, a composite conductive medium, maleic anhydride grafted non-polar rubber, maleic anhydride grafted polyolefin resin, polar rubber, white oil, a coupling agent, a compatilizer and a processability additive. The preparation method comprises the following steps: firstly, carrying out surface activation pretreatment on the composite conductive medium according to respective properties; then melt blending with polyolefin resin; then dynamically vulcanizing the base materials of the non-polar rubber, the maleic anhydride grafted non-polar resin, the coupling agent, the compatilizer and the conductive medium to prepare the high-conductivity elastomer. The invention has the advantages of good mechanical property on the premise of ensuring good high conductivity, high fluidity, easy processing, good weather resistance and aging resistance, and has important significance for widening the application field of the thermoplastic elastomer.
Description
Technical field:
The present invention relates to thermoplastic elastic material technical field more particularly to a kind of high conductivity and mechanical property taken into account
Thermoplastic elastomer (TPE) and preparation method thereof.
Background technique:
It between rubber and plastics is a kind of composite structured high-performance material that thermoplastic elastomer (TPE), which is physical property,
Material, it had not only had the elasticity of rubber, but also the workability with plastics.One new " raw material of industry system " is constituted, by people
Referred to as " third generation rubber ".It is known as TPV (Thermoplastic by elastomer prepared by substrate of EP rubbers
Vulcanization), because Technology of Dynamic Vulcanized obtains continuous phase and dispersed phase formation three-dimensional network shape island structure in system
Name.Its own possesses the physical property and functional character of thermoset rubber at normal temperature, possesses thermoplastic at high temperature
High fluidity and reprocessabilty, so that the features such as product possesses processing and forming simplicity, and material is Ke Xunhuanliyong, cost performance is high.
It is both widely used to the fields such as auto industry, building materials, electronic apparatus, health care and consumer appliance at present.Example
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization such as is disclosed in application No. is the Chinese patent of CN 101696279,
The component and proportion of composition are as follows: synthetic rubber 10~70%, synthetic resin 30~40%, softening agent 10~30, inorganic filler 5
~20%, 0.6~6 part of crosslinking agent 3~10%, promotor.The elastomer that the invention produces have high fluidity, high resiliency,
The characteristics of soft, and also have many advantages, such as that equipment is applicable extensively, preparation process is simple, process window mouth width in technique.
For being based primarily upon based on mental section in the selection of conductive material, but the lively type of metal itself causes daily
It aoxidizes, corrodes in, phenomena such as passivation, significantly impact the service life of material, while being directed to pair of certain occasions
Material elastic demand is even more that can not be competent at for metal material, therefore, in many occasions all using macromolecular material
As optimal selection, but elastomer sheet is as insulating material, need to can be at by adding conducting medium, when reaching threshold limit value
For conductive material, volume resistivity is based primarily upon for the use scope of conductive material to determine, when volume resistivity is 107-
1010It is semi-conducting rubber when Ω .cm, is used for telautogram plate, semi-conducting rubber sensitive tape；When volume resistivity is 104-107
It is antistatic rubber when Ω .cm, is used for antistatic shell, anti-static sole；When volume resistivity is 101-104Ω .cm Shi Weigao
Conducting rubber is used for elastic electrode, anti-overflow element；When volume resistivity is 10-3-101It is superconductivity rubber when Ω .cm
Glue is used for printed circuit board, conductive film.Wherein Highly-conductive elastomer is that substitution metal material is applied to sealing and electromagnetism
The optimal selection for shielding occasion, the preparation process about production high electroconductive rubber have certain technical foundation, such as in application number
100 parts of rubber constituent, 2-3 parts of crosslinking agent, 3-4 parts of vulcanization accelerator, oxygen are disclosed in Chinese patent for CN 101696279
Change zinc 5-8 parts, 25-30 parts of hard carbon black, 10-15 parts of conductive black, 30-40 parts of reinforcing filler, 8-12 parts of softening agent and its
5-10 parts of its material.The rubber that the invention produces has preferable electric conductivity and mechanical strength, has preparation process simple
Advantage.In addition, application No. is the Chinese patent of CN101434747 and CN1605604 also elaborate by addition active bamboo or
Metal powder reduces the volume resistivity of elastomer, shows preferable electric conductivity.
Increase elastomer conductive currently on the market mainly passes through addition conductive carbon black, metal as the description of above-mentioned patent
Powder or conductive carbon fibre, graphene increase electric conductivity, and institute's band product can reflect preferable electric conductivity under certain additive amount,
But its shortcoming uses single conductive component in the majority it is also obvious that product adds conducting medium, and before addition conductive filler
It is not pre-processed preferably, causes product that need to add a large amount of conducting medium and be just able to achieve preferable electric conductivity, it is also thus sacrificial
The domestic animal intensity and elasticity of elastomer itself, and for the heat resistance and weatherability of product there is shadow in a large amount of addition conductive fillers
It rings, limits the use of product occasion outdoors.Meanwhile for Highly-conductive elastomer, generally prepared using silicon rubber,
Costco Wholesale is high, and working process is difficult, and to product use scope, there are certain restrictions.
Summary of the invention:
To solve the above problems, the invention discloses a kind of thermoplastic elastomehcs for taking into account high conductivity and mechanical property
Property body and preparation method thereof, highly conductive thermoplastic elastomer (TPE) obtained uses a variety of composite conducting media, to medium before preparation
It is pre-processed, mode is kneaded using multistage afterwards, each component is promoted to disperse, overall performance is finally improved using Technology of Dynamic Vulcanized,
So that elastomer not only has good electric conductivity, also there is good processability and mechanical strength, price is relative to pure silicon rubber
Glue is cheap and preparation is easy, and has very big market potential in elastic electrode, electromagnetic shielding, anti-overflow original part etc..Its specific skill
Art scheme is as follows:
A kind of thermoplastic elastomer (TPE) for taking into account high conductivity and mechanical property, in parts by weight, including following components:
15-35 parts of EP rubbers,
0-20 parts of silicon rubber,
5-25 parts of polyolefin resin,
0-20 parts of conductive carbon black,
0-15 parts of carbon fiber,
0-10 parts of metal powder,
Maleic anhydride is grafted EP rubbers 0-10 parts,
0-10 parts of maleic anhydride stem grafting polyolefin resin,
0-15 parts of polar rubber,
0-20 parts of white oil,
0-10 parts of inorganic filler,
0-0.5 parts of antioxidant,
0-5 parts of dispersing agent,
0-5 parts of coupling agent,
Main crosslinking agent 0-1 parts,
0-2 parts of assistant crosslinking agent,
0-1 parts of release agent.
Further, the EP rubbers is one or two kinds of combinations of bibasic ethylene propylene rubber and ethylene propylene diene rubber；Institute
State silicon rubber be methyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorine silicone rubber one kind or
A variety of combinations；The maleic anhydride grafting EP rubbers is the bibasic ethylene propylene rubber of modified by maleic acid anhydride graft, maleic anhydride
One or two kinds of combinations of the ethylene propylene diene rubber of graft modification；The polar rubber is in nitrile rubber or neoprene
One or two combination.
Further, the EP rubbers is the EP rubbers of Mooney viscosity 20-100, and the silicon rubber is viscous for Mooney
The silicon rubber of 20-100 is spent, the polar rubber is the nitrile rubber or neoprene of Mooney viscosity 20-100.
Further, the polyolefin resin is polyethylene, polypropylene, polyphenylene oxide or polyethylene and polyacrylic mixed
Close one of object or any number of combination；The maleic anhydride stem grafting polyolefin resin is the poly- second of modified by maleic acid anhydride graft
One of alkene, the polyethylene of the polypropylene of modified by maleic acid anhydride graft and modified by maleic acid anhydride graft and polypropylene are any number of
Combination.
Further, the conductive black is 10-20nm partial size, the thermal cracking carbon black of meta-alkalescence, DBP absorption value 300-
500ml/g, iodine absorption value 800-1000Mg/g, specific surface area 750-1100m2/ kg, resistivity≤0.5 Ω .cm.
Further, the carbon fiber be 7.0-10.0 μm of filament diameter, tensile strength 3.5-4.0Gpa, phosphorus content >=
95%, volume resistivity≤1.5*10-3Ω.cm。
Further, the metal powder be 5.0-20.0 μm, volume resistivity≤5*10-2 Ω .cm copper powder, silver powder,
One kind or any number of combination of nickel coated graphite powder, nickel coated copper powder, aluminium silvering powder, copper silvering powder.
Further, the coupling agent is that titanate coupling agent, silane coupling agent or titanate coupling agent and silane are even
Join one of agent or any number of combination；The crosslinking agent is tert-butylperoxy isopropyl carbonate, cumyl peroxide, pungent
One of base phenolic resin or ethyl orthosilicate or any number of combination；The inorganic filler is calcium carbonate, talcum powder or kaolinite
One of soil or any number of combination；The assistant crosslinking agent is diphenyl-methane maleimide, triisopropyl isocyanates, methyl
One of allyl acrylate, ethylene glycol dimethacrylate, stannous chloride or dibutyl tin dilaurate are any number of
Combination.
The above-mentioned process for preparation of thermoplastic elastomer for taking into account high conductivity and mechanical property, includes the following steps:
A), will conductive carbon black, conductive carbon pricker dimension, metal powder be added coupling agent solution in respectively infiltrate, adjust pH value to
In alkalescent, heating water bath stirring is dried to obtain activation conducting medium；
B), in proportion by polyolefin resin and conductive carbon black after mixing, dispersing agent is added, it is molten through melting mixing equipment
After melting blending, conductive agglomerate is obtained；
C), by the resulting conductive agglomerate of step B), carbon fiber, metal powder, EP rubbers, polar rubber, maleic anhydride
It is uniform that graft modification EP rubbers, maleic acid change grafted polyolefinic resin, inorganic filler, antioxidant, dispersant
Afterwards, through melting mixing equipment mixing granulation, intermediate product is both obtained；
D), the intermediate product, white oil, crosslinking agent, assistant crosslinking agent, dispersing agent, antioxidant, release agent are mixed equal
It is even, after carrying out dynamic vulcanization in melting mixing equipment, highly conductive thermoplastic elastomer (TPE) is made.
Wherein, the melting mixing equipment is double screw extruder, and process conditions are 160~220 DEG C of temperature, revolving speed 200
~320rpm；Above-mentioned highly conductive thermoplastic elastic material is molded thickness 3mm's using vertical injection molding machine under the conditions of 180 DEG C
Print prepares tensile bars using universal sampling machine, the stretching for measuring material is strong using the volume resistance of resistance instrument measurement sample
The processing flowability of degree and elongation at break, material passes through the melt flows under the conditions of 230 DEG C of measuring temperature, load 5/10kg
Index characterizes.
The working principle of the invention is:
From realize satisfactory electrical conductivity, need to be associated with five factors of volume resistivity, it may be assumed that (1) elastomer from
Body resistivity and polarity, the resistivity of (2) filler grain, the resistivity between (3) filler grain, (4) are in galvanic circle
Number of particles, (5) conductive path quantity.For rubber components itself, it need to guarantee internal Mooney viscosity and molecular weight
It should not be too large, prevent from that conducting particles is hindered to disperse in system and prevent to reunite, while being directed to the nonpolarity of elastomer, by adding
Add modified grafting that polar rubber is added to realize the reduction of self-resistance rate.In order to realize resistivity energy between filler grain and particle
Conductive blacks enough that low resistivity is realized in elastomer, that DBP value and iodine absorption value should be selected to reduce on selecting filler grain,
Surface active is carried out to particle in the initial period simultaneously and increases polarity and specific surface area, in addition, in order to further decrease resistivity,
Rod-like fibre based carbon fiber and metal powder can additionally be added to realize, carbon fiber self-resistance rate is lower compared with carbon black, while benefit
Use rod-like fibre itself one-dimension oriented as bridge, connection is dispersed in conductive black in system, promotes to be formed more conductive logical
Road reduces overall resistivity, to realize preferable electronics transfer；Metal powder possesses lower volume compared to carbon pricker dimension
Resistivity, compared to carbon black, the lower region for being also more dispersible in carbon black and being not easy to disperse of metal powder itself autohemagglutination, and metal
Interparticle distance can construct preferable conductive path relatively far apart, while also by carbon fiber as intermediary, realize
Conductive carbon black, carbon fiber, metal powder three's medium construct conductive network jointly, compared to single conducting medium, realize lower
Additive amount reaches higher electric conductivity, while can preferably possess the mechanical property of former elastomer.
When adding more filler in system, easily there is decline phenomenon and removes to reduce fall in product mechanical property
Outside being pre-processed in advance to conducting medium, is taken in processing and different conducting mediums are added by type in different phase, one
Aspect is put into several times can increase material mixing number raising elastomer material feeding ability, and each component is promoted to form preferable continuous phase
And dispersed phase, it realizes microcosmos network topological structure, is on the other hand directed to conducting medium respectively property, selected in different phase different
Technological parameter can guarantee that each filler preferably disperses in system, avoid reunite influence mechanical strength.
Mechanical property is taken into account in order to realize, self assembly behavior can be used and processed, that is, conducting medium surface is allowed to coat
One layer of active material, it is compatible between avoiding powder autohemagglutination and promoting macromolecule, and using macromolecule viscositys different in elastomer,
The difference of the physical properties such as mobility, surface potential energy, induction conducting medium selectively in certain phases and distribute alternately, subtract
The formation of few invalid conductive path realizes preferable electric conductivity using less conducting medium to reach, and ensures mechanical property.
The present invention is first by activating conductive black, carbon fiber and metal powder, by wrapping amphiphilic activity on surface
On the one hand group chain prevents carbon black, metal powder autohemagglutination from ensuring there is good dispersibility in system, and active group chain possesses
Longer living chain can be more conducive to the formation of conductive path between particle, possess bigger specific surface simultaneously after on the other hand activating
The surface potential energy between macromolecule is reduced, it can be more effectively compatible with macromolecule.Then first by a certain proportion of conductive carbon black
Preparatory self assembly is carried out between good fluidity polyolefin resin and is mixed to form performed polymer, guarantees preferably to be dispersed in poly-
Small island structure is formed in olefin resin, guarantees that particle is capable of forming more conductive path in polyolefin resin.It then will be pre-
Aggressiveness is blended with EP rubbers, silicon rubber, polar rubber, while being promoted using compatilizer compatible between each rubber, furthermore puts into
Carbon fiber makes contacting with each other between carbon black and carbon fiber in system, forms primary conductive network structure, while throwing metal powder,
It is deposited at metal powder between the Rubber-resin network structure phase interface to be formed, prevents metal powder from migrating or precipitating, be prepared into
Highly conductive intermediate carries out dynamic vulcanization to EP rubbers and silicon rubber respectively using plyability crosslinking agent later, adjusts simultaneously
Technological parameter guarantees that synthetic rubber forms good crosslinking in smelting equipment, so that rubber particles partial size is smaller, guarantee system
Interior EP rubbers and silicon rubber form greater number of rubber and polyolefin under the premise of using polyolefin resin as continuous phase
The island phase gap interface formed between resin, constructs network topology structure jointly, conducting medium using crosslinking net it is existing between
Gap forms conductive path, while being also filled with reinforcement of the gap realization to elastomer.Network knot is reasonably constructed by each component
Structure realizes taking into account to the comprehensive performance of thermoplastic elastomer (TPE) mechanical property, electrical property and product processability.And compared to pure silicon rubber
Glue and pure metal powder or the conductive elastomer of pure carbon fiber medium preparation have higher cost performance.
The beneficial effects of the present invention are:
The thermoplastic elastomer (TPE) provided by the present invention for taking into account mechanical property and electric conductivity, using ethylene-propylene rubber/polyolefine tree
Rouge compound system is TPV substrate, and adds plyability conducting medium, by adjusting each rubber, polyolefin resin and conducting medium
Ratio, and select suitable white oil and multiple crosslinking agent control system hardness and strength, finally prepare simple process, Yi Jia
Work takes into account the antistatic material of electrical property and mechanical property.The compound system is a kind of thermoplasticity cross-linked network structure, is being based on
In the island structure of rubber phase and resin phase, conducting medium is more likely formed conductive path using existing interface phase network structure,
Therefore medium good dispersion, resistance to ag(e)ing is good, has preferable mechanical strength and has both stronger conductive stability.Therefore, in bullet
The similar fields such as property electrode, electromagnetic shielding and sealing are a kind of high conductive materials of great application prospect.
Specific embodiment:
The preferred embodiments of the present invention will be described in detail below, so that advantages and features of the invention can be easier to by this
Field personnel understanding, so as to make a clearer definition of the protection scope of the present invention.
Embodiment 1
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 1；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 1
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a1；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 1, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb1 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 101Ω .cm, tensile strength 8.5MPa, elongation at break 492%, MFR are 11.5g/10min (10kg).
Embodiment 2
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weigh 8 parts of conductive carbon blacks, 10 parts of conductive carbon fibres, the conductive black DBP absorption value is
170-185ml/g, iodine absorption value be 360Mg/g, partial size 9-17nm；The conductive carbon fibre filament diameter is 7.0-10.0
μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；It is added thereto stirring, then
Heating water bath makes ethyl alcohol volatilize, and after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and mixed at high speed is added
In machine, the polypropylene melt flow rate is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 is added
Part antioxidant, is stirred one minute, is eventually adding 0.5 part of lubricant, is processed and is granulated in double screw extruder after mediating one minute,
The temperature of double screw extruder heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200
DEG C, 200 DEG C, 200 DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 2；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 2
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a2；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 2, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb2 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 101Ω .cm, tensile strength 8.1MPa, elongation at break 463%, MFR are 10.8g/10min (10kg).
Embodiment 3
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weigh 8 parts of conductive carbon blacks, 10 parts of nickel coated graphite powders, the conductive black DBP absorption value is
170-185ml/g, iodine absorption value be 360Mg/g, partial size 9-17nm；；10.0 μm of the nickel coated copper powder partial size, volume resistivity
≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, after obtaining pretreatment hybrid conductive medium, then
It weighs 30 parts of random polypropylenes to be added in high-speed mixer, the polypropylene melt flow rate is 16 ± 3.Then 8 are added
Part conductive black, is added 0.3 part of stabilizer, 0.2 part of antioxidant, stirs one minute, is eventually adding 0.5 part of lubricant, mediates one
It processes and is granulated in double screw extruder after minute, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed
For 300rpm, conductive agglomerate 3 is obtained；
B), 10 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 3
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a3；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 3, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb3 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 8.7MPa, elongation at break 502%, MFR are 11.3g/10min (10kg).
Embodiment 2,3, which is based on embodiment 1, mainly will wherein carbon fiber or metal powder replace, compared to embodiment 1,
There is reduction in its tensile strength of embodiment 2 and elongation at break, volume resistivity is constant, reacts more carbon fiber and is unfavorable in body
It is compatible in system, lead to the decline of system mechanical strength.The metal powder of embodiment 3 is easier to be melted into rubber and plastic compared to carbon fiber
In component, certain reinforcing effect is played to elastomer, but reduce compared to its electric conductivity of carbon fiber.Show carbon black, carbon fiber, gold
Belong to powder and the optimization for being just able to achieve overall performance coexists in proportion.
Embodiment 4
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 4；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 4
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a4；
C), 4 0.3 part of crosslinking agent of addition and 0.6 part of assistant crosslinking agent in intermediate, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb4 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 9.3MPa, elongation at break 384%, MFR are 18.4g/10min (10kg).
Embodiment 5
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 8 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 5；
B), 32 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 5
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a5；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 5, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb5 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 7.4MPa, elongation at break 528%, MFR are 4.5g/10min (10kg).
Embodiment 4,5 mainly changes the proportional amount of wherein polyolefin resin and ethylene propylene diene rubber based on embodiment 1,
Compared to embodiment 1, the tensile strength of 4 system of embodiment increases, and elongation at break reduces, and melt index increases, system volume
Resistivity increases；The tensile strength of 5 system of embodiment declines, and elongation at break increases, and melt index increases, and volume resistivity increases
Add.Embodiment 4 reflects that polyolefin resin can be improved the mobility of product, but is easier to that product is made to show brittleness；Embodiment 5
The increase for reflecting ethylene propylene diene rubber improves whole elasticity, but is easier to the decline for processability occur.The two is compared to reality
Example 1 is applied, shows to form more network topology structures only in suitable rubber and plastic ratio, promote filler shape in system
At more conductive paths, there is the possibility for excessively easily causing and forming topological structure with rubber as continuous phase in polyolefin resin
Property reduce, rubber as dispersed phase exist excessively, viscosity is larger, is unfavorable for preferable dispersion of the conducting medium in system.By
This show the proportion of polyolefin resin and ethylene propylene diene rubber must control in reasonable range ability realizability can it is optimal
Change.
Embodiment 6
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 6；
B), 10 parts of ethylene propylene diene rubbers, 23 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 6
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a6；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 6, wherein crosslinking agent is 0.1 part of peroxidating
Isopropyl t-butyl carbonate and 0.2 part of ethyl orthosilicate；Assistant crosslinking agent is 0.2 part of diphenyl-methane maleimide and 0.4 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb6 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 101Ω .cm, tensile strength 8.1MPa, elongation at break 562%, MFR are 10.1g/10min (10kg).
Embodiment 7
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 7；
B), 10 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 23 parts of powder fourths are added in conductive agglomerate 7
Nitrile rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, the
Three content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a7；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 7, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb7 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 6.2MPa, elongation at break 377%, MFR are 6.5g/10min (10kg).
Embodiment 6,7 mainly changes the ratio of ethylene propylene diene rubber, silicon rubber, nitrile rubber based on embodiment 1, compared to
Embodiment 1,5 tensile strength of embodiment are declined slightly, and elongation at break increases, melt index slightly reduces, and volume resistivity is held
It is flat, show that silicon rubber possesses better elasticity compared to ethylene propylene diene rubber, but its price is higher compared to ethylene propylene diene rubber,
And silicon rubber is added, and it is limited to mechanical strength raising, do not show bigger advantage；Implement mechanical strength, the fracture of 6 systems
Elongation, melt index, electric conductivity are decreased obviously, though electric conductivity can be improved to a certain degree by showing as polar rubber, and it is excessive
Polar rubber decline compatible with non-polar rubber, layering effectively causes and can not form preferable island structure in system, cause
The reduction of comprehensive performance.
Embodiment 8
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), 17 parts of random polypropylenes are weighed to be added in high-speed mixers, the polypropylene melt flow rate is 16 ±
3.Then be added 8 parts of conductive blacks, the conductive black DBP absorption value is 170-185ml/g, iodine absorption value be 360Mg/g,
Partial size is 9-17nm；0.3 part of stabilizer, 0.2 part of antioxidant is added, stirs one minute, is eventually adding 0.5 part of lubricant, mediates
Process and be granulated in double screw extruder after one minute, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C,
160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (sequentially for from feed opening to head),
Revolving speed is 300rpm, obtains conductive agglomerate 8；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 8
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders, the conductive carbon fibre filament diameter be 7.0-10.0 μm, tensile strength 3.5-4.0Gpa,
Phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；10.0 μm of the nickel coated copper powder partial size, volume resistivity≤2.5*
10-2Ω .cm is stirred one minute, the polypropylene of 3 parts of modified by maleic acid anhydride graft is then added, 4 parts of maleic anhydrides are grafted ternary second
Third rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant are processed in double screw extruder after mediating one minute and are made
Grain, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate a8；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 8, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb8 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 103Ω .cm, tensile strength 6.3MPa, elongation at break 362%, MFR are 5.8g/10min (10kg).
Embodiment 8 is mainly omitted the pre-treatment step of conductive filler based on embodiment 1, compared to embodiment 1, is stretched
Intensity, elongation at break, fluidity of molten, electric conductivity are decreased obviously, and are shown by pretreatment, conductive filler and rubber and plastic component
Possess better compatibility, the decline of its own autohemagglutination, therefore can preferably disperse and play to elastomer conductive and power
The effect of the property learned enhancing.
Embodiment 9
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 9；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powdered nitrile rubbers are added in conductive agglomerate 9
Rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, third
Content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant are then added, pinches
Unify to process in double screw extruder after minute and be granulated, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C,
160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head),
Revolving speed 260rpm obtains intermediate a9；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 9, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb9 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 7.2MPa, elongation at break 389%, MFR are 7.7g/10min (10kg).
Embodiment 9 eliminates the addition in system with polyolefin resin and ethylene propylene diene rubber compatilizer based on embodiment 1,
Compared to embodiment 1, tensile strength, elongation at break, fluidity of molten, electric conductivity are decreased obviously, and show compatilizer energy
It is compatible between enough preferably promotion components, each component is connected as intermediary without compatilizer, easily there is phase between each component
Mutually repel and cause each component independent at phase, which is unfavorable for the raising of whole mechanical strength and electric conductivity, causes embodiment 9 comprehensive
Close the decline of performance.
Embodiment 10
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization after obtaining pretreatment hybrid conductive medium, then weighs 17 parts of random polypropylenes and is added in high-speed mixer, and described poly- third
Alkene melt flow rate (MFR) is 16 ± 3.Then 8 parts of conductive blacks are added, 0.3 part of stabilizer, 0.2 part of antioxidant, stirring one is added
Minute, it is eventually adding 0.5 part of lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder adds
The temperature of hot-zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C,
190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 10；
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powder fourths are added in conductive agglomerate 10
Nitrile rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, the
Three content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then 5 parts of conductive carbons are added in acrylonitrile content 33%
Fiber and 5 parts of nickel coated graphite powders stir one minute, polypropylene, the 4 parts of maleic acids of 3 parts of modified by maleic acid anhydride graft are then added
Acid anhydride is grafted ethylene propylene diene rubber, 0.3 part of stabilizer, 0.2 part of antioxidant, 0.5 part of lubricant, squeezes after mediating one minute in twin-screw
Process and be granulated in machine out, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains centre
Body a10；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 10, wherein crosslinking agent is 0.2 part of peroxidating
Diisopropylbenzene (DIPB) and acetoxylsilane more than 0.1 part；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part of two laurel
Sour dibutyl tin.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder, be granulated
In the process, pass through liquid spout be added 15 parts of white oils, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C,
160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head),
Antistatic thermoplastic elastomer (TPE) TPVb10 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 8.7MPa, elongation at break 463%, MFR are 10.2g/10min (10kg).
Embodiment 10 is mainly adjusted the main crosslinking agent of wherein ethylene propylene diene rubber and silicon rubber based on embodiment 1
Whole, compared to embodiment 1, the tensile strength of system is slightly increased, elongation at break decline, processability decline；System volume resistance
Rate increases, and shows compared to original main crosslinking agent, and under current processing technology and release more polyradical reality is not implemented
Under the now crosslinking of product and the technological temperature there is certain decompose for polyolefin resin and influence in main crosslinking agent, cause comprehensive performance
Decline.
Embodiment 11
The process for preparation of thermoplastic elastomer of high conductivity and mechanical property is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1 part of coupling agent, be put into ethanol solution and be stirred, and adjust PH
For alkalescent, make its hydrolysis, then weighs 8 parts of conductive carbon blacks, 5 parts of conductive carbon fibres, 5 parts of nickel coated graphite powders, the conductive charcoal
Black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm；The conductive carbon fibre monofilament
Diameter is 7.0-10.0 μm, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3Ω.cm；Institute
State 10.0 μm of nickel coated copper powder partial size, volume resistivity≤2.5*10-2Ω .cm is added thereto stirring, and then heating water bath makes ethyl alcohol
Volatilization obtains pretreatment hybrid conductive medium 11.
B), 23 parts of ethylene propylene diene rubbers, 10 parts of methyl vinyl silicone rubbers, 6 parts of powder fourths are added in conductive agglomerate 11
Nitrile rubber is put into high-speed mixer together, and the Mooney viscosity of the ethylene propylene diene rubber is 51, ethylene contents 67%, the
Three content of monomer 4.7%, and Third monomer is ethylidene-norbornene.The methyl vinyl silicone rubber contents of ethylene
23%, molecular weight 450,000, the powder nitrile rubber Mooney viscosity is 57, then hybrid conductive is added in acrylonitrile content 33%
Medium stirs one minute, then weighs 17 parts of random polypropylenes again and is added in high-speed mixer, the polypropylene melt flow
Rate is 16 ± 3.Obtain conductive agglomerate 1；The polypropylene of 3 parts of modified by maleic acid anhydride graft, 4 parts of maleic anhydrides are grafted ethylene-propylene-diene monomer
Glue, 0.6 part of stabilizer, 0.4 part of antioxidant, 1 part of lubricant are processed in double screw extruder after mediating one minute and are granulated, double
The temperature of screw extruder heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C,
185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate a11；
C), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent are added in intermediate 11, wherein crosslinking agent is 0.2 part of peroxidating
Isopropyl t-butyl carbonate and 0.1 part of ethyl orthosilicate；Assistant crosslinking agent is 0.4 part of diphenyl-methane maleimide and 0.2 part two
Dibutyl tin laurate.Then 0.1 part of release agent is added, after mediating 1-2 minutes, processes and is granulated in double screw extruder,
In granulation process, 15 parts of white oils, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 are added by liquid spout
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), antistatic thermoplastic elastomer (TPE) TPVb11 is finally made in revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 102Ω .cm, tensile strength 6.8MPa, elongation at break 352%, MFR are 6.4g/10min (10kg).
Embodiment 11 is based on embodiment 1 and is mainly changed to disposably by the addition of original conductive filler point different phase different process
It launches,
Compared to embodiment 1, the tensile strength of system declines, elongation at break decline, processability decline；System volume electricity
Resistance rate increases, and reflects that system is reduced because being kneaded number, and the disposable input amount of filler is excessive, and does not take temperature corresponding
Adjustment, preferable mixing and dispersion can not be realized within a short period of time by leading to conductive filler, resin, rubber, lead to body force
The property learned, electric conductivity, processability are decreased obviously.
Comparative example 1
Common thermoplastic's elasticity preparation, comprising the following steps:
A), measured according to weight ratio, first weigh 43 parts of ethylene propylene diene rubbers and be added in high-speed mixer, the ternary second
The Mooney viscosity of third rubber is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-drop ice
Piece alkene.Then 20 parts of random polypropylenes are added, wherein the polypropylene melt flow rate is 16 ± 3；Then 18 parts are added
Calcium carbonate, 0.6 part of stabilizer, 0.4 part of antioxidant stir one minute, are eventually adding 1 part of lubricant, double after mediating one minute
Process and be granulated in screw extruder, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm is obtained
Intermediate product；
B), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent is added in the midbody product, wherein crosslinking agent is peroxidating
Isopropyl t-butyl carbonate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1 part of release agent is added, mediates 1-2 minutes
Afterwards, the dynamic vulcanization in double screw extruder, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C,
170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed
A kind of common thermoplastic's elastomer is finally made in 260rpm.
Comparative example 2
Antistatic thermoplastic elastic preparation, comprising the following steps:
A), measured according to weight ratio, first weigh 43 parts of ethylene propylene diene rubbers and be added in high-speed mixer, the ternary second
The Mooney viscosity of third rubber is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-drop ice
Piece alkene.Then 20 parts of random polypropylenes are added, wherein the polypropylene melt flow rate is 16 ± 3；Then 18 parts are added
Conductive carbon black, the conductive black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm,
0.6 part of stabilizer, 0.4 part of antioxidant stir one minute, are eventually adding 1 part of lubricant, in twin-screw extrusion after mediating one minute
It processes and is granulated in machine, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185
DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate product；
B), 0.3 part of crosslinking agent and 0.6 part of assistant crosslinking agent is added in the midbody product, wherein crosslinking agent is peroxidating
Isopropyl t-butyl carbonate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1 part of release agent is added, mediates 1-2 minutes
Afterwards, the dynamic vulcanization in double screw extruder, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C,
170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed
A kind of antistatic thermoplastic elastomer (TPE) is finally made in 260rpm.
Highly-conductive elastomer 1 obtained is subjected to performance pair with conventional elastomers, antistatic elastomer in comparative example respectively
Than as a result as shown in table 1 below, it is as shown in table 2 below additionally individually to list the performance comparison of Highly-conductive elastomer after weathering:
1 elastomer performance contrast test result of table
The performance test results after 2 elastomer degradation of table
As can be seen from the table, Highly-conductive elastomer is compared with conventional elastomers: being adopted when preparing highly conductive flame-proof elastomer
With three-steps process, and filler and rubber, resin Composition use coupling agent, rubber and rubber, using compatible between rubber and resin
Each component in system is given in agent can possess better compatibility and dispersibility, and silicon rubber also possesses preferably elasticity and power
Intensity is learned, to sum up factor makes mechanical property possess better performance, and tensile strength, elongation at break and tearing strength etc. are compared
Intensity is all improved for the inorganic filler of equivalent filling, and the conduction that product itself has conventional elastomers and do not have
Property；With antistatic elastomer phase ratio, no matter from technique, or in the selection and processing of filler, Highly-conductive elastomer can
It allows filler and rubber and plastic component to possess better compatibility, conductive filler is preferably dispersed, formed more conductive logical
Road, therefore, other than showing larger difference in mechanical property, there is also apparent differences for electric conductivity.Simultaneously, high electricity
Elastomer the result shows that product is not much different after heat ageing with unaged, had differences in 7 days and 15 days heat ageings
Main cause is to cause tensile strength, stretching strength to increase based on white oil volatilization under high temperature, under elongation at break, tearing strength
Drop, though electric conductivity aging does not show biggish fluctuation, high conductivity elastic behavior goes out good resistance to ag(e)ing as a result,.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme；Therefore, although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement；And all do not depart from this
The technical solution and its improvement of the spirit and scope of invention, should all cover within the scope of the claims of the present invention.
Claims (10)
1. a kind of thermoplastic elastomer (TPE) for taking into account high conductivity and mechanical property, which is characterized in that by the raw material system of following parts by weight
At:
15-35 parts of EP rubbers,
0-20 parts of silicon rubber,
5-25 parts of polyolefin resin,
0-20 parts of conductive carbon black,
0-15 parts of carbon fiber,
0-10 parts of metal powder,
Maleic anhydride is grafted EP rubbers 0-10 parts,
0-10 parts of maleic anhydride stem grafting polyolefin resin,
0-15 parts of polar rubber,
0-20 parts of white oil,
0-10 parts of inorganic filler,
0-0.5 parts of antioxidant,
0-5 parts of dispersing agent,
0-5 parts of coupling agent,
Main crosslinking agent 0-1 parts,
0-2 parts of assistant crosslinking agent,
0-1 parts of release agent.
2. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that the second
Third rubber is one or two kinds of combinations of bibasic ethylene propylene rubber and ethylene propylene diene rubber；The silicon rubber is methyl silicone rubber, first
One or more combinations of base vinylsiloxane rubber, methyl phenyl vinyl silicone rubber and fluorine silicone rubber；The maleic anhydride
It is grafted the ethylene propylene diene rubber that EP rubbers is the bibasic ethylene propylene rubber of modified by maleic acid anhydride graft, modified by maleic acid anhydride graft
One or two combination；The polar rubber is the combination of one or both of nitrile rubber or neoprene.
3. the thermoplastic elastomer (TPE) according to claim 2 for taking into account high conductivity and mechanical property, which is characterized in that the second
Third rubber is the EP rubbers of Mooney viscosity 20-100, and the silicon rubber is the silicon rubber of Mooney viscosity 20-100, the pole
Property rubber be Mooney viscosity 20-100 nitrile rubber or neoprene.
4. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that described
Polyolefin resin is one of polyethylene, polypropylene, polyphenylene oxide or polyethylene and polyacrylic mixture or any number of group
It closes；The maleic anhydride stem grafting polyolefin resin is the polyethylene of modified by maleic acid anhydride graft, modified by maleic acid anhydride graft
One of polyethylene and polypropylene of polypropylene and modified by maleic acid anhydride graft or any number of combination.
5. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that described to lead
Electric carbon black is 10-20nm partial size, the thermal cracking carbon black of meta-alkalescence, DBP absorption value 300-500ml/g, iodine absorption value 800-
1000Mg/g, specific surface area 750-1100m2/ kg, resistivity≤0.5 Ω .cm.
6. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that the carbon
Fiber is 7.0-10.0 μm of filament diameter, tensile strength 3.5-4.0Gpa, phosphorus content >=95%, volume resistivity≤1.5*10-3
Ω.cm。
7. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that the gold
Belonging to powder is 5.0-20.0 μm, volume resistivity≤5*10-2 Ω .cm copper powder, silver powder, nickel coated graphite powder, nickel coated copper powder, aluminium
One kind or any number of combination of silvering powder, copper silvering powder.
8. the thermoplastic elastomer (TPE) according to claim 1 for taking into account high conductivity and mechanical property, which is characterized in that the idol
Connection agent is titanate coupling agent, silane coupling agent or one of titanate coupling agent and silane coupling agent or any number of group
It closes；The crosslinking agent is tert-butylperoxy isopropyl carbonate, cumyl peroxide, octyl phenolic or ethyl orthosilicate
One of or any number of combination；The inorganic filler is one of calcium carbonate, talcum powder or kaolin or any number of combination；
The assistant crosslinking agent is diphenyl-methane maleimide, triisopropyl isocyanates, allyl methacrylate, dimethyl allene
One of sour glycol ester, stannous chloride or dibutyl tin dilaurate or any number of combination.
9. a kind of preparation side of such as described in any item thermoplastic elastomer (TPE)s for taking into account high conductivity and mechanical property of claim 1-8
Method, which comprises the steps of:
A), conductive carbon black, conductive carbon pricker dimension, metal powder are added in coupling agent solution and are respectively infiltrated, adjust pH value to being in weak
Alkalinity, heating water bath stirring, is dried to obtain activation conducting medium；
B), in proportion by polyolefin resin and conductive carbon black after mixing, be added dispersing agent, through melting mixing equipment melt altogether
After mixed, conductive agglomerate is obtained；
C), the resulting conductive agglomerate of step B), carbon fiber, metal powder, EP rubbers, polar rubber, maleic anhydride are grafted
Modified EP rubbers, maleic acid change grafted polyolefinic resin, inorganic filler, antioxidant, dispersant it is uniform after, warp
Melting mixing equipment mixing granulation both obtains intermediate product；
D), the intermediate product, white oil, crosslinking agent, assistant crosslinking agent, dispersing agent, antioxidant, release agent are uniformly mixed,
After carrying out dynamic vulcanization in melting mixing equipment, highly conductive thermoplastic elastomer (TPE) is made.
10. the process for preparation of thermoplastic elastomer according to claim 9 for taking into account high conductivity and mechanical property, feature
It is, the melting mixing equipment is double screw extruder, and process conditions are 160~220 DEG C of temperature, 200~320rpm of revolving speed；
Above-mentioned highly conductive thermoplastic elastic material is molded under the conditions of 180 DEG C to the print of thickness 3mm using vertical injection molding machine, is used
Resistance instrument measures the volume resistance of sample, prepares tensile bars using universal sampling machine, measures the tensile strength and fracture of material
Elongation, the processing flowability of material is by the melt flow index under the conditions of 230 DEG C of measuring temperature, load 5/10kg come table
Sign.
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