CN111073086A - Rubber composition for high-wear-resistance green tire and preparation method thereof - Google Patents
Rubber composition for high-wear-resistance green tire and preparation method thereof Download PDFInfo
- Publication number
- CN111073086A CN111073086A CN201811220228.6A CN201811220228A CN111073086A CN 111073086 A CN111073086 A CN 111073086A CN 201811220228 A CN201811220228 A CN 201811220228A CN 111073086 A CN111073086 A CN 111073086A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- parts
- white carbon
- mass
- nano white
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 101
- 239000005060 rubber Substances 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 205
- 239000006229 carbon black Substances 0.000 claims abstract description 181
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 98
- 239000004568 cement Substances 0.000 claims abstract description 81
- 239000006185 dispersion Substances 0.000 claims abstract description 76
- 239000004793 Polystyrene Substances 0.000 claims abstract description 37
- 229920002223 polystyrene Polymers 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000005299 abrasion Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 229920001451 polypropylene glycol Polymers 0.000 claims description 18
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- -1 polyoxypropylene Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical group CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- ZJCZFAAXZODMQT-UHFFFAOYSA-N 2-methylpentadecane-2-thiol Chemical group CCCCCCCCCCCCCC(C)(C)S ZJCZFAAXZODMQT-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical group CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 35
- 239000000725 suspension Substances 0.000 description 15
- 229920005669 high impact polystyrene Polymers 0.000 description 14
- 239000004797 high-impact polystyrene Substances 0.000 description 14
- 238000005070 sampling Methods 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 11
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004927 clay Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 244000043261 Hevea brasiliensis Species 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 229920003052 natural elastomer Polymers 0.000 description 7
- 229920001194 natural rubber Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 241000872198 Serjania polyphylla Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000010866 blackwater Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 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 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The solution polymerized butadiene styrene rubber is filled with a high-dispersion nano white carbon black used as a rubber composition of a high-wear-resistance green tire tread. According to the invention, polyether polyol is adopted to anchor and modify the surface of nano white carbon black particles, then unsaturated acrylate is adopted to graft polystyrene, the surface of the nano white carbon black particles is coated with the unsaturated acrylate to form a hard shell with high obstruction to isolate nano white carbon black, then unsaturated acrylate is used to graft solution polymerized styrene-butadiene rubber cement, and finally high-dispersion nano white carbon black, the grafted solution polymerized styrene-butadiene rubber cement and the solution polymerized styrene-butadiene rubber cement are directly mixed and coagulated to prepare the rubber composition for the high-wear-resistance green tire tread. The invention solves the problem of poor compatibility of the self-polymerization and solution-polymerization styrene-butadiene rubber matrix of the white carbon black, enhances the modification effect of the nano white carbon black and can greatly improve the wear resistance of the rubber composition. The invention further provides a preparation method of the composition.
Description
Technical Field
The invention relates to a rubber composition for a high-wear-resistance green tire tread and a preparation method thereof, in particular to a rubber composition prepared by filling high-dispersion nano white carbon black into solution polymerized styrene butadiene rubber and used as the high-wear-resistance green tire tread and a preparation method thereof.
Background
Under the background that low carbon, green and environmental protection become common consensus of the whole society, the automobile tire industry is actively adapting and guiding the trend and trend, and the requirement for high performance of tires is higher and higher. This requires that the balance of the "magic triangle" performance of the tire tread rubber must be significantly improved, that is, the tire tread rubber has good wet skid resistance, excellent wear resistance and low rolling resistance.
In addition, the nano white carbon black is used as a reinforcing filler in the tire tread formula in the nineties of the last century, so that the performance of the tread rubber in the 'magic triangle' is obviously balanced and is difficult to replace in the preparation of energy-saving and environment-friendly 'green tire' tread rubber, and the application of the nano white carbon black in the aspect of tires is more and more extensive due to the higher and more requirements of the state on the aspect of tire environment protection and relevant regulations issued in the aspect of tire energy saving in the United states and European Union.
However, the nano white carbon black has small particle size, large specific surface area and high surface energy, and a large number of silicon hydroxyl groups exist on the surface, so that the nano white carbon black has the characteristics of hydrophilicity and easiness in self-polymerization, has poor compatibility with a polymer matrix, and is not easy to disperse uniformly in the mixing process of the nano white carbon black and a rubber material, thereby not only influencing the filling modification effect, but also damaging the performance of the rubber material. From the perspective of the expected effect of the inorganic powder filling modified synthetic rubber, the smaller the particle size of the inorganic powder particles, the better the modification effect, but in the application process of the high-fine inorganic powder, a technical problem inevitably occurs, namely, the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material because of the reduction of the particle size, the specific surface area is increased, the surface energy is improved, the self-aggregation capability is stronger, and the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material. Therefore, the problem of dispersion of the high-fine inorganic powder in the rubber has become a bottleneck in preparing high-performance rubber materials.
In the prior art, the research on the modified nano white carbon black filled rubber material is mainly prepared by a method of coating the modified nano white carbon black particle surface filled rubber material by a coupling agent or a surfactant and a graft polymer. Such as: CN200880002511.X discloses a rubber composition having independent cells, and containing (A) at least one rubber component selected from natural rubber and diene synthetic rubber, and 10-one to 100 parts by mass of the rubber component150 parts by mass of (B) silica and 0.02 to 20 parts by mass of (C) organic fiber, and containing a silane coupling agent in a proportion of 1 to 30% by mass relative to the silica of the (B) component. The rubber composition is excellent in handling properties during rubber processing, and can provide a pneumatic tire excellent in tire braking and driving properties (on-ice properties) on icy and snowy road surfaces and also excellent in wear resistance. CN200910238122.3 discloses a preparation method of a white carbon black/clay/rubber nano composite material, which comprises the steps of mixing a certain amount of clay and deionized water, strongly stirring for more than 5 hours, standing for more than 24 hours to obtain a stable clay suspension, and ensuring that the mass content of the clay is 1.5-3 wt%. And similarly, mixing a certain amount of white carbon black and deionized water, strongly stirring or ultrasonically vibrating to prepare a stable white carbon black/water suspension, so that the mass content of the white carbon black is 1-4 wt%, preparing a mixed suspension with the mass ratio of clay/white carbon black of 1/5-2/1 according to the content, and performing spray drying to prepare the clay/white carbon black composite filler. Then filling the clay/white carbon black composite filler and the silane coupling agent into the sizing material on an open mill to prepare the white carbon black/clay/rubber nano composite material. CN107189124A discloses a preparation method of an aging-resistant modified natural rubber, which comprises the steps of drying white carbon black for 4-8 hours at the temperature of 200-240 ℃, plastifying the dried white carbon black with abietic acid type resin acid accounting for 4-7% of the weight of the white carbon black and chlorohydrin rubber accounting for 12-18% of the weight of the white carbon black for 20-25 minutes at the temperature of 140-160 ℃, continuously extracting the white carbon black for 24 hours after discharging, and drying the white carbon black at the temperature of 120-150 ℃ after volatilizing the solvent; then mixing the natural rubber, the modified white carbon black and the multi-walled carbon nano-tubes according to the weight ratio of 10:1.3-1.6:0.6-0.7, mixing the rubber material in a double-roll open mill, mixing the rubber material into sheets, and finally granulating the obtained mixed rubber sheets in an extruder to obtain the anti-aging modified natural rubber. CN102558627A discloses a preparation method of white carbon black modified styrene-butadiene rubber for green tires, which comprises the steps of firstly mixing white carbon black and water to obtain white carbon black-water suspension, wherein the mass ratio of the white carbon black to the water is 5% -20%, then carrying out surface treatment on the white carbon black in a water bath environment to enable the surface of the white carbon black to be organized, adjusting the pH value of the white carbon black-water suspension to 9-12, and then carrying out surface treatment on the white carbon black-water suspensionAnd finally, taking the styrene butadiene rubber liquid slurry containing the white carbon black as a raw material, and preparing the modified styrene butadiene rubber containing the white carbon black by using an emulsion blending and co-flocculation process. CN106589485A discloses a modified white carbon black by using AEO (aliphatic polyoxyethylene ether) and silane coupling agent together and a method for compounding the modified white carbon black with rubber, which comprises the steps of firstly mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5-20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to 35-90 ℃ by a heating device, ensuring that the white carbon black suspension is in a flowing state during the period, then adding silane coupling agent into the white carbon black suspension, then adding AEO for modification, wherein the mass of AEO is 1-100% of the mass of the white carbon black, the mass of the silane coupling agent is 1-100% of the mass of the white carbon black, carrying out white carbon black modification for 0.5-10 hours by matching with ultrasound, finally mixing white carbon black modified by using AEO and silane coupling agent as raw materials, to prepare the rubber/modified white carbon black composite material. CN106832417A discloses a method for modifying white carbon black by using aliphatic polyoxyethylene ether and compounding the white carbon black with rubber, which comprises the steps of firstly mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5% -20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to be higher than the melting point of the aliphatic polyoxyethylene ether, ensuring that the white carbon black suspension is in a flowing state in the period, adding the aliphatic polyoxyethylene ether into the white carbon black suspension, fully modifying the white carbon black for 0.5-10 hours by matching with ultrasound, then dehydrating and drying the white carbon black suspension to obtain modified white carbon black powder, and finally compounding the white carbon black modified by the aliphatic polyoxyethylene ether with various rubbers to prepare the rubber/modified white carbon black composite material. CN1323687A discloses a method for preparing a rubber-polyurethane elastomer composite structure green tire by using nano white carbon black modified polyurethane, which comprises the steps of selecting fumed silica with the average particle size of 1-40 nm, adding an ethanol solution of a silane coupling agent containing isocyanate groups or amino groups, uniformly mixing, adding the mixture into oligomer polyol, and heating to 220 ℃. (to about: 100 ℃) while stirringSimultaneously vacuumizing to-0.095 to-0.098 Mpa at 240 ℃, and dehydrating and dealcoholizing for 2 to 3 hours; cooling to below 60 ℃, adding diisocyanate, reacting for 1-2 hours at 70-80 ℃ and under the vacuum degree of-0.095-0.098 Mpa to obtain the prepolymer of the nano white carbon black modified polyurethane, and finally mixing the prepolymer of the nano white carbon black modified polyurethane with the polyurethane elastomer to prepare the green tire product with the rubber-polyurethane elastomer composite structure. The high performance NR composites were exemplified by the kukukuuqiang ("latex blending method" natural rubber/silica nanocomposite microstructure and performance control, 2010, master thesis at hainan university): the natural rubber/silicon dioxide nano composite material is prepared by adopting a latex blending method, and the nano silicon dioxide (SiO) is modified by using a gamma-methacryloxypropyltrimethoxysilane coupling agent (MPS)2) Then grafting polymethyl methacrylate (PMMA) through emulsion polymerization to obtain nano silicon dioxide particles (SiO) with a core-shell structure2MPS-PMMA) and finally directly blended with MMA modified natural latex (NR-PMMA) to obtain natural rubber/silica nanocomposites. Lewenji et al prepared clay/white carbon black composite filler by spray drying process for replacing part of white carbon black to jointly reinforce solution polymerized butadiene styrene rubber/butadiene rubber composite material. Although the compatibility of the nano white carbon black and the rubber matrix is improved by the method, the methods have certain limitations, and mainly have the defects of long reaction time, high energy consumption, large environmental pollution, complex operation and the like.
Disclosure of Invention
The invention aims to provide a rubber composition which is prepared by filling solution polymerized styrene-butadiene rubber with high-dispersion nano white carbon black and is used as a high-wear-resistance green tire tread. According to the invention, polyether polyol is adopted to anchor and modify the surface of nano white carbon black particles, then unsaturated acrylate is adopted to graft polystyrene, the surface of the nano white carbon black particles is coated with the unsaturated acrylate to form a hard shell with high obstruction to isolate nano white carbon black, then unsaturated acrylate is used to graft solution polymerized styrene-butadiene rubber cement, and finally high-dispersion nano white carbon black, the grafted solution polymerized styrene-butadiene rubber cement and the solution polymerized styrene-butadiene rubber cement are directly mixed and coagulated to prepare the rubber composition for the high-wear-resistance green tire tread. The invention further provides a preparation method of the composition.
The "parts" in the present invention mean parts by mass.
The invention relates to a rubber composition for a high-wear-resistance green tire tread, which is prepared from solution-polymerized styrene-butadiene rubber cement (dry rubber) in percentage by mass and mainly comprises the following components:
(1) 100 percent of solution polymerized styrene-butadiene rubber cement (dry rubber)
(2) 60-100% of high-dispersion type nano white carbon black
(3) 5-15% of graft solution polymerized styrene-butadiene rubber cement
The high-dispersion nano white carbon black particles are subjected to anchoring modification on the surfaces of the nano white carbon black particles by adopting polyether polyol, then are subjected to grafting treatment on polystyrene by using unsaturated acrylate, and finally are coated on the surfaces of the nano white carbon black particles to form a hard shell with high connection strength and high obstruction to isolate the nano white carbon black. The white carbon black is selected from nano-scale, and the particle size is as follows: 10 to 100 nm. The polyether polyol is at least one selected from propylene glycol polyoxypropylene ether (PPG), ethylene glycol polyoxypropylene ether, propylene glycol polyoxyethylene ether, ethylene glycol polyoxyethylene ether, polytetrahydrofuran glycol (PTHF), trimethylolpropane polyoxypropylene ether and hydroxyl-terminated polytetrahydrofuran, and is preferably PPG. The unsaturated acrylate polar monomer is selected from one of Methyl Methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate, preferably MMA. The initiator may be selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dicumyl peroxide (DCP).
The polystyrene is a copolymer (HIPS) of styrene and polybutadiene rubber, can be powdery or granular resin, and has a Melt Flow Rate (MFR) of 0.5-20 g/10 min.
The solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 10-25 w%.
The preparation of the rubber composition can be carried out in a coagulation kettle, and the specific preparation process comprises the following steps:
(1) preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: adding 100 parts by mass of polystyrene and 300-500 parts by mass of solvent into a reaction kettle, heating to 50-70 ℃, stirring for 5-10 hours, adding 5-20 parts by mass of unsaturated acrylate and 0.05-0.5 part by mass of initiator after the polystyrene is completely dissolved, stirring for reaction for 2-5 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain the polystyrene graft (the grafting rate is 1.0% -7.0%).
b, preparing high-dispersion nano white carbon black: taking 100 parts by mass of nano white carbon black, adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of polyether polyol and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-25 parts of polystyrene graft, stirring and reacting for 2-4 hr, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, firstly adding 100-200 parts of solvent into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement and 0.05-0.5 part of molecular weight regulator, replacing with nitrogen, then adding 5-15 parts of unsaturated acrylate, stirring and heating, adding 0.1-0.4 part of initiator when the temperature of the polymerization kettle reaches 50-60 ℃, reacting for 2-5 hours, and then adding 1.0-3.0 parts of terminator to prepare the grafted rubber cement (the grafting rate of the solution-polymerized styrene-butadiene rubber cement is 1.0% -5.0%).
(3) Preparation of rubber composition for high abrasion Green tire Tread: taking 100 parts of solution-polymerized styrene-butadiene rubber cement dry rubber by mass, adding 100 parts of solution-polymerized styrene-butadiene rubber cement (dry rubber) and 400-600 parts of solvent into a coagulation kettle, stirring and mixing for 40-60 min, then adding 60-100 parts of high-dispersion nano white carbon black and 5-15 parts of grafted solution-polymerized styrene-butadiene rubber cement, stirring and mixing for 50-60 min when the temperature is raised to 50-70 ℃, and finally performing wet deashing, drying and briquetting to obtain the rubber composition for the high-wear-resistance green tire tread.
The invention does not specially limit the molecular weight regulator, the terminator, the solvent and the like, can adopt the common conventional auxiliary agents in the field, and the addition amount of the conventional auxiliary agents is also the conventional amount which can be calculated by the technical personnel in the field according to the amount of the dry glue, and is not specially limited in the invention.
The molecular weight regulator of the present invention may be selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and tertiary dodecyl mercaptan is preferred.
The terminating agent of the invention can be selected from one of diethylhydroxylamine, hydroxylamine sulfate and sodium fermet, and is preferably diethylhydroxylamine.
The solvent according to the invention may be selected from cyclohexane, carbon disulphide (CS)2) Nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, preferably cyclohexane.
The invention relates to a rubber composition which is prepared by filling high-dispersion nano white carbon black into a solution-polymerized styrene-butadiene rubber matrix and is used as a high-wear-resistant green tire tread, firstly, unsaturated acrylate is used for carrying out grafting reaction on HIPS (high impact polystyrene), then ether bonds (-R-O-R-) and hydroxyl groups (-OH) in polyether polyol are used as anchoring groups to carry out condensation reaction with hydroxyl groups on the surface of the nano white carbon black to form a chemical grafting structure, high-density polar anchoring points mainly comprising ether bonds (-R-O-R-) and hydroxyl groups (-OH) are formed on the surface of white carbon black particles, the anchoring points and the polar groups of the grafted HIPS generate mutual attraction force between molecules, and a hard shell polystyrene blocking layer can be formed on the surface of the nano white carbon black particles after coating. The barrier layer has high connection strength, is difficult to separate from white carbon black particles even under the action of high temperature and high shear, solves the problem of easy agglomeration of nano white carbon black, and can ensure that the white carbon black can stably exist in a single particle form. In addition, unsaturated acrylate is used for grafting solution polymerized styrene-butadiene rubber cement, the macromolecular chain structure of the rubber cement is the same as that of solution polymerized styrene-butadiene rubber, and the polar group is consistent with that of grafted HIPS (high impact polystyrene), according to the principle of 'similar compatibility and same polarity absorption', the grafted solution polymerized styrene-butadiene rubber cement can obviously improve the compatibility of white carbon black particles and solution polymerized styrene-butadiene rubber, solve the problem of poor bonding force of the white carbon black and a solution polymerized styrene-butadiene rubber matrix, endow the high dispersibility of the nano white carbon black in a solution polymerized styrene-butadiene rubber system, and realize stable and uniform dispersion in the solution polymerized styrene-butadiene rubber matrix (see attached figure 1).
Secondly, the high-dispersion nano white carbon black contains a polystyrene hard shell layer, so that the modulus of the white carbon black is greatly improved, the wear resistance of the tire is improved, and meanwhile, the solution polymerized styrene-butadiene rubber has high molecular weight and high styrene monomer content, and has a certain effect of improving the wear resistance of the tire, so that the wear resistance of the tire tread can be greatly improved under the mutual 'synergistic effect' of the high-dispersion nano white carbon black and the solution polymerized styrene-butadiene rubber. The method is environment-friendly, low in cost and suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope photograph of modified nano white carbon black in solution polymerized styrene butadiene rubber. As can be seen from the photographs: the high-dispersion nano white carbon black is uniformly dispersed in a solution polymerized styrene butadiene rubber matrix in a particle form of about 30-90 nm.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The "parts" described in examples and comparative examples each refer to parts by mass.
⑴ sources of raw materials:
nano white carbon black with particle size of 20-60 nm Weifang Wanli auxiliary agent Limited company
Polystyrene (HIPS), MFR2.9, Medium petrochemical Yanshan petrochemical division
SSBR72612 in styrene content of 27% or more, Dushan petrochemical Co
Methyl Methacrylate (MMA), Guangzhou Qitai chemical Co., Ltd
Propylene glycol polyoxypropylene Ether (PPG), Haian Yongsheng chemical Co., Ltd
Polytetrahydrofuran diol (PTHF), Haian Yongsheng chemical Co., Ltd
Dicumyl peroxide (DCP), Lanzhou adjuvant plant
Other reagents are all commercial products
⑵ analytical test methods:
determination of the graft ratio: taking about 4g of sample from a three-necked bottle by using a pipette, weighing, adding 2-3 drops of hydroquinone solution, drying to constant weight, putting the sample in a Soxhlet fat extractor, extracting and extracting for 24 hours by using toluene in a water bath at 90 ℃, and drying to constant weight. The monomer grafting was calculated as follows:
in the formula: m is0-total mass of latex (g); m-sample mass (g) weighed after reaction; m ism-total mass of monomers in the reactants (g); m isSBR-mass of styrene butadiene rubber in the sample (g); m is1-mass of sample after extraction (g).
Analyzing a sample by an electron microscope: and (3) carrying out dispersibility analysis on the sample before and after the modification of the nano white carbon black by adopting an XL-20 scanning electron microscope produced by Philips corporation in the Netherlands. And carrying out SEM analysis on the sample under the accelerating voltage of 20kV after the sample is subjected to gold spraying treatment by a surface treatment machine.
The abrasion resistance of the rubber is measured by using an MZ-4O61 type Akron abrasion tester (product of the open bead test mechanical factory in Jiangdu city) according to GB/T1689-1998, the angle between the test sample and the grinding wheel is 15 degrees, and the stress is 26.7N.
Tensile strength: the method in standard GB/T528-2009 is executed.
Dispersity: the method in the standard GB/T6030-1985 is executed.
Example 1
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: adding 100 parts of HIPS and 300 parts of cyclohexane into a reaction kettle, heating to 50 ℃, stirring for 5 hours, adding 5 parts of MMA and 0.1 part of DCP after polystyrene is completely dissolved, stirring for reaction for 2 hours, adding 5 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (a) (the grafting rate is 1.9%).
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 5 parts of PPG and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of HIPS-g-MMA (a), stirring and reacting for 2 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 100 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR72612 and 0.05 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 5 parts of MMA, stirring, heating, adding 0.1 part of DCP when the temperature of the polymerization kettle reaches 50 ℃, reacting for 2 hours, adding 1.0 part of diethylhydroxylamine, and stopping the reaction to obtain the grafted solution-polymerized styrene-butadiene rubber cement a (the grafting rate is 1.3%).
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 400 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 40min, then 60 parts of high-dispersion nano white carbon black and 5 parts of grafted solution polymerized styrene-butadiene rubber cement a are added, the mixture is stirred and mixed for 50min when the temperature is raised to 50 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 2
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 1.
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 6 parts of PPG and 220 parts of cyclohexane into a polymerization kettle, heating to 43 ℃, and stirring for reacting for 1.4 hr; then adding 12 parts of HIPS-g-MMA (a), stirring and reacting for 2.3 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 450 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 45min, then 70 parts of high-dispersion nano white carbon black and 7 parts of grafted solution polymerized styrene-butadiene rubber cement a are added, the mixture is stirred and mixed for 52min when the temperature is raised to 55 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: adding 100 parts of HIPS and 350 parts of cyclohexane into a reaction kettle, heating to 55 ℃, stirring for 7 hours, adding 9 parts of MMA and 0.2 part of DCP after polystyrene is completely dissolved, stirring for reaction for 3 hours, adding 7 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (b) (the grafting rate is 3.7%).
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of PPG and 270 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 16 parts of HIPS-g-MMA (b), stirring and reacting for 2.7 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 150 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR72612 and 0.3 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 11 parts of MMA, stirring, heating, adding 0.3 part of DCP when the temperature of the polymerization kettle reaches 56 ℃, reacting for 4 hours, adding 2.0 parts of diethylhydroxylamine, and stopping the reaction to obtain grafted solution-polymerized styrene-butadiene rubber cement b (the grafting rate is 4.1%).
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 500 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 50min, then 80 parts of high-dispersion nano white carbon black and 9 parts of grafted solution polymerized styrene-butadiene rubber cement b are added, the mixture is stirred and mixed for 52min when the temperature is raised to 56 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 3.
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 11 parts of PPG and 300 parts of cyclohexane into a polymerization kettle, heating to 53 ℃, and stirring for reaction for 2.2 hours; then adding 18 parts of HIPS-g-MMA (b), stirring and reacting for 3.0hr, and performing flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 530 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 52min, then 90 parts of high-dispersion nano white carbon black and 11 parts of grafted solution polymerized styrene-butadiene rubber cement b are added, the mixture is stirred and mixed for 55min when the temperature is raised to 60 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 5
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: adding 100 parts of HIPS and 500 parts of cyclohexane into a reaction kettle, heating to 70 ℃, stirring for 10 hours, adding 20 parts of MMA and 0.45 part of DCP after polystyrene is completely dissolved, stirring for reaction for 4.5 hours, adding 9 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (c) (the grafting rate is 6.1%).
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of PPG and 350 parts of cyclohexane into a polymerization kettle, heating to 57 ℃, and stirring for reacting for 2.6 hours; then adding 22 parts of HIPS-g-MMA (c), stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 200 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR72612 and 0.5 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 15 parts of MMA, stirring, heating, adding 0.4 part of DCP when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, adding 3.0 parts of diethylhydroxylamine, and terminating the reaction to obtain grafted solution-polymerized styrene-butadiene rubber cement c (the grafting rate is 4.7%).
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 550 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 55min, then 93 parts of high-dispersion nano white carbon black and 13 parts of grafted solution polymerized styrene-butadiene rubber cement c are added, the mixture is stirred and mixed for 55min when the temperature is raised to 60 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 5.
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14.5 parts of PTHF and 390 parts of cyclohexane into a polymerization kettle, heating to 59 ℃, and stirring for reacting for 2.8 hours; then adding 24 parts of HIPS-g-MMA (c), stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 5.
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 570 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 58min, then 97 parts of high-dispersion nano white carbon black and 14 parts of grafted solution polymerized styrene-butadiene rubber cement c are added, the mixture is stirred and mixed for 58min when the temperature is raised to 65 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 5.
b, preparing high-dispersion nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of PTHF and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reacting for 3.0 hr; then adding 25 parts of HIPS-g-MMA (c), stirring and reacting for 4.0hr, and carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 5.
(3) Preparation of rubber composition for high abrasion Green tire Tread: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 600 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 60min, then 100 parts of high-dispersion nano white carbon black and 15 parts of grafted solution polymerized styrene-butadiene rubber cement c are added, the mixture is stirred and mixed for 60min when the temperature is raised to 70 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 1
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the other conditions were the same as in example 1 except that the amount of MMA added during the preparation was 2.0 parts, that is: adding 100 parts of HIPS and 300 parts of cyclohexane into a reaction kettle, heating to 50 ℃, stirring for 5 hours, adding 2.0 parts of MMA and 0.1 part of DCP after polystyrene is completely dissolved, stirring for reaction for 2 hours, adding 5 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (a-1) (the grafting rate is 0.5%).
b, preparing high-dispersion nano white carbon black: the other conditions were the same as in example 1 except that HIPS-g-MMA (a) was not added in the preparation process, but HIPS-g-MMA (a-1), that is: adding 100 parts of nano white carbon black (40nm), 5 parts of PPG and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1 hr; then adding 10 parts of HIPS-g-MMA (a-1), stirring and reacting for 2 hours, and carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black a.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as those in example 1, except that the highly dispersed nano white carbon black a is added instead of the highly dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 400 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 40min, then 60 parts of high-dispersion nano white carbon black a and 5 parts of grafted solution polymerized styrene-butadiene rubber cement a are added, the mixture is stirred and mixed for 50min when the temperature is raised to 50 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 2.
b, preparing high-dispersion nano white carbon black: the same as in example 2.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 2.
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as example 2, except that the addition amount of the high-dispersion nano white carbon black in the preparation process is 30 parts, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 450 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 45min, then 30 parts of high-dispersion nano white carbon black and 7 parts of grafted solution polymerized styrene-butadiene rubber cement a are added, the mixture is stirred and mixed for 52min when the temperature is raised to 55 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the other conditions were the same as in example 3 except that the amount of DCP added during the preparation was 0.03 parts, that is: adding 100 parts of HIPS and 350 parts of cyclohexane into a reaction kettle, heating to 55 ℃, stirring for 7 hours, adding 9 parts of MMA and 0.03 part of DCP after polystyrene is completely dissolved, stirring for reaction for 3 hours, adding 7 parts of diethylhydroxylamine to terminate the reaction, and performing suction filtration and washing to obtain HIPS-g-MMA (b-1) (the grafting rate is 0.7%).
b, preparing high-dispersion nano white carbon black: the other conditions were the same as in example 3, except that HIPS-g-MMA (b) was not added in the preparation process, but HIPS-g-MMA (b-1), that is: adding 100 parts of nano white carbon black (40nm), 10 parts of PPG and 270 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 16 parts of HIPS-g-MMA (b-1), stirring and reacting for 2.7 hours, and carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black b.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as those in example 1, except that the highly dispersed nano white carbon black b is added instead of the highly dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 500 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 50min, then 80 parts of high-dispersion nano white carbon black and 9 parts of grafted solution polymerized styrene-butadiene rubber cement b are added, the mixture is stirred and mixed for 52min when the temperature is raised to 56 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 4.
b, preparing high-dispersion nano white carbon black: the same as in example 4.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as example 4, except that the addition amount of the graft solution polymerized styrene-butadiene rubber cement b in the preparation process is 2.0 parts, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 530 parts of cyclohexane are added into a coagulation kettle to be stirred and mixed for 52min, then 90 parts of high-dispersion nano white carbon black and 2.0 parts of grafted solution polymerized styrene-butadiene rubber cement b are added, the mixture is stirred and mixed for 55min when the temperature is raised to 60 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 5
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: same as example 5
b, preparing high-dispersion nano white carbon black: same as example 5
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 5 except that the amount of MMA added during the preparation was 3.0 parts, that is: adding 200 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 and 0.5 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 3.0 parts of MMA, stirring, heating, adding 0.4 part of DCP when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, adding 3.0 parts of diethylhydroxylamine, and terminating the reaction to obtain grafted solution polymerized styrene-butadiene rubber cement c-1 (the grafting rate is 0.5 percent).
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as example 5, except that the graft solution polymerized styrene-butadiene rubber cement c is not added in the preparation process, but the graft solution polymerized styrene-butadiene rubber cement c-1 is added, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 550 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 55min, then 93 parts of high-dispersion nano white carbon black and 13 parts of grafted solution polymerized styrene-butadiene rubber cement c-1 are added, the mixture is stirred and mixed for 55min when the temperature is raised to 60 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
(1) Preparing high-dispersion nano white carbon black: preparing high-dispersion nano white carbon black: the other conditions were the same as in example 6, except that HIPS-g-MMA (c) was not added during the preparation, but was added directly to HIPS, that is: adding 100 parts of nano white carbon black (40nm), 14.5 parts of PTHF and 390 parts of cyclohexane into a polymerization kettle, heating to 59 ℃, and stirring for reacting for 2.8 hours; then adding 24 parts of HIPS, stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion nano white carbon black c.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 6.
(3) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions are the same as those in example 6, except that the highly dispersed nano white carbon black c is added instead of the highly dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 570 parts of cyclohexane are added into a condensation kettle and stirred and mixed for 58min, then 97 parts of high-dispersion nano white carbon black c and 14 parts of grafted solution polymerized styrene-butadiene rubber cement c are added, the mixture is stirred and mixed for 58min when the temperature is raised to 65 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: the same as in example 7.
b, preparing high-dispersion nano white carbon black: the same as in example 7.
(2) Preparation of rubber composition for high abrasion Green tire Tread: the other conditions were the same as in example 7 except that no graft solution-polymerized styrene-butadiene rubber cement c was added during the preparation, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR72612 (dry rubber) and 600 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 60min, then 100 parts of high-dispersion nano white carbon black is added, the mixture is stirred and mixed for 60min when the temperature is raised to 70 ℃, and finally the rubber composition for the high-wear-resistance green tire tread is prepared through wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
TABLE 1 Properties of solution-polymerized styrene-butadiene rubber composition for high abrasion Green tire Tread
As can be seen from Table 1: in the examples of the performances of the solution polymerized styrene-butadiene rubber composition for the high-wear-resistance green tire tread, the volume value of wear is smaller than the ratio, which shows that the rubber composition has good wear resistance.
Claims (10)
1. A rubber composition for a high-abrasion green tire comprises the following components:
(1) 100 parts by mass of solution polymerized styrene-butadiene rubber cement
(2) 60-100 parts by mass of high-dispersion nano white carbon black
(3) 5-15 parts by mass of grafted solution-polymerized styrene-butadiene rubber cement
The method is characterized in that the high-dispersion nano white carbon black is prepared by performing anchoring modification on the surface of nano white carbon black particles by adopting polyether polyol in the presence of an initiator, then performing grafting treatment on polystyrene by using unsaturated acrylate, and finally coating the polystyrene on the surface of the nano white carbon black particles to form a hard shell with high connection strength and high obstruction to isolate the nano white carbon black.
2. The rubber composition for high-abrasion green tires according to claim 1, wherein the nano white carbon black has a particle size of 10 to 100 nm.
3. The highly abrasion-resistant rubber composition for green tires according to claim 1, wherein said polyether polyol is at least one member selected from the group consisting of propylene glycol polyoxypropylene ether, ethylene glycol polyoxypropylene ether, propylene glycol polyoxyethylene ether, ethylene glycol polyoxyethylene ether, polytetrahydrofuran glycol, trimethylolpropane polyoxypropylene ether, hydroxyl-terminated polytetrahydrofuran.
4. The rubber composition for high-abrasion green tires according to claim 3, wherein the polyether polyol is propylene glycol polyoxypropylene ether.
5. The rubber composition for high abrasion green tires according to claim 1, wherein the unsaturated acrylate polar monomer is one selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate and t-butyl methacrylate.
6. The rubber composition for high abrasion green tires according to claim 5, wherein the polar unsaturated acrylate monomer is methyl methacrylate.
7. The highly abrasion resistant rubber composition for green tires according to claim 1, wherein said initiator is one selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-t-butyl peroxide.
8. The rubber composition for high abrasion green tires according to claim 7, wherein the initiator is dicumyl peroxide.
9. A process for producing a rubber composition for a high abrasion green tire as claimed in claim 1, characterized in that the production process comprises the steps of:
(1) preparing high-dispersion nano white carbon black:
a preparation of grafted polystyrene: adding 100 parts by mass of polystyrene and 300-500 parts by mass of solvent into a reaction kettle, heating to 50-70 ℃, stirring for 5-10 hours, adding 5-20 parts by mass of unsaturated acrylate and 0.05-0.5 part by mass of initiator after the polystyrene is completely dissolved, stirring for reaction for 2-5 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain a polystyrene graft;
b, preparing high-dispersion nano white carbon black: adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of polyether polyol and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reacting for 1-3 hours; then adding 10-25 parts by mass of polystyrene graft, stirring for reaction for 2-4 hr, and performing flash evaporation, drying and grinding to obtain high-dispersion nano white carbon black;
(2) preparing graft solution polymerized styrene-butadiene rubber cement: adding 100-200 parts by mass of solvent into a polymerization kettle, sequentially adding 100 parts by mass of solution-polymerized styrene-butadiene rubber cement and 0.05-0.5 part by mass of molecular weight regulator, replacing with nitrogen, adding 5-15 parts by mass of unsaturated acrylate, stirring, heating, adding 0.1-0.4 part by mass of initiator when the temperature of the polymerization kettle reaches 50-60 ℃, reacting for 2-5 hours, and adding 1.0-3.0 parts by mass of terminator to prepare grafted rubber cement;
(3) preparation of rubber composition for high abrasion Green tire Tread: adding 100 parts by mass of solution polymerized styrene-butadiene rubber cement and 400-600 parts by mass of solvent into a coagulation kettle, stirring and mixing for 40-60 min, then adding 60-100 parts by mass of high-dispersion nano white carbon black and 5-15 parts by mass of grafted solution polymerized styrene-butadiene rubber cement, stirring and mixing for 50-60 min when the temperature is raised to 50-70 ℃, and finally performing wet deashing, drying and briquetting to obtain the high-wear-resistant green rubber composition for the tire tread.
10. The method of claim 9, wherein the molecular weight regulator is selected from the group consisting of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan, and tertiary hexadecyl mercaptan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811220228.6A CN111073086B (en) | 2018-10-18 | 2018-10-18 | Rubber composition for high-wear-resistance green tire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811220228.6A CN111073086B (en) | 2018-10-18 | 2018-10-18 | Rubber composition for high-wear-resistance green tire and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111073086A true CN111073086A (en) | 2020-04-28 |
| CN111073086B CN111073086B (en) | 2022-03-29 |
Family
ID=70309103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811220228.6A Active CN111073086B (en) | 2018-10-18 | 2018-10-18 | Rubber composition for high-wear-resistance green tire and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111073086B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011101A (en) * | 2022-07-14 | 2022-09-06 | 江苏长诺运动场地新材料有限公司 | High-suspension double-component polyurethane slurry and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1259565B1 (en) * | 2000-02-28 | 2008-11-26 | Pirelli Tyre S.p.A. | Silica reinforced rubber compositions of improved processability and storage stability |
| CN103524797A (en) * | 2012-07-05 | 2014-01-22 | 中国石油天然气股份有限公司 | Diene rubber composition and method for producing same |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN103665471A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Carbon black masterbatch rubber composition for tire and preparation method thereof |
| CN103665484A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber, composition and preparation method thereof |
| CN107266750A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | Rubber composition for tire tread and preparation method thereof |
-
2018
- 2018-10-18 CN CN201811220228.6A patent/CN111073086B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1259565B1 (en) * | 2000-02-28 | 2008-11-26 | Pirelli Tyre S.p.A. | Silica reinforced rubber compositions of improved processability and storage stability |
| CN103524797A (en) * | 2012-07-05 | 2014-01-22 | 中国石油天然气股份有限公司 | Diene rubber composition and method for producing same |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN103665471A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Carbon black masterbatch rubber composition for tire and preparation method thereof |
| CN103665484A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber, composition and preparation method thereof |
| CN107266750A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | Rubber composition for tire tread and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011101A (en) * | 2022-07-14 | 2022-09-06 | 江苏长诺运动场地新材料有限公司 | High-suspension double-component polyurethane slurry and preparation method thereof |
| CN115011101B (en) * | 2022-07-14 | 2023-11-21 | 江苏长诺运动场地新材料有限公司 | High-suspension-property double-component polyurethane slurry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111073086B (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107266750B (en) | Rubber composition for tire tread and preparation method thereof | |
| US7408005B2 (en) | Hairy polymeric nanoparticles | |
| CN107266748B (en) | Rubber composition containing modified nano white carbon black and preparation method thereof | |
| CN107266741B (en) | Rubber composition for tire tread and preparation method thereof | |
| EP1629021A1 (en) | Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire | |
| CN111073081B (en) | Rubber composition for green engineering tire and preparation method thereof | |
| CN111073086B (en) | Rubber composition for high-wear-resistance green tire and preparation method thereof | |
| CN113956376B (en) | Coupling agent for modifying liquid rubber, preparation method, application and modified white carbon black | |
| CN109627502B (en) | Composite material of natural rubber and preparation method thereof | |
| CN111073080B (en) | High-wear-resistance rubber composition for green tire and preparation method thereof | |
| Yin et al. | Preparation, properties of In‐situ silica modified styrene‐butadiene rubber and its silica‐filled composites | |
| CN111073077B (en) | Rubber composition for green engineering tire and preparation method thereof | |
| CN111073201A (en) | Anti-slippery rubber composition for green tire and preparation method thereof | |
| CN111073049A (en) | Modification method of nano white carbon black used as rubber filler | |
| CN111073078A (en) | Rubber composition for green tire tread and preparation method thereof | |
| CN111073079B (en) | Rubber composition for anti-slippery tire and preparation method thereof | |
| CN109897245B (en) | Preparation method of styrene butadiene rubber composition containing carbon nano tubes and used for tire tread | |
| CN111073200A (en) | Environment-friendly rubber composition and preparation method thereof | |
| CN111073039A (en) | Rubber composition for green tire tread and preparation method thereof | |
| CN111073045A (en) | Modification method of high-dispersion rubber filler nano white carbon black | |
| CN109897246B (en) | Preparation method of rubber composition containing high-dispersion carbon nano-tubes | |
| CN107266745B (en) | Rubber composition containing modified nano white carbon black and preparation method thereof | |
| CN111073044A (en) | Environment-friendly rubber composition and preparation method thereof | |
| CN111073076A (en) | Wet-skid-resistant rubber composition for green tire and preparation method thereof | |
| CN107266747A (en) | Rubber composition for tire tread and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |