CN103665491A - Oil-extended and carbon black-extended styrene-butadiene master batch, rubber composition and preparation method thereof - Google Patents
Oil-extended and carbon black-extended styrene-butadiene master batch, rubber composition and preparation method thereof Download PDFInfo
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- CN103665491A CN103665491A CN201210347107.4A CN201210347107A CN103665491A CN 103665491 A CN103665491 A CN 103665491A CN 201210347107 A CN201210347107 A CN 201210347107A CN 103665491 A CN103665491 A CN 103665491A
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- oil
- butylbenzene
- master batch
- nano silicon
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- 238000002360 preparation method Methods 0.000 title claims abstract description 86
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 81
- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000002174 Styrene-butadiene Substances 0.000 title abstract description 9
- 239000011115 styrene butadiene Substances 0.000 title abstract description 9
- 239000003921 oil Substances 0.000 claims abstract description 126
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 103
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000839 emulsion Substances 0.000 claims abstract description 100
- 229920000126 latex Polymers 0.000 claims abstract description 98
- 239000004816 latex Substances 0.000 claims abstract description 95
- 239000006229 carbon black Substances 0.000 claims abstract description 69
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 48
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 43
- -1 diene modified styrene-butadiene Chemical class 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 150000001993 dienes Chemical class 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims description 54
- 238000012986 modification Methods 0.000 claims description 54
- 239000003738 black carbon Substances 0.000 claims description 53
- PCJUMACLVAITCG-UHFFFAOYSA-N [C].C(CCC)C1=CC=CC=C1 Chemical compound [C].C(CCC)C1=CC=CC=C1 PCJUMACLVAITCG-UHFFFAOYSA-N 0.000 claims description 52
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 40
- 229960001866 silicon dioxide Drugs 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003995 emulsifying agent Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000003712 anti-aging effect Effects 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012874 anionic emulsifier Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- UNIYDALVXFPINL-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylsilicon Chemical compound CC(=C)C(=O)OCCC[Si] UNIYDALVXFPINL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- IOZVKVQMRQRJFK-UHFFFAOYSA-N propane;quinoline Chemical compound CCC.N1=CC=CC2=CC=CC=C21 IOZVKVQMRQRJFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 238000006557 surface reaction Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- PEUWKAAVXXUTRM-UHFFFAOYSA-N 1-chloropenta-1,3-diene Chemical compound CC=CC=CCl PEUWKAAVXXUTRM-UHFFFAOYSA-N 0.000 claims description 2
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 claims description 2
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 25
- 230000020169 heat generation Effects 0.000 abstract 1
- 229940105289 carbon black Drugs 0.000 description 62
- 235000019241 carbon black Nutrition 0.000 description 62
- 238000000034 method Methods 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 229920001195 polyisoprene Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000344 soap Substances 0.000 description 12
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000000051 modifying effect Effects 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 229920003052 natural elastomer Polymers 0.000 description 4
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- 238000005096 rolling process Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- NAOQESSEZUUFIL-UHFFFAOYSA-N C1(=CC=CC=C1)C.[Si](=O)=O Chemical compound C1(=CC=CC=C1)C.[Si](=O)=O NAOQESSEZUUFIL-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
An oil-extended carbon black-extended styrene-butadiene master batch, a rubber composition and a preparation method thereof. The oil-extended and carbon black-extended styrene-butadiene master batch is formed by mixing and condensing extended oil, carbon black slurry and silicon dioxide/poly-conjugated diene modified styrene-butadiene rubber latex, wherein the nano silicon dioxide/poly-conjugated diene modified styrene-butadiene rubber latex is prepared by blending nano silicon dioxide/poly-conjugated diene functional composite emulsion and styrene-butadiene rubber latex, and the functional composite emulsion is prepared by introducing nano silicon dioxide to a poly-conjugated diene molecular chain. The disclosed masterbatch and rubber composition have greatly reduced heat generation when applied to a tire tread, and have excellent combination of wet grip performance and wear resistance.
Description
Technical field
The present invention relates to a kind of butylbenzene master batch that fills oil black carbon, rubber combination and preparation method thereof, relate in particular a kind of for tire tread and can improve tyre performance fill oil black carbon butylbenzene master batch, rubber combination and preparation method thereof.
Background technology
Carbonblack master batch (Carbon Black Master batch, CBMB) refers to a kind of sizing material that is mixed with the fillers such as carbon black in rubber, and it can be pre-mixing sizing material work in-process, can be also a kind of final rubber compounding sizing material.
The preparation of carbonblack master batch is divided into two kinds of dry method and wet methods.Maskerbatch of dry process can be with conventional mixing facilities by powerful mechanical shearing, solid rubber is mixing with carbon black together with, this method technique is simple, easy to operate, General Purpose Rubber factory all can produce.Its shortcoming is that carbon black dispersion is poor, is difficult to continuously a large amount of production.
Wet masterbatch be by carbon black dispersion in the latex that polymerization forms, then carry out common cohesion, dehydration, the postprocessing working procedures such as dry and obtain.Technique sees the patent of nineteen thirty-five U. S. application the earliest, until within 1948, just there is commodity selling; Nineteen fifty-three succeeds in developing after the oversubscription arching pushing of carbon black, just gets rapid development.
Wet method carbonblack master batch can significantly improve the dispersiveness of carbon black in polymkeric substance.Because carbon black is greater than by glossy wet speed the speed being soaked by glue, thereby the dispersiveness of carbon black is much higher in oil-filled glue; This is also the reason of the not only oil-filled but also carbon black-filled butylbenzene master batch of current manufacturing enterprise direct production.
The cross-linked rubber of wet method oil extended black masterbatch has good physical and mechanical properties, and processing characteristics is good.Its technology of preparing has the feature that energy consumption is low, environmental pollution is little simultaneously.People's research in recent years such as K.Sone the physicals of wet method carbonblack master batch, result shows that carbon black dispersion significantly improves, master batch physical strength and rubber hardness obviously improves, easily processing, the tire making can meet the requirement of the riding tire of high-performance.The test-results of U.S. Cabot Co.,Ltd shows, it is that carbonblack master batch processing is more convenient that the dispersiveness of carbon black height makes sizing material add tire, and improved the salient features of product, coordinate the same recipe of technique to compare with using routine, wear resistance improves more than 20%, tan δ (60 ℃) reduces by 20%, thereby causes the rolling resistance of tread rubber to reduce, and rebound resilience improves 10% left and right.
Wet method oil extended black masterbatch can be used for any rubber item needing with black-reinforced, as travelling belt, sole, heel, machinework, pressing etc.In addition, go back a large amount of tread rubbers for the manufacture of various doughnuts, tractor tire and cycle tyre.Along with automobile at a high speed, the development of safe, energy-conservation, comfortableization direction, the requirement of tire high performance is also improved year by year, this just requires tire tread to have good wet-sliding resistant performance, excellent wear resistance and low rolling resistance.
Doughnut need to have specific performance, makes automobile have low specific fuel consumption on the one hand, with low fuel consumption, realizes long distance travel; Second aspect, tire has good Shi road and is grabbing performance, on wet road, has short braking distance; The third aspect, tire has good wear resistance, and surface of tyre is not easy to wear.Along with automobile at a high speed, the development of safe, energy-conservation, comfortableization direction, the requirement of tire high performance is also improved year by year, this just requires tire tread to have good wet-sliding resistant performance, excellent wear resistance and low rolling resistance.
Conventionally the rubber combination that comprises these rubber with introducing carbon black is wherein served as to the elastomeric material of tire, yet the rubber combination that this class comprises carbon black is unsafty at low-heat-generation aspect of performance.Nano silicon is commonly called as white carbon black, is the second largest strengthening agent that in rubber industry, consumption is only second to carbon black.From the nineties in last century, white carbon black is widely used in, in tire tread formula, making " devil's triangle " performance that above-mentioned tire tread requires obtain obvious balance as reinforced filling.Proposed to add silicon-dioxide to replace carbon black in rubber combination, to improve low-heat-generation, yet, introduced the rubber combination of silicon-dioxide and compared and there is poor wear resistance with the rubber combination of having introduced carbon black.This is to compare with carbon black and have poor and affinity rubber due to silicon-dioxide, and uses silicon-dioxide can not obtain satisfied reinforced effects.
Qiu Quanfang (control by " latex blending method " natural rubber/silicon dioxide nano composite material micro-structure and property, 2010, University Of Hainan's Master's thesis) research example high-performance NR matrix material: adopt latex blending method to prepare natural rubber/silicon dioxide nano composite material, first use γ-methacryloxypropyl trimethoxy silane coupling agent (MPS) modified manometer silicon dioxide (SiO2), the nano-silicon dioxide particle (SiO2-MPS-PMMA) that polymethylmethacrylate (PMMA) obtains nucleocapsid structure in letex polymerization grafting is again finally by itself and the directly blend of natural rubber latex (NR-PMMA) of using MMA modification, make natural rubber/silicon dioxide nano composite material.PMMA is a kind of important organic transparent structured material, and the natural rubber/silicon dioxide composite material film forming properties making by this invention is good, and mechanics performance of latex film is high, is mainly used in medical field.
Single common vetch (< < China Synthetic Rubber Industry > >; 2006; 29(6): 474) adopt anionic in-situ polymerization legal system for polyhutadiene/silicon dioxide nano composite material; first γ for nano silicon-(methacryloxy) propyl trimethoxy silicane (MPS) is processed; then the silicon-dioxide after modification is scattered in divinyl and cyclohexane solvent; after ultrasonic dispersion, add n-Butyl Lithium as initiator, polyreaction is carried out under nitrogen protection.Then product is joined and in ethanol, obtain white depositions, filtration drying has just obtained the PSN that silicon-dioxide quality mark is 3.1%.They have also studied structure and the performance of this kind of matrix material, and result shows that silicon dioxide granule and the polybutadiene-base body after MPS processes formed strong interfacial interaction, makes matrix material have excellent over-all properties.Because polyhutadiene/silicon dioxide composite material is to take n-Butyl Lithium to prepare by solution polymerization process as initiator, in preparation process, use a large amount of organic solvents, not only harmful to environment, and in solvent removal process, macromolecular chain is difficult to whole white carbon black particles are contained-cohesion, have mass loss, also may in common coagel matrix, assemble simultaneously, be difficult for realizing good distribution.In addition, the PSN molecular weight distribution that adopts solution polymerization process to prepare is narrower, in rubber post-treatment application process, also has certain difficulty.
The invention provides a kind of function composite emulsion, nano silicon is incorporated on poly-conjugated-diolefin molecular chain, and by functional latex blending and modifying styrene-butadiene latex, then adopt wet-mixed technique to prepare butylbenzene master batch and the rubber combination of filled rubber oil and carbon black, heat-dissipating reduces greatly when the tire tread, and has good Shi road and grabbing performance and wear resisting property over-all properties.
Summary of the invention
The object of the invention be to provide a kind of improve tire over-all properties fill oil black carbon butylbenzene master batch and rubber combination, during for tire tread, heat-dissipating reduces greatly, and has good Shi road and grabbing performance and wear resisting property over-all properties.
The oil black carbon butylbenzene master batch that fills disclosed in this invention, styrene butadiene rubber latex mixing cohesion by extending oil, carbon black slurry and the modification of silicon-dioxide/poly-conjugated-diolefin forms, in the butt quality of each component, extending oil: carbon black: the styrene-butadiene rubber(SBR) of silicon-dioxide/poly-conjugated-diolefin modification is 10～60:50～80:100; The styrene butadiene rubber latex of nano silicon/poly-conjugated-diolefin modification is prepared by nano silicon/poly-conjugated-diolefin function composite emulsion and styrene butadiene rubber latex blend, and the mass ratio of styrene butadiene rubber latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100:0.1～100; Nano silicon/poly-conjugated-diolefin function composite emulsion be take emulsion butt quality as 100 parts, 0.1～5 part of the nano silicon that contains surface-functionalized modification, nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50～80nm, number-average molecular weight is 100000～140000, and molecular weight distribution is 2～3.
Extending oil of the present invention is conventionally known to one of skill in the art, can be paraffinic base rubber filling oil, naphthenic rubber extending oil, aromatic base rubber filling oil, preferably naphthenic rubber extending oil, aromatic base rubber filling oil; Aromatic carbon content (the CA% that described extending oil preferably has; According to ASTMD3238, measure) be at least 5%, more preferably at least 10%, and paraffinic hydrocarbon content (CP%; According to ASTMD3238, measure) for being not more than 70%, more preferably no more than 60% be particularly preferably not more than 50%.If CA% is too little or CP% is too large, the tensile strength of vulcanization of rubber product and wear resistance may be poor.In addition, the polycyclic aromatic hydrocarbon content that extending oil preferably has (PCA measures by IP346 method) is for being less than 3.
Carbon black of the present invention can be general carbon black, and it is 60～120m that the present invention preferably uses nitrogen adsorption specific surface area
2g
-1, DBP absorption value is 60～120cm
3g
-1carbon black.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, the rubber of the nano silicon/poly-conjugated-diolefin modification of the amount of extending oil based on 100 weight parts, its add-on is 10～60, preferably 20～40 parts.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, described styrene butadiene rubber latex combined styrene content is 15～45%, mooney viscosity is 80～140, and when mooney viscosity is within the scope of this, oil-extended styrene-butadiene rubber has good processing characteristics and well balanced physicals.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, thereby in order to improve the dispersiveness of silicon-dioxide in emulsion, further improve the performance of functional latex, the present invention selects coupling agent treatment silicon-dioxide, make silicon-dioxide there is reactivity, re-use emulsion polymerization in situ and make the nano silicon/poly-conjugated-diolefin composite emulsion having good stability.Nano silicon/poly-conjugated-diolefin composite emulsion disclosed in this invention, take emulsion butt as 100 parts, 0.1～5 part of the nano silicon that contains surface-functionalized modification; Nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50～80nm, and number-average molecular weight is 10000～140000, and molecular weight distribution is 2～3.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, the nano silicon of described surface-functionalized modification refers to that silicon-dioxide adopts coupling agent to be processed and made the nano silicon with response type by surface functionalization, coupling agent is wherein siloxanes coupling agent, it accounts for 0.1～50% of surface-functionalized modified manometer silicon dioxide quality, and preferably 10～30%.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, affiliated nano silicon, so long as nano level, preferred 20～60nm.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, described siloxanes coupling agent, it can be vinyl siloxanes, one or more in methyl acrylic ester siloxanes, preferred vinyl triethoxyl silane (VTES), vinyltrimethoxy silane (VTMS), vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributyl ketoximyl silane, methyl tributanoximo silane, vinyl silane triisopropoxide, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, second diamino propyl trimethoxy silicane, vinyl trichloro silane, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane (MPS), one or more in three (trimethylsiloxy group) methacryloxypropyl silane (MPTS), more preferably one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) methacryloxypropyl silane.
The oil black carbon butylbenzene master batch that fills disclosed by the invention, described conjugated diene is C
4-C
12conjugated diene, is preferably 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 divinyl, 2,3-diethyl-1,3 divinyl, 2-methyl-3-ethyl-1,3 divinyl, the chloro-1,3-pentadiene of 2-, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, one or more in 1,3-hexadiene, more preferably 1,3-butadiene and/or isoprene.
The oil black carbon butylbenzene master batch that fills disclosed in this invention, can be prepared into oil blackextended styrene butadiene rubber composition, in each composition weight, contains 100 parts of oil blackextended styrene butadiene rubbers and 0.5～3 part of vulcanizing agent.Certainly, also can contain one or more in zinc oxide, stearic acid, anti-aging agent, promotor auxiliary agent in rubber combination, add-on be take main rubber as 100 weight parts, 1～5 part, zinc oxide, 1～4 part of stearic acid, 0.5～3 part of promotor, 0.5～2 part, anti-aging agent.When preparing rubber combination, make, each component can be added to mixing sulfuration.
The invention also discloses the preparation method who fills oil black carbon butylbenzene master batch, concrete preparation process is:
(1) preparation of nano silicon/poly-conjugated-diolefin function composite emulsion: for nano silicon/poly-conjugated-diolefin function composite emulsion, take conjugated diene monomer quality as 100 parts by seeding emulsion polyerization legal system:
A monomer pre-emulsion preparation: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator are mixed to pre-emulsification and be prepared into pre-emulsion for 15～45 minutes; Wherein the ratio of monomer and water is 1:1～1:2, and emulsifier is 3～20 parts, and buffer reagent consumption is 0.3～1 part, and initiator amount is 0.1～0.8 part;
B be take surface-functionalized modified manometer silicon dioxide and is prepared nano silicon/poly-conjugated-diolefin function composite emulsion as core: 0.1～5 part of nano silicon getting surface-functionalized modification joins in the reactor that 0.1～5 part of emulsifying agent and 10～50 parts of deionized waters are housed, stirring is warming up to 60～80 ℃, then getting 1/20～1/5 monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60～80 ℃, be incubated 0.5～1 hour, allow conjugated diene monomer by the coated also polymerization of surface-functionalized modified manometer silicon dioxide, and the seed using this as composite emulsion, in the reactor of seed emulsion is housed, drip remaining monomer pre-emulsion, and dropwised in 5～8 hours, obtain poly-conjugated-diolefin/nanometer titanium dioxide functional silicon composite emulsion,
(2) preparation of fat liquor: extending oil is warming up to 60 ~ 80 ℃, be convenient to take, then will in extending oil, add water and emulsifying agent, the rubber filling oil of 100 weight parts of take is basis, 1.0～4.5 parts of emulsifying agent add-ons are by oily emulsor, to prepare fat liquor at 60 ~ 80 ℃ at emulsifying temperature;
(3) fill the preparation of oil black carbon butylbenzene master batch: nano silicon/poly-conjugated-diolefin function composite emulsion is joined in styrene butadiene rubber latex, be fully uniformly mixed; Add above-mentioned fat liquor, mix, then add carbon black slurry to mix, then cohesion makes and fills oil black carbon butylbenzene master batch.
, when extending oil is added to while stirring in rubber latex, there is the solubleness lower problem of oil in rubber latex in the preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, therefore, oil is easily retained in water.In order to suppress this problem, the present invention adopts emulsifying agent first extending oil to be emulsified into the fat liquor of oil-in-water-type, then condenses with rubber latex blend.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, in the preparation of fat liquor, when the water yield increases, can cause the thermostability of oil in water emulsion to reduce, easily cause oily water separation phenomenon, during discharge reduction, be unfavorable for that pipeline carries, therefore add water and oily mass ratio to be preferably 1:1～1:3.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, described emulsifying agent is conventionally known to one of skill in the art, can be one or more in anionic emulsifier and nonionic emulsifying agent.Anionic emulsifier can be metal carboxylate, Sulfates, one or more in Sulfonates emulsifying agent, preferred fatty acid soap, resin acid soaps, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, more preferably sodium lauryl sulphate, nonionic emulsifying agent can be ester class, one or more in ethers, preferred polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, more preferably alkylphenol polyoxyethylene.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, described buffer reagent can be sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor, bicarbonate of ammonia, preferably sodium carbonate or sodium bicarbonate.
Initiator of the present invention is water-soluble thermal initiator, initiator system of ammonium persulfate, Potassium Persulphate, Sodium Persulfate, 2, two (the 2-amidine azoles quinoline propane) hydrochlorides, 2 of 2-azo, and 2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, more preferably Potassium Persulphate or Sodium Persulfate.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, described cohesion, adopts acid cure poly-, and this technology is general by those skilled in the art, and described acid is generally mineral acid, for example one or more in hydrochloric acid, sulfuric acid.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, described surface-functionalized modified manometer silicon dioxide is to adopt coupling agent to be processed and made the nano silicon with response type by surface functionalization the silicon-dioxide of 20～60nm, this technology is conventionally known to one of skill in the art, for example in the research > > of < < radiation research and radiation process journal > > 25 volumes the 5th phase < < surface modification of silica in 2007 and radiation initiation grafting GMA, disclose the method for nano-silica surface functional modification, the present invention is not particularly limited, the method that the present invention recommends is: take 0.1～50 part of nano silicon stand-by in oven drying, then with 5～500 parts of solvent after ultrasonic wave disperse fully, add 0.1～50 part of coupling agent after hydrolysis, stir post-heating to 80～120 ℃ and reflux 2～4 hours, filtration washing.Solvent is toluene, dimethylbenzene or methyl ethyl ketone, and its add-on is 5～500 parts, preferably 100～300 parts.
The preparation method who fills oil black carbon butylbenzene master batch disclosed by the invention, the preparation method of described carbon black slurry adopts the oversubscription arching pushing that does not add any tensio-active agent, in the situation that not destroying carbon blacksurface activity, be separated into submicron order, in the new development > > of < < off-colour industry > > the 6th phase < < carbon black dispersion technology in 2006 to not adding loose narration of carbon black oversubscription of any tensio-active agent.Carbon black slurry of the present invention is by not adding loose acquisition of oversubscription of any tensio-active agent, for example can be by mechanical means by carbon black fine dispersion to preparing in water.The mass concentration of carbon black slurry has good mobility with maintenance, and can fully mix and be as the criterion with latex, and run-of-the-mill concentration is 15%～20%, in order to improve the wetting rate of carbon black, shortens the jitter time of carbon black, and deionized water temperature is preferably 40～60 ℃.
The effect that the present invention is useful:
The oil black carbon butylbenzene master batch that fills of the present invention is by fat liquor, the styrene butadiene rubber latex of carbon black slurry and the modification of nano silicon/poly-conjugated-diolefin function composite emulsion is through condensing and make altogether, because nano silicon/poly-conjugated-diolefin function composite emulsion has satisfactory stability, particle diameter is controlled, be distributed in 50～80nm, disperse with styrene butadiene rubber latex, good mixing effect, the method that is used further to modified styrene butadiene rubber by preparing functional latex has effectively solved nano silicon scattering problem of (particularly nonpolar rubber) in rubber matrix.The styrene butadiene rubber latex of nano silicon/poly-conjugated-diolefin function composite emulsion modification and fat liquor and carbon black slurry good mixing effect, this mode adds carbon black to compare in the direct blend of the course of processing with various fillers, disperse more evenly, be more conducive to improve the over-all properties of tire; Function composite emulsion molecular weight and molecualr weight distribution is suitable, and the carbonblack master batch that fills of preparation is described, and heat-dissipating is low when mixing, mixing behavior good.The prepared 60 ℃ of dissipation factors of oil black carbon butylbenzene master batch (tan δ) of filling reduce, and illustrate that rolling resistance is low when for the preparation of tire.0 ℃ of tan δ is higher, illustrates that to prepare wet-sliding resistant performance good for tire.
In addition, the present invention is raw materials used to be easy to get, preparation process is easy to be easy to control, in functional latex preparation process not with an organic solvent, environmental protection, pollution-free, cost is low, adopts seeding emulsion polyerization method can make nano silicon with chemical bonding, can be good be scattered in poly-conjugated-diolefin.
Embodiment
Below by embodiment and comparative example, further illustrate effect of the present invention.
(1) raw material sources
Carbon black: Wuxi Shuan Cheng carbon black company limited produces;
Extending oil: DAE Ca value is 42%, Liaohe River petrochemical iy produced; TDAE, Ca value is 25%, German Han Sheng company limited produces; AP-15, Ca value is 15, Liaohe River petro-chemical corporation produces; AP-10, Ca value is 10%, Karamay Petrochemical Company produces; The special-purpose naphthenic oil of SBR1778, Ca value is 8%, Liaohe River petro-chemical corporation produces.
Nano silicon (20～60nm), 99.5%, Weifang Wan Li auxiliary agent company limited produces;
Silane coupling agent VTES, MPS, VTMS, MPTS, gamma-amino propyl trimethoxy silicane, vinyltriacetoxy silane, technical grade, is Qufu City Wanda Chemical Co., Ltd. and produces;
Divinyl, 99.5%, Lanzhou Petrochemical Company synthetic rubber plant produces;
Isoprene, 99.3%, Lanzhou Xin Lan petrochemical complex company limited produces;
Styrene butadiene rubber latex: SBR1712E basis latex, combined styrene content 23.5%, solid content 23%, mooney viscosity is respectively 80 and 114; SBR1756 basis latex, combined styrene content is 32%, solid content 19%, mooney viscosity 132; SBR1769E basis latex, combined styrene content 40%, solid content 20%, mooney viscosity 140; SBR1778E basis latex, combined styrene content 23.5%, solid content 21%, mooney viscosity 110, is Lanzhou Petrochemical Company and produces.
(2) analysis test method
Molecular weight and distribution thereof: adopt high temperature gel chromatogram analysis method (GPC), GPC experiment instrument is the GPCV2000 type high temperature gel chromatographic instrument of WATERS company.Take orthodichlorobenzene as solvent, at 135 ℃ by sample dissolution, placement filtration; Sample size 200 μ L/ posts, flow velocity 1ml/min, adopts HT6, HT5, HT4, HT3 post group.
0 ℃ and 60 ℃ of dissipation factors: adopt the DMA Q800 type dynamic thermomechanical analysis apparatus of TA company to analyze, select two cantilever chuck.-150 ℃～100 ℃ temperature programmings, temperature rise rate is 3 ℃/min, and amplitude is 10 μ m, and test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Particle diameter: the Zetasizer-3000HSA laser particle analyser that adopts Malvern company to produce is tested.
Dynamic compression heat-dissipating: the dynamic compression heat-dissipating instrument that adopts Beijing all things on earth Yifang Technology Co., Ltd. to produce, model is YS-III, and voltage is 380V, and power is 1.5KW, use the external force that stroke is 1MPa to carry out persistence impact to sample, measure permanentset and temperature change value that sample produces.
Akron abrasion volume; Method in operative norm GB/T 25262-2010.
Tensile strength, tensile yield and 300% stress at definite elongation: operative norm GB/T528-2009.
Carbon black dispension degree: method in operative norm GB/T6030-1985.
Embodiment 1
Nano-silica surface functional modification: take 150g nano silicon stand-by in oven drying, then after mixing with 1500g toluene, ultrasonic wave is disperseed fully, add the VTES after 300g hydrolysis, stir post-heating to 82 ℃ and reflux 3 hours, then filter, washing, vacuum-drying.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.1,3-butadiene 1200g, Sodium dodecylbenzene sulfonate 120g, deionized water 1800g, sodium hydroxide 12g, Potassium Persulphate 2.4g are mixed to pre-emulsification and within 20 minutes, be prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 3.6g that gets surface-functionalized modification joins in the reactor that 60g Sodium dodecylbenzene sulfonate and 480g deionized water are housed, stirring is warming up to 60 ℃, then getting 313g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60 ℃, be incubated 40 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 2821g monomer pre-emulsion, and dropwised in 7.5 hours, obtain poly-1,3-butadiene/nanometer titanium dioxide functional silicon composite emulsion.
(2) preparation of oil emulsion
200g extending oil AP-15 being warming up to 75 ℃, being convenient to take, then will in AP-15, add 200g water and 5g disproportionated rosin acid soap, is by oily emulsor preparation preparation fat liquor at 74 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Getting nano silicon/poly-1,3-butadiene functional latex butt 100g, to join butt be in 900g, the mooney viscosity SBR1712E basis latex that is 114, is fully uniformly mixed; Above-mentioned fat liquor is joined in the SBR1712E basis latex of nano silicon/poly-1,3-butadiene functional latex blending and modifying; By 510g carbon black N326(nitrogen adsorption specific surface area, be 78m
2g
-1, DBP absorption value is 70cm
3g
-1) join in 50 ℃ of deionized waters of 2890g the super carbon black slurry that is dispersed into, join in the mixture of above-mentioned SBR1712E styrene-butadiene latex and fat liquor and mix, with the dry SBR1712E oil extended black masterbatch that finally obtains nano silicon/poly-1,3-butadiene functional latex modification of sulfuric acid cohesion.
(4) preparation of rubber combination
By the blend sulfurized oil-extended rubber composition of preparing of SBR1712E oil extended black masterbatch, 580g carbon black, 35g zinc oxide, 38g stearic acid, 13g anti-aging agent 6PPD and 8g sulphur of 1000g nano silicon/poly-1,3-butadiene functional latex modification.
Embodiment 2
The nano silicon method of preparing surface-functionalized modification according to disclosed method in the research > > of < < radiation research and radiation process journal > > 25 volumes the 5th phase < < surface modification of silica in 2007 and radiation initiation grafting GMA: take 10g nano silicon in 50 ℃ of oven drying 5h, dried nano silicon is added in the aqueous solution that is dissolved with 98g coupling agent MPS to ultrasonic dispersion 1h.After dispersion, mixed solution is stirred to 8h at 110 ℃.After overanxious, by the silicon-dioxide toluene wash after modification, after products therefrom vacuum filtration, through Soxhlet, extract again, be finally positioned in baking oven dry.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.Isoprene 1200g, sodium lauryl sulphate 72g, deionized water 1200g, ammoniacal liquor 6g, ammonium persulphate 9.6g are mixed to pre-emulsification and within 15 minutes, be prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 60g that gets surface-functionalized modification joins in the reactor that 3.6g sodium lauryl sulphate and 180g deionized water are housed, stirring is warming up to 65 ℃, then getting 124g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 75 ℃, be incubated 20 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 2363g monomer pre-emulsion, and dropwised in 6.5 hours, finally obtain polyisoprene/nanometer titanium dioxide functional silicon composite emulsion.
(2) preparation of oil emulsion
100g extending oil TDAE being warming up to 60 ℃, being convenient to take, then will in TDAE, add 200g water and 3.2g fatty acid soaps, is by oily emulsor preparation preparation fat liquor at 62 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Getting nano silicon/polyisoprene functional latex butt 230g, to join butt be in 770g, the mooney viscosity SBR1769E basis latex that is 140, is fully uniformly mixed; Above-mentioned fat liquor is joined in the SBR1769E basis latex of nano silicon/polyisoprene functional latex blending and modifying; By 770g carbon black N330(nitrogen adsorption specific surface area, be 79m
2g
-1, DBP absorption value is 100cm
3g
-1) join the super carbon black slurry that is dispersed in the deionized water of 45 ℃ of 3000g, join in the mixture of above-mentioned SBR1769E styrene-butadiene latex and fat liquor and mix, with the dry SBR1769E oil extended black masterbatch that finally obtains the modification of nano silicon/polyisoprene functional latex of mixture coagulated of sulfuric acid and hydrochloric acid.
(4) preparation of rubber combination
By the SBR1769E oil extended black masterbatch of 1000g nano silicon/polyisoprene functional latex modification, 18g anti-aging agent 3PPD, 23g accelerant disulfide tetra methylthiuram and the blend sulfurized rubber combination of preparing of 23g sulphur.
Embodiment 3
Nano-silica surface functional modification: take 240g nano silicon stand-by in oven drying, then after mixing with 4800g dimethylbenzene, ultrasonic wave is disperseed fully, add the VTMS after 312g hydrolysis, stir post-heating to 93 ℃ and reflux 4 hours, then filter, washing, vacuum-drying.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.1,3-pentadiene 1200g, Sodium dodecylbenzene sulfonate 40g, alkylphenol polyoxyethylene 200g, deionized water 1920g, sodium carbonate 9.6g, Sodium Persulfate 9.8g are mixed to pre-emulsification and within 30 minutes, be prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 54g that gets surface-functionalized modification joins in the reactor that 54g fatty acid soaps and 456g deionized water are housed, stirring is warming up to 68 ℃, then getting 676g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 68 ℃, be incubated 60 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 2703g monomer pre-emulsion, and dropwised in 6 hours, obtain poly-1,3-pentadiene/nanometer titanium dioxide functional silicon composite emulsion.
(2) preparation of oil emulsion
500g extending oil DAE being warming up to 65 ℃, being convenient to take, then will in DAE, add 1500g water and 7.5g fatty acid soaps, is by oily emulsor preparation preparation fat liquor at 63 ℃ at emulsifying temperature.
(4) fill the preparation of oil black carbon butylbenzene master batch
Getting nano silicon/poly-1,3-pentadiene functional latex butt 300g, to join butt be in the mooney viscosity of the 700g SBR1712E basis latex that is 80, is fully uniformly mixed; Above-mentioned fat liquor is joined in the SBR1712E basis latex of nano silicon/poly-1,3-pentadiene functional latex blending and modifying and mix; By 600g carbon black N375(nitrogen adsorption specific surface area, be 93m
2g
-1, DBP absorption value is 115cm
3g
-1) join the super carbon black slurry that is dispersed in the deionized water of 42 ℃ of 3150g, join in the mixture of above-mentioned SBR1712E styrene-butadiene latex and fat liquor and mix, with the dry SBR1712E oil extended black masterbatch that finally obtains nano silicon/poly-1,3-pentadiene functional latex modification of hydrochloric acid cohesion.
(4) rubber combination preparation
By the blend sulfurized rubber combination of preparing of SBR1712E oil extended black masterbatch, 26g zinc oxide, 36g stearic acid, 29g promotor dithio-bis-benzothiazole and 18g sulphur of 1000g nano silicon/poly-1,3-pentadiene functional latex modification.
Embodiment 4
Nano-silica surface functional modification: take 456g nano silicon stand-by in oven drying, then after mixing with 5040g methyl ethyl ketone, ultrasonic wave is disperseed fully, add the MPTS after 576g hydrolysis, stir post-heating to 80 ℃ and reflux 3.2 hours, then filter, washing, vacuum-drying.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.By 2,3-dimethyl-1,3 divinyl 1200g, polyoxyethylene nonylphenol ether 180g, deionized water 1340g, sodium bicarbonate 11.04g, 2, two (2-amidine azoles quinoline propane) the hydrochloride 6g of 2-azo mix pre-emulsification and within 35 minutes, are prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 43.2g that gets surface-functionalized modification joins in the reactor that 10g polyoxyethylene nonylphenol ether, 20g fatty acid soaps and 120g deionized water are housed, stirring is warming up to 78 ℃, then getting 560g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 78 ℃, be incubated 55 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 3176g monomer pre-emulsion, and dropwised in 5.5 hours, obtain poly-2,3-dimethyl-1,3 divinyl/nanometer titanium dioxide functional silicon composite emulsion.With dry poly-2,3-dimethyl-1, the 3 divinyl/nano silicon functional composite material of finally obtaining of sulfuric acid cohesion.
(2) preparation of oil emulsion
580g extending oil AP-8 being warming up to 80 ℃, being convenient to take, then will in AP-8, add the mixture of 975g water and 20g fatty acid soaps and 8g Sodium dodecylbenzene sulfonate, is by oily emulsor preparation preparation fat liquor at 78 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Get nano silicon/poly-2,3-dimethyl-1,3 divinyl functional latex butt 500g join in the SBR1778E latex that butt is 500g, are fully uniformly mixed; Above-mentioned fat liquor is joined to nano silicon/poly-2,3-dimethyl-1, in the SBR1778E basis latex of 3 divinyl functional latex blending and modifyings, mix; By 650g carbon black N220(nitrogen adsorption specific surface area, be 115m
2g
-1, DBP absorption value is 106cm
3g
-1) join the super carbon black slurry that is dispersed in the deionized water of 60 ℃ of 2958g, join in the mixture of above-mentioned SBR1778E styrene-butadiene latex and fat liquor and mix, with dry nano silicon/poly-2 that finally obtain of hydrochloric acid cohesion, 3-dimethyl-1, the SBR1778E oil extended black masterbatch of 3 divinyl functional latex modifications.
(4) preparation of rubber combination
By 1000g nano silicon/poly-2,3-dimethyl-1, the SBR1778E oil extended black masterbatch of 3 divinyl functional latex modifications, 17g zinc oxide, 17g stearic acid, 10g anti-aging agent 6PPD, 19g accelerant disulfide tetra methylthiuram and the blend sulfurized rubber combination of preparing of 22g sulphur.
Embodiment 5
Nano-silica surface functional modification: take 540g nano silicon stand-by in oven drying, then after mixing with 3120g toluene, ultrasonic wave is disperseed fully, add the gamma-amino propyl trimethoxy silicane after 468g hydrolysis, stir post-heating to 98 ℃ and reflux 3.7 hours, then filter, washing, vacuum-drying.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.By 1,3-hexadiene 1200g, fatty acid soaps 48g, deionized water 1320g, bicarbonate of ammonia 6.96g, 2,2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride 3.6g mixes pre-emulsification and within 45 minutes, is prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 33.6g that gets surface-functionalized modification joins in the reactor that 21g alkylphenol polyoxyethylene, 21g fatty alcohol-polyoxyethylene ether and 300g deionized water are housed, stirring is warming up to 80 ℃, then getting 258g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 80 ℃, be incubated 45 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 2321g monomer pre-emulsion, and dropwised in 8 hours, obtain poly-1,3-hexadiene/nanometer titanium dioxide functional silicon composite emulsion.With sulfuric acid cohesion, be dried and finally obtain poly-1,3-hexadiene/nano silicon functional composite material.
(2) preparation of oil emulsion
350g extending oil AP-10 being warming up to 72 ℃, being convenient to take, then will in AP-10, add the mixture of 875g water and 1.8g disproportionated rosin acid soap and 2.2g alkylphenol polyoxyethylene, is by oily emulsor preparation preparation fat liquor at 70 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Getting nano silicon/poly-1,3-hexadiene functional latex butt 10g joins in the SBR1756 latex that butt is 990g, is fully uniformly mixed; Above-mentioned fat liquor is joined in the SBR1756 basis latex of nano silicon/poly-1,3-hexadiene functional latex blending and modifying; By 580g carbon black N351(nitrogen adsorption specific surface area, be 64m
2g
-1, DBP absorption value is 120cm
3g
-1) join the super carbon black slurry that is dispersed in the deionized water of 60 ℃ of 2320g, join in the mixture of above-mentioned SBR1756 styrene-butadiene latex and fat liquor and mix, with the dry SBR1756 oil extended black masterbatch that finally obtains nano silicon/poly-1,3-hexadiene functional latex modification of hydrochloric acid cohesion.
(4) preparation of rubber combination
By SBR1756 oil extended black masterbatch and the blend sulfurized rubber combination of preparing of 12g sulphur of 1000g nano silicon/poly-1,3-hexadiene functional latex modification.
Comparative example 1
(1) functional latex preparation
The nano silicon 10.8g that gets modification in embodiment 1 is scattered in 3600g1; in 3-divinyl and 5400g cyclohexane solvent, ultrasonic dispersion is 20 minutes; be heated to 60 ℃; after add 7.2g n-Butyl Lithium as initiator; polyreaction is carried out 7.5 hours under nitrogen protection; obtain poly-1,3-butadiene/nano silicon composite solution.
(2) preparation of oil emulsion
200g extending oil AP-15 being warming up to 75 ℃, being convenient to take, then will in AP-15, add 200g water and 5g disproportionated rosin acid soap, is by oily emulsor preparation preparation fat liquor at 74 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Get nano silicon prepared by aforesaid method/poly-1,3-butadiene function solution butt 100g and join in the SBR1712E latex that butt is 900g, be fully uniformly mixed stand-by; The mixture that above-mentioned oil emulsion is joined to the SBR1712E basis latex of nano silicon/poly-1,3-butadiene function solution blending modification is fully uniformly mixed; By 510g carbon black N326(nitrogen adsorption specific surface area, be 78m
2g
-1, DBP absorption value is 70cm
3g
-1) join in 50 ℃ of deionized waters of 2890g the super carbon black slurry that is dispersed into, then join in the mixture of above-mentioned SBR1712E latex and fat liquor mixture even, with the dry SBR1712E oil extended black masterbatch that finally obtains nano silicon/poly-1,3-butadiene functional latex modification of sulfuric acid cohesion.
(4) preparation of rubber combination
By the blend sulfurized rubber combination of preparing of SBR1712E oil extended black masterbatch, 35g zinc oxide, 38g stearic acid, 13g anti-aging agent 6PPD and 8g sulphur of 1000g nano silicon/poly-1,3-butadiene functional latex modification.
Comparative example 2
The nano silicon method of preparing surface-functionalized modification according to disclosed method in the research > > of < < radiation research and radiation process journal > > 25 volumes the 5th phase < < surface modification of silica in 2007 and radiation initiation grafting GMA: take 10g nano silicon in 50 ℃ of oven drying 5h, dried nano silicon is added in the aqueous solution that is dissolved with 98g coupling agent MPS to ultrasonic dispersion 1h.After dispersion, mixed solution is stirred to 8h at 110 ℃.After overanxious, by the silicon-dioxide toluene wash after modification, after products therefrom vacuum filtration, through Soxhlet, extract again, be finally positioned in baking oven dry.
(1) functional latex preparation
The first step, the preparation of monomer pre-emulsion.Isoprene 1200g, sodium lauryl sulphate 72g, deionized water 1200g, ammoniacal liquor 6g, ammonium persulphate 9.6g are mixed to pre-emulsification and within 15 minutes, be prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 60g that gets surface-functionalized modification joins in the reactor that 3.6g sodium lauryl sulphate and 180g deionized water are housed, stirring is warming up to 65 ℃, then getting 124g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 75 ℃, be incubated 20 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In the reactor of seed emulsion is housed, drip remaining 2363g monomer pre-emulsion, and dropwised in 6.5 hours, finally obtain polyisoprene/nanometer titanium dioxide functional silicon composite emulsion.With the dry polyisoprene/nanometer titanium dioxide functional silicon composite emulsion that finally obtains of sulfuric acid cohesion.
(2) preparation of oil emulsion
100g extending oil TDAE being warming up to 60 ℃, being convenient to take, then will in TDAE, add 200g water and 3.2g fatty acid soaps, is by oily emulsor preparation preparation fat liquor at 62 ℃ at emulsifying temperature.
(3) fill the preparation of oil black carbon butylbenzene master batch
Getting nano silicon/polyisoprene functional latex butt 230g, to join butt be in 770g, the mooney viscosity SBR1769E basis latex that is 140, is fully uniformly mixed; Above-mentioned fat liquor is joined in the SBR1769E basis latex of nano silicon/polyisoprene functional latex blending and modifying, with the dry SBR1769E oil-extended rubber that finally obtains the modification of nano silicon/polyisoprene functional latex of mixture coagulated of sulfuric acid and hydrochloric acid; By 770g carbon black N330(nitrogen adsorption specific surface area, be 79m
2g
-1, DBP absorption value is 100cm
3g
-1) prepare the SBR1769E oil extended black masterbatch of nano silicon/polyisoprene functional latex modification with the SBR1769E oil-extended rubber blend of nano silicon/polyisoprene functional latex modification
(4) preparation of rubber combination
By SBR1769E oil extended black masterbatch, 18g anti-aging agent 3PPD, 23g accelerant disulfide tetra methylthiuram and the blend sulfurized rubber combination of preparing of 23g sulphur of the 1000g nano silicon/polyisoprene functional latex modification obtaining.
Each embodiment and the explanation of comparative example test data in table 1, nano silicon/poly-conjugated-diolefin composite emulsion performance of the present invention is more excellent.
The mechanical mechanics property of each embodiment and comparative example styrene-butadiene rubber(SBR) product and the explanation of dynamic properties test data in table 2, modified styrene butadiene rubber product performance of the present invention are obviously better than the product performance of comparative example.
Each embodiment and comparative example dynamic properties in table 3, carbon black dispension degree, the explanation of dynamic compression heat-dissipating test data, adopt the inventive method prepared fill the product performance that oil black carbon butylbenzene master batch performance is obviously better than comparative example.
The data declaration such as each embodiment and comparative example dynamic properties, abrasion volume in table 4, the performance of the rubber combination that employing the present invention is prepared is obviously better than the product performance of comparative example.
Table 1 functional latex performance
| Function composite emulsion performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Particle diameter, nm | 58 | 62 | 55 | 68 | 72 | - |
| Number-average molecular weight Mn*10 -4 | 10.2 | 11.2 | 12.5 | 11.6 | 13.4 | 15 |
| Molecular weight and distribution Mw/Mn thereof | 2.81 | 2.65 | 2.23 | 2.58 | 2.69 | 1.78 |
Table 2 modified rubber product performance
| Modified rubber product performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Tensile strength, MPa(145 ℃, 35min) | 24.2 | 25.3 | 24.8 | 23.7 | 25.9 | 23.5 |
| Tensile yield, % | 462 | 525 | 455 | 441 | 482 | 400 |
| 300% stress at definite elongation, MPa(35min) | 14.5 | 13.5 | 15.5 | 12.1 | 13.8 | 18.1 |
| tanδ（0℃） | 0.332 | 0.315 | 0.347 | 0.304 | 0.341 | 0.258 |
Table 3 fills oil black carbon butylbenzene master batch performance
Table 4 building rubber compound physical performance
Claims (21)
1. fill oil black carbon butylbenzene master batch, by extending oil, the styrene butadiene rubber latex of carbon black slurry and the modification of silicon-dioxide/poly-conjugated-diolefin mixes cohesion and forms, butt quality in each component, extending oil: carbon black: the styrene-butadiene rubber(SBR) of silicon-dioxide/poly-conjugated-diolefin modification is 10～60:50～80:100, the styrene butadiene rubber latex that it is characterized in that the modification of nano silicon/poly-conjugated-diolefin is prepared by nano silicon/poly-conjugated-diolefin function composite emulsion and styrene butadiene rubber latex blend, the mass ratio of styrene butadiene rubber latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100:0.1～100, nano silicon/poly-conjugated-diolefin function composite emulsion be take emulsion butt quality as 100 parts, 0.1～5 part of the nano silicon that contains surface-functionalized modification, nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50～80nm, number-average molecular weight is 100000～140000, and molecular weight distribution is 2～3.
2. the oil black carbon butylbenzene master batch that fills according to claim 1, is characterized in that 20～40 parts of extending oils.
3. the oil black carbon butylbenzene master batch that fills according to claim 1, is characterized in that in styrene butadiene rubber latex, combined styrene content is 15～45%, and mooney viscosity is 80～140.
4. the oil black carbon butylbenzene master batch that fills according to claim 1, is characterized in that carbon black nitrogen adsorption specific surface area is 60～120m
2g
-1, DBP absorption value is 60～120cm
3g
-1.
5. the oil black carbon butylbenzene master batch that fills according to claim 1, is characterized in that extending oil is paraffinic base rubber filling oil, naphthenic rubber extending oil, aromatic base rubber filling oil.
6. the oil black carbon butylbenzene master batch that fills according to claim 5, is characterized in that the aromatic carbon content at least 5% of described extending oil, and paraffinic hydrocarbon content is not more than 70%.
7. the oil black carbon butylbenzene master batch that fills according to claim 6, it is characterized in that the aromatic carbon content at least 10% of described extending oil, and paraffinic hydrocarbon content is not more than 60%.
8. the oil black carbon butylbenzene master batch that fills according to claim 7, is characterized in that the paraffinic hydrocarbon content of described extending oil is not more than 50%.
9. the oil black carbon butylbenzene master batch that fills according to claim 5, is characterized in that the polycyclic aromatic hydrocarbon content of extending oil is less than 3, i.e. environment-protection filling oil.
10. the oil black carbon butylbenzene master batch that fills according to claim 1, the nano silicon that it is characterized in that surface-functionalized modification refers to that silicon-dioxide adopts the even oil-filled agent of siloxanes to be processed and made the nano silicon with response type by surface functionalization, and coupling agent is 0.1～50% of surface-functionalized modified manometer silicon dioxide quality.
The 11. oil black carbon butylbenzene master batchs that fill according to claim 10, is characterized in that coupling agent is surface-functionalized modified manometer silicon dioxide quality 10～30%.
The 12. oil black carbon butylbenzene master batchs that fill according to claim 11, it is characterized in that siloxanes coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributyl ketoximyl silane, methyl tributanoximo silane, vinyl silane triisopropoxide, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, second diamino propyl trimethoxy silicane, vinyl trichloro silane, vinyl trimethoxysilane oligomer, in γ-methacryloxypropyl trimethoxy silane and three (trimethylsiloxy group) methacryloxypropyl silane one or more.
The 13. oil black carbon butylbenzene master batchs that fill according to claim 1, is characterized in that conjugated diene is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 divinyl, 2,3-diethyl-1,3 divinyl, 2-methyl-3-ethyl-1,3 divinyl, the chloro-1,3-pentadiene of 2-, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, one or more in 1,3-hexadiene, more preferably 1,3-butadiene and/or isoprene.
14. 1 kinds contain the composition that fills oil black carbon butylbenzene master batch claimed in claim 1, it is characterized in that in each composition weight, contain 100 parts and fill oil black carbon butylbenzene master batch and 0.5～3 part of vulcanizing agent.
15. 1 kinds of compositions that fill oil black carbon butylbenzene master batch that contain described in claim 13, is characterized in that rubber combination contains one or more in zinc oxide, stearic acid, anti-aging agent, promotor auxiliary agent; 1～5 part, zinc oxide, 1～4 part of stearic acid, 0.5～3 part of promotor, 0.5～2 part, anti-aging agent.
16. 1 kinds of preparation methods that fill oil black carbon butylbenzene master batch claimed in claim 1, concrete preparation process is:
(1) preparation of nano silicon/poly-conjugated-diolefin function composite emulsion: for nano silicon/poly-conjugated-diolefin function composite emulsion, take conjugated diene monomer quality as 100 parts by seeding emulsion polyerization legal system:
A monomer pre-emulsion preparation: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator are mixed to pre-emulsification and be prepared into pre-emulsion for 15～45 minutes; Wherein the ratio of monomer and water is 1:1～1:2, and emulsifier is 3～20 parts, and buffer reagent consumption is 0.3～1 part, and initiator amount is 0.1～0.8 part;
B be take surface-functionalized modified manometer silicon dioxide and is prepared nano silicon/poly-conjugated-diolefin function composite emulsion as core: 0.1～5 part of nano silicon getting surface-functionalized modification joins in the reactor that 0.1～5 part of emulsifying agent and 10～50 parts of deionized waters are housed, stirring is warming up to 60～80 ℃, then getting 1/20～1/5 monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60～80 ℃, be incubated 0.5～1 hour, allow conjugated diene monomer by the coated also polymerization of surface-functionalized modified manometer silicon dioxide, and the seed using this as composite emulsion, in the reactor of seed emulsion is housed, drip remaining monomer pre-emulsion, and dropwised in 5～8 hours, obtain poly-conjugated-diolefin/nanometer titanium dioxide functional silicon composite emulsion,
(2) preparation of fat liquor: extending oil is warming up to 60 ~ 80 ℃, be convenient to take, then will in extending oil, add water and emulsifying agent, the rubber filling oil of 100 weight parts of take is basis, 1.0～4.5 parts of emulsifying agent add-ons are by oily emulsor, to prepare fat liquor at 60 ~ 80 ℃ at emulsifying temperature;
(3) fill the preparation of oil black carbon butylbenzene master batch: nano silicon/poly-conjugated-diolefin function composite emulsion is joined in styrene butadiene rubber latex, be fully uniformly mixed; Add above-mentioned fat liquor, mix, then add carbon black slurry to mix, then cohesion makes and fills oil black carbon butylbenzene master batch.
17. preparation methods according to claim 16, is characterized in that in the preparation of fat liquor, and water and oily mass ratio are 1:1～3.
18. preparation methods according to claim 16, it is characterized in that emulsifying agent be in anionic emulsifier and nonionic emulsifying agent one or more; Buffer reagent be in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor and bicarbonate of ammonia one or more; Initiator is water-soluble thermal initiator.
19. preparation methods according to claim 17, it is characterized in that anionic emulsifier be in metal carboxylate, Sulfates, Sulfonates emulsifying agent one or more; Nonionic emulsifying agent be in ester class, ethers emulsifying agent one or more; Buffer reagent is sodium carbonate and/or sodium bicarbonate; Water-soluble thermal initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate, 2, two (the 2-amidine azoles quinoline propane) hydrochlorides, 2 of 2-azo, 2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride.
20. preparation methods according to claim 18, it is characterized in that anionic emulsifier sodium lauryl sulphate, nonionic emulsifying agent is polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether.
21. preparation methods according to claim 16, the mass concentration that it is characterized in that carbon black slurry is 15～20%.
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| CN115716953A (en) * | 2021-08-24 | 2023-02-28 | 中国石油化工股份有限公司 | Composition for rubber processing aid, application of rubber processing aid in rubber processing and rubber processing method |
| CN115716953B (en) * | 2021-08-24 | 2024-03-26 | 中国石油化工股份有限公司 | Composition for rubber processing aid, application of rubber processing aid in rubber processing and rubber processing method |
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