CN103665511A - 导电性树脂组合物 - Google Patents
导电性树脂组合物 Download PDFInfo
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- CN103665511A CN103665511A CN201310435194.3A CN201310435194A CN103665511A CN 103665511 A CN103665511 A CN 103665511A CN 201310435194 A CN201310435194 A CN 201310435194A CN 103665511 A CN103665511 A CN 103665511A
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- Prior art keywords
- conductive resin
- resin composition
- acid
- ethylene
- nano fiber
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- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 239000002121 nanofiber Substances 0.000 claims abstract description 39
- 229920000767 polyaniline Polymers 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims description 29
- 239000002019 doping agent Substances 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920002313 fluoropolymer Polymers 0.000 claims description 9
- 239000004811 fluoropolymer Substances 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 9
- 229920005604 random copolymer Polymers 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 6
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 6
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001684 low density polyethylene Polymers 0.000 claims description 5
- 239000004702 low-density polyethylene Substances 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 230000036314 physical performance Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001112 grafted polyolefin Polymers 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- ILUAAIDVFMVTAU-OLQVQODUSA-N (1s,2r)-cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)[C@H]1CC=CC[C@H]1C(O)=O ILUAAIDVFMVTAU-OLQVQODUSA-N 0.000 description 1
- PAHUTFPWSUWSCR-BHPSOXLSSA-N (z)-2-methylbut-2-enedioic acid Chemical compound OC(=O)C(/C)=C\C(O)=O.OC(=O)C(/C)=C\C(O)=O PAHUTFPWSUWSCR-BHPSOXLSSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IQEFOZYTOZXEPZ-UHFFFAOYSA-N but-2-enoic acid prop-2-enoic acid Chemical compound C(C=C)(=O)O.CC=CC(=O)O IQEFOZYTOZXEPZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical compound [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- 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
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及一种包含聚烯烃树脂、特定相容剂、及聚苯胺纳米纤维的导电性树脂组合物。所述导电性树脂组合物既保证各组分之间的高度相容性,又具有高导电性、耐热性及优秀的防静电性能,并且可提供兼具优秀的机械物理性能、高导电性、耐热性及防静电性能的成形品。
Description
技术领域
本发明涉及一种导电性树脂组合物,更具体地涉及一种既保证各组分之间的高度相容性,又具有高导电性、耐热性及优秀的防静电性能的导电性树脂组合物。
背景技术
最近,随着电子设备和电子部件轻薄短小的发展趋势,电子元件的集成度也在提高,因此电子设备和电子部件的电磁波和静电产生量也大大增加。电磁波通过电子设备的接合部、连接部等泄漏,从而导致其他电子元件或者电子部件发生故障或者造成人体免疫功能低下等危害。而且,在电子设备及电子部件中产生的静电会导致产品本身功能低下或者损伤。
因此,一直以来针对可同时实现有效地屏蔽、消除或者吸收导致电子元件发生故障且对人体产生不良影响的电磁波或者静电的方案进行了各种研究。例如,为了屏蔽、消除或者吸收电磁波或者静电,以前采用了外部涂覆导电性材料的方法或者将导电性材料与聚合物树脂混合使用的方法。
具体地,已知的方法是在最终产品的表面上涂覆碳黑等导电性染料,或者将碳黑等导电性染料与聚合物树脂混合而制成最终树脂成形品。然而,如此在最终产品表面上涂覆导电性染料时,若所涂覆的外表面受损,可能会失去静电分散能力或者导电性。而且,将导电性染料与聚合物树脂混合时,为保证最终产品的静电分散能力或者导电性,需大幅增加导电性染料的添加量,因此与聚合物树脂的相容性会大幅降低,或者最终产品成形后,导电性染料从表面脱落(Sloughing),因而会导致电子产品或者电子元件的污染。
关于为实现电子设备所要求的导热性及电磁波吸收特性而填充有各种导电性填料的聚合物树脂材料,虽然有介绍,但由于相容性等原因,难以填充一定量以上的填料。若增加填料的填充量,就会出现聚合物树脂材料的机械物理性能降低,同时产品的导电性或者防静电性能降低的问题。
具体地,关于将碳纳米管、碳纤维或者石墨烯等导电性碳结构体添加到聚合物树脂中的材料,虽然有各种介绍,然而众所周知导电性碳结构体导电性虽高,但与聚合物树脂或者其他材料的相容性却不高,难以同时满足导电性或者防静电性能、及耐热性要求。例如,韩国授权专利第0532032号中介绍了混合氟化合物改性的聚烯烃树脂和导电性碳结构体的方法,然而存在聚烯烃树脂本身的特性未正常显现,或者还需要对所使用的导电性碳结构体进行改性的局限性。
专利文献1:韩国授权专利第0532032号
发明内容
本发明的目的在于提供一种既保证各组分之间的高度相容性,又具有高导电性、耐热性及优秀的防静电性能的导电性树脂组合物。
本发明提供一种导电性树脂组合物,包含:聚烯烃树脂;相容剂,包含选自乙烯丙烯酸(ethylene acrylic acid)、二羧酸(dicarboxylic acid)或者其酸酐接枝的改性聚烯烃树脂、乙烯醋酸乙烯酯(ethylene-vinyl acetate)、乙烯乙烯醇(ethylene-vinyl alcoh01)及丙烯酸酯类共聚物中的一种以上化合物;及聚苯胺纳米纤维(polyaniline nanofiber),具有1至100nm的截面直径和0.05至2μm的长度。
下面,进一步详细说明根据本发明具体实施例的导电性树脂组合物。
根据本发明的一具体实施例,可提供一种导电性树脂组合物,包含:聚烯烃树脂;相容剂,包含选自乙烯丙烯酸、二羧酸或者其酸酐接枝的改性聚烯烃树脂、乙烯醋酸乙烯酯、乙烯乙烯醇及丙烯酸酯类共聚物中的一种以上化合物;及聚苯胺纳米纤维,具有1至100nm的截面直径和0.05至2μm的长度。
关于具有进一步提高的导电性或者防静电性能和高耐热性的材料,本发明者们进行了研究,并通过实验确认了,在混合聚烯烃树脂与所述特定的相容剂和所述聚苯胺纳米纤维而形成的树脂组合物中,既能保证各组分之间的高度相容性,又能体现高导电性、耐热性及优秀的防静电性能,从而完成了发明。
所述导电性树脂组合物表示导电性聚合物树脂组合物或者导电性聚烯烃树脂组合物。
在所述树脂组合物中,能够以混合状态包含上述的聚烯烃树脂、相容剂及聚苯胺纳米纤维,还能够以熔融混合(melt compounding)状态包含所述聚烯烃树脂、相容剂及聚苯胺纳米纤维。
即,所述高耐热导电性树脂组合物可包含所述聚烯烃树脂、相容剂及聚苯胺纳米纤维的熔融混合物。所述熔融可在100℃以上或者150至270℃的温度范围内进行,具体地可通过双螺杆挤出机等来进行所述熔融混合。
另外,所述导电性树脂组合物可包含40至99.5重量%的所述聚烯烃树脂、0.1至30重量%的所述相容剂、及0.1至50重量%的所述聚苯胺纳米纤维。
在所述导电性树脂组合物中,若上述的相容剂含量低于0.1重量%,所述聚烯烃树脂和聚苯胺纳米纤维之间的相容性就会大幅降低,进而最终产品的机械物理性能、耐热性或者导电性会大幅降低。而且,若上述的相容剂含量超过30重量%,聚烯烃树脂的含量就会减少,进而难以充分显现树脂本身的物理性能,或者所述聚苯胺纳米纤维的含量会减少,进而可能很难充分保证耐热性或者导电性。
在所述导电性树脂组合物中,若聚苯胺纳米纤维的含量低于0.1重量%,就有可能无法充分显现所述树脂组合物或者由此制备的最终产品所具有的耐热性、导电性或者防静电性能。而且,若所述聚苯胺纳米纤维的含量超过30重量%,与所述聚烯烃树脂的相容性就会大幅降低,进而最终产品的机械物理性能、耐热性或者导电性会大幅降低。所述聚烯烃树脂虽然比重相对小,但耐化学品性、耐水性及电学性能优秀,因此易适用于电子设备及电子部件等所使用的材料或者成形品。
具体地,所述聚烯烃树脂可包含低密度聚乙烯、高密度聚乙烯、聚丙烯、丙烯类共聚物或者这些物质的一种以上混合物。
所述低密度聚乙烯可具有0.890g/cm3至0.940g/cm3的密度,并具有支链多、结晶性低的特征。所述高密度聚乙烯具有0.940g/cm3至0.980g/cm3的密度,并具有支链少、结晶性高的特征。
作为所述聚丙烯树脂可使用已知的常用于树脂成形品的聚丙烯聚合物,对此并没有特别限制,但优选使用熔融指数为1至100g/10分钟(ASTMD1238,230℃)的聚丙烯树脂。若所述聚丙烯树脂的熔融指数低于1g/10分钟(ASTM D1238,230℃),在成形过程中就会很难保证充分的加工性,并且因高粘度会妨碍所述聚苯胺纳米纤维的分散。而且,若所述聚丙烯树脂的熔融指数超过100g/10分钟(ASTM D1238,230℃),就会因低粘度最终产品很难具有适当的冲击强度,此外可能会降低机械物理性能。
所述丙烯类共聚物可包含乙烯-丙烯共聚物或者丁二烯-丙烯(butadiene propylene)共聚物。所述乙烯-丙烯共聚物或者丁二烯-丙烯共聚物分别可为乙烯重复单元及丙烯重复单元或者乙烯重复单元及丙烯重复单元形成嵌段的嵌段共聚物,而且可以是所述重复单元无规则排列的无规共聚物。所述丙烯类共聚物可具有30000至500000的重均分子量。
另外,作为所述相容剂可使用乙烯丙烯酸、二羧酸或者其酸酐接枝的改性聚烯烃树脂、乙烯醋酸乙烯酯、乙烯乙烯醇、丙烯酸酯类共聚物或者这些物质的两种以上混合物。
上述例的相容剂可使所述聚烯烃树脂和所述聚丙胺纳米纤维之间的混合变得容易并在树脂组合物中均匀地分散,而且在熔融混合或者成形为最终产品的过程中,可防止各成分分离或者剥离的现象。
具体地,所述乙烯丙烯酸可为乙烯重复单元及丙烯酸重复单元无规则排列的无规共聚物,可具有1至150mgKOH/g的酸值。
所述乙烯醋酸乙烯酯可为乙烯重复单元及醋酸乙烯酯重复单元无规则排列的无规共聚物,可包含1至50重量%的醋酸乙烯酯重复单元,并根据醋酸乙烯酯的含量,可具有0.924g/cm3至0.960g/cm3的密度。
所述乙烯乙烯醇可为乙烯重复单元和乙烯醇重复单元无规则排列的无规共聚物,可包含1至50重量%的乙烯醇重复单元,并根据醋酸乙烯酯的含量,可具有0.930至0.970g/cm3的密度。
所述丙烯酸酯类共聚物表示由(甲基)丙烯酸[CH2=CH-COOR或者CH2=C(CH3)-COOR]形成的共聚物,所述(甲基)丙烯酸的R基可决定共聚物的性质。所述丙烯酸酯类共聚物可为丙烯酸纤维、酯、酰胺等聚合物与由(甲基)丙烯酸衍生的聚合物的共聚物,并可根据丙烯酸酯的含量,可具有多种物理性能。所述(甲基)丙烯酸-的含义是包含丙烯酸-及(甲基)丙烯酸-。
所述“二羧酸或者其酸酐接枝的改性聚烯烃树脂”表示聚烯烃主链接枝二羧酸或者其酸酐而形成支链的聚合物。
而且,为了提高所述树脂组合物的各成分之间的相容性及制备的最终产品的物理性能,所述二羧酸可包含马来酸、酞酸、衣康酸、柠康酸(citraconic acid)、烯基琥珀酸、顺-1,2,3,6四氢邻苯二甲酸(cis-1,2,3,6-tetrahydrophthalic acid)、4-甲基-1,2,3,6四氢邻苯二甲酸(4-methyl-1,2,3,6-tetrahydrophthalic acid)或者这些物质的两种以上混合物,所述二羧酸的二酐可为上述例的二羧酸二酐(dicarboxylic aciddianhydride)。
所述改性聚烯烃树脂中接枝的二羧酸或者其酸酐的含量可为1重量%以上,优选可为2重量%至20重量%。如此,随着1重量%的以上的二羧酸或者其酸酐接枝到聚烯烃树脂,可提高所述聚烯烃树脂与聚苯胺纳米纤维之间的界面结合力,使得能够保证最终制备的树脂组合物具有更高的刚性及冲击强度等机械物理性能和优秀的耐热性及导电性。
由对所述改性聚烯烃树脂进行酸碱滴定而获得的结果,可测出二羧酸或者其酸酐的接枝比率。例如,150的水饱和二甲苯中加入约1g的所述改性聚丙烯树脂并回流两小时左右,然后加入1重量%的少量百里酚蓝-二甲基甲酰胺(thymol blue-dimethylformamide)溶液,并滴入稍过量的0.05N氢氧化钠-乙醇溶液获得群青色的溶液后,再对该溶液用0.05N的盐酸-异丙醇溶液进行逆滴定直到显示黄色为止,并求出酸值,由此可算出接枝到改性聚丙烯树脂的二羧酸的量。
所述二羧酸或者其酸酐接枝的聚烯烃树脂,其具体例没有那么多限制,但使用聚乙烯树脂或者聚丙烯树脂可有利于提高相容性及物理性能。这种聚烯烃树脂可具有30000至800000的重均分子量。
另外,所述聚苯胺纳米纤维可具有1至100nm的截面直径,优选为10至80nm,并且可具有0.05至2μm的长度,优选为0.1至1.5μm。所述截面直径表示所述聚苯胺纳米纤维截面形状的最大直径。
所述聚苯胺纳米纤维优选在表面上吸附有包含磺酸类化合物或者其盐的掺杂剂,以具有与聚烯烃树脂或者相容剂的更高的相容性,且体现高的导电性、防静电性能及耐热性。
表面上吸附有包含所述磺酸类化合物或者其盐的掺杂剂的聚苯胺纳米纤维,可通过以下的制备方法来制备。所述制备方法,包含:将包含苯胺类单体、无机酸的掺杂剂(dopant)及氧化剂混合并聚合;使所述聚合的产物与碱性化合物进行反应,以除去掺杂(dedoping);及使所述去掺杂(dedoping)的产物和包含磺酸类化合物或者其盐的掺杂剂进行反应。
随着将包含所述苯胺类单体和无机酸的掺杂剂分散在水溶液中,所述无机酸的氢离子结合在苯胺类单体上,从而可形成苯胺阳离子(anilinium)的微晶粒(micelle)。而且,将包含所述苯胺类单体和无机酸的掺杂剂分散在水溶液后,加入氧化剂就可以聚合出聚苯胺纳米纤维。
使所述聚合的产物即掺入有无机酸掺杂剂的聚苯胺纳米纤维与所述碱性化合物进行反应,所述无机酸掺杂剂就能被去掺杂(dedoping)。
而且,通过使所述去掺杂的产物与包含磺酸类化合物或者其盐的掺杂剂进行反应,能够提供表面上吸附有包含所述磺酸类化合物或者其盐的掺杂剂的聚苯胺纳米纤维。
如此获得的表面上吸附有包含磺酸类化合物或者其盐的掺杂剂的聚苯胺纳米纤维,与具有一定程度以上的导电率(electric conductivity)但耐热性大为降低的,简单掺杂无机酸而获得的聚苯胺纳米纤维相比有明显的区别。
具体地,表面上吸附有包含所述磺酸类化合物或者其盐的掺杂剂的聚苯胺纳米纤维的热解温度可为200℃以上、或者220℃至500℃,而且在常温下的导电率可为10-8S/cm以上、或者10-8S/cm至10S/cm。
所述“热解温度”表示从上述所制备的聚苯胺纳米纤维中残留溶剂或者残留单体等被蒸发及去除后,以盐的形式吸附的掺杂剂开始被蒸发、分解或者去除的温度。在显示TGA数据的图表中,这种热解温度可为倾斜度最先急剧变化的拐点,例如在根据温度变化的重量变化率的图表中,可以是倾斜度的变化率达到最大时的温度。所述“常温”表示10至40℃的温度范围。
所述磺酸类化合物可为十二烷基磺酸(dodecyl sulfonic acid)、樟脑磺酸(camphosulfonic acid)、聚苯乙烯磺酸(polystyrene sulfonic acid)或者这些的混合物,也可使用这种磺酸类化合物的金属盐(例如,钠盐或者钾盐)或者铵盐等。
对于可用于所述聚合的无机酸,并没有那么多限制,具体可使用盐酸、硝酸、硫酸、苯磺酸、十二烷基磺酸、樟脑磺酸、甲苯磺酸(toluene sulfonicacid)或者这些的混合物。
所述氧化剂可起到所述聚合反应的引发剂作用,对于可用作这种氧化剂的化合物,并没有那么多限制,具体可使用过硫酸盐、碘酸盐、氯酸盐、重铬酸盐、金属氯化物、过氧二硫酸盐(peroxydisulfate)或者这些的混合物。
对于可用作所述碱性化合物的化合物,并没有那么多限制,只要能除去所述无机酸掺杂剂即可。例如,可使用氢氧化铵、氢氧化钠、氢氧化锂、氢氧化钡、氢氧化钾、氢氧化钙或者这些的混合物。
所述高耐热导电性树脂组合物还可包含抗冲击改性剂、紫外线稳定剂、热稳定剂或者抗氧化剂等添加剂。
所述高耐热导电性树脂组合物可体现高导电性及优秀的防静电性能,并且具体可具有1.0x1012Ω/sq以下、或者1.0x1012Ω/sq至1.0x102Ω/sq的表面阻抗
若利用所述树脂组合物,可提供兼具优秀的机械物理性能、高导电性、耐热性及防静电性能的树脂成形品或者聚合物膜等,这种树脂成形品或者聚合物膜等可适用于导电性膜、静电分散发泡体、静电分散片、静电分散注塑产品等领域。
根据本发明可提供一种既保证各组分之间的高度相容性,又具有高导电性、耐热性及优秀的防静电性能的导电性树脂组合物,并且利用所述树脂组合物就可提供兼具优秀的机械物理性能、高导电性、耐热性及防静电性能的树脂成形品。
具体实施方式
在下面的实施例中进一步详细说明本发明。但下述实施例只是本发明的示例而已,本发明的保护范围并不局限于下述实施例。
[制备例:聚苯胺纳米纤维的制备]
5L反应器中加入2L蒸馏水,在150rpm下进行搅拌,作为掺杂剂滴入1.4mole盐酸,并滴入1.1mole苯胺单体。搅拌30分钟,以使因从盐酸解离的氢离子而生成的苯胺离子充分形成微晶粒,然后滴入作为引发剂的0.53mole过硫酸铵。接着,约1分钟后,确认溶液的颜色从无色转变为黑绿色开始聚合,并搅拌约两小时后,倒入3L乙醇结束反应。
将所述反应的产物再分散到1.5L蒸馏水中,并加入1.1mole氢氧化铵后搅拌约30分钟。之后,余量的氨水用乙醇清洗,并将获得的产物分散到乙醇中后,添加1.2mole十二烷基苯磺酸(DBSA)进行搅拌。此时,将所获得的产物用乙醇及丙酮分别清洗一次,并在90℃的烤箱中进行干燥,从而制备表面上吸附有十二烷基苯磺酸掺杂剂的聚苯胺纳米纤维(截面直径:500nm,长度:1μm,导电性[常温]:1S/cm,热解温度:300℃)。
[实施例及比较例:树脂组合物的制备]
实施例1
以下表1所示的含量混合低密度聚乙烯、从所述制备例中得到的表面上吸附有十二烷基苯磺酸掺杂剂的聚苯胺纳米纤维、及20重量份的相容剂乙烯丙烯酸(EAA,酸值:70mgKOH/g)。接着,对这一混合物在40mm双螺杆挤出机(Twin screw extruder)中进行熔融混合,从而制备5kg树脂组合物。将该组合物在90℃烤箱(oven)中进行干燥后,利用布拉本达膜(Brabender Film)成形机成形为聚合物膜。
实施例2至4
如下表1所示,除了改变使用成分或者含量之外,以与实施例1相同的方法制备了树脂组合物及聚合物膜。
比较例1
如下表1所示,除了未使用相容剂之外,以与实施例1相同的方法制备了树脂组合物及聚合物膜。
比较例2
如下表1所示,除了未使用聚苯胺纳米纤维之外,以与实施例1相同的方法制备了树脂组合物和聚合物膜。
[实验例:聚合物膜的表面阻抗测量]
使用表面阻抗测试仪(R8340,Advantest corp.),根据ASTM D257,并以55%RH、23℃、500V施加电压及环形电极测量了在所述实施例及比较例中得到的聚合物膜的表面阻抗。
将所述实施例及比较例中制备的树脂组合物和实验例的结果示于下表1中.
[表1]
实施例和比较例的树脂组合物和实验例的结果
a)LD:低密度聚乙烯(1.1g/10分钟的熔融指数-ASTM D1238,230℃)
b)PP:聚丙烯树脂(35g/10分钟的熔融指数-ASTM D1238,230℃)
c)PE-g-MAH(改性聚乙烯树脂):4.75wt%马来酸酐接枝的分子量为50000的聚乙烯
d)乙烯丙烯酸(EAA,酸值:70mgKOH/g)
如上表1所示,确认到与未加入相容剂或者所述制备例的聚苯胺纳米纤维的比较例1,2相比,实施例中制备的聚合物树脂膜具有较低的表面阻抗。而且,观察实施例中制备的的聚合物树脂膜表面的结果显示,膜整体厚度均匀,并且没有观察到一定成分聚集而形成的区域(domain)。即,若使用实施例的树脂组合物,可提供既保证各组分之间的高度相容性,又兼具高导电性、耐热性及优秀的防静电性能的聚合物膜。
Claims (12)
1.一种导电性树脂组合物,包含:
聚烯烃树脂;
相容剂,包含选自乙烯丙烯酸、二羧酸或者其酸酐接枝的改性聚烯烃树脂、乙烯醋酸乙烯酯、乙烯乙烯醇及丙烯酸酯类共聚物中的一种以上化合物;及
聚苯胺纳米纤维,具有1至100nm的截面直径和0.05至2μm的长度。
2.根据权利要求1所述的导电性树脂组合物,包含:
所述聚烯烃树脂、相容剂、及聚苯胺纳米纤维的熔融混合物。
3.根据权利要求1所述的导电性树脂组合物,包含:
40至99.5重量%的所述聚烯烃树脂;
0.1至30重量%的所述相容剂;及
0.1至50重量%的所述聚苯胺纳米纤维。
4.根据权利要求1所述的导电性树脂组合物,其中,
所述聚烯烃树脂包含选自低密度聚乙烯、高密度聚乙烯、聚丙烯及丙烯类共聚物中的一种以上聚合物树脂。
5.根据权利要求1所述的导电性树脂组合物,其中,
所述二羧酸或者其酸酐接枝的改性聚烯烃树脂中接枝的二羧酸或者其酸酐的含量为1重量%以上。
6.根据权利要求1所述的导电性树脂组合物,其中,
所述乙烯丙烯酸包含无规共聚物,所述无规共聚物包含乙烯重复单元和丙烯酸重复单元。
7.根据权利要求1所述的导电性树脂组合物,其中,
所述乙烯醋酸乙烯酯包含无规共聚物,所述无规共聚物包含乙烯重复单元、醋酸乙烯酯重复单元,并具有0.924至0.960g/cm3的密度。
8.根据权利要求1所述的导电性树脂组合物,其中,
所述乙烯乙烯醇包含乙烯重复单元、乙烯醇重复单元及具有0.930至0.970g/cm3的密度的无规共聚物。
9.根据权利要求1所述的导电性树脂组合物,其中,
所述聚苯胺纳米纤维包含表面上吸附有包含磺酸类化合物或者其盐的掺杂剂的聚苯胺纳米纤维。
10.根据权利要求1所述的导电性树脂组合物,其中,
所述聚苯胺纳米纤维在常温下的导电率为10-8S/cm以上。
11.根据权利要求1所述的导电性树脂组合物,其中,
所述聚苯胺纳米纤维的热解温度为200℃以上。
12.根据权利要求1所述的导电性树脂组合物,具有1.0x1012Ω/sq以下的表面阻抗。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103965514A (zh) * | 2014-04-29 | 2014-08-06 | 中原工学院 | 一种聚苯胺/二醋酸纤维素复合导电塑料的制备方法 |
CN103965513A (zh) * | 2014-04-29 | 2014-08-06 | 中原工学院 | 聚苯胺纳米纤维/二醋酸纤维素复合导电材料的制备方法 |
CN104861276A (zh) * | 2015-06-16 | 2015-08-26 | 中原工学院 | 乙烯-乙酸乙烯共聚物/聚苯胺/高密度聚乙烯复合导电材料的制备方法 |
CN110325595A (zh) * | 2017-02-28 | 2019-10-11 | 三井化学株式会社 | 导电性树脂组合物、其制造方法及由其得到的成型体 |
CN112743258A (zh) * | 2020-12-18 | 2021-05-04 | 南阳金牛电气有限公司 | 一种氧化锌电阻片端面焊接剂 |
CN113512256A (zh) * | 2021-08-18 | 2021-10-19 | 苏州度辰新材料有限公司 | 一种抗静电聚烯烃母料及其制备方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022108208A1 (ko) * | 2020-11-20 | 2022-05-27 | 엘에스전선 주식회사 | 비가교 절연 케이블 |
CN114634706A (zh) * | 2022-03-29 | 2022-06-17 | 广东奇德新材料股份有限公司 | 一种纳米抗静电玻纤增强聚酰胺复合材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1962972A (zh) * | 2006-11-23 | 2007-05-16 | 华东理工大学 | 一种导电聚苯胺纳米纤维的制备方法 |
CN101003683A (zh) * | 2007-01-17 | 2007-07-25 | 大连理工大学 | 聚苯胺纳米纤维/高岭土纳米复合材料及其制备方法 |
CN102329511A (zh) * | 2010-07-14 | 2012-01-25 | 中国科学院金属研究所 | 耐脱掺杂性染料掺杂聚苯胺及其制备方法和应用 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995006685A1 (en) * | 1993-09-03 | 1995-03-09 | Neste Oy | Electrically conducting compositions |
FI101078B (fi) * | 1994-02-10 | 1998-04-15 | Neste Oy | Sähköä johtava polymeeri ja menetelmä sen valmistamiseksi |
US5629050A (en) * | 1995-08-30 | 1997-05-13 | The Dow Chemical Company | Process for preparing coated articles |
KR100725151B1 (ko) * | 2001-02-07 | 2007-06-04 | 주식회사 새 한 | 수용성 전도성 폴리아닐린 제조방법 |
US6437049B1 (en) * | 2001-02-27 | 2002-08-20 | P. Group S.R.L. | Process for modifying polypropylene with maleic anhydride |
US7462298B2 (en) * | 2002-09-24 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Water dispersible polyanilines made with polymeric acid colloids for electronics applications |
JP3902186B2 (ja) * | 2003-04-21 | 2007-04-04 | 日東電工株式会社 | 帯電防止型光学フィルム、その製造方法、及び画像表示装置 |
KR100532032B1 (ko) | 2003-11-28 | 2005-11-30 | 한국화학연구원 | 나노복합재료의 제조방법 |
KR100718908B1 (ko) | 2005-12-29 | 2007-05-16 | 호남석유화학 주식회사 | 도전성 폴리프로필렌계 수지 조성물 및 그를 이용하여제조된 발포체 |
KR101386215B1 (ko) * | 2006-06-07 | 2014-04-17 | 삼성디스플레이 주식회사 | 전도성 고분자 조성물 및 이를 채용한 유기 광전 소자 |
JP2008174598A (ja) * | 2007-01-17 | 2008-07-31 | Toyo Ink Mfg Co Ltd | 樹脂組成物 |
JP2008214409A (ja) * | 2007-03-01 | 2008-09-18 | Yokohama Rubber Co Ltd:The | 導電性組成物および帯電防止材 |
JP5099816B2 (ja) * | 2007-03-14 | 2012-12-19 | 出光興産株式会社 | ポリアニリン複合体溶液及びその硬化物 |
JP2009103798A (ja) * | 2007-10-22 | 2009-05-14 | Fuji Xerox Co Ltd | 樹脂組成物、樹脂成形物、ベルト張架装置、プロセスカートリッジ、および画像形成装置 |
CN101582302B (zh) * | 2008-05-14 | 2011-12-21 | 清华大学 | 碳纳米管/导电聚合物复合材料 |
CN101659789B (zh) * | 2008-08-29 | 2012-07-18 | 清华大学 | 碳纳米管/导电聚合物复合材料的制备方法 |
JP5362312B2 (ja) * | 2008-10-06 | 2013-12-11 | 三菱樹脂株式会社 | 導電性樹脂成形物 |
CN102060993A (zh) * | 2009-11-13 | 2011-05-18 | 中国科学院合肥物质科学研究院 | 可溶性聚苯胺导电纳米纤维及其制备方法 |
KR20110054916A (ko) * | 2009-11-18 | 2011-05-25 | 정우혁 | 침상 폴리아닐린을 사용한 전기전도성 복합재료의 제조방법 |
WO2011087913A1 (en) * | 2010-01-14 | 2011-07-21 | The Regents Of The University Of California | A universal solution for growing thin films of electrically conductive nanostructures |
-
2012
- 2012-09-26 KR KR1020120107327A patent/KR101384324B1/ko active IP Right Grant
-
2013
- 2013-09-12 JP JP2013189115A patent/JP5857371B2/ja active Active
- 2013-09-18 TW TW102133929A patent/TWI534836B/zh active
- 2013-09-23 CN CN201310435194.3A patent/CN103665511A/zh active Pending
- 2013-09-24 EP EP13185791.4A patent/EP2712891B1/en active Active
- 2013-09-26 US US14/037,779 patent/US20140084215A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1962972A (zh) * | 2006-11-23 | 2007-05-16 | 华东理工大学 | 一种导电聚苯胺纳米纤维的制备方法 |
CN101003683A (zh) * | 2007-01-17 | 2007-07-25 | 大连理工大学 | 聚苯胺纳米纤维/高岭土纳米复合材料及其制备方法 |
CN102329511A (zh) * | 2010-07-14 | 2012-01-25 | 中国科学院金属研究所 | 耐脱掺杂性染料掺杂聚苯胺及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
CHANG SU,ET AL: "Melt-Processed Polyaniline Nanofibers/LDPE/EAA Conducting Composites", 《POLYMER COMPOSITES》, vol. 29, no. 10, 14 August 2008 (2008-08-14), pages 1177 - 1182 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103965514A (zh) * | 2014-04-29 | 2014-08-06 | 中原工学院 | 一种聚苯胺/二醋酸纤维素复合导电塑料的制备方法 |
CN103965513A (zh) * | 2014-04-29 | 2014-08-06 | 中原工学院 | 聚苯胺纳米纤维/二醋酸纤维素复合导电材料的制备方法 |
CN103965513B (zh) * | 2014-04-29 | 2016-04-27 | 中原工学院 | 聚苯胺纳米纤维/二醋酸纤维素复合导电材料的制备方法 |
CN103965514B (zh) * | 2014-04-29 | 2017-01-18 | 中原工学院 | 一种聚苯胺/二醋酸纤维素复合导电塑料的制备方法 |
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CN113512256A (zh) * | 2021-08-18 | 2021-10-19 | 苏州度辰新材料有限公司 | 一种抗静电聚烯烃母料及其制备方法 |
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KR101384324B1 (ko) | 2014-04-10 |
JP2014065905A (ja) | 2014-04-17 |
EP2712891B1 (en) | 2015-02-11 |
TWI534836B (zh) | 2016-05-21 |
US20140084215A1 (en) | 2014-03-27 |
KR20140040521A (ko) | 2014-04-03 |
JP5857371B2 (ja) | 2016-02-10 |
TW201413737A (zh) | 2014-04-01 |
EP2712891A1 (en) | 2014-04-02 |
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