CN103524970B - Carbon black masterbatch for tire and preparation method thereof - Google Patents
Carbon black masterbatch for tire and preparation method thereof Download PDFInfo
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- CN103524970B CN103524970B CN201210230030.2A CN201210230030A CN103524970B CN 103524970 B CN103524970 B CN 103524970B CN 201210230030 A CN201210230030 A CN 201210230030A CN 103524970 B CN103524970 B CN 103524970B
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- 239000006229 carbon black Substances 0.000 title claims abstract description 88
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 116
- 239000000839 emulsion Substances 0.000 claims abstract description 103
- 229920000126 latex Polymers 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000004816 latex Substances 0.000 claims abstract description 64
- 238000012986 modification Methods 0.000 claims abstract description 52
- 230000004048 modification Effects 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 20
- 150000001993 dienes Chemical class 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000006557 surface reaction Methods 0.000 claims abstract description 4
- 229940105289 carbon black Drugs 0.000 claims description 81
- 235000019241 carbon black Nutrition 0.000 claims description 81
- 239000000178 monomer Substances 0.000 claims description 39
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- -1 diamino propyl Chemical group 0.000 claims description 24
- 229960001866 silicon dioxide Drugs 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-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
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 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 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 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
- 239000011159 matrix material Substances 0.000 claims description 5
- 229920006173 natural rubber latex Polymers 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 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
- 238000011049 filling Methods 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 150000002148 esters 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 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
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000003643 water by type Substances 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
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 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
- 238000012545 processing Methods 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims 1
- 229920003244 diene elastomer Polymers 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229920001195 polyisoprene Polymers 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 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
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NAOQESSEZUUFIL-UHFFFAOYSA-N C1(=CC=CC=C1)C.[Si](=O)=O Chemical class C1(=CC=CC=C1)C.[Si](=O)=O NAOQESSEZUUFIL-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000286663 Ficus elastica Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- IOZVKVQMRQRJFK-UHFFFAOYSA-N propane;quinoline Chemical compound CCC.N1=CC=CC2=CC=CC=C21 IOZVKVQMRQRJFK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 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
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A carbon black masterbatch for tires and a preparation method thereof. The carbon black masterbatch is prepared by dispersing 10-50 parts of carbon black by mass of solid into deionized water to form carbon black slurry, uniformly mixing the carbon black slurry with 100 parts of nano silicon dioxide/poly conjugated diene graft modified rubber latex by mass of dry basis, and condensing the mixture; the nano silicon dioxide/poly conjugated diene graft modified rubber latex is prepared by graft polymerization of nano silicon dioxide/poly conjugated diene functional composite emulsion and diene rubber latex in the presence of an initiator, wherein the mass ratio of the diene rubber latex dry basis to the nano silicon dioxide/poly conjugated diene composite emulsion dry basis is 100: 0.1-100 parts of nano silicon dioxide/poly conjugated diene functional composite emulsion, by taking 100 parts of dry emulsion base mass, containing 0.1-5 parts of nano silicon dioxide with surface functionalization modification; the nano silicon dioxide/poly conjugated diene composite emulsion has the particle size of 50-80 nm, the number average molecular weight of 100000-140000 and the molecular weight distribution of 2-3.
Description
Technical field
The present invention relates to a kind of master batch and its preparation method that fill carbon black, say more specifically relate to a kind of for tire tread and can improve tyre performance fill carbonblack master batch and its preparation method.
Background technology
Along with automobile at a high speed, the development in safe, energy-conservation, comfortableization direction, the requirement of tire high performance is also improved year by year, this just requires that tire tread has good wet-sliding resistant performance, excellent wear resistance and low rolling resistance.
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 90's of last century, white carbon black is widely used in tire tread formula as reinforced filling, and " devil's triangle " performance that above-mentioned tire tread is required obtains significantly balance.
The present invention provides a kind of function and service emulsion, on the poly-conjugated-diolefin molecular chain introduce nano silicon, and is prepared the master batch material of carbon black high dispersing by functional latex/latex/carbon black wet mixing process, it is possible to improve tire over-all properties.
Summary of the invention
It is an object of the present invention to provide a kind of improve tire over-all properties fill carbonblack master batch material.
The carbonblack master batch that fills for tire disclosed in this invention count taking solid masses 10��50 parts of carbon black dispersion are become carbon black slurry in deionized water and mixes with the rubber latex taking dry matrix gauge as 100 parts of nano silicons/poly-conjugated-diolefin graft modification, and cohesion is obtained;The rubber latex of nano silicon/poly-conjugated-diolefin graft modification by nano silicon/poly-conjugated-diolefin function and service emulsion and polydiene latex under initiator existent condition graft polymerization and obtain, the mass ratio of the dry base of polydiene latex and nano silicon/dry base of poly-conjugated-diolefin composite emulsion is 100:0.1��100, the dry matrix amount of nano silicon/poly-conjugated-diolefin function and service emulsion is 100 parts of meters, the nano silicon containing surface-functionalized modification 0.1��5 part; Nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50��80nm, and number-average molecular weight is 100000��140000, and molecular weight distribution is 2��3.
Polydiene latex of the present invention can be content of polybutadiene rubber latex, natural rubber latex, styrene butadiene rubber latex.
The preparation method of carbon black slurry of the present invention is the super dispersion method adopting and not adding any tensio-active agent, it is separated into submicron order when not destroying carbon blacksurface activity, has been described the carbon black oversubscription not adding any tensio-active agent is loose in " off-colour industry " the 6th phase in 2006 " new development of carbon black dispersion technology ". To be that the oversubscription by not adding any tensio-active agent is loose obtain carbon black slurry of the present invention, such as, will can be prepared in carbon black fine dispersion to water by mechanical means. The concentration of carbon black slurry has good mobility to keep, and can fully mix with latex and be as the criterion, and general mass concentration is 15%��20%, in order to improve the wetting speed of carbon black, shortens the jitter time of carbon black, and the temperature of deionized water is preferably 40��60 DEG C.
Carbon black of the present invention can be general carbon black, and the present invention preferably uses N2 adsorption specific surface area to be 60��120m2��g-1, DBP absorption value is 60��120cm3��100g-1Carbon black.
In order to improve the dispersion of silicon-dioxide in emulsion thus improve the performance of functional latex further, the present invention selects coupling agent treatment silicon-dioxide, make silicon-dioxide have reactivity, re-use emulsion polymerization in situ and obtain the nano silicon/poly-conjugated-diolefin composite emulsion having good stability. Nano silicon disclosed in this invention/poly-conjugated-diolefin composite emulsion, counts taking the dry base of emulsion as 100 parts, the nano silicon containing surface-functionalized modification 0.1��5 part; Nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50��80nm, and number-average molecular weight is 100000��140000, and molecular weight distribution is 2��3.
The nano silicon of surface-functionalized modification of the present invention refers to that silicon-dioxide adopts coupling agent to make the nano silicon with response type by surface functionalization process, coupling agent wherein is siloxanes coupling agent, it accounts for the 0.1��50% of surface-functionalized modified manometer silicon dioxide quality, it is preferable that 10��30%.
Nano silicon belonging to the present invention, as long as nano level, it is preferable that 20��60nm.
Siloxanes coupling agent of the present invention, 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 tributanoximo silane, methyl tributanoximo silane, vinyl silane triisopropoxide, gamma-amino propyl trimethoxy silicane, �� aminopropyltriethoxy silane, second diamino propyl trimethoxy silicane, vinyl trichloro silane, vinyl trimethoxysilane oligomer, ��-methacryloxypropyl trimethoxy silane (MPS), one or more in three (trimethylsiloxy group) methacryloxypropyl silane (MPTS),More preferably vinyltriethoxysilane, vinyltrimethoxy silane, one or more in three (trimethylsiloxy group) methacryloxypropyl silane.
Conjugated diene of the present invention is C4-C12 conjugated diene, it is preferable to 1,3-divinyl, 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-divinyl, one or more in 1,3-hexadiene, it is more preferable to 1,3-divinyl and/or isoprene.
The invention also discloses the preparation method filling carbonblack master batch, it be specially:
(1) nano silicon/poly-conjugated-diolefin function and service emulsion preparation
Prepare nano silicon/poly-conjugated-diolefin composite emulsion by seeding emulsion polyerization method, count as 100 parts taking conjugated diene monomer quality:
Prepared by monomer pre-emulsion: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator mixing pre-emulsification were prepared into pre-emulsion in 15��45 minutes; Wherein the ratio of monomer and water is 1:1��1:2, and emulsifying agent consumption is 3��20 parts, and buffer reagent consumption is 0.3��1 part, and initiator amount is 0.1��0.8 part;
Nano silicon/poly-conjugated-diolefin composite emulsion is prepared: the nano silicon 0.1��5 part 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 by core of surface-functionalized modified manometer silicon dioxide, stirring is warming up to 60��80 DEG C, then getting 1/20��1/5 monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 60��80 DEG C, it is incubated 0.5��1 hour, allow conjugated diene monomer by coated for surface-functionalized modified manometer silicon dioxide and be polymerized, and using this seed as composite emulsion, it is being equipped with in the reactor of seed emulsion to drip add remaining monomer pre-emulsion, and was dropwising in 5��8 hours, finally obtaining nano silicon/poly-conjugated-diolefin function and service emulsion,
(2) nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modified rubber latex
Nano silicon/poly-conjugated-diolefin function and service emulsion is joined in rubber latex, mix, 0.08��0.12 part of initiator is added under 65��85 DEG C and agitation condition, carry out graft polymerization reaction 5��8h, prepare nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modified diene class rubber latex.
(3) preparation of carbonblack master batch is filled
Carbon black dispersion forms carbon black slurry in deionized water and polydiene latex with nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modification is fully uniformly mixed, cohesion.
Emulsifying agent of the present invention is conventionally known to one of skill in the art, it is possible to 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 ether class, preferred polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride list cetylate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, more preferably alkylphenol polyoxyethylene.
Buffer reagent of the present invention can be sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor, bicarbonate of ammonia, it is preferable that 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-tetrahydroglyoxaline propane) hydrochloride, 2 of 2-azo, 2-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, it is more preferable to Potassium Persulphate or Sodium Persulfate.
Cohesion of the present invention, adopts acid cure to gather, and this technology is general for those skilled in the art, and described acid is generally mineral acid, such as hydrochloric acid, one or more in sulfuric acid.
Surface-functionalized modified manometer silicon dioxide of the present invention is that the silicon-dioxide of 20��60nm adopts coupling agent make the nano silicon with response type by surface functionalization process, this technology is conventionally known to one of skill in the art, such as, discloses the method for nano-silica surface functional modification in " radiation research and radiation process journal " 25 volumes the 5th phase in 2007 " research of nano-silica surface modification and radiation initiation grafting GMA "; The present invention is not particularly limited to, the method that the present invention recommends is: take 0.1��50 part of nano silicon stand-by in oven drying, then after mixing with 5��500 parts of solvents, ultrasonic wave dispersion is fully, add the coupling agent after 0.1��50 part of hydrolysis, stir post-heating to 80��120 DEG C backflow 2��4 hours, filtration washing. Solvent is toluene, dimethylbenzene or methyl ethyl ketone, and its add-on is 5��500 parts, it is preferable that 100��300 parts.
The effect that the present invention is useful:
The carbonblack master batch that fills of the present invention is obtained through cohesion altogether by the rubber latex of carbon black slurry and nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modification, owing to nano silicon/poly-conjugated-diolefin function and service emulsion has satisfactory stability, size tunable, it is distributed in 50��80nm, with rubber latex dispersion, good mixing effect, the method being used further to graft modification rubber by preparing functional latex effectively solves nano silicon scattering problem of (particularly nonpolar rubber) in rubber matrix. The rubber latex of nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modification and carbon black slurry good mixing effect, this kind of mode add carbon black and various filler directly blended in the course of processing compared with, disperse more even, be more conducive to improving the over-all properties of tire; Function and service emulsion molecular weight and molecualr weight distribution be suitable for, illustrates prepare fill carbonblack master batch mixing time heat-dissipating low, mixing behavior good. The prepared carbonblack master batch 60 DEG C of dissipation factors (tan ��) that fills reduces, and illustrates when low for the preparation of rolling resistance during tire. 0 DEG C of tan �� is higher, illustrates and is used for tire to prepare wet-sliding resistant performance good.
In addition, the present invention is raw materials used to be easy to get, preparation process simplicity is easy to control, functional latex preparation process does not use organic solvent, environmental protection, pollution-free, cost is low, adopts seeding emulsion polyerization method that nano silicon can be made with chemical bonding, it is possible to good is scattered in poly-conjugated-diolefin.
Embodiment
The effect of the present invention is described further below by embodiment and comparative example.
(1) raw material sources
Carbon black: Wuxi Shuan Cheng carbon black company limited 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;
Content of polybutadiene rubber latex, solid content 50%, Lanzhou Petrochemical Company is produced;
Styrene butadiene rubber latex: SBR1500, SBR1502, combined styrene content 23.5%, solid content 23%, Lanzhou Petrochemical Company is produced;
(2) analysis test method
Molecular weight and distribution thereof: adopting high temperature gel chromatogram analysis method (GPC), GPC tests the GPCV2000 type high temperature gel chromatographic instrument that instrument used is WATERS company. Take orthodichlorobenzene as solvent, at 135 DEG C by sample dissolution, placement and filter; Sample size 200 �� L/ post, flow velocity 1ml/min, adopts HT6, HT5, HT4, HT3 post group.
0 DEG C and 60 DEG C of dissipation factors: adopt the DMAQ800 type dynamic thermomechanical analysis apparatus of TA company to analyze, select two cantilever chuck.-150 DEG C��100 DEG C temperature programmings, temperature rise rate is 3 DEG C/min, and amplitude is 10 ��m, and test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Particle diameter: the Zetasizer-3000HSA laser particle analyser adopting Malvern company to produce is tested.
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 dispersion is fully, add the VTES after 300g hydrolysis, stir post-heating to 82 DEG C backflow 3 hours, then filtration, washing, vacuum-drying.
Prepared by functional latex
The first step, prepared by monomer pre-emulsion. 1,3-divinyl 1200g, Sodium dodecylbenzene sulfonate 120g, deionized water 1800g, sodium hydroxide 12g, Potassium Persulphate 2.4g are mixed pre-emulsification and within 20 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 3.6g getting surface-functionalized modification joins in the reactor that 60g Sodium dodecylbenzene sulfonate and 480g deionized water are housed, stirring is warming up to 60 DEG C, then getting 313g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 60 DEG C, it is incubated 40 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 2821g monomer pre-emulsion, and was dropwising in 7.5 hours, obtaining poly-1,3-divinyl/nano silicon function and service emulsion.
Prepared by graft modification rubber latex
Get nano silicon/poly-1,3-divinyl functional latex dry base 100g joins in the SBR1500 latex that dry base is 980g, fully it is uniformly mixed, under 75 DEG C and agitation condition, add 92g Potassium Persulphate carry out graft polymerization reaction 6h, obtain the latex of the SBR1500 of nano silicon/poly-1,3-divinyl graft modification.
Fill carbonblack master batch preparation
By 225g carbon black N326, (N2 adsorption specific surface area is 78m2��g-1, DBP absorption value is 70cm3��100g-1) join in 1275g50 DEG C of deionized water and super to be dispersed into carbon black slurry, then with nano silicon/poly-1, the SBR1500 of 3-divinyl graft modification is fully uniformly mixed, with the dry SBR1500 carbonblack master batch finally obtaining nano silicon/poly-1,3-divinyl functional latex modification of sulfuric acid cohesion.
Embodiment 2
The nano silicon method of surface-functionalized modification is prepared: take 10g nano silicon in 50 DEG C of oven drying 5h according to method disclosed in " radiation research and radiation process journal " 25 volumes the 5th phase in 2007 " research of nano-silica surface modification and radiation initiation grafting GMA ", dried nano silicon is added in the aqueous solution being dissolved with 98g coupling agent MPS, ultrasonic disperse 1h.After dispersion, mixed solution is stirred 8h at 110 DEG C. After overanxious, by modified silicon-dioxide toluene wash, again through surname extraction after products therefrom vacuum filtration, finally it is positioned in baking oven dry.
Prepared by functional latex
The first step, prepared by monomer pre-emulsion. Isoprene 1200g, sodium lauryl sulphate 72g, deionized water 1200g, ammoniacal liquor 6g, ammonium persulphate 9.6g are mixed pre-emulsification and within 15 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 60g getting 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 DEG C, then getting 124g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 75 DEG C, it is incubated 20 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 2363g monomer pre-emulsion, and was dropwising in 6.5 hours, finally obtaining polyisoprene/nano silicon function and service emulsion.
Prepared by graft modification rubber latex
Get nano silicon/polyisoprene functional latex dry base 230g and join the natural rubber latex Ruzhong that dry base is 1000g, fully it is uniformly mixed, under 65 DEG C and agitation condition, add 102g Potassium Persulphate carry out graft polymerization reaction 6.5h, obtain the natural rubber latex of nano silicon/polyisoprene graft modification.
Fill carbonblack master batch preparation
By 150g carbon black N330, (N2 adsorption specific surface area is 79m2��g-1, DBP absorption value is 100cm3��100g-1) join and super in the deionized water of 600g45 DEG C be dispersed into carbon black slurry, then natural rubber latex with 3000g nano silicon/polyisoprene graft modification is fully uniformly mixed, with the dry natural rubber carbonblack master batch finally obtaining nano silicon/polyisoprene modified of sulfuric acid cohesion.
Embodiment 3
Nano-silica surface functional modification: take 240g nano silicon stand-by in oven drying, then after mixing with 4800g dimethylbenzene, ultrasonic wave dispersion is fully, add the VTMS after 312g hydrolysis, stir post-heating to 93 DEG C backflow 4 hours, then filtration, washing, vacuum-drying.
Prepared by functional latex
The first step, prepared by 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 pre-emulsification and within 30 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 54g getting surface-functionalized modification joins in the reactor that 54g fatty acid soaps and 456g deionized water are housed, stirring is warming up to 68 DEG C, then getting 676g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 68 DEG C, it is incubated 60 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 2703g monomer pre-emulsion, and was dropwising in 6 hours, obtaining poly-1,3-pentadiene/nano silicon function and service emulsion.
Prepared by graft modification rubber latex
Get nano silicon/poly-1,3-pentadiene functional latex dry base 300g joins in the SBR1502 latex that dry base is 660g, fully it is uniformly mixed, under 72 DEG C and agitation condition, add 86g Potassium Persulphate carry out graft polymerization reaction 5.8h, obtain the SBR1502 latex of nano silicon/poly-1,3-pentadiene functional latex graft modification.
Fill carbonblack master batch preparation
Get nano silicon/poly-1,3-pentadiene functional latex dry base 300g to join in the SBR1502 latex that dry base is 660g, fully it is uniformly mixed stand-by; By 280g carbon black N375, (N2 adsorption specific surface area is 93m2��g-1, DBP absorption value is 115cm3��100g-1) join and super in the deionized water of 1470g42 DEG C be dispersed into carbon black slurry, then with 2500g poly-1, the mixture of 3-pentadiene/nano silicon function and service emulsion and SBR1502 latex is fully uniformly mixed, with the dry SBR1502 carbonblack master batch finally obtaining poly-1,3-pentadiene/nano-silicon dioxide modified of sulfuric acid cohesion.
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 dispersion is fully, add the MPTS after 576g hydrolysis, stir post-heating to 80 DEG C backflow 3.2 hours, then filtration, washing, vacuum-drying.
Prepared by functional latex
The first step, prepared by monomer pre-emulsion. 2,3-dimethyl-1,3-divinyl 1200g, polyoxyethylene nonylphenol ether 180g, deionized water 1340g, two (2-amidine azoles quinoline propane) the hydrochloride 6g of sodium bicarbonate 11.04g, 2,2-azo are mixed pre-emulsification and within 35 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 43.2g getting 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 DEG C, then getting 560g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 78 DEG C, it is incubated 55 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 3176g monomer pre-emulsion, and was dropwising in 5.5 hours, obtaining poly-2,3-dimethyl-1,3-divinyl/nano silicon function and service emulsion. Condense drying with sulfuric acid and finally obtain poly-2,3-dimethyl-1,3-divinyl/nano silicon functional composite material.
Prepared by graft modification rubber latex
Get nano silicon/poly-2,3-dimethyl-1,3-divinyl functional latex dry base 520g joins in the content of polybutadiene rubber latex that dry base is 600g, fully it is uniformly mixed, under 78 DEG C and agitation condition, add 82g Potassium Persulphate carry out graft polymerization reaction 7.2h, obtain the content of polybutadiene rubber latex of nano silicon/poly-2,3-dimethyl-1,3-divinyl functional latex graft modification.
Fill carbonblack master batch preparation
By 78g carbon black N220, (N2 adsorption specific surface area is 115m2��g-1, DBP absorption value is 106cm3��100g-1) join and super in the deionized water of 355g60 DEG C be dispersed into carbon black slurry, then with 3100g nano silicon/poly-2,3-dimethyl-1, it is even that the content of polybutadiene rubber latex of 3-divinyl functional latex graft modification is fully uniformly mixed thing, condense drying with sulfuric acid and finally obtain poly-2, the polybutadiene rubber carbonblack master batch of 3-dimethyl-1,3-divinyl/nano-silicon dioxide modified.
Embodiment 5
Nano-silica surface functional modification: take 540g nano silicon stand-by in oven drying, then after mixing with 3120g toluene, ultrasonic wave dispersion is fully, add the gamma-amino propyl trimethoxy silicane after 468g hydrolysis, stir post-heating to 98 DEG C backflow 3.7 hours, then filtration, washing, vacuum-drying.
Prepared by functional latex
The first step, prepared by monomer pre-emulsion. 1,3-hexadiene 1200g, fatty acid soaps 48g, deionized water 1320g, bicarbonate of ammonia 6.96g, 2,2-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride 3.6g are mixed pre-emulsification and within 45 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 33.6g getting 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 DEG C, then getting 258g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 80 DEG C, it is incubated 45 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 2321g monomer pre-emulsion, and was dropwising in 8 hours, obtaining poly-1,3-hexadiene/nano silicon function and service emulsion. Condense drying with sulfuric acid and finally obtain poly-1,3-hexadiene/nano silicon functional composite material.
Prepared by graft modification rubber latex
Get nano silicon/poly-1,3-hexadiene functional latex dry base 620g joins in the SBR1502 latex that dry base is 620g, fully it is uniformly mixed, under 68 DEG C and agitation condition, add 95g ammonium persulphate carry out graft polymerization reaction 7.8h, obtain the SBR1502 latex of nano silicon/poly-1,3-hexadiene functional latex graft modification.
Fill carbonblack master batch preparation
By 140g carbon black N351, (N2 adsorption specific surface area is 64m2��g-1, DBP absorption value is 120cm3��100g-1) join and super in the deionized water of 560g60 DEG C be dispersed into carbon black slurry, then with 3100g nano silicon/poly-1, the SBR1500 latex of 3-hexadiene functional latex graft modification is fully uniformly mixed, with the dry SBR1500 carbonblack master batch finally obtaining poly-1,3-hexadiene/nano-silicon dioxide modified of sulfuric acid cohesion.
Comparative example 1
Nano-silica surface functional modification: take 240g nano silicon stand-by in oven drying, then after mixing with 4800g dimethylbenzene, ultrasonic wave dispersion is fully, add the VTMS after 312g hydrolysis, stir post-heating to 93 DEG C backflow 4 hours, then filtration, washing, vacuum-drying.
Prepared by functional latex
The first step, prepared by 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 pre-emulsification and within 30 minutes, be prepared into pre-emulsion.
2nd step is that core prepares functional latex taking modified manometer silicon dioxide. The nano silicon 54g getting surface-functionalized modification joins in the reactor that 54g fatty acid soaps and 456g deionized water are housed, stirring is warming up to 68 DEG C, then getting 676g monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 68 DEG C, it is incubated 60 minutes, allow monomer by coated for nano silicon and be polymerized, and using this seed as composite emulsion. It is being equipped with in the reactor of seed emulsion to drip add remaining 2703g monomer pre-emulsion, and was dropwising in 6 hours, obtaining poly-1,3-pentadiene/nano silicon function and service emulsion.
Graft modification rubber is standby
Get nano silicon/poly-1,3-pentadiene functional latex dry base 300g joins in the SBR1502 latex that dry base is 660g, fully it is uniformly mixed, under 72 DEG C and agitation condition, add 86g Potassium Persulphate carry out graft polymerization reaction 5.8h, obtain the SBR1502 latex of nano silicon/poly-1,3-pentadiene functional latex graft modification, add calcium chloride and sulfuric acid carries out flocculate and break emulsion, coprecipitated plastic emitting, drying obtains the pentylene modified SBR1502 of nano silicon/poly-1,3-.
Fill black rubber preparation
By 150g carbon black N330, (N2 adsorption specific surface area is 79m2��g-1, DBP absorption value is 100cm3��100g-1) the blended SBR1502 carbon black materials preparing nano silicon/polyisoprene modified of the SBR1502 pentylene modified with nano silicon/poly-1,3-.
In table 1, each embodiment and comparative example test data illustrate, the product performance of the nano silicon in the present invention/poly-conjugated-diolefin function and service emulsion are more excellent.
In table 2, each embodiment and comparative example dynamic properties test data and carbon black dispension degree illustrate, the present invention's adopt carbon black slurry and functional latex to condense altogether product performance that prepared product performance are obviously better than comparative example.
Table 1
Table 2
| Carbonblack master batch performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| tan��(60��) | 0.179 | 0.184 | 0.182 | 0.196 | 0.177 | 0.274 |
| tan��(0��) | 0.345 | 0.342 | 0.381 | 0.355 | 0.372 | 0.301 |
| Carbon black dispension degree (%) | 98.4 | 97.6 | 97.2 | 98.1 | 98.2 | 87.5 |
Claims (17)
1. one kind is filled carbonblack master batch for tire, it is characterized in that filling carbonblack master batch is count taking solid masses 10��50 parts of carbon black dispersion are become carbon black slurry in deionized water and mix with the rubber latex taking dry matrix gauge as 100 parts of nano silicons/poly-conjugated-diolefin graft modification, and cohesion is obtained; Nano silicon/poly-conjugated-diolefin graft modification rubber latex by nano silicon/poly-conjugated-diolefin function and service emulsion and polydiene latex under initiator existent condition graft polymerization and obtain, the mass ratio of the dry base of polydiene latex and nano silicon/dry base of poly-conjugated-diolefin composite emulsion is 100:0.1��100, the dry matrix amount of nano silicon/poly-conjugated-diolefin function and service emulsion is 100 parts of meters, the nano silicon containing surface-functionalized modification 0.1��5 part; Nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50��80nm, number-average molecular weight is 100000��140000, molecular weight distribution is 2��3, described nano silicon/poly-conjugated-diolefin function and service emulsion, taking the nano silicon of surface-functionalized modification as core, conjugated diene monomer is by coated for the nano silicon of described surface-functionalized modification and be polymerized, and using this seed as composite emulsion, is prepared by seeding emulsion polyerization method.
2. according to claim 1 fill carbonblack master batch, it is characterised in that polydiene latex is selected from content of polybutadiene rubber latex, natural rubber latex, styrene butadiene rubber latex.
3. according to claim 1 fill carbonblack master batch, it is characterised in that the mass concentration of carbon black slurry is 15%��20%, and the temperature of deionized water is 40��60 DEG C.
4. according to claim 1 fill carbonblack master batch, it is characterised in that the N2 adsorption specific surface area of carbon black is 60��120m2��g-1, DBP absorption value is 60��120cm3��100g-1��
5. according to claim 1 fill carbonblack master batch, it is characterized in that the nano silicon of surface-functionalized modification refers to that silicon-dioxide adopts silane coupling agent to make the nano silicon with response type by surface functionalization process, silane coupling agent quality is the 0.1��50% of surface-functionalized modified manometer silicon dioxide quality.
6. according to claim 5 fill carbonblack master batch, it is characterised in that in the nano silicon of surface-functionalized modification, the mass percent of silane coupling agent is 10��30%.
7. according to claim 5 fill carbonblack master batch, it is characterised in that silane coupling agent is one or more in vinyl silane, methyl acrylic ester silane.
8. according to claim 5 fill carbonblack master batch, it is characterized in that silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributanoximo silane, methyl tributanoximo silane, vinyl silane triisopropoxide, gamma-amino propyl trimethoxy silicane, �� aminopropyltriethoxy silane, second diamino propyl trimethoxy silicane, vinyl trichloro silane, vinyl trimethoxysilane oligomer, in ��-methacryloxypropyl trimethoxy silane and three (trimethylsiloxy group) methacryloxypropyl silane one or more.
9. according to claim 1 fill carbonblack master batch, it is characterised in that conjugated diene is C4��C12Conjugated diene.
10. according to claim 9 fill carbonblack master batch, it is characterised in that conjugated diene is 1,3-divinyl, 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, in 2-phenyl-1,3-divinyl and 1,3-hexadiene one or more.
11. according to claim 1 fill carbonblack master batch, it is characterized in that the processing condition of nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modified rubber latex are that nano silicon/poly-conjugated-diolefin composite emulsion joins in polydiene latex, mix, under 65��85 DEG C and agitation condition, add 0.08��0.12 part of initiator, carry out graft polymerization reaction 5��8 hours.
12. 1 kinds of preparation methods filling carbonblack master batch according to claim 1, it is characterised in that preparation process is:
(1) nano silicon/poly-conjugated-diolefin function and service emulsion preparation
Prepare nano silicon/poly-conjugated-diolefin composite emulsion by seeding emulsion polyerization method, count as 100 parts taking conjugated diene monomer quality:
Prepared by monomer pre-emulsion: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator mixing pre-emulsification were prepared into pre-emulsion in 15��45 minutes; Wherein the ratio of monomer and water is 1:1��1:2, and emulsifying agent consumption is 3��20 parts, and buffer reagent consumption is 0.3��1 part, and initiator amount is 0.1��0.8 part;
Nano silicon/poly-conjugated-diolefin composite emulsion is prepared: the nano silicon 0.1��5 part 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 by core of surface-functionalized modified manometer silicon dioxide, stirring is warming up to 60��80 DEG C, then getting 1/20��1/5 monomer pre-emulsion joins in reactor, control temperature of reaction kettle is 60��80 DEG C, it is incubated 0.5��1 hour, allow conjugated diene monomer by coated for surface-functionalized modified manometer silicon dioxide and be polymerized, and using this seed as composite emulsion, it is being equipped with in the reactor of seed emulsion to drip add remaining monomer pre-emulsion, and was dropwising in 5��8 hours, finally obtaining nano silicon/poly-conjugated-diolefin function and service emulsion,
(2) nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modified rubber latex
Nano silicon/poly-conjugated-diolefin composite emulsion is joined in polydiene latex, mixes, under 65��85 DEG C and agitation condition, add 0.08��0.12 part of initiator, carry out graft polymerization reaction 5��8h;
(3) preparation of carbonblack master batch is filled
Carbon black dispersion forms carbon black slurry in deionized water and rubber latex with nano silicon/poly-conjugated-diolefin function and service emulsion graft polymerization modification is fully uniformly mixed, cohesion.
13. preparation methods according to claim 12, it is characterised in that emulsifying agent be in anionic emulsifier and/or 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.
14. preparation methods according to claim 13, it is characterised in that anionic emulsifier be in metal carboxylate, Sulfates, Sulfonates emulsifying agent one or more; Nonionic emulsifying agent be in ester class, ether class 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, 2,2-azo two (2-tetrahydroglyoxaline propane) hydrochloride, 2,2-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride.
15. preparation methods according to claim 14, it is characterized in that anionic emulsifier is sodium lauryl sulphate, nonionic emulsifying agent is polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride list cetylate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether.
16. preparation methods according to claim 15, it is characterised in that alkylphenol polyoxyethylene is polyoxyethylene nonylphenol ether.
17. preparation methods according to claim 12, it is characterised in that condensing for acid cure gathers, acid is hydrochloric acid and/or sulfuric acid.
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| CN201210230030.2A CN103524970B (en) | 2012-07-04 | 2012-07-04 | Carbon black masterbatch for tire and preparation method thereof |
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| CN201210230030.2A CN103524970B (en) | 2012-07-04 | 2012-07-04 | Carbon black masterbatch for tire and preparation method thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210230030.2A Active CN103524970B (en) | 2012-07-04 | 2012-07-04 | Carbon black masterbatch for tire and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211267A (en) * | 1996-12-16 | 1999-03-17 | 株式会社普利司通 | Rubber composition and pneumatic tires produced therefrom |
| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
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2012
- 2012-07-04 CN CN201210230030.2A patent/CN103524970B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211267A (en) * | 1996-12-16 | 1999-03-17 | 株式会社普利司通 | Rubber composition and pneumatic tires produced therefrom |
| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
Non-Patent Citations (2)
| Title |
|---|
| 有机化白炭黑与异戊二烯的共聚合研究;徐健;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20110115(第1期);摘要,第5~6页第1.3.2节,第16页第2.3.2节，第20页第2.5.2.1节，第23页第3.1.3节第1段,第35页第3.2.5节，第42页第2段，第51~52页第3.5.2节和第56页最后1段 * |
| 胶乳共混法天然橡胶/二氧化硅纳米复合材料的制备及性能;罗勇悦 等;《高分子材料科学与工程》;20100630;第26卷(第6期);全文 * |
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| CN103524970A (en) | 2014-01-22 |
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