CN102731874B - Modified rubber and preparation method thereof - Google Patents
Modified rubber and preparation method thereof Download PDFInfo
- Publication number
- CN102731874B CN102731874B CN201110086058.9A CN201110086058A CN102731874B CN 102731874 B CN102731874 B CN 102731874B CN 201110086058 A CN201110086058 A CN 201110086058A CN 102731874 B CN102731874 B CN 102731874B
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- emulsion
- conjugated
- nano silicon
- poly
- rubber
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000005060 rubber Substances 0.000 title claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 124
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920000126 latex Polymers 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 64
- -1 diene compound Chemical class 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 150000001993 dienes Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 229920001519 homopolymer Polymers 0.000 claims abstract description 6
- 239000004816 latex Substances 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 45
- 238000012986 modification Methods 0.000 claims description 42
- 230000004048 modification Effects 0.000 claims description 42
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 34
- 229960001866 silicon dioxide Drugs 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000872 buffer Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 238000004945 emulsification 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
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 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
- 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 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 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent 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
- 238000001914 filtration Methods 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 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 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000003643 water by type Substances 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
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-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
- 150000003851 azoles Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004567 concrete Substances 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
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 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
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- OBQLIGVXQZHXTE-UHFFFAOYSA-N C=CC.BrC1=CC=CC=C1 Chemical group C=CC.BrC1=CC=CC=C1 OBQLIGVXQZHXTE-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- 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
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- 238000010998 test method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
A modified rubber and a preparation method thereof. The modified rubber is prepared by mixing (1) rubber latex and (2) nano-silica/poly-conjugated diene composite emulsion, and then coagulating, demulsifying and coprecipitating, wherein the mass ratio of the rubber latex dry basis to the nano-silica/poly-conjugated diene composite emulsion dry basis is 100: 0.1-100; the nano silicon dioxide/poly-conjugated diene composite emulsion comprises 0.1-5 parts of surface functionalized modified nano silicon dioxide by taking 100 parts of emulsion dry basis, wherein the particle size of the nano silicon dioxide/poly-conjugated diene composite emulsion is 50-80 nm, the number average molecular weight is 100000-120000, and the molecular weight distribution is 2-3; the rubber latex is a homopolymer or a copolymer of a poly-conjugated diene compound prepared by emulsion polymerization.
Description
Technical field
The present invention relates to a kind of modified rubber and preparation method thereof, relate in particular the preparation method of a kind of nano silicon/poly-conjugated-diolefin composite emulsion and modified rubber thereof.
Background technology
In recent years, the preparation of organic polymer/inorganic nanometer particle compesite has become one of hot subject of various countries' research.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.
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.
200810056820.7 disclose a kind of preparation method of white carbon black/solution polymerized butadiene styrene rubber nano-composite material, the method is after Nano carbon white powder is fully mixed with silane coupling agent, condensation reaction is carried out at high temperature thermal treatment, obtain the white carbon black powder of organic modification, then the white carbon black powder of this organic modification is dissolved in organic solvent and is joined in solution polymerized butylbenzene glue again, stirring, desolvation, oven dry, obtain white carbon black/solution polymerized butadiene styrene rubber nano-composite material prepared by co-agglomeration.Physical and mechanical properties, the dynamic properties of sizing material prepared by employing the method are more excellent, but the white carbon black preparation process of organic modification and with glue mixing process in all adopted the organic solvents such as a large amount of ethanol, hexanaphthene, in solvent removal process, macromolecular chain is difficult to whole white carbon black particles are coated-cohesion, have mass loss, also may in common coagel matrix, assemble simultaneously, be difficult for realizing good distribution.
Ye Xin etc. disclose in < < rubber science and technology market > > the 10th phase in 2009 preparation method that a kind of wet method compounding technology is prepared white carbon black/styrene-butadiene rubber composite material, in the method, first adopt wet method compounding technology that white carbon black in water is carried out to organic modification of surface, then mix the white carbon black/styrene-butadiene rubber composite material of solidifying preparation modification altogether with styrene-butadiene latex, the advantage of the method maximum is that the dispersiveness of filler is better, can effectively avoid the pollution of flying upward of filler, but white carbon black is free settling loss in wet method recombining process.
Summary of the invention
The object of the invention is to provide a kind of modified rubber, and this modified rubber has good physical and mechanical properties, dynamic properties and good processing characteristics.Another object of the present invention is to provide the preparation method of this rubber.
Modified rubber disclosed in this invention, with cohesion, breakdown of emulsion co-precipitation after (1) rubber latex and the blending of (2) nano silicon/poly-conjugated-diolefin composite emulsion, be prepared from, the mass ratio of rubber latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100: 0.1～100; Nano silicon/poly-conjugated-diolefin composite emulsion, 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, number-average molecular weight is 100000～120000, and molecular weight distribution is 2～3; Rubber latex is prepared homopolymer or multipolymer containing polymerized conjugated diene hydrocarbon compound of letex polymerization.
Rubber latex of the present invention is by conventional emulsion polymerization prepared homopolymer or multipolymer containing conjugated diolefine hydrocarbon compound: its homopolymer is content of polybutadiene rubber latex, chloroprene rubber latex, natural rubber latex etc., its multipolymer is conjugated diolefine hydrocarbon compound and aryl ethylene compounds, monoene compounds, acrylic compounds, the binary of acrylic ester compound or terpolymer, described aryl ethylene compounds can be vinylbenzene, alpha-methyl styrene, 2-phenylallene, 1-bromobenzene propylene, ethyl styrene and their derivative, described monoene compounds can be ethene, vinylchlorid, propylene, 1-butylene, 2-amylene, vinyl cyanide and their derivative, described acrylic compounds can be vinylformic acid, methacrylic acid and their derivative, described acrylic ester compound can be methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, ethyl propenoate and their derivative, multipolymer can be styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex.
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 100000～120000, 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 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%.
Nano silicon under the present invention, so long as nano level, preferred 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 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.
Conjugated diene of the present invention 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 invention also discloses the preparation method of modified rubber: the method for latex coprecipitation, concrete preparation process is:
(1) preparation of nano silicon/poly-conjugated-diolefin composite emulsion: for nano silicon/poly-conjugated-diolefin 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 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) nano silicon/poly-conjugated-diolefin composite emulsion is joined in rubber latex, be fully uniformly mixed, cohesion, breakdown of emulsion, precipitation, the dry rubber product that obtains modification.
Thereby in order to improve the dispersiveness of silicon-dioxide in emulsion, further improve the performance of composite emulsion, 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.
Emulsifying agent of the present invention 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.
Buffer reagent of the present invention 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, 2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, more preferably Potassium Persulphate or Sodium Persulfate.
Surface-functionalized modified manometer silicon dioxide of the present invention 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 flocculate and break emulsion of nano silicon/poly-conjugated-diolefin composite emulsion of the present invention and rubber latex, precipitation, dry processing condition adopt the flocculate and break emulsion of normal latex, precipitation, dry processing condition, this technology is that those skilled in the art are in common knowledge, for example < < China Synthetic Rubber Industry > > 32 volumes the 4th application > > of phase < < latex coprecipitation method styrene-butadiene rubber(SBR)/organic montmorillonite nano composite material in tire tread in 2009 just narrated these processing condition.The processing condition that the present invention recommends are: add one or more in the flocculation agent such as sodium-chlor, Repone K, magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate, hydrochloric acid, sulfuric acid to carry out flocculate and break emulsion, coprecipitated plastic emitting, dry.
The effect that the present invention is useful:
Modified rubber of the present invention is made as functional latex and rubber latex blending, cohesion, breakdown of emulsion, precipitation, after dry by nano silicon and poly-conjugated-diolefin composite emulsion, because function composite emulsion has satisfactory stability, particle diameter is controlled, be distributed in 50～80nm, can directly be used as modified rubber emulsion, good with rubber latex consistency, and technique is simple, and easy to operate; Nano silicon/poly-conjugated-diolefin the functional materials that adopts the present invention to prepare has good dynamic properties simultaneously, and 60 ℃ of dissipation factors (tan δ) reduce, and illustrate that rolling resistance is low when for the preparation of tire.Molecular weight and molecualr weight distribution has important impact to mixing behavior, and the molecular weight and molecualr weight distribution of nano silicon/poly-conjugated-diolefin functional materials of the present invention is suitable, and when mixing as functional composite material, heat-dissipating is low, mixing behavior good.Therefore, this modified rubber product has excellent physical and mechanical properties, dynamic properties and good processing characteristics.
Modified rubber physical and mechanical properties of the present invention is excellent, and particularly tensile strength can be significantly improved.0 ℃ of tan δ of styrene-butadiene rubber(SBR) after modification is higher, illustrates after modification that rubber product is prepared wet-sliding resistant performance for tire and damping performance is good.The method that is used further to modified rubber by preparing functional latex has effectively solved nano silicon scattering problem of (particularly nonpolar rubber) in rubber matrix, is therefore applied to show good over-all properties after 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 bonds, 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:
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 latex SBR1500, combined styrene content 23.5%, solid content 23%, Lanzhou Petrochemical Company is produced;
Styrene-butadiene latex SBR1502, combined styrene content 23.5%, solid content 22.6%, Lanzhou Petrochemical Company is produced;
Styrene-butadiene latex SBR1712, combined styrene content 23.5%, solid content 22.6%, Lanzhou Petrochemical Company is produced;
Nitrile rubber N41, in conjunction with nitrile content 29%, solid content 22.8%, Lanzhou Petrochemical Company is produced;
Nitrile rubber N32, in conjunction with nitrile content 33%, solid content 23.1%, Lanzhou Petrochemical Company is produced;
Polychloroprene latex CR121, solid content 39.1%, long-lived Chemical Co., Ltd. produces.
Various unmodified rubber performances are in Table 1.
The unmodified rubber product performance of table 1
| Performance/glue kind | SBR1500 | N41 | SBR1712 | SBR1502 | CR121 | N32 |
| Tensile strength, MPa | 24.5 | 25.4 | 19.4 | 25.5 | 22.8 | 26.2 |
| Tensile yield, % | 484 | 455 | 438 | 407 | 880 | 585 |
| 300% stress at definite elongation, MPa (35min) | 16.8 | 11.2 | 12.1 | 18.9 | 2.8 | 10.5 |
| tanδ(0℃) | 0.158 | - | 0.204 | 0.169 | - | - |
(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.
Embodiment 1
Nano-silica surface functional modification: take 120g nano silicon in oven drying, then after mixing with 1200g toluene, ultrasonic wave is disperseed fully, add the VTES after 240g hydrolysis, be heated with stirring to 82 ℃ and reflux 2.3 hours, then filter, washing, vacuum-drying.
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.With sulfuric acid cohesion, be dried and finally obtain poly-1,3-butadiene/nano silicon functional composite material.
Graft modification rubber: get nano silicon/poly-1,3-divinyl functional latex butt 100g joins in the SBR1500 latex that butt is 980g, is fully uniformly mixed, and then adds sodium-chlor and sulfuric acid to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry SBR1500 modified product that obtains.
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 6g nano silicon in 50 ℃ of oven drying 5h, dried nano silicon is added in the aqueous solution that is dissolved with 96g coupling agent MPS to ultrasonic dispersion 1h.After dispersion, mixed solution is stirred to 8h at 110 ℃.After filtration, by the silicon-dioxide toluene wash after modification, after products therefrom vacuum filtration, through Soxhlet, extract again, be finally positioned in baking oven dry.
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/nano silicon functional composite material that finally obtains of sulfuric acid cohesion.
Graft modification rubber: get nano silicon/polyisoprene functional latex butt 230g and join in the N41 latex that butt is 1000g, be fully uniformly mixed, then add calcium chloride to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry N41 modified product that obtains.
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.
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.With sulfuric acid cohesion, be dried and finally obtain poly-1,3-pentadiene/nano silicon functional composite material.
Graft modification rubber: get nano silicon/poly-1,3-pentadiene functional latex butt 300g joins in the SBR1712 latex that butt is 660g, is fully uniformly mixed, and then adds magnesium sulfate to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry SBR1712 modified product that obtains.
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.
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.
Graft modification rubber: get nano silicon/poly-2,3-dimethyl-1,3 divinyl functional latex butt 520g join in the SBR1502 latex that butt is 600g, fully be uniformly mixed, then add magnesium chloride to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry SBR1502 modified product that obtains.
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.
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.
Graft modification rubber: get nano silicon/poly-1,3-hexadiene functional latex butt 620g joins in the CR244 latex that butt is 620g, is fully uniformly mixed, and then adds calcium sulfate to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry CR244 modified product that obtains.
Embodiment 6
Nano-silica surface functional modification: take 24g nano silicon stand-by in oven drying, then after mixing with 120g dimethylbenzene, ultrasonic wave is disperseed fully, add the vinyltriacetoxy silane after 36g hydrolysis, stir post-heating to 100 ℃ and reflux 2.6 hours, then filter, washing, vacuum-drying.
Functional latex preparation:
The first step, the preparation of monomer pre-emulsion.Isoprene 500g, 1,3-butadiene 700g, polyoxyethylene nonylphenol ether 108g, sodium lauryl sulphate 108g, deionized water 1620g, sodium carbonate 4.32g, Potassium Persulphate 1.8g are mixed to pre-emulsification and within 40 minutes, be prepared into pre-emulsion.
Second step, the modified manometer silicon dioxide of take is prepared functional latex as core.The nano silicon 7.2g that gets surface-functionalized modification joins in the reactor that 12g polyoxyethylene sorbitan monolaurate and 600g deionized water are housed, stirring is warming up to 70 ℃, then getting 547g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 70 ℃, be incubated 30 minutes, allow monomer by the coated also polymerization of nano silicon, and the seed using this as composite emulsion.In being housed, the reactor of seed emulsion drips remaining 2494g monomer pre-emulsion, and dropwised in 5 hours, obtain poly-1,3-hexadiene/nanometer titanium dioxide functional silicon composite emulsion, with sulfuric acid cohesion, be dried and obtain poly-1,3-butadiene-isoprene/nano silicon functional composite material.
Graft modification rubber: get nano silicon/polyisoprene functional latex butt 380g and join in the N32 latex that butt is 550g, fully be uniformly mixed, then add calcium chloride and sulfuric acid to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry N32 modified product that obtains.
Comparative example 1
Comparative example 1.The nano silicon 3.6g that gets modification in embodiment 1 is scattered in 1200g and 1800g cyclohexane solvent ultrasonic dispersion 20 minutes; be heated to 60 ℃; after add 2.4g n-Butyl Lithium as initiator; polyreaction is carried out 7.5 hours under nitrogen protection; then product is joined and in ethanol, obtain white depositions; filtration drying has just obtained poly-1,3-butadiene/nanometer silicon dioxide composite material.
Each embodiment and the explanation of comparative example test data in table 2, nano silicon/poly-conjugated-diolefin composite emulsion performance of the present invention is more excellent.
Table 2 nano silicon/poly-conjugated-diolefin composite emulsion performance
| Functional latex/material property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Particle diameter, nm | 58 | 62 | 55 | 68 | 72 | 50 | - |
| Number-average molecular weight Mn * 10 -4 | 10.2 | 11.3 | 12.5 | 11.6 | 13.4 | 10.8 | 15 |
| Molecular weight distribution mw/mn | 2.81 | 2.65 | 2.23 | 2.58 | 2.69 | 2.75 | 1.78 |
| tanδ(60℃) | 0.254 | 0.286 | 0.273 | 0.269 | 0.243 | 0.238 | 0.316 |
Comparative example 2
Comparative example 3.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, stirring post-heating to 93 ℃ refluxes 4 hours, then the nano silicon butt quality 300g of this organic modification is joined in the SBR1712 latex that butt quality is 660g, add magnesium sulfate to carry out flocculate and break emulsion, coprecipitated plastic emitting, the dry SBR1712 modified product that obtains modification.
Obtain the white carbon black/styrene-butadiene rubber composite material of modification.In lime set, there is obvious white depositions altogether, due to nano silicon sedimentation.
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 3, modified styrene butadiene rubber product performance of the present invention are obviously better than the product performance of comparative example.
Table 3 modified rubber product performance
| Modified rubber product performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 2 |
| Tensile strength, and MPa (145 ℃, 35min) | 25.8 | 26.9 | 23.1 | 27.1 | 24.3 | 28.5 | 21.9 |
| Tensile yield, % | 430 | 436 | 426 | 385 | 860 | 542 | 426 |
| 300% stress at definite elongation, MPa (35min) | 18.2 | 13.6 | 14.5 | 21.1 | 3.5 | 11.6 | 13.6 |
| tanδ(0℃) | 0.238 | - | 0.288 | 0.304 | - | - | 0.218 |
Claims (13)
1. a modified rubber, be characterised in that: modified rubber is prepared from cohesion, breakdown of emulsion co-precipitation after (1) rubber latex and the blending of (2) nano silicon/poly-conjugated-diolefin composite emulsion, and the mass ratio of rubber latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100:0.1～100; Nano silicon/poly-conjugated-diolefin composite emulsion, 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, number-average molecular weight is 100000～120000, and molecular weight distribution is 2～3; Rubber latex is prepared homopolymer or multipolymer containing polymerized conjugated diene hydrocarbon compound of letex polymerization; The concrete preparation process of modified rubber is:
(1) preparation of nano silicon/poly-conjugated-diolefin composite emulsion: for nano silicon/poly-conjugated-diolefin 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 1:1～2, 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 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) nano silicon/poly-conjugated-diolefin composite emulsion is joined in rubber latex, be fully uniformly mixed, cohesion, breakdown of emulsion, precipitation, the dry modified rubber product that obtains.
2. modified rubber according to claim 1, the nano silicon that it is characterized in that surface-functionalized modification refers to that silicon-dioxide adopts silane coupling agent to be processed and made the nano silicon with response type by surface functionalization, and silane coupling agent is 0.1～50% of surface-functionalized modified manometer silicon dioxide quality.
3. modified rubber according to claim 1, it is characterized in that silane 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.
4. modified rubber according to claim 1, is characterized in that the conjugated diene in nano silicon/poly-conjugated-diolefin composite emulsion 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, in 2-phenyl-1,3-butadiene and 1,3-hexadiene one or more; The rubber latex that contains the homopolymer of conjugated diolefine hydrocarbon compound is content of polybutadiene rubber latex, chloroprene rubber latex, natural rubber latex; Containing the rubber latex of the multipolymer of conjugated diolefine hydrocarbon compound, be binary or the terpolymer of conjugated diolefine hydrocarbon compound and aryl ethylene compounds, monoene compounds, acrylic compounds, acrylic ester compound.
5. modified rubber according to claim 4, is characterized in that aryl ethylene compounds is vinylbenzene, alpha-methyl styrene, 2-phenylallene, 1-bromobenzene propylene, ethyl styrene and their derivative; Monoene compounds is ethene, vinylchlorid, propylene, 1-butylene, 2-amylene, vinyl cyanide and their derivative; Acrylic compounds is vinylformic acid, methacrylic acid and their derivative; Acrylic ester compound is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, ethyl propenoate and their derivative; Conjugated diene is 1,3-butadiene and/or isoprene.
6. modified rubber according to claim 4, is characterized in that the rubber latex containing the multipolymer of conjugated diolefine hydrocarbon compound is styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex.
7. a preparation method for modified rubber claimed in claim 1, concrete preparation process is:
(1) preparation of nano silicon/poly-conjugated-diolefin composite emulsion: for nano silicon/poly-conjugated-diolefin 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 1:1～2, 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 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) nano silicon/poly-conjugated-diolefin composite emulsion is joined in rubber latex, be fully uniformly mixed, cohesion, breakdown of emulsion, precipitation, the dry modified rubber product that obtains.
8. preparation method according to claim 7, the preparation method who it is characterized in that surface-functionalized modified manometer silicon dioxide is: take 0.1～50 part of nano silicon dry, 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.
9. preparation method according to claim 8, is characterized in that solvent is toluene, dimethylbenzene or methyl ethyl ketone.
10. preparation method according to claim 7, 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.
11. preparation methods according to claim 10, 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 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.
12. preparation methods according to claim 11, 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; Water-soluble thermal initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate.
13. preparation methods according to claim 7, the flocculation agent adding while it is characterized in that condensing be in sodium-chlor, Repone K, magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate, hydrochloric acid and sulfuric acid one or more.
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| CN104650421B (en) * | 2013-11-19 | 2017-01-11 | 中国石油天然气股份有限公司 | Preparation method of rice hull ash modified styrene butadiene rubber |
| CN104650414B (en) * | 2013-11-19 | 2016-09-07 | 中国石油天然气股份有限公司 | Preparation method of rice hull ash modified powder butadiene-acrylonitrile polymer |
| CN105017483A (en) * | 2015-06-24 | 2015-11-04 | 淄博腾辉油脂化工有限公司 | Preparation method of emulsion polymerized butadiene styrene rubber special-purpose emulsifier |
| CN105820294A (en) * | 2016-04-05 | 2016-08-03 | 大连理工大学 | Method for preparing white carbon black/rubber composite |
| CN107266710B (en) * | 2016-04-08 | 2019-11-08 | 中国石油天然气股份有限公司 | Modification method of nano white carbon black |
| CN106699968A (en) * | 2016-11-23 | 2017-05-24 | 厦门大学 | Method for preparing nanosilicon dioxide modified styrene-butadiene latex |
| CN108250371B (en) * | 2016-12-28 | 2020-06-02 | 北京化工大学 | Bonding type polymer/silicon dioxide hybrid material and preparation method thereof |
| CN107573550A (en) * | 2017-09-25 | 2018-01-12 | 芜湖凯奥尔环保科技有限公司 | A kind of preparation method of nano-silicon dioxide modified rubber composite |
| CN115043980B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
| CN115232374B (en) * | 2022-08-29 | 2023-08-22 | 三维控股集团股份有限公司 | Super wear-resistant conveyor belt covering rubber and rubber conveyor belt with super wear-resistant working surface |
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