MXPA97005947A - Rubber compositions charged with silice and the propagation of mis - Google Patents
Rubber compositions charged with silice and the propagation of misInfo
- Publication number
- MXPA97005947A MXPA97005947A MXPA/A/1997/005947A MX9705947A MXPA97005947A MX PA97005947 A MXPA97005947 A MX PA97005947A MX 9705947 A MX9705947 A MX 9705947A MX PA97005947 A MXPA97005947 A MX PA97005947A
- Authority
- MX
- Mexico
- Prior art keywords
- silica
- silane
- weight
- modified elastomer
- butadiene
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 95
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 77
- 239000000806 elastomer Substances 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 36
- -1 aromatic vinyl compound Chemical class 0.000 claims description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 27
- 229910000077 silane Inorganic materials 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 19
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 150000001993 dienes Chemical class 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N Dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 34
- 239000008079 hexane Substances 0.000 description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 description 15
- 239000002174 Styrene-butadiene Substances 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- 239000003707 silyl modified polymer Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000003961 organosilicon compounds Chemical class 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011414 polymer cement Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000930 thermomechanical Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 240000008528 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000111 anti-oxidant Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 238000010059 sulfur vulcanization Methods 0.000 description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N 2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N N,N,N',N'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N 1,2-Dimethoxybenzene Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,2-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UYMQPNRUQXPLCY-UHFFFAOYSA-N 1-(2-piperidin-1-ylethyl)piperidine Chemical compound C1CCCCN1CCN1CCCCC1 UYMQPNRUQXPLCY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GHHGVSCQWPVENX-UHFFFAOYSA-N 2-methylpent-1-en-3-one Chemical compound CCC(=O)C(C)=C GHHGVSCQWPVENX-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UHBSMIYRAQANCI-UHFFFAOYSA-N C(C)C(CCSSSSCCC(CC)(CC)[SiH2]OC)([SiH2]OC)CC Chemical compound C(C)C(CCSSSSCCC(CC)(CC)[SiH2]OC)([SiH2]OC)CC UHBSMIYRAQANCI-UHFFFAOYSA-N 0.000 description 1
- LYPJSBQIFJESQY-UHFFFAOYSA-N C(CC)C(CCSSCCC(CCC)[SiH](OCC)OCC)[SiH](OCC)OCC Chemical compound C(CC)C(CCSSCCC(CCC)[SiH](OCC)OCC)[SiH](OCC)OCC LYPJSBQIFJESQY-UHFFFAOYSA-N 0.000 description 1
- BULPGPDAJKQNHS-UHFFFAOYSA-N C(CCC)C(CCSSSCCC(CCCC)[SiH](OC)OC)[SiH](OC)OC Chemical compound C(CCC)C(CCSSSCCC(CCCC)[SiH](OC)OC)[SiH](OC)OC BULPGPDAJKQNHS-UHFFFAOYSA-N 0.000 description 1
- GPRMZRVUGCUUCQ-UHFFFAOYSA-N C1(=CC=CC=C1)C(CCSSCCC(C1=CC=CC=C1)(C1=CC=CC=C1)[SiH2]OC1CCCCC1)([SiH2]OC1CCCCC1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(CCSSCCC(C1=CC=CC=C1)(C1=CC=CC=C1)[SiH2]OC1CCCCC1)([SiH2]OC1CCCCC1)C1=CC=CC=C1 GPRMZRVUGCUUCQ-UHFFFAOYSA-N 0.000 description 1
- AIQUYWRDQFFHKH-UHFFFAOYSA-N C1(=CC=CC=C1)C(CCSSSSCCC(C1=CC=CC=C1)[SiH](OC)OC)[SiH](OC)OC Chemical compound C1(=CC=CC=C1)C(CCSSSSCCC(C1=CC=CC=C1)[SiH](OC)OC)[SiH](OC)OC AIQUYWRDQFFHKH-UHFFFAOYSA-N 0.000 description 1
- PWRCPTKSXMCQLS-UHFFFAOYSA-N C=1C=CC=CC=1C(C=1C=CC=CC=1)([SiH2]OC(C)C)CCSSSSCCC([SiH2]OC(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)([SiH2]OC(C)C)CCSSSSCCC([SiH2]OC(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 PWRCPTKSXMCQLS-UHFFFAOYSA-N 0.000 description 1
- AWJOGEUUYZRGOU-UHFFFAOYSA-N CC(CCSSSSCCC(C)(C)[SiH2]SCC)([SiH2]SCC)C Chemical compound CC(CCSSSSCCC(C)(C)[SiH2]SCC)([SiH2]SCC)C AWJOGEUUYZRGOU-UHFFFAOYSA-N 0.000 description 1
- YOSRRIGSGJDAJR-UHFFFAOYSA-N CC(CSSSCC(C)[SiH](OC)OC)[SiH](OC)OC Chemical compound CC(CSSSCC(C)[SiH](OC)OC)[SiH](OC)OC YOSRRIGSGJDAJR-UHFFFAOYSA-N 0.000 description 1
- CSIPGRDAPMEMLW-UHFFFAOYSA-N CC(CSSSSCC(C)[SiH2]OCCCOCC)[SiH2]OCCCOCC Chemical compound CC(CSSSSCC(C)[SiH2]OCCCOCC)[SiH2]OCCCOCC CSIPGRDAPMEMLW-UHFFFAOYSA-N 0.000 description 1
- NVHLTUPSVCBIJJ-UHFFFAOYSA-N COC(C([SiH2]C1=CC=CC=C1)(OC)SSC(C(C)(OC)C)(OC)[SiH2]C1=CC=CC=C1)(C)C Chemical compound COC(C([SiH2]C1=CC=CC=C1)(OC)SSC(C(C)(OC)C)(OC)[SiH2]C1=CC=CC=C1)(C)C NVHLTUPSVCBIJJ-UHFFFAOYSA-N 0.000 description 1
- LAQYGVFTFKGFLA-UHFFFAOYSA-N COC(OC)[SiH2]CCCCCSSSCCCCC[SiH2]C(OC)OC Chemical compound COC(OC)[SiH2]CCCCCSSSCCCCC[SiH2]C(OC)OC LAQYGVFTFKGFLA-UHFFFAOYSA-N 0.000 description 1
- 241000252505 Characidae Species 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- ROHRITLNTPSREP-UHFFFAOYSA-N ClC1=C(C(=C(C(=C1S(=S)=S)Cl)Cl)Cl)Cl Chemical compound ClC1=C(C(=C(C(=C1S(=S)=S)Cl)Cl)Cl)Cl ROHRITLNTPSREP-UHFFFAOYSA-N 0.000 description 1
- PLCLTJXFCNRYTQ-UHFFFAOYSA-N ClCCCO[SiH3] Chemical compound ClCCCO[SiH3] PLCLTJXFCNRYTQ-UHFFFAOYSA-N 0.000 description 1
- FIZFZXNUMWYKRM-UHFFFAOYSA-N ClC[SiH2]OCCC Chemical compound ClC[SiH2]OCCC FIZFZXNUMWYKRM-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920002456 HOTAIR Polymers 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N Phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N Piperylene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 229920001021 Polysulfide Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M Sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N Tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- TWJORKMNYIIKCR-UHFFFAOYSA-N buta-1,3-diene;hexane Chemical compound C=CC=C.CCCCCC TWJORKMNYIIKCR-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Chemical group 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-M carbamodithioate Chemical compound NC([S-])=S DKVNPHBNOWQYFE-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003111 delayed Effects 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- CFNDRVCFJKQSHT-UHFFFAOYSA-N dodecyl benzenesulfonate;potassium Chemical compound [K].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 CFNDRVCFJKQSHT-UHFFFAOYSA-N 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005677 ethinylene group Chemical class [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000004968 halobutyl group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical group [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- ATYIZISYPACGCO-UHFFFAOYSA-N tributoxy-[3-(3-tributoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCSSCCC[Si](OCCCC)(OCCCC)OCCCC ATYIZISYPACGCO-UHFFFAOYSA-N 0.000 description 1
- RLQRJIRGQDCNKY-UHFFFAOYSA-N tricyclopentyloxy-[3-(3-tricyclopentyloxysilylpropyltrisulfanyl)propyl]silane Chemical compound C1CCCC1O[Si](OC1CCCC1)(OC1CCCC1)CCCSSSCCC[Si](OC1CCCC1)(OC1CCCC1)OC1CCCC1 RLQRJIRGQDCNKY-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- KORAJTACFWEGPU-UHFFFAOYSA-N triethoxy-[6-(6-triethoxysilylhexyltetrasulfanyl)hexyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCSSSSCCCCCC[Si](OCC)(OCC)OCC KORAJTACFWEGPU-UHFFFAOYSA-N 0.000 description 1
- XGVRSFOOQXXSDO-UHFFFAOYSA-N trihexoxy-[3-(3-trihexoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCCCCCO[Si](OCCCCCC)(OCCCCCC)CCCSSCCC[Si](OCCCCCC)(OCCCCCC)OCCCCCC XGVRSFOOQXXSDO-UHFFFAOYSA-N 0.000 description 1
- XQCNPXMIHJAHGO-UHFFFAOYSA-N trimethoxy-[(trimethoxysilylmethyltetrasulfanyl)methyl]silane Chemical compound CO[Si](OC)(OC)CSSSSC[Si](OC)(OC)OC XQCNPXMIHJAHGO-UHFFFAOYSA-N 0.000 description 1
- SVNJQEIWNMNTBW-UHFFFAOYSA-N trimethoxy-[18-(18-trimethoxysilyloctadecyltetrasulfanyl)octadecyl]silane Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCCCCCCCCSSSSCCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SVNJQEIWNMNTBW-UHFFFAOYSA-N 0.000 description 1
- IPBOZRUUILDBBF-UHFFFAOYSA-N trimethoxy-[2-methyl-1-[(2-methyl-1-trimethoxysilylpropyl)tetrasulfanyl]propyl]silane Chemical compound CO[Si](OC)(OC)C(C(C)C)SSSSC(C(C)C)[Si](OC)(OC)OC IPBOZRUUILDBBF-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- YGLOWFUKVQMIQC-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropylhexasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSSSCCC[Si](OC)(OC)OC YGLOWFUKVQMIQC-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- KOFGNZOFJYBHIN-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSCCC[Si](OC)(OC)OC KOFGNZOFJYBHIN-UHFFFAOYSA-N 0.000 description 1
- BPBNXPYFZUPVRY-UHFFFAOYSA-N trimethoxy-[3-(4-trimethoxysilylbut-1-en-2-yltetrasulfanyl)but-3-enyl]silane Chemical compound CO[Si](OC)(OC)CCC(=C)SSSSC(=C)CC[Si](OC)(OC)OC BPBNXPYFZUPVRY-UHFFFAOYSA-N 0.000 description 1
- WUMASLCNJBRHDA-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyltetrasulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSSSCCCC[Si](OC)(OC)OC WUMASLCNJBRHDA-UHFFFAOYSA-N 0.000 description 1
- ORMMMPDHLQZPEB-UHFFFAOYSA-N trioctoxy-[3-(3-trioctoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCCCCCCCO[Si](OCCCCCCCC)(OCCCCCCCC)CCCSSSSCCC[Si](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC ORMMMPDHLQZPEB-UHFFFAOYSA-N 0.000 description 1
- VKJFZCCNSAEGRS-UHFFFAOYSA-N tripropoxy-[18-(18-tripropoxysilyloctadec-1-enyltetrasulfanyl)octadec-17-enyl]silane Chemical compound CCCO[Si](OCCC)(OCCC)CCCCCCCCCCCCCCCCC=CSSSSC=CCCCCCCCCCCCCCCCC[Si](OCCC)(OCCC)OCCC VKJFZCCNSAEGRS-UHFFFAOYSA-N 0.000 description 1
- HRAOIWWIABULSC-UHFFFAOYSA-N tripropoxy-[2-(2-tripropoxysilylethylpentasulfanyl)ethyl]silane Chemical compound CCCO[Si](OCCC)(OCCC)CCSSSSSCC[Si](OCCC)(OCCC)OCCC HRAOIWWIABULSC-UHFFFAOYSA-N 0.000 description 1
- IRNPVNAUHNTHDI-UHFFFAOYSA-N tris(6-methylheptoxy)-[3-[3-[tris(6-methylheptoxy)silyl]propyltetrasulfanyl]propyl]silane Chemical compound CC(C)CCCCCO[Si](OCCCCCC(C)C)(OCCCCCC(C)C)CCCSSSSCCC[Si](OCCCCCC(C)C)(OCCCCCC(C)C)OCCCCCC(C)C IRNPVNAUHNTHDI-UHFFFAOYSA-N 0.000 description 1
- CONCKWGHNZAEBO-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[3-[3-[tris[(2-methylpropan-2-yl)oxy]silyl]propyldisulfanyl]propyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCSSCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C CONCKWGHNZAEBO-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to rubber compositions loaded with silica and its processing method. The rubber compositions contain a mixture of 10 to 150 phr of a particulate precipitated silica having from 1 to 20 percent by weight dispersed therein, based on the weight of the silica, of a silica-modified elastomer.
Description
"COMPOSITIONS OF RUBBER LOADED WITH SILICA AND THE PROCESSING OF THE SAME"
BACKGROUND OF THE INVENTION
U.S. Patent Nos. 3,842,111, 3,873,489 and 3,978,103 disclose the preparation of various organosilicon compounds containing sulfur. Sulfur-containing organosilicon compounds are useful as reactive coupling agents between rubber and silica fillers or fillers providing improved physical properties. They are also useful as adhesion primers for glass substrates, metals and other substrates. U.S. Patent No. 5,409,969 relates to a tread rubber of a pneumatic tire, characterized by 10 to 150 parts by weight of a silica filler or filler and a silane modified polymer having a transition temperature of vitreous state not less than -50 ° C and obtained by reacting an active terminal of a living polymer resulting through the polymerization of 1,3-butadiene or the copolymerization of 1,3-butadiene and styrene, in an organic solvent inert, in the presence of an alkali metal initiator with a silane compound.
COMPENDIUM OF THE INVENTION
The present invention relates to silica-loaded rubber compositions containing a precipitated silica in particles having dispersed therein an elastomer modified with its silane. The present invention also relates to an efficient method for processing silica-loaded rubber compositions.
DETAILED DESCRIPTION OF THE INVENTION
A method for processing a silica loaded rubber composition comprising mixing (i) 100 parts by weight of at least one vulcanizable elastomer with sulfur selected from homopolymers and copolymers of conjugated diene and copolymers is disclosed. minus a conjugated diene and an aromatic vinyl compound; and (ii) from 10 to 150 phr of a particulate precipitated silica having from 1 to 20 weight percent dispersed therein, based on the weight of the silica, of a silane modified elastomer. Also disclosed is a silica-loaded rubber composition comprising a mixture of (i) 100 parts by weight of at least one sulfur vulcanizable elastomer selected from conjugated diene homopolymers and copolymers and copolymers of at least a conjugated diene and an aromatic vinyl compound; and (ii) from 10 to 150 phr of a particulate precipitated silica having from 1 to 20 percent by weight dispersed therein based on the weight of the silica of a silane-modified elastomer. Also disclosed is a method for reducing the energy required to mix the silica loaded rubber composition comprising mixing (i) 100 parts by weight of at least one vulcanizable elastomer with sulfur selected from homopolymers and copolymers of conjugated diene. and of copolymers of at least one conjugated diene and an aromatic vinyl compound; and (ii) from 10 to 150 phr of a precipitated silica in particles having therein dispersed from 1 percent to 20 weight percent, based on the weight of the silica, of a silane modified elastomer.
The present invention can be used to process vulcanizable elastomers or rubbers containing sulfur containing olefinic unsaturation. The phrase "rubber or elastomer containing olefinic unsaturation" is intended to include both natural rubber and its various raw and regenerated forms as well as the various synthetic rubbers. In the description of this invention, the terms "rubber" and "elastomer" can be used interchangeably, unless otherwise stated. The terms "rubber composition", "stirred or combined rubber" and "rubber compound" are used interchangeably to refer to rubber that has been blended or combined with different ingredients and materials and the terms are well known to those skilled in the art. the rubber mixing branch or rubber combination. Representative synthetic polymers are the homopolymerization products of butadiene and its homologs and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene as well as copolymers such as those formed of butadiene or its homologs or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, acetylene vinyl; olefins, for example, isobutylene, which is copolymerized with isoprene to form the butyl rubber; vinyl compounds, for example, acrylic acid, acrylonitrile (which polymerizes with butadiene to form the NBR), methacrylic acid and styrene, the latter compound is polymerized with butadiene to form SBR, as well as vinyl esters and the various unsaturated aldehydes , ketones and ethers, e.g., acrolein, ethyl isopropenyl ketone and vinylethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, halobutyl rubber such as chlorobutyl rubber or rubber. of bromobutyl, styrene / isoprene / butadiene rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene / propylene terpolymers, also known as ethylene / propylene monomer / diene (EPDM), and in particular, the ethylene / propylene / dicyclopentadiene terpolymers. The preferred rubber or elastomers are polybutadiene and SBR. In one aspect, the rubber composition purchased from at least two diene-based rubbers. For example, a combination of two or more rubbers such as cis-1,4-polyisoprene rubbers (natural or synthetic, even when natural is preferred), 3-4-polyisoprene rubber, styrene / isoprene rubber / butadiene, styrene / butadiene rubbers derived from emulsion and solution polymerization, cis-1, 4-polybutadiene rubbers and butadiene / acrylonitrile copolymers prepared by emulsion polymerization. In one aspect of this invention, a styrene / butadiene rubber (E-SBR) derived from emulsion polymerization, having a relatively conventional styrene content of from about 20 percent to about 28 percent styrene combined, or could be used, for some applications, an E-SBR having a combined medium to relatively high styrene content, namely, a combined styrene content of from about 30 percent to about 55 percent. The relatively high styrene content of about 30 percent to about 55 percent for the E-SBR can be considered beneficial for the purpose of improving the traction, or skid resistance, of the tire tread surface. The presence of E-SBR itself is considered beneficial for the purpose of improving the processability of the mixture of the uncured elastomeric composition especially compared to a use of an SBR (S-SBR) prepared by solution polymerization.
By means of E-SBR prepared by emulsion polymerization, it is meant that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. This is well known to those skilled in this art. The combined styrene content can vary, for example, from about 5 percent to about 50 percent. In one aspect, the E-SBR may also contain acrylonitrile to form a terpolymer rubber such as E-SBAR, in amounts, for example, from about 2 percent to about 20 percent by weight of acrylonitrile combined in the terpolymer. Styrene / butadiene / acrylonitrile copolymer rubbers prepared by emulsion polymerization containing from about 2 percent to about 40 weight percent of acrylonitrile combined in the copolymer are also proposed as diene-based rubbers for use in this invention . The SBR (S-SBR) prepared by solution polymerization typically has a combined styrene content within the range of about 5 percent to about 50 percent, preferably from about 9 percent to about 36 percent. The S-SBR can conveniently be prepared, for example, by catalysing organolithium in the presence of an organic hydrocarbon solvent. An object of using the S-SBR is due to its improved rim rolling resistance as a result of the lower hysteresis when used in a tread surface composition. The 3,4-polyisoprene (3,4-PI) rubber is considered beneficial for the purpose of improving the traction of the rim when it is used in a tread surface composition. 3,4-PI and the use thereof, are more fully described in U.S. Patent No. 5,087,668 which is incorporated herein by reference. The Tg refers to the glass transition temperature which can be conveniently determined by a differential scanning calorimeter at a heating rate of 10 ° C per minute. The rubber of cis-1,4-polybutadiene (BR) is considered to be beneficial for the purpose of improving wear of the running surface of the rim or duration of the running surface. This BR can also be prepared, for example, by polymerization by organic solution of 1,3-butadiene. The BR can be conveniently characterized, for example, having at least a cis-1,4 content of 90 percent. Cis-1, 4-polyisoprene and the natural rubber of cis-1,4-polyisoprene are well known to those skilled in the rubber art. The term "phr" as used herein, and in accordance with conventional practice, refers to "parts by weight of a respective material per 100 parts by weight of a rubber or elastomer". The rubber composition should contain a sufficient amount of pretreated silica (a term used interchangeably herein, to describe a precipitated silica in particles that has dispersed therein from 1 percent to 20 percent by weight, based on the weight of the silica , of a silane-modified elastomer described herein), and non-pretreated silica, if used to contribute to a reasonably high modulus and high breaking strength. The pretreated silica filler or filler material can be added in amounts ranging from 10 to 150 phr. Preferably, the pretreated silica is present in an amount ranging from 15 to 80 phr. If untreated silica is also present, the amount of unpretreated silica, if used, may vary. Generally speaking, the amount of non-pretreated silica will vary from 0 to 80 phr. Preferably, the amount of the non-pretreated silica will vary from 0 to 40 phr. When the rubber composition contains both pretreated silica and unpretreated silica, the weight ratio of the silica pretreated to the untreated silica can vary. For example, the weight ratio can be as low as 1: 5 with respect to a weight ratio of 30: 1 of a pretreated silica to a non-pretreated silica. Preferably, the weight ratio of the pretreated to the pretreated silica varies from 1: 3 to 5: 1. The combined weight of the pretreated silica and the unpretreated silica as mentioned herein may be as low as about 10 phr, but preferably is about 45 to about 90 phr. The precipitated siliceous pigments commonly used in rubber blending or combination applications can be used as the silica pretreated and not pretreated in this invention. The siliceous pigments preferably used in this invention are obtained by acidification of a soluble silicate, v.gr, sodium silicate. These silicas could be characterized, for example, by having a BET surface area as measured using nitrogen gas, preferably within the range of about 40 to about 600, and more usually within the range of about 50 to about 300 square meters. per gram. The BET method for measuring surface area is described in Journal of the American Chemical Society, Volume 60, page 304 (1930). The silica can also typically be characterized having an absorption value of dibutyl phthalate (DBP) within the range of from about 100 to about 400, and more usually from about 150 to about 300. The silica could be expected to have a final particle size average, for example, within the range of 0.01 to 0.05 micron as determined by an electron microscope, even though the silica particles may be of an even smaller, or possibly larger, size. The various silicas commercially obtainable for use in this invention may be considered such as, for example only and without limitation, the silicas commercially available from PPG Industries under the trademark Hi-Sil with designations 210, 243, etc.; the silicas obtainable from Rhone-Poulenc, with, for example, designations of Z1165MP, Z165GR and silicas obtainable from Degussa AG, for example, with designations VN2 and VN3, etc. As mentioned above, prior to mixing with an elastomer, the precipitated silica is pretreated or has a silane-modified elastomer dispersed thereon. The polymer to be dispersed on the surface of the silica is a silane-modified polymer having a glass transition temperature of not less than -50 ° C. Generally speaking, the vitreous state transition temperature ranges from about -50 ° C to -90 ° C, with a scale of about -60 ° C to -75 ° C being preferred. The silane-modified polymer per se can be prepared according to the teachings of U.S. Patent No. 5,409,969. Therefore, the polymer can be obtained by reacting an active terminal of a living polymer resulting through the polymerization of 1,3-butadiene or the copolymerization of 1,3-butadiene and styrene with an organic alkali metal initiator with a silane compound represented by the following general formula XyWySMOR1 ^ I wherein X is halogen selected from the group consisting of chlorine, bromine and iodine; W is an alkylene radical having from 1 to 8 carbon atoms; Y is 0 or 1, R1 is independently selected from the group consisting of alkyl radicals having from 1 to 8 carbon atoms and aryl radicals having from 6 to 24 carbon atoms; yz is 4 when y is 0 and z is 3 when y is 1. Preferably y is 0, R ^ - is an alkylene group having 2 carbon atoms and z is 4. The polymer used in the invention can be produced by the Well-known method using an organic alkali metal initiator. The production of this polymer is usually carried out in an inert organic solvent. As the inert organic solvent, pentane, hexane, cyclohexane, heptane, benzene, xylene, toluene, tetrahydrofuran, diethyl ether and the like can be used. First, the polymerization of 1,3-butadiene or the copolymerization of 1,3-butadiene and styrene is carried out in the presence of an organic alkali metal initiator. As the organic alkali metal initiator, examples include alkyl lithiums, such as n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, butane 1-di-lithium, a butyl lithium reaction product and divinylbenzene and the like; alkylene di-lithium, phenyl-lithium, di-lithium stilbene. di-lithium diisopropylbenzene, sodium naphthalene, lithium naphthalene, etc.
In the case of copolymerization, a Lewis base can be used as a random agent and a regulating agent for the microstructure of the butadiene unit in the copolymer, if necessary. Examples of the Lewis base include ethers and tertiary amines, such as dimethoxybenzene, tetrahydrofuran, dimethoxyethane, dibutyl ether of diethylene glycol, dimethyl ether of diethylene glycol, triethylamine, pyridine, morpholine of N-methyl, ethylenediamine of N, N, N ', N'-tetramethyl, 1,2-dipiperidinoethane and the like. In addition, the content of the combined styrene in the copolymer can be controlled by varying the amount of the styrene monomer in the monomer mixture, while introducing a single styrene chain into the copolymer; that is, the placement of the chain of styrenes without sequence of the styrene chain unit can be controlled by the use of an organic potassium compound, such as potassium dodecylbenzene sulfonate or the like. In addition, the content of the 1,2-linkage in the butadiene unit of the copolymer molecule can be controlled by varying the polymerization temperature. Also, the living polymer can be produced by charging the monomers: that is, 1,3-butadiene or 1,3-butadiene and styrene, the inert organic solvent, the organic alkali metal initiator, and if necessary, the base Lewis in a reaction vessel purged with nitrogen gas, all at once, discontinuously or continuously. The polymerization temperature is usually
-120 ° C to + 150 ° C, preferably from -88 ° C to + 120 ° C, and the polymerization time is usually from 5 minutes to 24 hours, preferably from 10 minutes to 10 hours. The polymerization temperature can be maintained at a constant value within the aforementioned scale or it can be raised or adiabatic. Also, the polymerization reaction can be carried out by an intermittent system or a continuous system. In addition, the concentration of the monomer in the solvent is usually from 5 percent to 50 percent by weight, preferably from 10 percent to 35 percent by weight. In the formation of the living polymer, it is necessary to prevent the incorporation of a compound exhibiting a deactivation function, such as a halogen compound, oxygen, water, carbon dioxide gas or the like in the polymerization system, as much as possible. possible in order to avoid the deactivation of the organic alkali metal initiator and the resulting living polymer. Representative examples of the silane of the formula I include, tetramethoxy silane, tetraethoxy silane, tetrapropoxy silane, tetrabutoxy silane, tetrahexoxy silane, tetraheptoxy silane, tetrabutoxy silane, tetra (2-ethylhexoxy) silane, tetrafenoxi, chloropropoxy silane, chloromethylpropoxy silane (mention all the others of importance). This silane-modified polymer is obtained by reacting the active terminal of the above-mentioned living polymer with the silane compound of the formula I. The amount of the silane compound that is used is not less than 0.7 molecule per active terminal of the living polymer. Preferably, the amount varies from 0.7 to 5.0 and, more specifically from 0.7 to 2.0. When the amount of the silane compound used is less than 0.7 molecule per active terminal of the living polymer, the production of the branched polymer becomes larger and the change in molecular weight distribution is large, and therefore, the control of the Molecular weight and molecular weight distribution is difficult, whereas when it exceeds 5.0 molecules per active terminal of the living polymer, the effect to improve wear resistance and fracture properties becomes saturated and becomes unfavorable in view of economic reasons . In the production of the silane-modified polymer, the addition of two steps wherein a small amount of the silane compound is first added to the active terminal of the living polymer can be used., in order to form a polymer having a branched structure and then another silane compound is added to the remaining active terminal. The reaction between the active terminal of the living polymer and the functional group of the silane compound is carried out by adding the silane compound to the solution in the living polymer system, or by adding the solution of the living polymer to an organic solvent solution which contains the silane compound. The reaction temperature is from -120 ° C to + 150 ° C, preferably from -80 ° C to + 120 ° C and the reaction time is from 1 minute to 5 hours, preferably from 5 minutes to 2 hours. After the completion of the reaction, the silane-modified polymer can be obtained by blowing steam into the polymer solution to remove the solvent or by adding a lean solvent, such as methanol or the like to solidify the resulting polymer modified with silane, then drying through cylinders. hot or under reduced pressure. Alternatively, the solvent can be removed directly from the polymer solution under reduced pressure to obtain a silane modified polymer. Even though the molecular weight of the silane-modified polymer can be varied across a wide scale, the Mooney viscosity (MLi + 4, 100 ° C) should preferably be within the slat from 10 to 150. When the Mooney viscosity is lower of 10, the wear resistance is deficient, while when it exceeds 150 the processability is deficient. Pretreatment of the silica precipitated with the silane-modified polymer is usually carried out in the presence of an appropriate solvent. The main criterion is to use a solvent that does not react with the starting materials or the final product. Representative organic solvents include chloroform, dichloromethane, carbon tetrachloride, hexane, heptane, cyclohexane, xylene, benzene, toluene, aliphatic and cycloaliphatic alcohols. Preferably, the water is avoided to prevent reaction with the reactable siloxy groups of the silane-modified polymers. The first step in the pretreatment step is to dissolve the silane-modified polymer in the solvent containing the silica. The silane-modified polymer should be added in an amount ranging from about 2 percent to 30 percent by weight, based on the weight of the untreated silica. Preferably, the amount of the silane modified polymer is added in an amount ranging from 10 percent to 20 percent by weight. The reaction should be carried out at a temperature ranging from about 50 ° C to about 200 ° C. The reaction time may vary. In general, the reaction time varies from approximately 1 to 24 hours. The final step in the pretreatment procedure is to remove the pretreated silica from the solvent. This separation step can be achieved by well-known means such as filtration, drying of the heat and vacuum pre-treated silica and the like. Upon completion of the pretreatment step, a silica having dispersed in the same silane modified elastomer identified above is provided. The silane-modified elastomer is generally present at a level ranging from 1 percent to 20 percent by weight based on the weight of the silica. Preferably, the silane modified elastomer is present at a level ranging from 5 percent to 15 percent by weight, based on the weight of the silica. Although the pretreated silica contains suspended alkoxysilane residues, this pretreated silica loaded rubber composition may also contain known symmetrical sulfur-containing organosilicon compounds. Examples of suitable sulfur-containing organosilicon compounds are of the formula:
Z-Alq-Sn-Alq-Z (II)
where Z is selected from the group consisting of
R3 R I -Si - R3 -Si - R4 -Si - R4
R4 R4 R4
wherein R3 is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; R 4 is alkoxy of 1 to 8 carbon atoms or cycloalkoxy of 5 to 8 carbon atoms;
Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8. Specific examples of the sulfur-containing organosilicon compounds that can be used in accordance with the present invention include: 3, 3'-bis ( trimethoxysilylpropyl) disulfide, 3,3'-bis (triethoxysilylpropyl) tetrasulfide, 3,3'-bis (triethoxysilylpropyl) octasulfide, 3,3'-bis (trimethoxysilylpropyl) tetrasulfide, 2,2'-bis (triethoxysilylethyl) tetrasulfide, 3, 3'-bis (trimethoxysilylpropyl) trisulfide, 3,3'-bis (triethoxysilylpropyl) trisulfide, 3,3'-bis (tributoxysilylpropyl) disulfide, 3,3'-bis (trimethoxysilylpropyl) hexasulfide, 3,3'-bis (trimethoxysilylpropyl) ) octasulfide, 3,3'-bis (trioctoxysilylpropyl) tetrasulfide, 3,3'-bis (trihexoxysilylpropyl) disulfide, 3,3'-bis (tri-2"-ethylhexosilylpropyl) trisulfide, 3,3'-bis (triisooctoxysilylpropyl) tetrasulfide, 3, 3'-bis (tri-t-butoxysilylpropyl) disulfide, 2,2'-bis (methoxy diethoxy silylethyl) tetras ulfuro, 2,2'-bis (tripropoxysilylethyl) pentasulfide, 3,3'-bis (tricyclonexoxysilylpropyl) tetrasulfide, 3,3'-bis (tricyclopentoxysilylpropyl) trisulfide, 2,2'-bis (tri-2"-methylcyclohexoxysilylethyl) tetrasulfide , bis (trimethoxysilylmethyl) tetrasulfide, 3-methoxy ethoxy propoxysilyl 3'-diethoxybutoxy-silylpropyltetrasulfide, 2,2'-bis (dimethylmethoxysilyl) disulfide, 2,2'-bis (dimethyl sec.-butoxysilylethyl) trisulfide, 3'3'- bis (methyl butylethoxysilylpropyl) tetrasulfide, 3, 3'-bis (di t -butylmethoxysilylpropyl) tetrasulfide, 2,2'-bis (phenylmethylmethoxylethyl) trisulfide, 3,3'-bis (diphenyl isopropoxysilylpropyl) tetrasulfide, 3, 3 ' bis (diphenyl cyclohexoxysilylpropyl) disulfide,
3, 3'-bis (dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2,2'-bis (methyl dimethoxysilylethyl) trisulfide, 2,2'-bis (methyl ethoxypropoxysilylethyl) tetrasulfide,
3, 3'-bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3'-bis (ethyl di.sec-butoxysilylpropyl) disulfide, 3,3'-bis (propyl-diethoxysilylpropyl) disulfide, 3,3'-bis (butyl-dimethoxysilylpropyl) trisulfide , 3, 3'-bis (phenyl dimethoxysilylpropyl) tetrasulfide, 3-phenyl-ethoxybutoxysilyl-3'-trimethoxysilylpropyl tetrasulfide, 4,4'-bis (trimethoxysilylbutyl) tetrasulfide, 6,6'-bis (triethoxysilylhexyl) tetrasulfide, 12, 12 '- bis (triisopropoxysilyl dodecyl) disulfide, 18,18'-bis (trimethoxysilyloctadecyl) tetrasulfide, 18,18'-bis (tripropoxysilyloctadecenyl) tetrasulfide, 4, '-bis (trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4' - bis (trimethoxysilylcyclohexylene) tetrasulfide, 5,5'-bis (dimethoxymethylsilylpentyl) trisulfide, 3,3 * -bis (trimethoxysilyl-2-methylpropyl) tetrasulfide, 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide. Preferred sulfur-containing organosilicon compounds are the 3,3'-bis (trimethoxy or triethoxy silylpropyl) sulfides. The especially preferred compound is 3, 3'-bis (triethoxysilylpropyl) tetrasulfide. Therefore, as for formula II, preferably Z is
- Si - R4 I R4 wherein R4 is an alkoxy of 2 to 4 carbon atoms, with the 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer from 3 to 5, with 4 being particularly preferred. The amount of the sulfur-containing organosilicon compound of the formula II in a rubber composition will vary, depending on the level of the silica used. Generally speaking, the amount of the compound of the formula II will vary from .00 to 1.0 part by weight per part by weight of the silica. Preferably the amount will vary from .00 to 0.4 part by weight per part by weight of the silica. It will be readily understood by those skilled in the art that the rubber composition would be combined or stirred by methods generally known in the rubber combination branch., such as mixed with the various constituent rubbers vulcanizable with sulfur with various materials used as an additive, such as for example sulfur donors, curing aids such as activators and retarders and processing additives, such as oils, resins including tackifying resins and plasticizers , fillers or fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents. As is known to those skilled in the art, depending on the use to which the material vulcanized with sulfur or vulcanized with sulfur (rubbers) is intended, the aforementioned additives are selected and commonly used in conventional amounts. Typical amounts of the carbon black (s) of the reinforcing type for this invention, if used, are noted herein. Representative examples of sulfur donors include elemental sulfur (free sulfur) an amine disulfide, polymeric polysulfide and sulfur olefin adducts. Preferably the sulfur vulcanization agent is elemental sulfur. The sulfur vulcanization agent can be used in an amount ranging from 0.5 to 8 phr, with a scale of 1.5 to 6 phr being preferred. Typical amounts of the tackifying resins if used comprise from 0.5 to about 10 phr, usually from about 1 to about 5 phr. Typical amounts of processing aids comprise from about 1 to about 50 phr. These processing aids may include, for example, aromatic, naphthenic and / or paraffinic oils. Typical amounts of antioxidants comprise from about 1 to about 5 phr. Representative antioxidants, for example may be diphenyl-p-phenylenediamine and others, such as for example those disclosed in Vanderbilt Rubber Handbook (1978), pages 344 to 346. Typical amounts of antiozonants comprise from about 1 to about 5 phr. Typical amounts of fatty acids if used, which may include stearic acid comprise from about 0.5 to about 5 phr. Typical amounts of zinc oxide comprise from about 2 to about 5 phr. Typical amounts of waxes comprise from about 1 to about 5 phr. Microcrystalline waxes are frequently used. Typical amounts of peptizers comprise from about 0.1 to about 1 phr. Typical peptizers, for example, may be pentachlorothiophenol disulfide and dibenzamidodiphenyl disulfide. In one aspect of the present invention, the rubber composition vulcanizable with sulfur is then cured with sulfur or vulcanized with sulfur. Accelerators are used to control the time and / or temperature that are required for vulcanization and to improve the properties of the vulcanized material. In one embodiment, a single accelerator system, ie, a primary accelerator, can be used. The primary accelerator (s) can be used in total amounts ranging from about 0.5 to about 4, preferably from about 0.8 to about 2.5 phr. In another embodiment, combinations of a primary accelerator and a secondary accelerator could be used, with the secondary accelerator being used in amounts ranging from about 0.05 to about 3 phr, in order to activate and improve the properties of the vulcanized material. The combinations of these accelerators could be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by the use of any single accelerator. In addition, delayed action accelerators which are not affected by normal processing temperatures can be used, but produce a satisfactory cure at regular vulcanization temperatures. Vulcanization retarders could also be used. The appropriate types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiouramyls, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a secondary accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or a thiouramyl compound. The mixing of the rubber composition can be achieved by methods known to those skilled in the rubber mixing field. For example, the ingredients are typically mixed in at least two stages, namely at least one non-productive step followed by a productive mixing step. The final curing agents, including sulfur vulcanization agents, are typically mixed in the final stage which is conventionally called the "productive" mixing step, in which mixing typically occurs at a temperature or final temperature lower than the temperature (s) of the mixture, than in the previous nonproductive mixing stage (s). Rubber, pretreated silica, and carbon black, if used, are mixed in one or more non-productive mixing stages. The terms "non-productive" and "productive" mixing stages are also known to those skilled in the field of rubber mixing. The sulfur vulcanizable rubber composition containing the vulcanizable rubber and generally at least part of the pretreated silica, as well as any optional sulfur-containing organosilicon compound, if used, must be subjected to a thermomechanical mixing step. The thermomechanical mixing step, generally, comprises a mechanical treatment in a mixer or extrusion apparatus for an appropriate period of time in order to produce a rubber temperature of between 140 ° C and 190 ° C. The proper duration of the thermomechanical treatment varies as a function of the operating conditions and the volume and nature of the components. For example, the thermomechanical treatment can be from 1 to 20 minutes. The vulcanization of the rubber composition of the present invention is, in general, carried out at conventional temperatures ranging from about 100 ° C to 200 ° C. Preferably, the vulcanization is carried out at temperatures ranging from about 110 ° C to 180 ° C. Any of the usual vulcanization processes such as heating in a press or mold, heating with superheated steam or hot air or in a salt bath can be used. During the vulcanization of the composition vulcanized with sulfur, the rubber composition of this invention can be used for various purposes. For example, the rubber composition vulcanized with sulfur can be in the form of a rim, a belt or a hose. In case of a tire, it can be used for different rim components. These rims can be made, shaped, molded and cured by different methods that are known and will be readily apparent to those skilled in this art. Preferably, the rubber composition is used on the running surface of a rim. As will be appreciated, the rim can be a rim for passenger cars, a tire for airplanes or a tire for trucks and the like. Preferably the rim is a rim for passenger cars. The rim can also be a radial or skewed rim, with the radial rim being preferred. Even though certain embodiments and representative details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
Example 1 Preparation of Pretreated Silica
In a meticulously dry stirred reactor with a capacity of 3.79 liters, 2,000 grams of a dried butadiene-hexane mixture (15 weight percent / 85 weight percent) and 3 millimole of n-butyllithium were charged. The reactor was heated at 60 ° C for 4 hours. Two millimoles of tetrahydroxysilane (Li / Si = 1) were added and heating continued for another hour. The batch was stopped with an excess of methanol. Six grams of 2,6-di-t-butyl-p-cresol was added to the solution, and the polymer was isolated by removing the hexane. Five hundred grams of silica Zeosil 1165MP were loaded into a 4 liter beaker together with 306 grams of silylated polymer cement (50 grams of dry polymer and 256 grams of hexane) the slurry was stirred followed by removal of the hexane at 70 ° C under reduced pressure in a vacuum oven. The amount of the polymer functionalized on the silica was calcined to be 10 weight percent.
Example 2 Preparation of Pretreated Silica
In a meticulously dry stirred reactor with a capacity of 3.79 liters, 2,000 grams of a mixture of dry butadiene / hexane (15 weight percent / 85 weight percent) and 3 millimole of n-butyllithium were charged. The reactor was heated at 60 ° C for 4 hours. 2 millimoles of chloropropyltriethoxysilane (Li / Si = 1) were added and heating was continued for another hour. The batch was stopped with an excess of methanol. Six grams of 2,6-di-t-butyl-p-crucible was added to the solution, and the polymer was isolated by removing the hexane. Five hundred grams of silica Zeosil 1165MP was charged into a 4 liter beaker together with 306 grams of silylated polymer cement (50 grams of dry polymer and 256 grams of hexane). The slurry was stirred followed by evasion of hexane at 70 ° C under reduced pressure in a vacuum oven. The amount of functionalized polymer in the silica was calculated as being 10 percent.
Example 3 Preparation of Pretreated Silica In a meticulously dry reactor with a capacity of 3.79 liters, 2,000 grams of a dry mixture of styrene / butadiene / hexane (1.5 weight percent / 13.5 weight percent / 85 weight percent) were charged, 1.0 millimole of tetraethylethylene diamine and 3 millimole of n-butyl lithium. The reactor was heated at 60 ° C for 4 hours. 2 millimoles of teratoxysilane (Li / Si = 1) were added and heating continued for another hour. The batch was stopped with excess methanol. 6 grams of 2,6-di-t-butyl-p-crucible was added to the solution and the polymer isolated by removing the hexane. Five hundred grams of the silica Zeosil 1165MP was charged into a beaker of 4 liters capacity together with 306 grams of silylated polymer cement (50 grams of dry polymer and 256 grams of hexane). The slurry was stirred followed by removal of the hexane at 70 ° C under reduced pressure in a vacuum oven.
Example 4 Preparation of Pretreated Silica
To a meticulously dry stirred reactor with a capacity of 3.79 liters, 2,000 grams of a dry mixture of styrene / butadiene / hexane (3.75 weight percent / 11.25 weight percent / 85 weight percent), 1.0 millimole of tetraethylethylenediamine and 3 mmol of n-butyl-lithium. The reactor was heated at 60 ° C for 4 hours. 2 millimoles of teratoxysilane (Li / Si = 1) were added and the heating was continued for another hour. The batch was stopped with excess methanol. To the solution were added 6 grams of 2,6-di-t-butyl-p-pot and the polymer was isolated by removing the hexane. Five hundred grams of the silica Zeosil 1165MP was charged into a beaker of 4 liters capacity together with 306 grams of silylated polymer cement (50 grams of dry polymer and 256 grams of hexane). The slurry was stirred followed by removal of the hexane at 70 ° C under reduced pressure in a vacuum oven.
Example 5
Table I below shows the basic rubber compound that was used in this example. The rubber materials were prepared in order to compare the effects of using precipitated silicas on pretreated particles that were prepared in Examples 1 and 2 versus the control compound that does not contain these pretreated silicas, but that have modified polymers and silica added separately .
The combination or stirring procedure involved mixing the non-productive ingredients at 60 revolutions per minute until a rubber temperature of 160 ° C was achieved, followed by a reduction in the revolutions per minute to maintain a temperature of 160 ° C for a certain period. of time. The total mixing times for the non-productive stages are shown in Table II. All the mixing of the productive stage was 2 minutes. The physical data for each sample is also shown in Table II. Table I
Ctrl Ctrl Ctrl Displays 1 2 4
Non-productive
Natural rubber 25 25 25 10
IBRJ 30 30 30 30 30
E-SBR2 61. 88 61. 88 61. 88 61. 88 61.88
Si693 11.0 11.0 11.0 11.0 11.0
Aromatic Oil 10.0 10.0 10.0 10.0 10.0
Wax 3.5 3.5 3.5 3.5 3.5 Stearic Acid 2 2 2 2 2
Antidegradants of Amine 2 2 2 2 2
Silica4 70 70 0 70 0
Modified PBD of Example l5
Silica of Example 1 (77
Modified PBD of Example 27
Silica of Example 2 0 0 0 0 77
Productive
Cyclobenzylsulfenamide 1.7 1.7 1.7 1.7 1.7
Diphenylguanidine 2.0 2.0 2.0 2.0 2.0
Sulfur 1.4 1.4 1.4 1.4 1.4
Zinc Oxide 3.5 3.5 3.5 3.5 3.5 1 Isoprene-butadiene rubber polymerized by solution having a Tg of -45 ° C. 2 Styrene-butadiene rubber emulsion polymerized having 40 weight percent styrene combined. It was added as 61.88 phr of rubber diluted with oil (45 phr of rubber and 16.88 phr of oil). 3 A composition of bis (3-triethoxysilylpropyl) tetrasulfide and carbon black N330 (weight ratio of 50/50, and therefore was considered to be 50 percent active) that can be obtained commercially as X50S from Degussa Ag. 4 A silica obtained as Zeosil ™ 1165MP from Rhone Poulenc Company and, supposedly has a BET surface area of about 165 and a DBP absorption value of about 260-280. 5 As prepared in Example 1. 6 As prepared in Example 1. 7 As prepared in Example 1. 8 As prepared in Example 2.
Table II
Ctrl Ctrl Ctrl Sample 1 2 3 4 5
Silica 70 70 0 70 0
Modified PBD of Example 1 0 7 0 0 0
Silica of Example 1 0 0 77 0 0
Modified PBD of Example 2 0 0 0 7 0
Silica of Example 2 0 0 0 0 77
Mixing Treatment (MJ / m3) 2009 1681 1676 1909 1703
Effort-Deformation - 18 * / 150 ° C
Module at 100% ((MPa) 2.08 1.95 1.98 1.89 2.01 Module at 330% (MPa) 8.36 8.14 8.4 7.91 8.63
M / 300 / M100 4.02 4.17 4.24 4.19 4.29
Resistance to breakage, (MPa) 18. 67 19.26 20. 38 18. 56 19. fifteen
Elongation at break (%) 621 631 648 625 600
Shore Hardness A Ambient Temperature 66.4 63.9 64.1 63.1 63.4
100 ° C 59.4 57.9 57.9 56.4 57.7
Reboiling Ambient Temperature 35.9 39.3 39.8 39.3 40.2
100 ° C 60.1 61.7 61.4 59.7 62.9
Abrasion of DIN (ce) 122 100 105 114 107 Both treated silicas of the present invention (Examples 3 and 5) show a reduced working input required during mixing, a higher modulus ratio (M300 / M100), higher bounce and better DIN abrasion (lower) compared to control 1. These properties indicate an improved energy construction, improved interaction of the filler or polymer charge, better fuel economy of the rim and longer duration tires. The silica of Example 2 (Sample 5) shows a clear advantage with respect to Sample 4 (Control) in the required mixing treatment, higher modules, higher tensile strength, higher rebore and lower DIN abrasion. The lower DIN abrasion values indicate better abrasion resistance which correlates with longer lasting rubber when used as a tread surface. This indicates that it is advantageous to pretreat the silica before mixing.
Claims (10)
1. A method for processing a silica loaded rubber composition which is characterized by mixing (i) 100 parts by weight of at least one vulcanizable elastomer with sulfur which is selected from homopolymers and copolymers of conjugated diene and copolymers of at least one conjugated diene and an aromatic vinyl compound; and (ii) from 10 to 150 phr of precipitated particulate silica having from 1 to 20 weight percent dispersed therein based on the weight of the silica, of a silane modified elastomer.
The method according to claim 1, characterized in that the precipitated silica before having dispersed the silane-modified elastomer thereon has a BET surface area within the range of 40 to 600 square meters per gram; an absorption value of dibutyl phthalate (DBP) within the range of 100 to about 400; and an average final particle size within the range of 0.01 to 0.05 micron.
3. The method according to claim 1, characterized in that the particulate precipitated silica having the silane-modified elastomer dispersed thereon is obtained by reacting the silica in an inert organic solvent in the presence of a silane-modified elastomer.
The method according to claim 1, characterized in that the silane modified elastomer is obtained by reacting an active terminal of a living polymer resulting through the polymerization of 1,3-butadiene or the copolymerization of 1,3-butadiene and styrene in an inert organic solvent, in the presence of an organic alkali initiator with a silane compound of the formula XyWySMOR1 ^ wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine; W is an alkylene radical having from 1 to 8 carbon atoms; And it is 0 or 1; R1 is independently selected from the group consisting of alkyl radicals having from 1 to 8 carbon atoms and aryl radicals having from 6 to 24 carbon atoms; yz is 4 when y is 0 and z is 3 when y is 1.
5. A silica-loaded rubber composition that is prepared by the process characterized by mixing (i) 100 parts by weight of at least one vulcanizable elastomer with sulfur that is selected from homopolymers and copolymers of conjugated diene and copolymers of at least one conjugated diene and an aromatic vinyl compound; and (ii) from 10 to 150 phr of a particulate precipitated silica having from 1 to 20 weight percent dispersed thereon, based on the weight of the silica, of a silane modified elastomer.
The composition according to claim 5, characterized in that the silica precipitated before having the silane-modified elastomer dispersed thereon has a BET surface area within the range of 40 to 600 square meters per gram; an absorption value of dibutyl phthalate (DBP) within the range of 100 to about 400; and an average final particle size within the range of 0.01 to 0.05 micron.
The composition according to claim 5, characterized in that the particulate precipitated silica having the silane modified elastomer dispersed thereon is obtained by reacting the silica in an inert organic solvent in the presence of the silane modified elastomer.
8. The composition according to claim 5, characterized in that the silane modified elastomer is obtained by reacting an active terminal of the resulting living polymer through the polymerization of 1,3-butadiene or the copolymerization of 1,3-butadiene and styrene in an inert organic solvent, in the presence of an organic alkaline initiator with a silane compound of the formula XyWySITOR1 ^ wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine; W is an alkylene radical having from 1 to 8 carbon atoms; and is 0 or 1; RI is independently selected from the group consisting of alkyl radicals having from 1 to 8 carbon atoms and aryl radicals having from 6 to 24 carbon atoms; and z is 4 when y is 0 and z is 3 when y is 1.
9. The composition according to claim 5, characterized in that it is in the form of a pneumatic tire, belt or hose.
10. The composition according to claim 9, characterized in that it is in the form of a pneumatic tire.
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US08/698,532 US5708053A (en) | 1996-08-15 | 1996-08-15 | Silica-filled rubber compositions and the processing thereof |
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KR100394130B1 (en) * | 1995-03-29 | 2003-10-22 | 제온 코포레이션 | Diene rubber composition |
US6228908B1 (en) | 1997-07-11 | 2001-05-08 | Bridgestone Corporation | Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds |
US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US6384117B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US5872176A (en) | 1997-07-11 | 1999-02-16 | Bridgestone Corporation | Addition of salts to improve the interaction of silica with rubber |
US6369138B2 (en) | 1997-07-11 | 2002-04-09 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
DE19915281A1 (en) * | 1999-04-03 | 2000-10-05 | Degussa | Rubber compounds |
DE19959932A1 (en) * | 1999-12-11 | 2001-06-28 | Continental Ag | Production of a silica-containing rubber composition useful for making abrasion-resistant tire treads, comprises mixing carbon black and silica with separate rubber components |
FR2804120A1 (en) * | 2000-01-24 | 2001-07-27 | Michelin Soc Tech | Use of mixture of aldimine and guanidine derivative as coupling agent activator in silica or alumina filled diene rubber compositions for fabrication of tire parts, especially treads |
FR2804121A1 (en) | 2000-01-24 | 2001-07-27 | Michelin Soc Tech | Rubber composition for manufacture of tires comprises filled elastomer with polysulfide coupling agent and dihydro pyridine derivative |
MXPA01012725A (en) | 2000-04-25 | 2002-07-22 | Michelin Rech Tech | Block copolymers for rubber compositions for use in tyres. |
AU2001265999A1 (en) * | 2000-05-22 | 2001-12-03 | Michelin Recherche Et Technique S.A. | Composition for tyre running tread and method for preparing same |
KR100337545B1 (en) * | 2000-05-23 | 2002-05-22 | 조충환 | Tire tread composition |
BR0106664A (en) | 2000-05-26 | 2002-04-02 | Michelin Soc Tech | Crosslinkable or crosslinked rubber composition that can be used to form a tire tread, process for preparing a crosslinkable rubber composition, and tire tread |
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JPS53109545A (en) * | 1977-03-08 | 1978-09-25 | Asahi Chem Ind Co Ltd | New composite and thermoplastic resin |
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-
1996
- 1996-08-15 US US08/698,532 patent/US5708053A/en not_active Expired - Lifetime
-
1997
- 1997-06-30 CA CA002209350A patent/CA2209350A1/en not_active Abandoned
- 1997-08-04 MX MX9705947A patent/MX9705947A/en not_active IP Right Cessation
- 1997-08-06 EP EP97113559A patent/EP0824133B1/en not_active Expired - Lifetime
- 1997-08-06 BR BR9704277A patent/BR9704277A/en active Search and Examination
- 1997-08-06 DE DE69721151T patent/DE69721151T2/en not_active Expired - Fee Related
- 1997-08-14 KR KR1019970038801A patent/KR19980018676A/en not_active Application Discontinuation
- 1997-08-14 JP JP9219355A patent/JPH1087890A/en not_active Ceased
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