WO2014018980A1 - Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions - Google Patents
Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions Download PDFInfo
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- WO2014018980A1 WO2014018980A1 PCT/US2013/052574 US2013052574W WO2014018980A1 WO 2014018980 A1 WO2014018980 A1 WO 2014018980A1 US 2013052574 W US2013052574 W US 2013052574W WO 2014018980 A1 WO2014018980 A1 WO 2014018980A1
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- WIPO (PCT)
- Prior art keywords
- weight percent
- silica
- group
- silane
- rubber
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 281
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 37
- 229920001971 elastomer Polymers 0.000 claims abstract description 52
- 239000005060 rubber Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 33
- 229920000126 latex Polymers 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 150000001993 dienes Chemical class 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 35
- 229910000077 silane Inorganic materials 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002174 Styrene-butadiene Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004816 latex Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000004606 Fillers/Extenders Substances 0.000 claims description 10
- -1 acryloxy group Chemical group 0.000 claims description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011115 styrene butadiene Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000459 Nitrile rubber Polymers 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 6
- 229920001021 polysulfide Polymers 0.000 claims description 6
- 150000008117 polysulfides Polymers 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
- 150000001282 organosilanes Chemical class 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 229920001059 synthetic polymer Polymers 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 abstract description 25
- 238000009472 formulation Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000010058 rubber compounding Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 238000010186 staining Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002209 Crumb rubber Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920013648 Perbunan Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
- C08J2309/08—Latex
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Definitions
- the present embodiments generally relate to a filled rubber composition formed using multiple coupling agents with silica.
- the present embodiments relate to a filled rubber composition formed using multiple coupling agents with silica capable of producing a tire with improved wet skid resistance and grip performance and for assisting a vehicle in achieve at least 35mpg.
- a benefit of this formulation is that two silane coupling agents can be used with silica to reduce sulfur content in a final rubber formulation.
- a benefit of this formation is that with the two silane coupling agents, a rubber is produced that has improved rolling resistance such as from 12 percent to 15 percent improve rolling resistance, as measured by tangent delta at 60 degrees Celsius.
- a benefit of this formulation is that tensile strength of the final rubber is expected to improve using at least two two silane coupling agents simultaneously.
- Still another benefit of this formulation is that improved elongation of the resultant polymeric rubber occurs by about 10 percent.
- the resultant rubber formulation for use in tires is more resilient, due to both a reduction in sulfur in the overall formulation and the usage of a second silane, which provides enhanced structural properties, such as at elevated temperatures.
- the presence of sulfur can be detrimental to long life in a rubber formulation.
- formulation provides a lower Mooney viscosity for the resultant composite, with the Mooney viscosity reduced by about 10 percent over formulations that contain only one silane coupling agent.
- a lower Mooney viscosity results because the two different silanes, bond to two different sites, wherein one of the sites would have been seized by the sulfur.
- Still another benefit of the unique dual silane silica masterbatch is reduced scorch for a final rubber formulation using the masterbatch.
- the scorch is expected to be reduced by at least 2 percent.
- dry silica can be used for forming the filled rubber.
- the dry silica can be powdered, pelletized, or flakes. It is important that the silica is dry, having no liquid component.
- the silica can have from 4 weight percent to 8 weight percent moisture in an embodiment, and up to 10 percent moisture in other embodiments, and still be usable herein.
- the silica can have a usable specific surface area in the range of 100 to 300 m 2 /g m.
- Usable dry silica can be HISILTM 233 available from PPG Industries of Pittsburg, Pennsylvania.
- the dry silica which is not pretreated can be flakes/granular material such as HISILTM 243 LD available from PPG Industries.
- Embodiments can depict that more than two, such as three different silanes can also be added and coupled to silica by this process.
- two or more silane coupling agents can be added directly to the rubber formulation in an internal mixer through dry blending and are then introduced into the rubber only after the silanes are attached onto the silica filler, such as by dry blending or by wet masterbatch process.
- the mixtures of multiple coupling agents synergistically provide enhanced mechanical properties like lower rolling resistance, and enhanced tear strength.
- silica is discussed as one of the fillers to which the multiple silanes can couple
- other usable fillers can be inorganic clays to which the multiple silanes can be bound prior to introduction into the polymeric rubber, such as styrene-butadiene.
- the silica in an embodiment can be a highly dispersible filler with a regular or consistent shape.
- the individual silane coupling agents can contain one or more of the following functionalities; polysulfide, mercapto, thiocyanato, alkoxy, halogen, amino or none [-CH 2 - linkages].
- the individual weight percentages for each of the two silanes can range from 0.1 percent to 99.9 percent of the total filler weight percentage in the formulation.
- the silane coupling agents can be from 1 weight percent to 15 weight percent of the final mastserbatch.
- the silane can be attached to the silica in a single, monolayer, process, such as by spraying the silane onto the silica while mixing in a ribbon mixer.
- the silica with attached silanes can be added to a styrene butadiene rubber or similar polymeric rubber and form a wet polymer silica masterbatch from 40 weight percent to 90 weight percent of rubber latex; and from 1 weight percent to 40 weight percent of a functionalized silica.
- Additives and other components can be added to the silica wet masterbatch by different techniques, namely:
- silica wet masterbatch (i) direct addition to the silica wet masterbatch by mixing in an internal mixer, extruder, or other compounding mixer the silica wet masterbatch with other compound ingredients, such as oil, or a carbon black as an antistatic agent, or a colorant, such as a pigment, or an additive, or an antioxidant, or combinations of these other compound ingredients;
- other compound ingredients such as oil, or a carbon black as an antistatic agent, or a colorant, such as a pigment, or an additive, or an antioxidant, or combinations of these other compound ingredients
- the final rubber composite can contain from 10 weight percent to 50 weight percent silica and can be used with styrene-butadiene, (SBR), synthetic rubber copolymer of acrylomtrile (ACN) and butadiene also known as Buna-N, Perbunan, (NBR).
- SBR styrene-butadiene
- ACN acrylomtrile
- NBR butadiene also known as Buna-N, Perbunan,
- Styrene-butadiene or styrene-butadiene rubber is a synthetic rubber copolymer consisting of styrene and butadiene.
- SBR has abrasion resistance and good aging stability when protected by additives, and is widely used in tires, where it can be blended with natural rubber.
- SBR can be produced by two basically different processes: the process known as solution (S-SBR) or the process known as emulsion processing.
- the process of the formulation can include installing the dual coupling agents into the silica and then installing the functionalized silica into the styrene-butadiene rubber using the emulsion process.
- the reaction is by ionic polymerization, in the emulsion polymerization case, the reaction is via free radical polymerization.
- Nitrile butadiene rubber is a family of unsaturated copolymers of 2- propenenitrile and various butadiene monomers (1,2-butadiene and 1,3 -butadiene) usable herein. Although its physical and chemical properties vary depending on the polymer's composition of nitrile, this NBR form of synthetic rubber is generally resistant to oil, fuel, and other chemicals (the more nitrile within the polymer, the higher the resistance to oils but the lower the flexibility of the material.
- Nitrile rubber lattices along with other rubber compound ingredients, including other rubbers, stabilizers, extenders, and additives can be used to form the latex formulation.
- the resultant material with the silica having two coupling agents will release fewer volatile organic compounds, such as ethanol, in-part because a coupling of ethoxy groups or methoxy groups with two different silanol groups with silica, compared without silica with only one coupling agent, thereby significantly reducing the possibility of ethanol or methanol evolution.
- the resultant material having the dual silane coupling on the silica in the rubber is expected to improve safety in a chemical plant making the rubber composite by reducing the presence of volatile organic compounds in the plant containing the resultant product, thereby reducing the chance of a fire or an explosion or a major incident, from a reaction with ethanol vapors.
- the invention is expected to improve the American economy because the composition is expected to produce tires with improved gas mileage allowing compliance with a corporate average fleet economy (CAFE) regulation, namely 35 mpg, which allows the American consumers to save money on gasoline.
- CAFE corporate average fleet economy
- This formulation will result in products that prevent fines from being levied on American car manufacturers for tire non-compliance, thereby making them more competitive in the world marketplace.
- the silica can be dry silica which is untreated.
- One of the untreated silicas usable herein can be HISIL from PPG known as HISIL
- a usable silica herein can be a pretreated silica, such as a silica that has been modified to have the following physical and/or chemical parameters: a loss on drying ranging from about 0.1 percent to about 10 percent as determined by the Deutsches Institut Fur Normung E.V. (DIN), International Organization for Standardization (ISO) 787/2; a loss on ignition ranging from 2 percent to 25 percent as determined by the Deutsches Institut Fur Normung E.V., International Organization for Standardization (ISO) 3262/11 ; a methanol wettability ranging from 20 percent to 80 percent (titrated); a carbon content ranging from 1 percent to 30 percent, and a sulfur content ranging from 0.1 percent to 10 percent.
- a loss on drying ranging from about 0.1 percent to about 10 percent as determined by the Deutsches Institut Fur Normung E.V. (DIN), International Organization for Standardization (ISO) 787/2
- a loss on ignition ranging from 2 percent to 25 percent as determined by the Deutsches
- the untreated or pretreated silica used for silane coupling is envisioned to be from
- a first silane usable with the silica as a coupling agent can be an organosilicon derived from an organic silane having the structure: Z 1 Z 2 Z 3 Si(CH 2 ) y X(CH 2 ) y SIZ 1 Z 2 Z 3 .
- X can be a polysulfide
- Y can be an integer equal to or greater than 1
- Zi, Z 2 , and Z 3 can each be independently selected from the group consisting of hydrogen, alkoxy, halogen, and hydroxyl.
- a second silane usable with the silica as a coupling agent simultaneously with the first silane can be an organosilicon, which can be derived from an organic silane x— (c3 ⁇ 4) y — f Si— z 2
- X can be a functional group selected from the group consisting of: hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group, and a methacryloxy group.
- the Y can be an integer equal to or greater than 0.
- the Zi, Z 2 , and Z3 can each be independently selected from the group consisting of hydrogen, alkoxy, halogen, and hydroxyl.
- the organosilicon bonds to a surface of the silica.
- the amount of the organosilicon that is bonded to the surface of the silica can range from about 2 weight percent to about 25 weight percent per weight of the silica.
- the organosilicon can have three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon.
- the organosilicon can have at least one organic group attached directly to the silicon atom of the organosilicon.
- the organic group can contain at least one functional group.
- the two different coupling agents can have different functionalities, such as one can be a mercapto, another can be a cycloalkyl.
- the coupling agents can be different functionalities selected from the group: polysulfide, mercapto, thiocyanato, halogen, amino, or aliphatic, aromatic, vinylic, cycloalkyl and combinations thereof.
- a third silane can be added to two selected silanes for use on the silica.
- the third coupling agent can be an ethanol free silane, such as those from the family of NXTTM silanes available from Momentive Performance Materials of Wilton, Connecticut.
- the third type of silane in an embodiment can have a silicon end of the molecule with silicon atoms bridged through non- volatile diols.
- the mercapto and blocked mercapto groups of this third silane offer different coupling reactivity with the polymer when compared to the first two mentioned silanes.
- the mercapto group reacts with the polymer during nonproductive mixing stages while the blocked mercapto group aids in the dispersion of the silica.
- the octanoyl-blocking group is removed during the productive mixing stage and curing step, additional mercapto silane is formed.
- Proton donors can include the vulcanization ingredients, which can assist in the removal of the octanoyl blocking group for improved physical properties.
- the silica can be coupled to the silane coupling agents by spraying the dry untreated or pretreated silica with the coupling agents, such as with an air carrier, or simply with pressure from a pump, in a ribbon blender or a fluidized bed.
- the ribbon blender can mix at a rate ranging from 5 revolutions per minute to 20 revolutions per minute.
- Embodiments can include forming a functionalized silica for blending with organic polymers that includes from 0.1 weight percent to 25 weight percent of a plurality of silane coupling agents simultaneously on the silica.
- the plurality of silane coupling agents can be a first silane that is an organosilicon derived from an organic silane having the structure:ZiZ2Z 3 Si(CH2) y X(CH2)ySIZiZ2Z 3 , wherein X is a polysulfide, wherein Y is an integer equal to or greater than 1 ; and wherein Zi, Z 2 , and Z3 are each independently selected from the group consisting of hydrogen, alkoxy, halogen, and hydroxyl.
- a second silane can be an organo silane an organosilicon derived from an organic
- silane having the structure 3 ⁇ 4 wherein:X is a functional group selected from the group consisting of: hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group and a methacryloxy group; Y is an integer equal to or greater than 0; and Z l 5 Z 2 , and Z 3 are each independently selected from the group consisting of: hydrogen, alkoxy, halogen, and hydroxyl, and combinations thereof.
- the resulting functionalized silica has a sulfur content ranging from
- the organosilicon bonded to a surface of the silica has three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon, and has at least one organic group attached directly to the silicon atom.
- the organosilicon bonded to a surface of the silica has an organic group attached directly to a silicon atom of the organosilicon.
- the organic group contains at least one functional group.
- a mercapto group is used in one of the silanes, the mercapto group can have a sulfur content from 0.1 weight percent to 10 weight percent.
- the present embodiments relate to blending at least two different silanes and then attaching the two different silanes onto the silica forming treated silica and then further incorporating the treated silica with at least two silanes into a rubber component that includes a styrene-butadiene copolymer rubber, or a blend of the styrene-butadiene copolymer rubber, and another conjugated diene base rubbers as noted above in the description of the SBR and NBR.
- the rubber can be a polymeric rubber latex which can be styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyvinylchloride, acrylonitrile-butadiene-styrene polymer, carboxylated styrene butadiene, carboxylated acrylonitrile-butadiene, styrene-acrylonitrile copolymer, polybutadiene, polyisoprene, polychloroprene, neoprene, polybutadiene-isoprene, or combinations thereof.
- styrene-butadiene rubber acrylonitrile-butadiene rubber
- polyvinylchloride acrylonitrile-butadiene-styrene polymer
- carboxylated styrene butadiene carboxylated acrylonitrile-butadiene
- the rubber component can also be a polymeric rubber latex of copolymers including a copolymer of: styrene and butadiene, styrene and isoprene, styrene and acrylonitrile, or butadiene and acrylonitrile.
- An example of a usable additive is an oil extender, such as SANDEXTM 8000 EU oil
- antioxidants such as non-staining
- NAUGARDTM RM 51 from Chemtura, or a staining antioxidant known as SANTOFLEXTM134PD from Flexsys America.
- additives can be added into the rubber composition filled with silica having two silanes coupled thereto.
- An example of another usable additive is a lubricant such as wax.
- Other usable additives enhance cure, such as zinc oxide and stearic acid.
- resins, such as phenols formaldehyde can be added as a tackifier for the rubber.
- Still other additives include colorants and pigments such as titanium dioxide as an opacifier.
- the resultant formulation can be used in the production of car tires.
- Formulations with staining properties can be used for tires and inner tubes, conveyor belts, footwear, cables, hosepipes and various technical rubber articles.
- Non-staining grades of the composite rubber formed with the plurality of silane attached to the filler silica can include rubber appropriate for compounds used in the production of floor coverings, bicycle tires, footwear, children toys, cables, hosepipes and various rubber articles having light color shades.
- a pretreated silica can be treated with a first silane then coupled to a second silane and then added to the latex slurry.
- the rubber and the silane coupled silica slurries can then be coagulated.
- the coagulating agents can include: a solution of calcium chloride, zinc chloride, salts of aluminum, salts of magnesium, sulfuric acid, citric acid coagulate, ferric chloride, isopropanol, or combinations thereof.
- one or more embodiments can include blending calcium chloride in water to dilute from about 0.5 weight percent to about 5 weight percent of the calcium chloride in the water; thereby forming a calcium chloride solution as the coagulant.
- the rubber formulation can be made by adding the latex slurry to the coagulant, such as the calcium chloride solution, while continually stirring.
- the coagulate can be added to the latex slurry at a rate of 10 gallons a minute, with the coagulate at an ambient temperatures and the latex at 70 degrees Celsius for a time sufficient to obtain a uniform mixture as observed by visual inspection.
- the formulation can be produced while allowing coagulation of the latex slurry, for about 30 seconds to about 10 minutes to form the functionalized silica loaded polymeric rubber composite.
- dry silica as used herein can mean silica pretreatment by blending a dry silica with dry silane coupling agents in a blender without adding additional aqueous solution during blending and continuing to blend at a desired temperature with one or more usable catalysts.
- the embodiments further relate to a wet polymer silica masterbatch formed using the silica with two silanes coupled thereto.
- a wet polymer masterbatch can be made from an emulsion latex of a styrene butadiene synthetic rubber and a functionalized silica wherein the dry silica contains from 0.1 weight percent to 25 weight percent of the plurality of silane coupling agents, simultaneously.
- an emulsion styrene butadiene rubber latex can be used with 10 weight percent to 75 weight percent of polymer molecules in water.
- the wet polymer silica masterbatch can include an oil extender, forming a polymer rubber composite with 1 weight percent to 35 weight percent of the functionalized silica, from 1 weight percent to 35 weight percent of the oil extender, and from 30 weight percent to 98 weight percent of the styrene butadiene rubber.
- an oil extender can be SANDEXTM
- the wet polymer silica masterbatch can include an antioxidant. If only an antioxidant is used, the formed polymer rubber composite can have from 1 weight percent to 35 weight percent of the functionalized silica, from 0.1 weight percent to 2 weight percent of an antioxidant, and from 67 weight percent to 99 weight percent of the styrene butadiene rein.
- an antioxidant can be a non-staining antioxidant, such as NAUGARDTM RM 51 from Chemtura, or a staining antioxidant known as S ANTOFLEXTM 134PD from Flexsys America.
- the oil extender can be added to the antioxidant and then both can be added to the formulation of silanized silica in the rubber latex.
- the wet polymer silica masterbatch can include a carbon black slurry.
- a usable carbon black slurry can contain from 4 weight percent to 6 weight percent carbon black in water.
- the composition of the polymer rubber composite can be from 1 weight percent to 35 weight percent functionalized silica, from 1 weight percent to 49 weight percent of carbon black, and from 16 weight percent to 98 weight percent of the styrene butadiene producing a composite with an improved tear strength.
- the carbon black can be added to the oil extender and then added to the rubber latex.
- the carbon black can be added to the antioxidant and then added to the rubber latex prior to blending.
- the carbon black, antioxidant, and oil extender can all be blended into the latex simultaneously.
- the formed composite can be used to form an article made of the polymeric rubber material, such as a retread, or a tennis or safety shoe sole.
- Example 1- Forming A Functionalized Silica By Spraying Blends of Silane Onto
- OTES from Gelest are stirred together in a beaker or other vessel for about 10 minutes at an ambient temperature.
- the silanes can be sprayed into the silica using a pump which increases flow pressure by using a narrow tube with 1-2 mm diameter pin holes and a conical flow pattern.
- the temperature in the ribbon blender is raised to 120 degrees Celsius and blended at the elevated temperature for 2 hours.
- the blender is allowed to cool to an ambient temperature and the treated silica is discharged from the blender.
- the treated silica is then weighed to produce slurry with 17 weight percent treated silica in water.
- the silica and water are stirred at room temperature under high shear blending conditions for about an hour.
- Example 2 Forming A Polymeric Rubber Composite Using Pretreated Silica
- silanes are deposited on the silica such as by spraying as described earlier.
- the treated silica is then added to a carrier to make a slurry with 17 weight percent treated silica in water.
- the treated silica slurry is then heated forming a heated slurry.
- Carbon black slurry can be added to the heated slurry. 0.2 pounds of carbon black is then mixed with water to form a carbon black slurry. 5.5 pounds of carbon black slurry is added at ambient temperatures to the heated slurry and then the carbon black heated mixture is heated to 70 degrees Celsius forming a carbon black silica heated slurry.
- the carbon black silica heated slurry is added to the latex slurry, forming a blend of two slurries.
- the blend of the two slurries is mixed while maintaining a temperature of about 70 degrees Celsius for a time period of about 2 minutes until uniform mixing is achieved by visual inspection.
- Coagulant is slowly added to the heated blend of two slurries changing the pH of the blend to a desired pH to provide desired coagulated crumb rubber properties.
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Abstract
A rubber composition and a tire using the rubber composition utilizing a functionalized silica dry precipitated silica with a specific surface area in the range of 100 to 300 m2/gm treated with a plurality of silanes coupling agents to form a wet polymer silica masterbatch, then blending the masterbatch with a latex rubber component that includes a styrene-butadiene copolymer rubber or a blend of the styrene-butadiene copolymer rubber and another conjugated diene base rubber using a plurality of coupling agents simultaneously.
Description
TITLE: FUNCTIONALIZED SILICA FOR SILICA WET MASTERBATCHES AND STYRENE BUTADIENE RUBBER COMPOSITIONS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to and the benefit of co-pending US Patent
Application Serial No.: 13/560,844 filed on July 27, 2012, entitled "FUNCTIONALIZED SILICA FOR SILICA WET MASTERBATCHES AAD STYRENE BUTADIENE RUBBER COMPOSITIONS," which claims priority to US Provisional Patent Application Serial No. 61/594,259 filed on February 02, 2012, entitled "FUNCTIONALIZED SILICA FOR RUBBER MASTERBATCH" and is a Continuation in Part of co-pending US Patent Application Serial No. 13/525,199 filed on June 15, 2012, entitled "METHOD FOR PRODUCING HIGH SILICA LOADED POLYMERIC RUBBER COMPOSITE WITH A PRETREATED SILICA," which claims priority to US Provisional Patent Application Serial No. 61/497,312 filed on June 15, 2011, entitled "METHOD FOR PRODUCING HIGH SILICA LOADED POLYMERIC RUBBER COMPOSITE WITH A PRETREATED SILICA." These references are hereby incorporated in its entirety.
FIELD
The present embodiments generally relate to a filled rubber composition formed using multiple coupling agents with silica.
BACKGROUND
[0003] A need exists for filler that can be easily incorporated into styrene-butadiene during an emulsion process. [0004] A need exists for a silica filler that provides mixing and performance benefits as well as a resulting rubber formulation with reduced sulfur content.
[0005] A need exists for a rubber composition for use in tires formulated using an emulsion styrene butadiene rubber process with a silica masterbatch having multiple coupling agents simultaneously.
[0006] The present embodiments meet these needs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] N/A
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0008] Before explaining the present formulation in detail, it is to be understood that the formulation is not limited to the particular embodiments and that it can be practiced or carried out in various ways.
[0009] The present embodiments relate to a filled rubber composition formed using multiple coupling agents with silica capable of producing a tire with improved wet skid resistance and grip performance and for assisting a vehicle in achieve at least 35mpg.
[00010] A benefit of this formulation is that two silane coupling agents can be used with silica to reduce sulfur content in a final rubber formulation.
[00011] A benefit of this formation is that with the two silane coupling agents, a rubber is produced that has improved rolling resistance such as from 12 percent to 15 percent improve rolling resistance, as measured by tangent delta at 60 degrees Celsius.
[00012] A benefit of this formulation is that tensile strength of the final rubber is expected to improve using at least two two silane coupling agents simultaneously.
[00013] Still another benefit of this formulation is that improved elongation of the resultant polymeric rubber occurs by about 10 percent.
[00014] By using at least two coupling agents simultaneously, the resultant rubber
formulation for use in tires is more resilient, due to both a reduction in sulfur in the overall formulation and the usage of a second silane, which provides enhanced structural properties, such as at elevated temperatures. The presence of sulfur can be detrimental to long life in a rubber formulation.
Another benefit of this formulation is that the formulation provides a lower Mooney viscosity for the resultant composite, with the Mooney viscosity reduced by about 10 percent over formulations that contain only one silane coupling agent.
A lower Mooney viscosity results because the two different silanes, bond to two different sites, wherein one of the sites would have been seized by the sulfur.
It is expected with the final rubber formulation improved processability for the rubber composite by reducing heating times and curing times by improving compatibilization between the silica and the rubber.
Still another benefit of the unique dual silane silica masterbatch is reduced scorch for a final rubber formulation using the masterbatch. The scorch is expected to be reduced by at least 2 percent.
In this composition, dry silica can be used for forming the filled rubber.
In an embodiment, the dry silica can be powdered, pelletized, or flakes. It is important that the silica is dry, having no liquid component.
The silica can have from 4 weight percent to 8 weight percent moisture in an embodiment, and up to 10 percent moisture in other embodiments, and still be usable herein.
In embodiments where the silica is powdered, the silica can have a usable specific surface area in the range of 100 to 300 m2/g m.
Usable dry silica can be HISIL™ 233 available from PPG Industries of Pittsburg, Pennsylvania. The dry silica which is not pretreated can be flakes/granular material
such as HISIL™ 243 LD available from PPG Industries.
Embodiments can depict that more than two, such as three different silanes can also be added and coupled to silica by this process.
In this process, two or more silane coupling agents can be added directly to the rubber formulation in an internal mixer through dry blending and are then introduced into the rubber only after the silanes are attached onto the silica filler, such as by dry blending or by wet masterbatch process.
The mixtures of multiple coupling agents synergistically provide enhanced mechanical properties like lower rolling resistance, and enhanced tear strength.
Although silica is discussed as one of the fillers to which the multiple silanes can couple, other usable fillers can be inorganic clays to which the multiple silanes can be bound prior to introduction into the polymeric rubber, such as styrene-butadiene.
The silica in an embodiment can be a highly dispersible filler with a regular or consistent shape.
The individual silane coupling agents can contain one or more of the following functionalities; polysulfide, mercapto, thiocyanato, alkoxy, halogen, amino or none [-CH2- linkages].
When used in an embodiment, the individual weight percentages for each of the two silanes can range from 0.1 percent to 99.9 percent of the total filler weight percentage in the formulation. The silane coupling agents can be from 1 weight percent to 15 weight percent of the final mastserbatch.
In an embodiment, the silane can be attached to the silica in a single, monolayer, process, such as by spraying the silane onto the silica while mixing in a ribbon mixer. The silica with attached silanes can be added to a styrene butadiene rubber or similar
polymeric rubber and form a wet polymer silica masterbatch from 40 weight percent to 90 weight percent of rubber latex; and from 1 weight percent to 40 weight percent of a functionalized silica.
Additives and other components can be added to the silica wet masterbatch by different techniques, namely:
(i) direct addition to the silica wet masterbatch by mixing in an internal mixer, extruder, or other compounding mixer the silica wet masterbatch with other compound ingredients, such as oil, or a carbon black as an antistatic agent, or a colorant, such as a pigment, or an additive, or an antioxidant, or combinations of these other compound ingredients;
(ii) addition by adding the compound ingredients to the silica pretreated with the chosen coupling agents in an internal mixer, extruder or other compounding mixer prior to forming the wet masterbatch; or
(iii) addition prior to rubber compounding but after the wet rubber masterbatch is formed by incorporating the silica pretreated with the chosen silane coupling blend via a wet rubber master batch process prior to compounding the rubber in an internal mixer, extruder, or other compounding mixer with other compound ingredients.
The final rubber composite can contain from 10 weight percent to 50 weight percent silica and can be used with styrene-butadiene, (SBR), synthetic rubber copolymer of acrylomtrile (ACN) and butadiene also known as Buna-N, Perbunan, (NBR).
Styrene-butadiene or styrene-butadiene rubber (SBR) is a synthetic rubber copolymer consisting of styrene and butadiene. SBR has abrasion resistance and good aging stability when protected by additives, and is widely used in tires, where it can be blended with natural rubber. SBR can be produced by two basically different processes: the process known as
solution (S-SBR) or the process known as emulsion processing.
[00037] The process of the formulation can include installing the dual coupling agents into the silica and then installing the functionalized silica into the styrene-butadiene rubber using the emulsion process.
[00038] In the solution process, the reaction is by ionic polymerization, in the emulsion polymerization case, the reaction is via free radical polymerization.
[00039] Nitrile butadiene rubber (NBR) is a family of unsaturated copolymers of 2- propenenitrile and various butadiene monomers (1,2-butadiene and 1,3 -butadiene) usable herein. Although its physical and chemical properties vary depending on the polymer's composition of nitrile, this NBR form of synthetic rubber is generally resistant to oil, fuel, and other chemicals (the more nitrile within the polymer, the higher the resistance to oils but the lower the flexibility of the material.
[00040] Nitrile rubber lattices, along with other rubber compound ingredients, including other rubbers, stabilizers, extenders, and additives can be used to form the latex formulation.
[00041] The resultant material with the silica having two coupling agents, will release fewer volatile organic compounds, such as ethanol, in-part because a coupling of ethoxy groups or methoxy groups with two different silanol groups with silica, compared without silica with only one coupling agent, thereby significantly reducing the possibility of ethanol or methanol evolution.
[00042] The resultant material having the dual silane coupling on the silica in the rubber is expected to improve safety in a chemical plant making the rubber composite by reducing the presence of volatile organic compounds in the plant containing the resultant product, thereby reducing the chance of a fire or an explosion or a major incident, from a reaction with ethanol vapors.
[00043] The invention is expected to improve the American economy because the composition is expected to produce tires with improved gas mileage allowing
compliance with a corporate average fleet economy (CAFE) regulation, namely 35 mpg, which allows the American consumers to save money on gasoline. This formulation will result in products that prevent fines from being levied on American car manufacturers for tire non-compliance, thereby making them more competitive in the world marketplace.
[00044] The following is more detail on the ingredients that can be used in creating the unique rubber composite.
[00045] In one or more embodiments, the silica can be dry silica which is untreated.
[00046] One of the untreated silicas usable herein can be HISIL from PPG known as HISIL
233, which has the following chemical/physical properties: 113 meters squared per gram.
[00047] In another embodiment, a usable silica herein, can be a pretreated silica, such as a silica that has been modified to have the following physical and/or chemical parameters: a loss on drying ranging from about 0.1 percent to about 10 percent as determined by the Deutsches Institut Fur Normung E.V. (DIN), International Organization for Standardization (ISO) 787/2; a loss on ignition ranging from 2 percent to 25 percent as determined by the Deutsches Institut Fur Normung E.V., International Organization for Standardization (ISO) 3262/11 ; a methanol wettability ranging from 20 percent to 80 percent (titrated); a carbon content ranging from 1 percent to 30 percent, and a sulfur content ranging from 0.1 percent to 10 percent.
[00048] The untreated or pretreated silica used for silane coupling is envisioned to be from
10 weight percent to 40 weight percent of the final composite.
[00049] A first silane usable with the silica as a coupling agent can be an organosilicon derived from an organic silane having the structure: Z1Z2Z3Si(CH2)yX(CH2)ySIZ1Z2Z3. Within the structure, X can be a polysulfide, Y can be an integer equal to or greater than 1, and Zi, Z2, and Z3 can each be independently selected from the group consisting of hydrogen, alkoxy, halogen, and
hydroxyl.
[00050] A second silane usable with the silica as a coupling agent simultaneously with the first silane, can be an organosilicon, which can be derived from an organic silane x— (c¾)y— f Si— z2
having the chemical structure ¾ . Within the chemical structure, the
X can be a functional group selected from the group consisting of: hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group, and a methacryloxy group. Within the chemical structure, the Y can be an integer equal to or greater than 0. Within the chemical structure, the Zi, Z2, and Z3 can each be independently selected from the group consisting of hydrogen, alkoxy, halogen, and hydroxyl.
[00051] The organosilicon bonds to a surface of the silica. The amount of the organosilicon that is bonded to the surface of the silica can range from about 2 weight percent to about 25 weight percent per weight of the silica.
[00052] The organosilicon can have three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon.
[00053] The organosilicon can have at least one organic group attached directly to the silicon atom of the organosilicon. The organic group can contain at least one functional group.
[00054] As mentioned earlier the two different coupling agents can have different functionalities, such as one can be a mercapto, another can be a cycloalkyl. The coupling agents can be different functionalities selected from the group: polysulfide, mercapto, thiocyanato, halogen, amino, or aliphatic, aromatic, vinylic, cycloalkyl and combinations thereof.
[00055] A third silane can be added to two selected silanes for use on the silica. The third coupling agent can be an ethanol free silane, such as those from the family of
NXT™ silanes available from Momentive Performance Materials of Wilton, Connecticut.
[00056] The third type of silane in an embodiment can have a silicon end of the molecule with silicon atoms bridged through non- volatile diols. The mercapto and blocked mercapto groups of this third silane offer different coupling reactivity with the polymer when compared to the first two mentioned silanes.
[00057] For this third silane, the mercapto group reacts with the polymer during nonproductive mixing stages while the blocked mercapto group aids in the dispersion of the silica. When the octanoyl-blocking group is removed during the productive mixing stage and curing step, additional mercapto silane is formed. Proton donors can include the vulcanization ingredients, which can assist in the removal of the octanoyl blocking group for improved physical properties.
[00058] The combinations of the multiple silanes, create different couplings which increase coupling between silica and polymer but reduce sulfur presence in the formulation.
[00059] The silica can be coupled to the silane coupling agents by spraying the dry untreated or pretreated silica with the coupling agents, such as with an air carrier, or simply with pressure from a pump, in a ribbon blender or a fluidized bed.
[00060] If a ribbon blender is used, it is anticipated that the ribbon blender can mix at a rate ranging from 5 revolutions per minute to 20 revolutions per minute.
[00061] Embodiments can include forming a functionalized silica for blending with organic polymers that includes from 0.1 weight percent to 25 weight percent of a plurality of silane coupling agents simultaneously on the silica.
[00062] The plurality of silane coupling agents can be a first silane that is an organosilicon derived from an organic silane having the structure:ZiZ2Z3Si(CH2)yX(CH2)ySIZiZ2Z3, wherein X is a polysulfide, wherein Y is an integer equal to or greater than 1 ; and wherein Zi, Z2, and Z3 are each independently selected from the group consisting of hydrogen, alkoxy, halogen, and
hydroxyl.
[00063] A second silane can be an organo silane an organosilicon derived from an organic
X (CH2)y Si Z2
silane having the structure ¾ , wherein:X is a functional group selected from the group consisting of: hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group and a methacryloxy group; Y is an integer equal to or greater than 0; and Zl 5 Z2, and Z3 are each independently selected from the group consisting of: hydrogen, alkoxy, halogen, and hydroxyl, and combinations thereof.
[00064] In embodiments, the resulting functionalized silica has a sulfur content ranging from
0.1 weight percent to 10 weight percent.
[00065] In embodiments, the organosilicon bonded to a surface of the silica, has three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon, and has at least one organic group attached directly to the silicon atom.
[00066] In an embodiment, the organosilicon bonded to a surface of the silica has an organic group attached directly to a silicon atom of the organosilicon. The organic group contains at least one functional group.
[00067] In one or more embodiments, a mercapto group is used in one of the silanes, the mercapto group can have a sulfur content from 0.1 weight percent to 10 weight percent.
[00068] The present embodiments relate to blending at least two different silanes and then attaching the two different silanes onto the silica forming treated silica and then further incorporating the treated silica with at least two silanes into a rubber component that includes a styrene-butadiene copolymer rubber, or a blend of the styrene-butadiene copolymer rubber, and another conjugated diene base rubbers as noted above in the description of the SBR and NBR.
[00069] The rubber can be a polymeric rubber latex which can be styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyvinylchloride, acrylonitrile-butadiene-styrene polymer, carboxylated styrene butadiene, carboxylated acrylonitrile-butadiene, styrene-acrylonitrile copolymer, polybutadiene, polyisoprene, polychloroprene, neoprene, polybutadiene-isoprene, or combinations thereof.
[00070] The rubber component can also be a polymeric rubber latex of copolymers including a copolymer of: styrene and butadiene, styrene and isoprene, styrene and acrylonitrile, or butadiene and acrylonitrile.
[00071] Other additives can be added to the silica treated with the two or more silanes.
[00072] An example of a usable additive is an oil extender, such as SANDEX™ 8000 EU oil
- which yields a final rubber formulation with a lower viscosity and improved processability.
[00073] Another additive usable herein can include antioxidants such as non-staining
NAUGARD™ RM 51 from Chemtura, or a staining antioxidant known as SANTOFLEX™134PD from Flexsys America.
[00074] Other additives can be added into the rubber composition filled with silica having two silanes coupled thereto. An example of another usable additive is a lubricant such as wax. Other usable additives enhance cure, such as zinc oxide and stearic acid. Additionally resins, such as phenols formaldehyde can be added as a tackifier for the rubber. Still other additives include colorants and pigments such as titanium dioxide as an opacifier.
[00075] The resultant formulation can be used in the production of car tires. Formulations with staining properties can be used for tires and inner tubes, conveyor belts, footwear, cables, hosepipes and various technical rubber articles.
[00076] Non-staining grades of the composite rubber formed with the plurality of silane attached to the filler silica can include rubber appropriate for compounds used in the production of floor coverings, bicycle tires, footwear, children toys, cables,
hosepipes and various rubber articles having light color shades.
[00077] In embodiments, a pretreated silica can be treated with a first silane then coupled to a second silane and then added to the latex slurry.
[00078] The rubber and the silane coupled silica slurries can then be coagulated. The coagulating agents can include: a solution of calcium chloride, zinc chloride, salts of aluminum, salts of magnesium, sulfuric acid, citric acid coagulate, ferric chloride, isopropanol, or combinations thereof.
[00079] For example, one or more embodiments can include blending calcium chloride in water to dilute from about 0.5 weight percent to about 5 weight percent of the calcium chloride in the water; thereby forming a calcium chloride solution as the coagulant.
[00080] In an embodiment, the rubber formulation can be made by adding the latex slurry to the coagulant, such as the calcium chloride solution, while continually stirring. The coagulate can be added to the latex slurry at a rate of 10 gallons a minute, with the coagulate at an ambient temperatures and the latex at 70 degrees Celsius for a time sufficient to obtain a uniform mixture as observed by visual inspection.
[00081] The formulation can be produced while allowing coagulation of the latex slurry, for about 30 seconds to about 10 minutes to form the functionalized silica loaded polymeric rubber composite.
[00082] The term "dry silica" as used herein can mean silica pretreatment by blending a dry silica with dry silane coupling agents in a blender without adding additional aqueous solution during blending and continuing to blend at a desired temperature with one or more usable catalysts.
[00083] The embodiments further relate to a wet polymer silica masterbatch formed using the silica with two silanes coupled thereto.
[00084] A wet polymer masterbatch can be made from an emulsion latex of a styrene
butadiene synthetic rubber and a functionalized silica wherein the dry silica contains from 0.1 weight percent to 25 weight percent of the plurality of silane coupling agents, simultaneously.
[00085] For the wet polymer silica masterbatch an emulsion styrene butadiene rubber latex can be used with 10 weight percent to 75 weight percent of polymer molecules in water.
[00086] In an embodiment, the wet polymer silica masterbatch can include an oil extender, forming a polymer rubber composite with 1 weight percent to 35 weight percent of the functionalized silica, from 1 weight percent to 35 weight percent of the oil extender, and from 30 weight percent to 98 weight percent of the styrene butadiene rubber.
[00087] In one or more embodiments, and example of an oil extender can be SANDEX™
8000 EU oil added to create a rubber composite with a low Mooney viscosity and improved processability for resultant tire formulations.
[00088] In an embodiment, the wet polymer silica masterbatch can include an antioxidant. If only an antioxidant is used, the formed polymer rubber composite can have from 1 weight percent to 35 weight percent of the functionalized silica, from 0.1 weight percent to 2 weight percent of an antioxidant, and from 67 weight percent to 99 weight percent of the styrene butadiene rein. In one or more embodiments, and example of an antioxidant can be a non-staining antioxidant, such as NAUGARD™ RM 51 from Chemtura, or a staining antioxidant known as S ANTOFLEX™ 134PD from Flexsys America.
[00089] In one or more embodiments, the oil extender can be added to the antioxidant and then both can be added to the formulation of silanized silica in the rubber latex.
[00090] In one or more embodiments, the wet polymer silica masterbatch can include a carbon black slurry. A usable carbon black slurry can contain from 4 weight percent to 6 weight percent carbon black in water. When the carbon black slurry is used, the
composition of the polymer rubber composite can be from 1 weight percent to 35 weight percent functionalized silica, from 1 weight percent to 49 weight percent of carbon black, and from 16 weight percent to 98 weight percent of the styrene butadiene producing a composite with an improved tear strength.
[00091] In one or more embodiments, the carbon black can be added to the oil extender and then added to the rubber latex.
[00092] In one or more embodiments, the carbon black can be added to the antioxidant and then added to the rubber latex prior to blending.
[00093] In one or more embodiments, the carbon black, antioxidant, and oil extender can all be blended into the latex simultaneously.
[00094] The formed composite can be used to form an article made of the polymeric rubber material, such as a retread, or a tennis or safety shoe sole.
[00095] Example 1- Forming A Functionalized Silica By Spraying Blends of Silane Onto
Silica Using An Air Carrier And Mixing the Sprayed Silanes Into the Silica Using A Ribbon Blender
[00096] In this example, 0.35 pounds of SI 69 silane and 0.35 pounds of octyl triethoxysilane
OTES from Gelest are stirred together in a beaker or other vessel for about 10 minutes at an ambient temperature.
[00097] Once the silanes are blended, 5 pounds of silica is placed into the ribbon blender.
[00098] In this example, 0.7 pounds of the blended silanes, and 0.1 pounds of acetic acid are then sprayed over the 5 pounds of silica in the ribbon blender and then the mixture is allowed to tumble at an ambient temperature for about 1 hour in the ribbon blender.
[00099] The silanes can be sprayed into the silica using a pump which increases flow pressure by using a narrow tube with 1-2 mm diameter pin holes and a conical flow pattern.
[000100] The temperature in the ribbon blender is raised to 120 degrees Celsius and blended at the elevated temperature for 2 hours.
[000101] The blender is allowed to cool to an ambient temperature and the treated silica is discharged from the blender.
[000102] The treated silica is then weighed to produce slurry with 17 weight percent treated silica in water. The silica and water are stirred at room temperature under high shear blending conditions for about an hour.
[000103] Example 2 - Forming A Polymeric Rubber Composite Using Pretreated Silica
[000104] In this example, a slurry of silanes is created as in Example 1.
[000105] The silanes are deposited on the silica such as by spraying as described earlier.
[000106] The treated silica is then added to a carrier to make a slurry with 17 weight percent treated silica in water. The treated silica slurry is then heated forming a heated slurry.
[000107] Carbon black slurry can be added to the heated slurry. 0.2 pounds of carbon black is then mixed with water to form a carbon black slurry. 5.5 pounds of carbon black slurry is added at ambient temperatures to the heated slurry and then the carbon black heated mixture is heated to 70 degrees Celsius forming a carbon black silica heated slurry.
[000108] Separately, about 17 pounds of preheated polymer rubber latex with 21 weight percent solids is blended with 0.1 pounds non-staining antioxidant NAUGARD™ RM51 emulsion, and 1.3 pounds of Ergon BO300 oil emulsion are blended at a temperature of 70 degrees Celsius for a time period of 5 minutes forming a latex slurry.
[000109] The carbon black silica heated slurry is added to the latex slurry, forming a blend of two slurries.
[000110] The blend of the two slurries is mixed while maintaining a temperature of about 70 degrees Celsius for a time period of about 2 minutes until uniform mixing is achieved by visual inspection.
[000111] Coagulant is slowly added to the heated blend of two slurries changing the pH of the blend to a desired pH to provide desired coagulated crumb rubber properties.
[000112] While these embodiments have been described with emphasis on the embodiments, it should be understood that within the scope of the appended claims, the embodiments might be practiced other than as specifically described herein.
Claims
; claimed is:
A functionalized silica useful for blending with organic polymers comprising: a) dry precipitated silica with a specific surface area in the range of from 100 m2/gm to 300 m2/gm; and b) from 0.1 weight percent to 25 weight percent of a plurality of silane coupling agents simultaneously, wherein the plurality of silane coupling agents comprises:
(i) a first silane is an organosilicon derived from an organic silane having the structure: ZiZ2Z3Si(CH2)yX(CH2)ySIZiZ2Z3, wherein X is a polysulfide, wherein y is an integer equal to or greater than 1 ; and wherein Zi, Z2, and Z3 are each independently selected from the group consisting of hydrogen, alkoxy, halogen, and hydroxyl; and
(ii) a second silane is an organo silane an organosilicon derived from an
X (CH2)y f Si Z2
organic silane having the structure ¾ , wherein:
(1) X is a functional group selected from the group consisting of: hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group and a methacryloxy group;
(2) Y is an integer equal to or greater than 0; and
(3) Zi, Z2, and Z3 are each independently selected from the group consisting of: hydrogen, alkoxy, halogen, and hydroxyl, and combinations thereof.
2. The functionalized silica of claim 1, further comprising a sulfur content ranging from 0.1
weight percent to 10 weight percent.
The functionalized silica of claim 1 , wherein the organosilicon is bonded to a surface of the silica, has three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon, and has at least one organic group attached directly to the silicon atom.
The functionalized silica of claim 1 , wherein the organosilicon is bonded to a surface of the silica and has an organic group attached directly to a silicon atom of the organosilicon that contains at least one functional group.
The functionalized silica of claim 1, wherein the mercapto group has a sulfur content ranging from 0.1 weight percent to 10 weight percent.
The functionalized silica of claim 1, further comprising a third silane coupling agent, from a family of silca coupling agents, wherein silcon atoms are bridged through nonvolatile diols.
A wet polymer silica masterbatch comprising: a) from 40 weight percent to 90 weight percent of a styrene butadiene rubber latex; and b) from 1.0 weight percent to 40 weight percent of a functionalized silica comprising:
(i) dry precipitated silica with a specific surface area in the range of 100 to 300 m2/gm; and
(ii) from 0.1 weight percent to 25 weight percent of a plurality of silane coupling agents simultaneously, wherein the plurality of silane coupling agents comprises:
1. a first silane is an organosilicon derived from an organic silane having the structure: ZiZ2Z3Si(CH2)yX(CH2)ySIZiZ2Z3, wherein X is a polysulfide, wherein Y is an integer equal to or greater than 1 ;
and wherein Zi, Z2, and Z3 are each independently selected from the group consisting of: hydrogen, alkoxy, halogen, and hydroxyl; and
2. a second silane is an organo silane an organosilicon derived from
X (CH2)y f Si Z2 an organic silane having the structure ¾ , wherein: a) X is a functional group selected from the group consisting of: a hydrogen, an amino group, a polyamino alkyl group, a mercapto group, a thiocyanato group, an epoxy group, a vinyl group, a halogen, an acryloxy group and a methacryloxy group; b) Y is an integer equal to or greater than 0; and c) Zi, Z2, and Z3 are each independently selected from the group consisting of: hydrogen, alkoxy, halogen, and hydroxyl, and combinations thereof.
8. The wet polymer silica masterbatch of claim 7, wherein the styrene butadiene rubber is an emulsion styrene butadiene rubber latex with from 10 weight percent to 75 weight percent polymer molecules in water.
9. The wet polymer silica masterbatch of claim 7, wherein the styrene butadiene rubber comprises: natural rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyvinylchloride, acrylonitrile-butadiene-styrene polymer, carboxylated styrene butadiene, carboxylated acrylonitrile-butadiene, styrene-acrylonitrile copolymer, polybutadiene, polyisoprene, polychloroprene, neoprene, polybutadiene-isoprene, or combinations thereof.
10. The wet polymer silica masterbatch of claim 7, wherein the styrene butadiene rubber comprises a copolymer of: styrene and butadiene, styrene and isoprene, styrene and acrylonitrile, or butadiene and acrylonitrile.
11. The wet polymer silica masterbatch of claim 7, further comprising a sulfur content ranging from 0.1 weight percent to 10 weight percent.
12. The wet polymer silica masterbatch of claim 7, wherein the organosilicon is bonded to a surface of the silica, has three readily hydrolyzable groups attached directly to a silicon atom of the organosilicon, and has at least one organic group attached directly to the silicon atom.
13. The wet polymer silica masterbatch of claim 7, wherein the organosilicon is bonded to a surface of the silica and has an organic group attached directly to a silicon atom of the organosilicon that contains at least one functional group.
14. The wet polymer silica masterbatch of claim 7, wherein the mercapto group has a sulfur content ranging from 0.1 weight percent to 10 weight percent.
15. The wet polymer silica masterbatch as defined in claim 7, wherein the synthetic polymer is a polymer selected from the group consisting of: a polymer of a conjugated diene, a vinyl monomer, and combinations thereof.
16. The wet polymer silica masterbatch of claim 7, further comprising an oil extender, forming a polymer rubber composite with from 1 weight percent to 35 weight percent of the functionalized silica, from 1 weight percent to 35 weight percent of the oil extender, and from 30 weight percent to 98 weight percent of the styrene butadiene rubber.
17. The wet polymer silica masterbatch of claim 7, further comprising an antioxidant, forming a polymer rubber composite with from 1 weight percent to 35 weight percent of the functionalized silica, from 0.1 weight percent to 2 weight percent of an antioxidant, and from 67 weight percent to 99 weight percent of the styrene butadiene rubber.
18. The wet polymer silica masterbatch of claim 7, further comprising a carbon black slurry
comprising from 4 weight percent to 6 weight percent carbon black in water, wherein the composition of the polymer rubber composite is from 1 weight percent to 35 weight percent functionalized silica, from 1 weight percent to 49 weight percent of carbon black, and from 16 weight percent to 98 weight percent the styrene butadiene.
19. The wet polymer silica masterbatch of claim 7, further comprising a third silane coupling agent, from a family of silca coupling agents, wherein silcon atoms are bridged through non-volatile diols.
Priority Applications (2)
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EP13823883.7A EP2877531A4 (en) | 2012-07-27 | 2013-07-29 | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
KR1020157005095A KR102145643B1 (en) | 2012-07-27 | 2013-07-29 | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
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US13/560,844 | 2012-07-27 | ||
US13/560,844 US9267019B2 (en) | 2011-06-15 | 2012-07-27 | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
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EP (1) | EP2877531A4 (en) |
KR (1) | KR102145643B1 (en) |
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KR102070987B1 (en) | 2018-04-20 | 2020-01-29 | 주식회사 미래에스아이 | Styrene-butadiene rubber compound with high contents of silica and the process thereof |
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US5780538A (en) * | 1996-03-11 | 1998-07-14 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5914364A (en) * | 1996-03-11 | 1999-06-22 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5763388A (en) * | 1996-12-18 | 1998-06-09 | Dsm Copolymer, Inc. | Process for producing improved silica-reinforced masterbatch of polymers prepared in latex form |
US6221943B1 (en) * | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US7307121B2 (en) * | 2004-03-19 | 2007-12-11 | The Goodyear Tire & Rubber Company | Silica containing rubber composition |
US7960460B2 (en) * | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
KR100910256B1 (en) * | 2007-12-24 | 2009-07-31 | 금호석유화학 주식회사 | Silica master batch elastomers filled with organically modified silica for a tire and preparation method thereof |
KR101240602B1 (en) * | 2010-12-24 | 2013-03-06 | 금호석유화학 주식회사 | Master batch elastomer containing organized silica and method of the same |
-
2013
- 2013-07-29 WO PCT/US2013/052574 patent/WO2014018980A1/en active Application Filing
- 2013-07-29 EP EP13823883.7A patent/EP2877531A4/en not_active Withdrawn
- 2013-07-29 MX MX2013008803A patent/MX345946B/en active IP Right Grant
- 2013-07-29 KR KR1020157005095A patent/KR102145643B1/en active IP Right Grant
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US4076550A (en) * | 1971-08-17 | 1978-02-28 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
US20030097966A1 (en) * | 1996-05-06 | 2003-05-29 | Agritec, Inc. | Precipitated silicas, silica gels with and free of deposited carbon from caustic biomass ash solutions and processes |
US20050277717A1 (en) * | 2002-07-09 | 2005-12-15 | Joshi Prashant G | Silica-rubber mixtures having improved hardness |
US20060036034A1 (en) * | 2004-08-13 | 2006-02-16 | General Electric Company | Diol-derived organofunctional silane and compositions containing same |
US20100022684A1 (en) * | 2008-07-24 | 2010-01-28 | Wallen Peter J | Processes for making silane, hydrophobated silica, silica masterbatch and rubber products |
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MX345946B (en) | 2017-02-27 |
KR102145643B1 (en) | 2020-08-19 |
KR20150093145A (en) | 2015-08-17 |
EP2877531A4 (en) | 2016-06-22 |
MX2013008803A (en) | 2014-06-24 |
EP2877531A1 (en) | 2015-06-03 |
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