CN108192138A - Modification method of carbon nano tube used as rubber filler - Google Patents
Modification method of carbon nano tube used as rubber filler Download PDFInfo
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- CN108192138A CN108192138A CN201611122877.3A CN201611122877A CN108192138A CN 108192138 A CN108192138 A CN 108192138A CN 201611122877 A CN201611122877 A CN 201611122877A CN 108192138 A CN108192138 A CN 108192138A
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- carbon nanotube
- carbon
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- rubber cement
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Links
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 113
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 239000000945 filler Substances 0.000 title claims abstract description 8
- 238000002715 modification method Methods 0.000 title description 2
- 239000004568 cement Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 106
- 238000002360 preparation method Methods 0.000 claims description 56
- -1 hydroxyl carbon nano tubes Chemical compound 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 29
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 12
- 239000005639 Lauric acid Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical group CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 150000001993 dienes Chemical class 0.000 claims 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical group CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 230000033444 hydroxylation Effects 0.000 abstract 1
- 238000005805 hydroxylation reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 17
- 238000005070 sampling Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000009102 absorption Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 8
- 230000000640 hydroxylating effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- OYYFSKLLXXTKNM-UHFFFAOYSA-N butane-1,1-diol dodecanoic acid Chemical class C(CCC)(O)O.C(CCCCCCCCCCC)(=O)O OYYFSKLLXXTKNM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- UWLPCYBIJSLGQO-UHFFFAOYSA-N dodecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCC(O)=O UWLPCYBIJSLGQO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention aims to provide a method for modifying a high-dispersion carbon nano tube for a rubber filler. The invention adopts strong oxidizing acid and polyalcohol to carry out hydroxylation treatment on the surface of the carbon nano tube, then adopts unsaturated acrylate polar monomer to carry out graft polymerization on solution polymerized styrene-butadiene rubber cement, and finally prepares the high-dispersion carbon nano tube through coating treatment. The method solves the problem of easy agglomeration of the carbon nano tube, and has the advantages of high dispersibility of the carbon nano tube in the solution polymerized styrene butadiene rubber matrix, low modification cost, small environmental pollution, suitability for industrial production and the like.
Description
Technical field
The present invention relates to a kind of preparation methods of synthetic rubber filler high-dispersibility carbon nanotube.
Background technology
Carbon nanotube (Carbon Nanotube, abbreviation CNT) is a kind of novel carbon structure being just found for 1991, is
The tube body being rolled by the graphite flake layer that carbon atom is formed.Since carbon atom takes full SP in carbon nanotube2Hydridization links, compared to SP3
Hydridization SP2S orbital compositions are more in hydridization, and carbon-carbon bond bond energy is big, therefore carbon nanotube is made to have high-modulus, high intensity, and tension is strong
Degree reaches 50~200GPa, is 100 times of steel, and density but only has the 1/6 of steel；Its elasticity modulus is up to 100TPa, with diamond
Elasticity modulus is suitable.Thus the excellent mechanical property of carbon nanotube would be even more beneficial to assign high molecular material high intensity, low bulk,
The characteristics such as high abrasion are increasingly subject to the concern of people in the application prospect of field of rubber materials.But since carbon nanotube category is received
Rice material, grain size is small, specific surface is big, surface energy is high, easily reunites, and holds very much in the process participating in the mixed and modified of rubber material
Useless agglomerate is easily gathered into, causes to disperse non-uniform problem appearance, can not only influence filling-modified effect in this way, but also
The performance of rubber material can be damaged.
Carbon nanotube composite modification material studies oneself as one of hot spot of current Material Field research.So far, specially
There are many carbon nano-tube modification method of sharp document report.ZL200310109074.0 first to carbon nano tube surface carry out polarity and
Nonpolarity processing, is allowed to have amphiphilic performance, then carries out surface cladding processing with polyolefin, polyacrylic polymer, from
And obtain carbon nanotube/high molecule nano composite material.ZL 200510009769.0 provides a kind of utilization ultrasonic wave and high-speed stirring
The effects that mixing the dispersion, crushing, activation of disperser, the aggregation and winding of destroying carbon nanometer tube in itself；Utilize surfactant
Organo-functional group carries out chemisorbed or chemical reaction with carbon nano tube surface, and surfactant is made to be covered in carbon nanotube table
Face, so as to fulfill dispersion to surface modification of carbon nanotube and its in the epoxy.ZL200410089036.8 is with poly- second
Alkene imidazoles is polymerized monomer, then by the use of silane, Wo Lan or titanate esters as coupling agent, through hydroxyl chemical etching method and micro- slurry polymerization
The carbon nanotube/polyvinylimidazole nanocomposites materials that method prepares.ZL200410017699.9 is by the strong oxygen of carbon nanotube
After the property changed acid processing, react with dichloro Asia alum, products therefrom and binary ammonia or diol reaction obtain surface carry amino or
The modified carbon nano-tube of hydroxyl；Modified carbon nano-tube and binary or multicomponent isocyanate of the surface with amino or hydroxyl is anti-
Should, obtain the functionalized carbon nano-tube that surface carries isocyanate groups.After ZL200310109072.1 handles carbon nanotube
Its surface is made to carry specific initiation group；Then cause tert-butyl methacrylate monomer with atom transition free radical polymerization reaction
Polymerization, then tert-butyl methacrylate is hydrolyzed, it is allowed to slough tertiary butyl, generates carboxyl, obtain more carboxyls and gather
Close the water-soluble carbon nanometer tube of object grafting.
Invention content
Present invention aims at provide a kind of method of modifying as gum filler high dispersive carbon nanotube.The invention uses
Acid with strong oxidizing property and polyalcohol carry out hydroxylating processing to carbon nano tube surface, then using unsaturated acrylate polar monomer
It is graft-polymerized to solution polymerized butylbenzene rubber cement, high dispersive type carbon nanotube is prepared finally by cladding processing.This method solution
The easy agglomeration traits for carbon nanotube of having determined impart polymolecularity of the carbon nanotube in solution polymerized butadiene styrene rubber matrix.
" part " of the present invention each means mass parts.
A kind of method of modifying of gum filler high dispersive carbon nanotube of the present invention, specific preparation process are：
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 150~200 parts of concentrated nitric acids, 10~50 parts of H2O2
It is put into togerther in reactor and mixes, with 50~100kHz, 1~2hr of ultrasonication, be then heated to 50~150 DEG C, stirring acid
1~10hr is boiled, cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 200~500 parts of polyalcohols, are heated to 50~90
DEG C, 1~5hr is stirred to react, filters, wash, is dry, obtains the carbon nanotube that surface carries hydroxyl.
(2) it is grafted the preparation of rubber cement：300~600 parts of solvents are firstly added in polymeric kettle and then sequentially add 100 parts
Solution polymerized butylbenzene rubber cement, 0.05~0.5 part of molecular weight regulator after being replaced with nitrogen, add in 5~10 parts of unsaturated acrylate
Polar monomer, stirring, heating, 0.05~0.5 part of initiator of addition when kettle temperature degree to be polymerized reaches 40~60 DEG C, reaction 4~
After 10hr, 0.1~0.5 part of terminator is added in, grafting rubber cement (0.5 ﹪ of grafting rate of solution polymerized butylbenzene rubber cement~2 ﹪) is made.
(3) preparation of modified carbon nano-tube：Take 100 parts of hydroxyl carbon nano tubes and 1~5 part of surfactant, 300~
500 parts of solvents are added in polymeric kettle and are stirred 10~30min；Then 5~15 parts of grafting rubber cements are added in, stirring is warming up to 50
~80 DEG C, after being stirred to react 2~6hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.
Carbon nanotube of the present invention is nano level, and grain size is：0.3~30nm.
Solution polymerized butylbenzene rubber cement of the present invention be passed through by conjugated diene hydrocarbon compound and aryl ethylene class compound it is molten
Liquid polymerization is copolymerized.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound is selected from benzene
One kind in ethylene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative.Wherein solution polymerized butylbenzene rubber cement
Solid content be 5~20w%.
One kind in ethylene glycol, propylene glycol, glycerine, butanediol, pentaerythrite of polyalcohol of the present invention or
It is a variety of.
Unsaturation acrylate polar monomer of the present invention is selected from methyl methacrylate (MMA), methacrylic acid
One or more of ethyl ester, butyl methacrylate and Tert-butyl Methacrylate, preferably MMA.
Initiator of the present invention is water-soluble thermal initiator, in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
One kind, preferably potassium peroxydisulfate.
Solvent of the present invention can be selected from hexamethylene, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethanes,
One kind in toluene and dimethylbenzene, preferably hexamethylene.
Surfactant of the present invention is selected from lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine
It is one or more in ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
Molecular weight regulator of the present invention is selected from ten carbon mercaptan of uncle, tert-dodecyl mercaptan, 14 carbon mercaptan of uncle, uncle ten
One kind in six carbon mercaptan, preferably tert-dodecyl mercaptan.
The one kind of terminator of the present invention in diethyl hydroxylamine, hydroxyl sulfate, Sodium Dimethyldithiocarbamate, preferably Sodium Dimethyldithiocarbamate.
A kind of carbon nanotube of the present invention is used as the method for modifying of gum filler, first using acid with strong oxidizing property and more
First alcohol carries out hydroxylating processing to carbon nano tube surface so that carbon nano tube surface carries hydroxyl, by " hydrogen bond action " and more
First alcohol ester links together, and the single-point anchor point based on carbonyl is formed in carbon nano tube surface.The anchor point is contained intermingle with grafting
The polar group ester group of butylbenzene rubber cement generates the mutual attractive force between molecule, and solution polymerized butylbenzene is formed in carbon nanotube particle surface
The clad of rubber cement.The chain structure of the clad not only has the characteristics that nonpolarity, the effect not attracted each other, and simultaneously
Contain benzene ring structure again, molecule space steric effect is big, can be between carbon nanotube particle under this 2 points synergistic effect
Firm space bit resistance layer is established, hinders the mutual reunion between particle.Simultaneously can also significantly improve carbon nanotube with it is molten
The compatibility of poly- butadiene-styrene rubber can be stablized, be evenly dispersed in butadiene-styrene rubber matrix.The modified at low cost, environment of the present invention
Pollute small, operating method is simple, the advantages that being suitble to industrialized production.
Description of the drawings
Attached drawing 1 is carbon nanotube (a) and the infrared spectrum spectrogram of high dispersive type carbon nanotube (b).As can be seen from the figure：
The FTIR spectrograms of sample b are in 1715cm-1There is apparent absorption peak.Wherein wave number is 1715cm-1The absorption peak at place is ester group
Characteristic absorption peak, and the FTIR spectrograms of sample a occur here without absorption peak.Illustrate unsaturated acrylate polar monomer with
The graft polymers of solution polymerized butylbenzene rubber cement has been deposited on carbon nanotube particle surface.
Specific embodiment
Following embodiment and comparative example are enumerated to illustrate the invention effect of the present invention, but protection scope of the present invention is not
It is only limitted in these embodiment and comparative examples." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
(2) analysis test method：
The measure of grafting rate：The sample of about 4g is taken in measuring cup with pipette from three-necked bottle, and 2~3 are added in after weighing
Quinol solution is dripped, drying to constant weight, and then above-mentioned sample is placed in Soxhlet extractor, with toluene in 90 DEG C of water-baths
Upper extractive distillation for 24 hours, is then being dried to constant weight.Monomer grafting rate is calculated as follows:
In formula：m0- rubber cement gross mass (g)；The sample quality (g) weighed after m-reaction；mmMonomer is total in-reactant
Quality (g)；mSBRThe quality (g) of butadiene-styrene rubber in-sample；m1The quality (g) of sample after-extraction.
Sample infrared spectrum analysis：Nano carbon white is modified using German Bruke spectral instruments company infrared spectrometer
Front and rear sample carries out functional group analysis.Sample at 100 DEG C in vacuum drying oven is dried, using pressing potassium bromide troche, acquires wave number
400-4000cm of range—1。
The assay method of settling volume：Weigh the tool plug graduated cylinder that 10g modified Nano white carbons are placed in graduated 100mL
It is interior, a certain amount of dispersant (atoleine) is added in, Nano carbon white to be modified adds liquid by after atoleine complete wetting
Body paraffin fully vibrates 5min with the frequency of oscillation of 30 times/1min, makes modified Nano white carbon in liquid to the scale of 100mL
It is uniformly dispersed in paraffin, then stands, read the solid volume of different time.The settling volume of same time can be in certain journey
Reflect the quality of compatibility between particle and organic solvent on degree, settling volume is big, and it is good to make carbon black dispersion clear, easily compatible.
The assay method of oil absorption：Reference《The assay method of the aluminium hydroxide used as filling material oil absorptions of YS/T618-2007》, take
Quantitative modified Nano white carbon is put into surface plate, and diisooctyl phthalate is added dropwise by each 0.2mL, after being added dropwise every time,
It is fully ground, can be sticked into until agglomerate do not split to powder, oil absorption is with the volume V of every 100g samples institute oil suction with toolsetting0
(mL) it represents, is calculated as follows:
In formula, v is the volume (mL) of the diisooctyl phthalate of consumption；M is the quality (g) of sample.Oil absorption exists
The specific surface area of modified Nano white carbon is reflected in a way, and specific surface area is lower, and oil absorption is lower, and wettability is got over
Good, vice versa.
Embodiment 1
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 150 parts of concentrated nitric acids, 10 parts of H2O2It is put into togerther
It mixes in reactor, with 50kHz ultrasonication 1hr, is then heated at 50 DEG C, stirring acid boils 1hr, and cooling filters, washing
It is in neutrality to filtrate, is eventually adding 200 parts of ethylene glycol, is heated at 50 DEG C, be stirred to react 1hr, filtered, wash, is dry, obtaining
The carbon nanotube a of hydroxyl is carried to surface.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：300 parts of hexamethylenes are firstly added in polymeric kettle and then are sequentially added
100 parts of solution polymerized butylbenzene rubber cement SSBR2564s, 0.05 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 5 parts of MMA, and stirring adds
Heat, kettle temperature degree to be polymerized adds in 0.05 part of potassium peroxydisulfate when reaching 40 DEG C, after reacting 4hr, adds in 0.1 part of Sodium Dimethyldithiocarbamate, is made and connects
Branch solution polymerized butylbenzene rubber cement a (0.7 ﹪ of grafting rate).
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube a and 1 part of lauric acid glycol ester,
300 parts of hexamethylenes are added in polymeric kettle and are stirred 10min；Then 5 parts of grafting solution polymerized butylbenzene rubber cement a, stirring heating are added in
To 50 DEG C, after being stirred to react 2hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard examination is made
Sample, after tested performance be shown in Table 1.
Embodiment 2
(1) preparation of carbon nanotube hydroxyl：With embodiment 1.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 1.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube a and 1.5 parts of lauric acid ethylene glycol
Ester, 350 parts of hexamethylenes are added in polymeric kettle and are stirred 15min；Then 7 parts of grafting solution polymerized butylbenzene rubber cement a are added in, stirring rises
Temperature is to 60 DEG C, after being stirred to react 3hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard is made
Sample, after tested performance be shown in Table 1.
Embodiment 3
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 180 parts of concentrated nitric acids, 25 parts of H2O2It is put into togerther
It mixing in reactor, with 60kHz ultrasonication 1.5hr, is then heated at 100 DEG C, stirring acid boils 5hr, cool down, filter,
Washing is in neutrality to filtrate, is eventually adding 400 parts of ethylene glycol, is heated at 70 DEG C, is stirred to react 3hr, is filtered, washing, is done
It is dry, obtain the carbon nanotube b that surface carries hydroxyl.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：450 parts of hexamethylenes are firstly added in polymeric kettle and then are sequentially added
100 parts of solution polymerized butylbenzene rubber cement SSBR2564s, 0.25 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 8 parts of MMA, and stirring adds
Heat, kettle temperature degree to be polymerized adds in 0.3 part of potassium peroxydisulfate when reaching 50 DEG C, after reacting 5hr, adds in 0.3 part of Sodium Dimethyldithiocarbamate, grafting is made
Solution polymerized butylbenzene rubber cement b (1.4 ﹪ of grafting rate).
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube b and 2 parts of lauric acid glycol esters,
400 parts of hexamethylenes are added in polymeric kettle and are stirred 20min；Then 9 parts of grafting solution polymerized butylbenzene rubber cement b, stirring heating are added in
To 65 DEG C, after being stirred to react 3.5hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard is made
Sample, after tested performance be shown in Table 1.
Embodiment 4
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube b and 3 parts of lauric acid glycol esters,
420 parts of hexamethylenes are added in polymeric kettle and are stirred 20min；Then 11 parts of grafting solution polymerized butylbenzene rubber cement b, stirring heating are added in
To 65 DEG C, after being stirred to react 4hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard examination is made
Sample, after tested performance be shown in Table 1.
Embodiment 5
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube b and 3.5 parts of lauric acid ethylene glycol
Ester, 450 parts of hexamethylenes are added in polymeric kettle and are stirred 25min；Then 12 parts of grafting solution polymerized butylbenzene rubber cement b, stirring are added in
70 DEG C, after being stirred to react 4.5hr are warming up to, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：It is made
Standard sample, after tested performance be shown in Table 1.
Embodiment 6
(1) preparation of carbon nanotube hydroxyl：By 100 parts of carbon nanotubes and 200 parts of concentrated nitric acids, 50 parts of H2O2It is put into togerther
It mixing in reactor, with 100kHz ultrasonication 2hr, is then heated at 150 DEG C, stirring acid boils 10hr, cool down, filter,
Washing is in neutrality to filtrate, is eventually adding 500 parts of ethylene glycol, is heated at 90 DEG C, is stirred to react 3hr, is filtered, washing, is done
It is dry, obtain the carbon nanotube c that surface carries hydroxyl.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：600 parts of hexamethylenes are firstly added in polymeric kettle and then are sequentially added
100 parts of solution polymerized butylbenzene rubber cement SSBR2564s, 0.5 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 10 parts of methacrylic acids
Butyl ester, stirring, heating, kettle temperature degree to be polymerized adds in 0.5 part of potassium peroxydisulfate when reaching 60 DEG C, after reacting 10hr, adds in 0.5 part of good fortune
Grafting solution polymerized butylbenzene rubber cement c (1.9 ﹪ of grafting rate) is made in U.S. sodium.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube c and 4 parts of lauric acid butanediol esters,
470 parts of hexamethylenes are added in polymeric kettle and are stirred 28min；Then 13.5 parts of grafting solution polymerized butylbenzene rubber cement c are added in, stirring rises
Temperature is to 75 DEG C, after being stirred to react 5hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard is made
Sample, after tested performance be shown in Table 1.
Embodiment 7
(1) preparation of carbon nanotube hydroxyl：With embodiment 6.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 6.
(3) preparation of high dispersive type carbon nanotube：Take 100 parts of hydroxyl carbon nano tube c and 5 parts of lauric acid butanediol esters,
500 parts of hexamethylenes are added in polymeric kettle and are stirred 30min；Then 15 parts of grafting solution polymerized butylbenzene rubber cement c, stirring heating are added in
To 80 DEG C, after being stirred to react 6hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard examination is made
Sample, after tested performance be shown in Table 1.
Comparative example 1
(1) preparation of carbon nanotube hydroxyl：With embodiment 1.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 1.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 1, and the difference lies in preparation process
The addition of middle grafting solution polymerized butylbenzene rubber cement a is 4 parts, i.e.,：Take 100 parts of hydroxyl carbon nano tube a and 1 part of lauric acid ethylene glycol
Ester, 300 parts of hexamethylenes are added in polymeric kettle and are stirred 10min；Then 4 parts of grafting solution polymerized butylbenzene rubber cement a are added in, stirring rises
Temperature is to 50 DEG C, after being stirred to react 2hr, through flashing, drying, grinding high dispersive type carbon nanotube is made.Sampling analysis：Standard is made
Sample, after tested performance be shown in Table 1.
Comparative example 2
(1) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 1.
(2) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 2, and the difference lies in preparation process
In be added without hydroxyl carbon nano tube a, but be directly added into not hydroxylated carbon nanotube, i.e.,：100 parts of non-hydroxylating carbon is taken to receive
Mitron and 1.5 parts of lauric acid glycol esters, 350 parts of hexamethylenes are added in polymeric kettle and are stirred 15min；Then 7 parts are added in
Solution polymerized butylbenzene rubber cement a is grafted, stirring is warming up to 60 DEG C, after being stirred to react 3hr, through flashing, drying, grind obtained high dispersive type carbon
Nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 3
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 3, and the difference lies in preparation process
In be added without grafting solution polymerized butylbenzene rubber cement b, i.e.,：Take 100 parts of hydroxyl carbon nano tube b and 2 parts of lauric acid glycol esters, 400 parts
Hexamethylene, which is added in polymeric kettle, is stirred 20min；Stirring is warming up to 65 DEG C, after being stirred to react 3.5hr, through flashing, drying,
High dispersive type carbon nanotube is made in grinding.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 4
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：With embodiment 3.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 4, and the difference lies in preparation process
In be added without lauric acid glycol ester, i.e.,：100 parts of hydroxyl carbon nano tube b and 420 parts of hexamethylenes is taken to be added in polymeric kettle and stir
Mix mixing 20min；Then 11 parts of grafting solution polymerized butylbenzene rubber cement b are added in, stirring is warming up to 65 DEG C, after being stirred to react 4hr, through dodging
It steams, is dry, high dispersive type carbon nanotube is made in grinding.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 5
(1) preparation of carbon nanotube hydroxyl：With embodiment 3.
(2) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 5, and the difference lies in preparation process
In be added without grafting solution polymerized butylbenzene rubber cement b, but add in solution polymerized butylbenzene rubber cement SSBR2564s, i.e.,：100 parts of hydroxylating carbon is taken to receive
Mitron b and 3.5 parts of lauric acid glycol esters, 450 parts of hexamethylenes are added in polymeric kettle and are stirred 25min；Then 12 are added in
Part solution polymerized butylbenzene rubber cement SSBR2564s, stirring are warming up to 70 DEG C, after being stirred to react 4.5hr, through flashing, drying, grind and be made high
Dispersing type carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 6
(1) preparation of carbon nanotube hydroxyl：With embodiment 6.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：Other conditions are same as Example 6, and the difference lies in preparation process
The addition of middle butyl methacrylate is 4 parts, i.e.,：600 parts of hexamethylenes are firstly added in polymeric kettle and then are sequentially added
100 parts of solution polymerized butylbenzene rubber cement SSBR2564s, 0.5 part of tert-dodecyl mercaptan after being replaced with nitrogen, add in 4 parts of methacrylic acid fourths
Ester, stirring, heating, kettle temperature degree to be polymerized adds in 0.5 part of potassium peroxydisulfate when reaching 60 DEG C, after reacting 10hr, adds in 0.5 part of good fortune U.S.
Grafting solution polymerized butylbenzene rubber cement c-1 (0.3 ﹪ of grafting rate) is made in sodium.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 6, and the difference lies in preparation process
In be added without grafting solution polymerized butylbenzene rubber cement c, but add in grafting solution polymerized butylbenzene rubber cement c-1, i.e.,：Take 100 parts of hydroxylating carbon nanometers
Pipe c and 4 parts of lauric acid butanediol esters, 470 parts of hexamethylenes are added in polymeric kettle and are stirred 28min；Then 13.5 parts are added in
Solution polymerized butylbenzene rubber cement c-1 is grafted, stirring is warming up to 75 DEG C, after being stirred to react 5hr, through flashing, drying, grind obtained high dispersive type
Carbon nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
Comparative example 7
(1) preparation of carbon nanotube hydroxyl：With embodiment 6.
(2) it is grafted the preparation of solution polymerized butylbenzene rubber cement：Other conditions are same as Example 6, and the difference lies in preparation process
In be added without potassium peroxydisulfate, i.e.,：600 parts of hexamethylenes are firstly added in polymeric kettle and then sequentially add 100 parts of Butadiene-Styrene Rubbers
SSBR2564s, 0.5 part of tert-dodecyl mercaptan to be starched, after being replaced with nitrogen, adds in 10 parts of butyl methacrylates, stirring is heated,
When kettle temperature degree to be polymerized reaches 60 DEG C, after reacting 10hr, 0.5 part of Sodium Dimethyldithiocarbamate is added in, grafting solution polymerized butylbenzene rubber cement c-2 is made.
(3) preparation of high dispersive type carbon nanotube：Other conditions are same as Example 7, and the difference lies in preparation process
In be added without grafting solution polymerized butylbenzene rubber cement c, but add in grafting solution polymerized butylbenzene rubber cement c-2, i.e.,：Take 100 parts of hydroxylating carbon nanometers
Pipe c and 5 parts of lauric acid butanediol esters, 500 parts of hexamethylenes are added in polymeric kettle and are stirred 30min；Then 15 parts are added in connect
Branch solution polymerized butylbenzene rubber cement c-2, stirring are warming up to 80 DEG C, after being stirred to react 6hr, through flashing, drying, grind obtained high dispersive type carbon
Nanotube.Sampling analysis：Standard sample is made, performance is shown in Table 1 after tested.
The settling volume and oil absorbency of 1 high dispersive type carbon nanotube of table
As shown in Table 1：The settling volume of embodiment is big than comparative example under same time, and oil absorption is below comparing
Example illustrates that the modified effect of the present invention is apparent.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (16)
1. a kind of method of modifying for being used as gum filler carbon nanotube, which is characterized in that include the following steps：
(1) preparation of carbon nanotube hydroxyl：In parts by mass, by 100 parts of carbon nanotubes and 150~200 parts of concentrated nitric acids, 10~
50 parts of H2O2It is put into togerther in reactor and mixes, with 50~100kHz, 1~2hr of ultrasonication, be then heated to 50~150 DEG C,
Stirring acid boils 1~10hr, and cooling, suction filtration, washing are in neutrality to filtrate, are eventually adding 200~500 parts of polyalcohols, are heated to
50~90 DEG C, 1~5hr is stirred to react, filters, wash, is dry, obtains the carbon nanotube that surface carries hydroxyl；
(2) it is grafted the preparation of rubber cement：In parts by mass, 300~600 parts of solvents are firstly added in polymeric kettle and then are added successively
Enter 100 parts of solution polymerized butylbenzene rubber cements, 0.05~0.5 part of molecular weight regulator, after being replaced with nitrogen, add in 5~10 parts of unsaturation
Acrylate polar monomer, stirring, heating, kettle temperature degree to be polymerized add in 0.05~0.5 part of initiator when reaching 40~60 DEG C, instead
After answering 4~10hr, 0.1~0.5 part of terminator is added in, grafting rubber cement is made；
(3) preparation of modified carbon nano-tube：In parts by mass, take 100 parts of hydroxyl carbon nano tubes and 1~5 part of surfactant,
300~500 parts of solvents are added in polymeric kettle and are stirred 10~30min；Then 5~15 parts of grafting rubber cements are added in, stirring rises
Temperature is to 50~80 DEG C, after being stirred to react 2~6hr, through flashing, drying, grinding modified version carbon nanotube is made.
2. the method as described in claim 1, which is characterized in that the carbon nanotube be it is nano level, grain size for 0.3~
30nm。
3. method as claimed in claim 1 or 2, which is characterized in that the polyalcohol be selected from ethylene glycol, propylene glycol, glycerine,
The mixture of one or more of butanediol, pentaerythrite.
4. method as claimed in claim 1 or 2, which is characterized in that the solution polymerized butylbenzene rubber cement is by conjugated diene chemical combination
Object and aryl ethylene class compound are copolymerized by polymerisation in solution.
5. method as claimed in claim 4, which is characterized in that the conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbonylation
Close object.
6. method as claimed in claim 4, which is characterized in that the aryl ethylene class compound is selected from styrene, Alpha-Methyl
One kind in styrene, 2- propenyl benzenes, ethyl styrene and their derivative.
7. method as claimed in claim 4, which is characterized in that the solid content of the solution polymerized butylbenzene rubber cement is 5~20w%.
8. method as claimed in claim 1 or 2, which is characterized in that the unsaturation acrylate polar monomer is selected from methyl
One or more of methyl acrylate, ethyl methacrylate, butyl methacrylate and Tert-butyl Methacrylate.
9. method as claimed in claim 8, which is characterized in that the unsaturation acrylate polar monomer is methacrylic acid
Methyl esters.
10. method as claimed in claim 1 or 2, which is characterized in that the initiator is water-soluble thermal initiator, is selected from
One kind in ammonium sulfate, potassium peroxydisulfate and sodium peroxydisulfate.
11. method as claimed in claim 10, which is characterized in that the initiator is potassium peroxydisulfate.
12. method as claimed in claim 1 or 2, which is characterized in that the solvent is selected from hexamethylene, carbon disulfide, nitro
One kind in benzene, petroleum ether, tetrachloroethanes, toluene and dimethylbenzene.
13. method as claimed in claim 1 or 2, which is characterized in that the surfactant be selected from lauric acid glycol ester,
It is one or more in lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
14. method as claimed in claim 1 or 2, which is characterized in that the molecular weight regulator is selected from ten carbon mercaptan of uncle, uncle
One kind in DDM dodecyl mercaptan, 14 carbon mercaptan of uncle and uncle 16 carbon mercaptan.
15. method as claimed in claim 14, which is characterized in that the molecular weight regulator is tert-dodecyl mercaptan.
16. method as claimed in claim 1 or 2, which is characterized in that the terminator is selected from diethyl hydroxylamine, hydroxyl sulfate
With one kind in Sodium Dimethyldithiocarbamate.
Priority Applications (1)
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| CN111073039A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Rubber composition for green tire tread and preparation method thereof |
| CN111073200A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Environment-friendly rubber composition and preparation method thereof |
| CN111073050A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Preparation method of nano white carbon black for high-dispersion rubber filler |
| CN111073201A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Anti-slippery rubber composition for green tire and preparation method thereof |
| CN111073049A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Modification method of nano white carbon black used as rubber filler |
| CN111073045A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Modification method of high-dispersion rubber filler nano white carbon black |
| CN115418182A (en) * | 2022-09-20 | 2022-12-02 | 江苏斯瑞达材料技术股份有限公司 | High-temperature-resistant high-conductivity pressure-sensitive adhesive and preparation method thereof |
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| CN115418182B (en) * | 2022-09-20 | 2023-10-24 | 江苏斯瑞达材料技术股份有限公司 | High-temperature-resistant high-conductivity pressure-sensitive adhesive and preparation method thereof |
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