US20020026001A1 - Processability of silica-filled rubber stocks - Google Patents
Processability of silica-filled rubber stocks Download PDFInfo
- Publication number
- US20020026001A1 US20020026001A1 US09/961,710 US96171001A US2002026001A1 US 20020026001 A1 US20020026001 A1 US 20020026001A1 US 96171001 A US96171001 A US 96171001A US 2002026001 A1 US2002026001 A1 US 2002026001A1
- Authority
- US
- United States
- Prior art keywords
- silane
- compound
- elastomer
- silica
- alkylalkoxysilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 41
- 239000005060 rubber Substances 0.000 title abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000000806 elastomer Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 22
- 150000001993 dienes Chemical class 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 239000000194 fatty acid Substances 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 229920001519 homopolymer Polymers 0.000 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 125000002897 diene group Chemical group 0.000 claims abstract 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 28
- 229910000077 silane Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 14
- -1 sorbitan ester Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 10
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 239000001593 sorbitan monooleate Substances 0.000 claims description 5
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 5
- 150000005671 trienes Chemical class 0.000 claims description 4
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims description 3
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 3
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- 229940023569 palmate Drugs 0.000 claims description 3
- 229940114926 stearate Drugs 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 2
- 230000000704 physical effect Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 description 23
- 235000019241 carbon black Nutrition 0.000 description 16
- 238000009472 formulation Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229950004959 sorbitan oleate Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000006236 Super Abrasion Furnace Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000006238 High Abrasion Furnace Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006242 Semi-Reinforcing Furnace Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZXHLQRSUVYZJGB-UHFFFAOYSA-N 1-(1-piperidin-1-ylethyl)piperidine Chemical compound C1CCCCN1C(C)N1CCCCC1 ZXHLQRSUVYZJGB-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- TTZKGYULRVDFJJ-GIVMLJSASA-N [(2r)-2-[(2s,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-[(z)-octadec-9-enoyl]oxyethyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1O TTZKGYULRVDFJJ-GIVMLJSASA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 125000000753 cycloalkyl 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- UANQEZRLOVWKTN-UHFFFAOYSA-N lithium;azanidacycloheptane Chemical compound [Li+].C1CCC[N-]CC1 UANQEZRLOVWKTN-UHFFFAOYSA-N 0.000 description 1
- NVMMPHVQFFIBOS-UHFFFAOYSA-N lithium;dibutylazanide Chemical compound [Li+].CCCC[N-]CCCC NVMMPHVQFFIBOS-UHFFFAOYSA-N 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 1
- OWYFNXMEEFAXTO-UHFFFAOYSA-N lithium;dipropylazanide Chemical compound [Li+].CCC[N-]CCC OWYFNXMEEFAXTO-UHFFFAOYSA-N 0.000 description 1
- CKVWBMJEETWJTF-UHFFFAOYSA-N lithium;tributyltin Chemical compound CCCC[Sn]([Li])(CCCC)CCCC CKVWBMJEETWJTF-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DRXHEPWCWBIQFJ-UHFFFAOYSA-N methyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)OC1=CC=CC=C1 DRXHEPWCWBIQFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000005475 oxolanyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000003707 silyl modified polymer Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10855—Characterized by the carcass, carcass material, or physical arrangement of the carcass materials
Definitions
- the subject invention relates to the processing and vulcanization of diene polymer and copolymer elastomer containing rubber stocks. More specifically, the present invention relates to the processing and vulcanization of diene polymer and copolymer elastomer-containing, silica-filled rubber stocks using a mixture of silanes as processing aids.
- the hysteresis of an elastomer refers to the difference between the energy applied to deform an article made from the elastomer and the energy released as the elastomer returns to its initial, undeformed state.
- lowered hysteresis properties are associated with reduced rolling resistance and heat build-up during operation of the tire. These properties, in turn, result in lowered fuel consumption of vehicles using such tires.
- the property of lowered hysteresis of compounded, vulcanizable elastomer compositions is particularly significant.
- compounded elastomer systems are known to the art and are comprised of at least one elastomer (that is, a natural or synthetic polymer exhibiting elastomeric properties, such as a rubber), a reinforcing filler agent (such as finely divided carbon black, thermal black, or mineral fillers such as clay and the like) and a vulcanizing system such as sulfur-containing vulcanizing (that is, curing) system.
- Si69 processing aid in the formulation of silica-frilled rubber stocks has been successful, but generally requires a large amount of the additive, such as 10% by weight based on the weight of silica, in order to be effective.
- Precipitated silica has been increasingly used as a reinforcing particulate filler in carbon black-filled rubber components of tires and mechanical goods.
- Silica-loaded rubber stocks exhibit relatively poor processability.
- the present invention provides a mixture of silanes for use as processing aids for silica-filled rubber stocks, which greatly improve the processability and properties of the formulations and resulting vulcanized product.
- the present invention provides a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising: mixing an elastomer with an amorphous silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide, an alkylalkoxysilane and a cure agent; and, effecting vulcanization.
- the elastomer is a diene monomer homopolymer or a copolymer of a diene monomer and a monovinyl aromatic monomer.
- the present invention further provides a vulcanizable silica-filled compound comprising an elastomer, a silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide (Si69), an alkylalkoxysilane and a cure agent.
- the elastomer is styrene butadiene rubber, optionally containing a carbon black filler. The compound is more readily processable during mixing, due to the use of the mixture of silane processing aids.
- the present invention further provides a pneumatic tire comprising tread stock vulcanized from the inventive vulcanizable silica-filled compound.
- the present invention provides a means to reduce the level of Si69 needed to obtain good physical properties in a cured rubber stock containing silica as a filler.
- the present invention further provides maintenance of the processability of the compounded stock, as measured by Mooney viscosity, at the same level as achieved with high levels of Si69.
- the present invention utilizes the presence of an alkylalkoxysilane as a silica hydrophobating agent, such that minimal amounts of Si69 are needed to obtain good processability, and yet still give good physical properties. According to the invention, therefore, a less costly silane can be substituted for the majority or all of the Si69 that would be normally used without any loss of processability or properties. Additionally, remilling can be eliminated, and the cure of the rubber stock is not dependent on the high sulfur level present in the Si69.
- the silica-hydrophobating agents useful according to the present invention include those alkylalkoxysilanes of the formula (R 1 ) 2 Si(OR 2 ) 2 or R 1 Si(OR 2 ) 3 , wherein the alkoxy groups are the same or are different; each R 1 independently comrising C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, or about C6 to about C18 aromatic, preferably C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, or about C6 to about C12 aromatic; and each R 2 independently containing from one to about 6 carbon atoms.
- Representative examples include octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropylrimethoxy silane, (3-glycidoxypropylriethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacryoltrimethoxy silane, i-butyltriethoxy silane, and the like. Of these, octyltriethoxysilane is preferred.
- polymerized elastomer is compounded in the rubber stock, e.g., polybutadiene, polyisoprene and the like, and copolymers thereof with monovinyl aromatics such as styrene, alpha methyl styrene and the like, or trienes such as myrcene.
- the elastomers include diene homopolymers, A, and copolymers thereof with monovinyl aromatic polymers, B.
- Exemplary diene homopolymers are those prepared from diolefin monomers having from 4 to about 12 carbon atoms.
- Exemplary vinyl aromatic polymers are those prepared from monomers having from 8 to about 20 carbon atoms.
- conjugated diene monomers and the like useful in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene, and aromatic vinyl monomers include styrene, ⁇ -metliylstyrene, p-metliylstyrene, vinyltoluenes and vinylnaphthalenes.
- the conjugated diene monomer and aromatic vinyl monomer are normally used at the weight ratios of about 90:10 to about 55:45, preferably about 80:20 to about 65:35.
- Preferred elastomers include diene homopolymers such as polybutadiene and polyisoprene and copolymers such as styrene butadiene rubber (SBR).
- Copolymers can comprise from about 99 to 20 percent by weight of diene units and from about 1 to about 80 percent by weight of monovinyl aromatic or triene units, totaling 100 percent.
- the polymers and copolymers of the present invention may have the diene portion with a 1,2-microstructure contents ranging from about 10 to about 80 percent, with the preferred polymers or copolymers having 1,2-microstructure contents of from about 25 to 65 percent.
- the molecular weight of the polymer that is produced according to the present invention is preferably such that a proton-quenched sample will exhibit a gum Mooney viscosity (ML 4 /212° F.) of from about 2 to about 150.
- the copolymers are preferably random copolymers which result from simultaneous copolymerization of the monomers, as is known in the art. Also included are nonfunctionalized cis-polybutadiene, ethylene-propylene-diene monomer (EPDM), emulsion SBR and natural rubber.
- Initiators known in the art such as an organolithium initiator, preferably an alkyllithium initiator, can be employed to prepare the elastomer. More particularly, the initiators used in the present invention include N-lithio-hexamethyleneimine, organolithium compounds such as n-butyllithium, tributyltin lithium, dialkylaminolithium compounds such as dimethylaminolithium, diethylaminolithium, dipropylaminolithium, dibutylaminolithium and the like, dialkylaminoalkyllithium compounds such as diethylaminopropyllithium and the like, and trialkyl stanyl lithium, wherein the alkyl group contains 1 to about 12 carbon atoms, preferably 1 to about 4 carbon atoms.
- organolithium compounds such as n-butyllithium, tributyltin lithium
- dialkylaminolithium compounds such as dimethylaminolithium, diethy
- Polymerization is usually conducted in a conventional solvent for anionic polymerizations such as the various cyclic and acyclic hexanes, heptanes, octanes, pentanes, their alkylated derivatives, and mixtures thereof. Other techniques for polymerization, such as semi-batch and continuous polymerization may be employed.
- a coordinator may optionally be added to the polymerization ingredients. Amounts range between 0 to 90 or more equivalents per equivalent of lithium. The amount depends upon the amount of vinyl desired, the level of styrene employed and the temperature of the polymerizations, as well as the nature of the specific polar coordinator employed.
- Compounds useful as coordinators are organic and include those having an oxygen or nitrogen hetero-atom and a non-bonded pair of electrons. Examples include dialkyl ethers of mono and oligo alkylene glycols; “crown” ethers; tertiary amines such as tetramethylethylene diamine (TMEDA); THF; TIF oligomers; linear and cyclic oligomeric oxolanyl alkanes, such as 2-2′-di(tetrahydrofuryl) propane, di-piperidyl ethane, hexamethylphosphoramide, N-N ′-dimethylpiperazine, diazabicyclooctane, diethyl ether, tributylamine and the like. Details of linear and cyclic oligomeric oxolanyl coordinators can be found in U.S. Pat. No. 4,429,091, owned by the Assignee of record, the subject matter of which is incorporated
- Polymerization is usually begun by charging a blend of the monomer(s) and solvent to a suitable reaction vessel, followed by the addition of the coordinator and the initiator solution previously described.
- the monomer and coordinator can be added to the initiator.
- the procedure is carried out under anhydrous, anaerobic conditions.
- the reactants are heated to a temperature of from about 10° to 150° C. and are agitated for about 0.1 to 24 hours.
- tile product is removed from the heat and terminated in one or more ways.
- terminating agents may provide the resulting polymer with a multifunctionality. That is, the polymers initiated according to the present invention, carry at least one amine functional group as discussed hereinabove, and may also carry a second functional group selected and derived from the group consisting of terminating agents, coupling agents and linking agents.
- Examples of terminating agents according to the present invention include those commonly employed in the art, including hydrogen, water, steam, an alcohol such as isopropanol, 1,3-dimethyl-2-imidazolidinone (DMI), carbodiimides, N-methylpyrrolidine, cyclic amides, cyclic ureas, isocyanates, Schiff bases, 4,4′-bis(diethylamino) benzophenone, and the like.
- Other useful terminating agents may include those of the structural formula (R 1 ) a ZX b , wherein Z is tin or silicon. It is preferred that Z is tin.
- R 1 is an alkyl having from about 1 to about 20 carbon atoms; a cycloalkyl having from about 3 to about 20 carbon atoms; an aryl having from about 6 to about 20 carbon atoms; or, an aralkyl having from about 7 to about 20 carbon atoms.
- R 1 may include methyl, ethyl, n-butyl, neophyl, phenyl, cyclohexyl or the like.
- terminating agents include tin tetrachloride, (R 1 ) 3 SnCl, (R 1 ) 2 SnCl 2 , R 1 SnCl 3 , and R 1 SiCl 3 as well as methyltriphenoxysilane (MeSi(OPh 3 )).
- the terminating agent is added to the reaction vessel, and the vessel is agitated for about 1 to about 1000 minutes. As a result, an elastomer is produced having an even greater affinity for silica compounding materials, and hence, even further reduced hysteresis.
- Additional examples of terminating agents include those found in U.S. Pat. No. 4,616,069 which is herein incorporated by reference. It is to be understood that practice of the present invention is not limited solely to these terminators inasmuch as other compounds that are reactive with the polymer bound lithium moiety can be selected to provide a desired functional group.
- Quenching is usually conducted by stirring the polymer and quenching agent for about 0.05 to about 2 hours at temperatures of from about 30° to 120° C. to ensure complete reaction.
- Polymers terminated with a functional group as discussed hereinabove, can be subsequently quenched with alcohol or other quenching agents as described hereinabove.
- the solvent is removed from the polymer by conventional techniques such as drum drying, extruder drying, vacuum drying or the like, which may be combined with coagulation with water, alcohol or steam, thermal desolventization, or any other suitable method. If coagulation with water or steam is used, oven drying may be desirable.
- the elastomeric polymers can be utilized as 100 parts of the rubber in the treadstock compound or, they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof.
- treadstock rubber which includes natural rubber, synthetic rubber and blends thereof.
- Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene/butadiene rubber (SBR), polybutadiene, butyl rubber, Neoprene, ethylene/propylene rubber, ethylene/propylene/diene rubber (EPDM), acrylonitrile/butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers, chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers, hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber and the like.
- SBR styrene
- the amounts can vary widely with a range comprising about 5 to about 99 percent by weight of the total rubber. It is to be appreciated that the minimum amount will depend primarily upon the degree of reduced hysteresis that is desired.
- amorphous silica (silicon dioxide) is utilized as a filler for the diene polymer or copolymer elastomer-containing vulcanizable compound.
- Silicas are generally classed as wet-process, hydrated silicas because they are produced by a chemical reaction in water, from which they are precipitated as ultrafine, spherical particles.
- the surface area as measured by the BET method gives the best measure of the reinforcing character of different silicas.
- the surface area should be about 32 to about 400 m 2 /g, with the range of about 100 to about 250 m 2 /g being preferred, and the range of about 150 to about 220 m 2 /g being most preferred.
- the pH of the silica filler is generally about 5.5 to about 7 or slightly over, preferably about 5.5 to about 6.8.
- Silica can be employed in the amount of about 1 part to about 100 parts per 100 parts of polymer (phr), preferably in an amount from about 5 to about 80 phr.
- the useful upper range is limited by the high viscosity imparted by fillers of this type.
- Some of the commercially available silicas which may be used include: Hi-Sil® 215, Hi-Si® 233, and Hi-Sil® 190, all produced by PPG Industries. Also, a number of useful commercial grades of different silicas are available from De Gussa Corporation, Rhone Poulenc, and J.M. Huber Corporation.
- the polymers can be compounded with all forms of carbon black in amounts ranging from about 2 to about 50 parts by weight, per 100 parts of rubber (phr), with about 5 to about 40 phr being preferred.
- the carbon blacks may include any of the commonly available, commercially-produced carbon blacks but those having a surface area (EMSA) of at least 20 m 2 /gram and more preferably at least 35 m 2 /gram up to 200 m 2 /gram or higher are preferred.
- SMA surface area
- Surface area values used in this application are those determined by ASTM test D-1765 using the cetyltrimethyl-ammonium bromide (CTAB) technique.
- CTAB cetyltrimethyl-ammonium bromide
- the useful carbon blacks are furnace black, channel blacks and lamp blacks.
- examples of the carbon blacks include super abrasion furnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace (FF) blacks, intermediate super abrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks, medium processing channel blacks, hard processing channel blacks and conducting channel blacks.
- SAF super abrasion furnace
- HAF high abrasion furnace
- FEF fast extrusion furnace
- FF fine furnace
- ISIF intermediate super abrasion furnace
- SRF semi-reinforcing furnace
- the carbon blacks utilized in the preparation of the rubber compounds of the invention may be in pelletized form or an unpelletized flocculent mass. Preferably, for more uniform mixing, unpelletized carbon black is preferred.
- the reinforced rubber compounds can be cured in a conventional manner with known vulcanizing agents at about 0.2 to about 5 phr.
- vulcanizing agents sulfur or peroxide-based curing systems may be employed.
- suitable vulcanizing agents one can refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Wiley Interscience, N.Y. 1982, Vol. 20, pp. 365-468, particularly “Vulcanization Agents and Auxiliary Materials” pp. 390-402. Vulcanizing agents can be used alone or in combination.
- Vulcanizable elastomeric compositions of the invention can be prepared by compounding or mixing the elastomeric polymer with silica, optionally carbon black, the silica-hydrophobating agent according to the present invention, a minimal amount of Si69, and other conventional rubber additives including for example, fillers, plasticizers, antioxidants, curing agents and the like, using standard rubber mixing equipment and procedures.
- SBR styrene butadiene rubber
- the present invention can thus further utilize the presence of an ester of a fatty acid or an ester of a polyol as a processing aid to replace the silane Si69 to give equal processability of the vulcanizable compound, and better hot tear strength and lower hysteresis of the vulcanized rubber stock, without loss of the other measured physical properties.
- the further processing aid such as the preferred sorbitan oleate
- the sorbitan oleate is lower in cost and more storage stable than Si69, and when used with a silica filler and a silane terminated polymer, gives similar reduction of ML 4 , and tan ⁇ with an increase in tear strength.
- the additional processing aids useful according to the present invention include esters of fatty acids or esters of polyols.
- Representative examples include the sorbitan oleates, such as sorbitan monooleate, dioleate, trioleate and sesquioleate, as well as sorbitan esters of laurate, palmate and stearate fatty acids, and the polyoxyethylene derivatives of each, and other polyols, including glycols such as polyhydroxy compounds and the like. Of these, sorbitan monooleate is preferred.
- the present invention provides a means for improving the processability of formulations of diene polymer elastomers with silica-filler, reducing the viscosity of silica-filled elastomeric vulcanizable compounds. It is further demonstrated that the present invention provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties.
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- Organic Chemistry (AREA)
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Abstract
A processable rubber stock is produced by the preparation of a silica-filled, vulcanized elastomeric compound comprising mixing an elastomer with an amorphous silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide, an alkylalkoxysilane and a cure agent. A further processing aid comprising at least one of an ester of a fatty acid or an ester of a polyol is preferred. The elastomer is preferably a diene monomer homopolymer or a copolymer of at least one diene and at least one monovinyl aromatic monomer. By effecting vulcanization, a vulcanized elastomeric compound is produced containing good physical properties for use as tread stock for a pneumatic tire.
Description
- The subject invention relates to the processing and vulcanization of diene polymer and copolymer elastomer containing rubber stocks. More specifically, the present invention relates to the processing and vulcanization of diene polymer and copolymer elastomer-containing, silica-filled rubber stocks using a mixture of silanes as processing aids.
- In the art it is desirable to produce elastomeric compounds exhibiting reduced hysteresis when properly compounded with other ingredients such as reinforcing agents, followed by vulcanization. Such elastomers, when compounded, fabricated and vulcanized into components for constructing articles such as tires, power belts, and the like, will manifest properties of increased rebound, decreased rolling resistance and less heat-build up when subjected to mechanical stress during normal use.
- The hysteresis of an elastomer refers to the difference between the energy applied to deform an article made from the elastomer and the energy released as the elastomer returns to its initial, undeformed state. In pneumatic tires, lowered hysteresis properties are associated with reduced rolling resistance and heat build-up during operation of the tire. These properties, in turn, result in lowered fuel consumption of vehicles using such tires.
- In such contexts, the property of lowered hysteresis of compounded, vulcanizable elastomer compositions is particularly significant. Examples of such compounded elastomer systems are known to the art and are comprised of at least one elastomer (that is, a natural or synthetic polymer exhibiting elastomeric properties, such as a rubber), a reinforcing filler agent (such as finely divided carbon black, thermal black, or mineral fillers such as clay and the like) and a vulcanizing system such as sulfur-containing vulcanizing (that is, curing) system.
- Previous attempts at preparing readily processable, vulcanizable, silica-filled rubber stocks containing natural rubber or diene polymer and copolymer elastomers have focused upon the sequence of adding ingredients during mixing (Bomal, et al.,Influence of Mixing procedures on the Properties of a Silica Reinforced Agricultural Tire Tread, May 1992), the addition of de-agglomeration agents such as zinc methacrylate and zinc octoate, or SBR-silica coupling agents such as mercapto propyl trimethoxy silane (Hewwitt, Processing Technology of Silica Reinforced SBR, Elastomerics, pp 33-37, March 1981), and the use of bis[3-(triethoxysilylropyl]tetrasulfide (Si69) processing aid (Degussa, PPG).
- The use of Si69 processing aid in the formulation of silica-frilled rubber stocks has been successful, but generally requires a large amount of the additive, such as 10% by weight based on the weight of silica, in order to be effective.
- Precipitated silica has been increasingly used as a reinforcing particulate filler in carbon black-filled rubber components of tires and mechanical goods. Silica-loaded rubber stocks, however, exhibit relatively poor processability.
- The present invention provides a mixture of silanes for use as processing aids for silica-filled rubber stocks, which greatly improve the processability and properties of the formulations and resulting vulcanized product.
- It is therefore an object of the present invention to provide rubber stock processing aids which improve the processability of formulations of diene polymer elastomers with silica-filler.
- It is another object of the present invention to provide a method for reducing the viscosity of silica-filled elastomeric vulcanizable compounds.
- It is another object of the present invention to provide a method for enhancing the processability of silica-filled elastomeric vulcanizable compounds.
- It is another object of the present invention to provide vulcanizable silica-filled elastomeric compounds having enhanced physical properties.
- The foregoing objects, together with the advantages thereof over the existing art, which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described and claimed.
- The present invention provides a process for the preparation of a silica-filled, vulcanized elastomeric compound comprising: mixing an elastomer with an amorphous silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide, an alkylalkoxysilane and a cure agent; and, effecting vulcanization. Preferably, the elastomer is a diene monomer homopolymer or a copolymer of a diene monomer and a monovinyl aromatic monomer.
- The present invention further provides a vulcanizable silica-filled compound comprising an elastomer, a silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide (Si69), an alkylalkoxysilane and a cure agent. Preferably, the elastomer is styrene butadiene rubber, optionally containing a carbon black filler. The compound is more readily processable during mixing, due to the use of the mixture of silane processing aids.
- The present invention further provides a pneumatic tire comprising tread stock vulcanized from the inventive vulcanizable silica-filled compound.
- In general, the present invention provides a means to reduce the level of Si69 needed to obtain good physical properties in a cured rubber stock containing silica as a filler. In addition, the present invention further provides maintenance of the processability of the compounded stock, as measured by Mooney viscosity, at the same level as achieved with high levels of Si69.
- The present invention utilizes the presence of an alkylalkoxysilane as a silica hydrophobating agent, such that minimal amounts of Si69 are needed to obtain good processability, and yet still give good physical properties. According to the invention, therefore, a less costly silane can be substituted for the majority or all of the Si69 that would be normally used without any loss of processability or properties. Additionally, remilling can be eliminated, and the cure of the rubber stock is not dependent on the high sulfur level present in the Si69.
- The silica-hydrophobating agents useful according to the present invention include those alkylalkoxysilanes of the formula (R1)2Si(OR2)2 or R1Si(OR2)3, wherein the alkoxy groups are the same or are different; each R1 independently comrising C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, or about C6 to about C18 aromatic, preferably C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, or about C6 to about C12 aromatic; and each R2 independently containing from one to about 6 carbon atoms. Representative examples include octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropylrimethoxy silane, (3-glycidoxypropylriethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacryoltrimethoxy silane, i-butyltriethoxy silane, and the like. Of these, octyltriethoxysilane is preferred.
- According to the present invention, polymerized elastomer is compounded in the rubber stock, e.g., polybutadiene, polyisoprene and the like, and copolymers thereof with monovinyl aromatics such as styrene, alpha methyl styrene and the like, or trienes such as myrcene. Thus, the elastomers include diene homopolymers, A, and copolymers thereof with monovinyl aromatic polymers, B. Exemplary diene homopolymers are those prepared from diolefin monomers having from 4 to about 12 carbon atoms. Exemplary vinyl aromatic polymers are those prepared from monomers having from 8 to about 20 carbon atoms. Examples of conjugated diene monomers and the like useful in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene, and aromatic vinyl monomers include styrene, α-metliylstyrene, p-metliylstyrene, vinyltoluenes and vinylnaphthalenes. The conjugated diene monomer and aromatic vinyl monomer are normally used at the weight ratios of about 90:10 to about 55:45, preferably about 80:20 to about 65:35.
- Preferred elastomers include diene homopolymers such as polybutadiene and polyisoprene and copolymers such as styrene butadiene rubber (SBR). Copolymers can comprise from about 99 to 20 percent by weight of diene units and from about 1 to about 80 percent by weight of monovinyl aromatic or triene units, totaling 100 percent. The polymers and copolymers of the present invention may have the diene portion with a 1,2-microstructure contents ranging from about 10 to about 80 percent, with the preferred polymers or copolymers having 1,2-microstructure contents of from about 25 to 65 percent. The molecular weight of the polymer that is produced according to the present invention, is preferably such that a proton-quenched sample will exhibit a gum Mooney viscosity (ML4/212° F.) of from about 2 to about 150. The copolymers are preferably random copolymers which result from simultaneous copolymerization of the monomers, as is known in the art. Also included are nonfunctionalized cis-polybutadiene, ethylene-propylene-diene monomer (EPDM), emulsion SBR and natural rubber.
- Initiators known in the art such as an organolithium initiator, preferably an alkyllithium initiator, can be employed to prepare the elastomer. More particularly, the initiators used in the present invention include N-lithio-hexamethyleneimine, organolithium compounds such as n-butyllithium, tributyltin lithium, dialkylaminolithium compounds such as dimethylaminolithium, diethylaminolithium, dipropylaminolithium, dibutylaminolithium and the like, dialkylaminoalkyllithium compounds such as diethylaminopropyllithium and the like, and trialkyl stanyl lithium, wherein the alkyl group contains 1 to about 12 carbon atoms, preferably 1 to about 4 carbon atoms.
- Polymerization is usually conducted in a conventional solvent for anionic polymerizations such as the various cyclic and acyclic hexanes, heptanes, octanes, pentanes, their alkylated derivatives, and mixtures thereof. Other techniques for polymerization, such as semi-batch and continuous polymerization may be employed. In order to promote randomization in copolymerization and to increase vinyl content, a coordinator may optionally be added to the polymerization ingredients. Amounts range between 0 to 90 or more equivalents per equivalent of lithium. The amount depends upon the amount of vinyl desired, the level of styrene employed and the temperature of the polymerizations, as well as the nature of the specific polar coordinator employed.
- Compounds useful as coordinators are organic and include those having an oxygen or nitrogen hetero-atom and a non-bonded pair of electrons. Examples include dialkyl ethers of mono and oligo alkylene glycols; “crown” ethers; tertiary amines such as tetramethylethylene diamine (TMEDA); THF; TIF oligomers; linear and cyclic oligomeric oxolanyl alkanes, such as 2-2′-di(tetrahydrofuryl) propane, di-piperidyl ethane, hexamethylphosphoramide, N-N ′-dimethylpiperazine, diazabicyclooctane, diethyl ether, tributylamine and the like. Details of linear and cyclic oligomeric oxolanyl coordinators can be found in U.S. Pat. No. 4,429,091, owned by the Assignee of record, the subject matter of which is incorporated herein by reference.
- Polymerization is usually begun by charging a blend of the monomer(s) and solvent to a suitable reaction vessel, followed by the addition of the coordinator and the initiator solution previously described. Alternatively, the monomer and coordinator can be added to the initiator. The procedure is carried out under anhydrous, anaerobic conditions. The reactants are heated to a temperature of from about 10° to 150° C. and are agitated for about 0.1 to 24 hours. After polymerization is complete, tile product is removed from the heat and terminated in one or more ways.
- To terminate the polymerization, a terminating agent, coupling agent or linking agent may be employed, all of these agents being collectively referred to herein as “terminating agents”. Certain of these agents may provide the resulting polymer with a multifunctionality. That is, the polymers initiated according to the present invention, carry at least one amine functional group as discussed hereinabove, and may also carry a second functional group selected and derived from the group consisting of terminating agents, coupling agents and linking agents.
- Examples of terminating agents according to the present invention include those commonly employed in the art, including hydrogen, water, steam, an alcohol such as isopropanol, 1,3-dimethyl-2-imidazolidinone (DMI), carbodiimides, N-methylpyrrolidine, cyclic amides, cyclic ureas, isocyanates, Schiff bases, 4,4′-bis(diethylamino) benzophenone, and the like. Other useful terminating agents may include those of the structural formula (R1)a ZXb, wherein Z is tin or silicon. It is preferred that Z is tin. R1 is an alkyl having from about 1 to about 20 carbon atoms; a cycloalkyl having from about 3 to about 20 carbon atoms; an aryl having from about 6 to about 20 carbon atoms; or, an aralkyl having from about 7 to about 20 carbon atoms. For example, R1 may include methyl, ethyl, n-butyl, neophyl, phenyl, cyclohexyl or the like. X is a halogen, such as chlorine or bromine, or an alkoxy (—OR1), “a” is from 0 to 3, and “b” is from about 1 to 4; where a+b=4. Examples of such terminating agents include tin tetrachloride, (R1)3SnCl, (R1)2SnCl2, R1SnCl3, and R1SiCl3 as well as methyltriphenoxysilane (MeSi(OPh3)).
- The terminating agent is added to the reaction vessel, and the vessel is agitated for about 1 to about 1000 minutes. As a result, an elastomer is produced having an even greater affinity for silica compounding materials, and hence, even further reduced hysteresis. Additional examples of terminating agents include those found in U.S. Pat. No. 4,616,069 which is herein incorporated by reference. It is to be understood that practice of the present invention is not limited solely to these terminators inasmuch as other compounds that are reactive with the polymer bound lithium moiety can be selected to provide a desired functional group.
- Quenching is usually conducted by stirring the polymer and quenching agent for about 0.05 to about 2 hours at temperatures of from about 30° to 120° C. to ensure complete reaction. Polymers terminated with a functional group as discussed hereinabove, can be subsequently quenched with alcohol or other quenching agents as described hereinabove.
- Lastly, the solvent is removed from the polymer by conventional techniques such as drum drying, extruder drying, vacuum drying or the like, which may be combined with coagulation with water, alcohol or steam, thermal desolventization, or any other suitable method. If coagulation with water or steam is used, oven drying may be desirable.
- The elastomeric polymers can be utilized as 100 parts of the rubber in the treadstock compound or, they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof. Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene/butadiene rubber (SBR), polybutadiene, butyl rubber, Neoprene, ethylene/propylene rubber, ethylene/propylene/diene rubber (EPDM), acrylonitrile/butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers, chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers, hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber and the like. When the polymers discussed hereinabove are blended with conventional rubbers, the amounts can vary widely with a range comprising about 5 to about 99 percent by weight of the total rubber. It is to be appreciated that the minimum amount will depend primarily upon the degree of reduced hysteresis that is desired.
- According to the present invention, amorphous silica (silicon dioxide) is utilized as a filler for the diene polymer or copolymer elastomer-containing vulcanizable compound. Silicas are generally classed as wet-process, hydrated silicas because they are produced by a chemical reaction in water, from which they are precipitated as ultrafine, spherical particles.
- These primary particles strongly associate into aggregates, which in turn combine less strongly into agglomerates. The surface area, as measured by the BET method gives the best measure of the reinforcing character of different silicas. For silicas of interest for the present invention, the surface area should be about 32 to about 400 m2/g, with the range of about 100 to about 250 m2/g being preferred, and the range of about 150 to about 220 m2/g being most preferred. The pH of the silica filler is generally about 5.5 to about 7 or slightly over, preferably about 5.5 to about 6.8.
- Silica can be employed in the amount of about 1 part to about 100 parts per 100 parts of polymer (phr), preferably in an amount from about 5 to about 80 phr. The useful upper range is limited by the high viscosity imparted by fillers of this type. Some of the commercially available silicas which may be used include: Hi-Sil® 215, Hi-Si® 233, and Hi-Sil® 190, all produced by PPG Industries. Also, a number of useful commercial grades of different silicas are available from De Gussa Corporation, Rhone Poulenc, and J.M. Huber Corporation.
- The polymers can be compounded with all forms of carbon black in amounts ranging from about 2 to about 50 parts by weight, per 100 parts of rubber (phr), with about 5 to about 40 phr being preferred. The carbon blacks may include any of the commonly available, commercially-produced carbon blacks but those having a surface area (EMSA) of at least 20 m2/gram and more preferably at least 35 m2/gram up to 200 m2/gram or higher are preferred. Surface area values used in this application are those determined by ASTM test D-1765 using the cetyltrimethyl-ammonium bromide (CTAB) technique. Among the useful carbon blacks are furnace black, channel blacks and lamp blacks. More specifically, examples of the carbon blacks include super abrasion furnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace (FF) blacks, intermediate super abrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks, medium processing channel blacks, hard processing channel blacks and conducting channel blacks. Other carbon blacks which may be utilized include acetylene blacks. Mixtures of two or more of the above blacks can be used in preparing the carbon black products of the invention. Typical values for surface areas of usable carbon blacks are summarized in the Table I hereinbelow.
TABLE I Carbon Blacks ASTM Designation Surface Area (m2/g) (D-1765-82a) (D-3765) N-110 126 N-220 111 N-339 95 N-330 83 N-351 74 N-550 42 N-660 35 - The carbon blacks utilized in the preparation of the rubber compounds of the invention may be in pelletized form or an unpelletized flocculent mass. Preferably, for more uniform mixing, unpelletized carbon black is preferred.
- The reinforced rubber compounds can be cured in a conventional manner with known vulcanizing agents at about 0.2 to about 5 phr. For example, sulfur or peroxide-based curing systems may be employed. For a general disclosure of suitable vulcanizing agents one can refer to Kirk-Othmer,Encyclopedia of Chemical Technology, 3rd ed., Wiley Interscience, N.Y. 1982, Vol. 20, pp. 365-468, particularly “Vulcanization Agents and Auxiliary Materials” pp. 390-402. Vulcanizing agents can be used alone or in combination.
- Vulcanizable elastomeric compositions of the invention can be prepared by compounding or mixing the elastomeric polymer with silica, optionally carbon black, the silica-hydrophobating agent according to the present invention, a minimal amount of Si69, and other conventional rubber additives including for example, fillers, plasticizers, antioxidants, curing agents and the like, using standard rubber mixing equipment and procedures.
- In order to demonstrate the preparation and properties of silica-filled, diene elastomer containing rubber stocks prepared according to the present invention, styrene butadiene rubber (SBR) polymers were prepared and were compounded using the formulations set forth in Tables II and III below.
- Test results for the Control, C-A, using the Si69 processing aid only, and Examples 1-3, using silane processing aids according to the invention in Formulation A, are reported in Table II.
TABLE II Formulation A for the Partial Replacement of Si69 and Physical Test Results Material Amount (phr) Example No. C-A 1 2 3 SBR 100 100 100 100 Oil 20 20 20 20 Silica 60 60 60 60 Carbon Black 6 6 6 6 Stearic Acid 2 2 2 2 Wax 0.75 0.75 0.75 0.75 Si-69 5.4 0.6 0.6 0.6 Silane (Type) — Octyl Methacroyl Dimethyl Trimethoxy Trimethoxy Dimethoxy Silane (Amount) 0 4.71 4.99 3.62 Tackifier 3.5 3.5 3.5 3.5 Antioxidant 0.95 0.95 0.95 0.95 Sulfur 1.4 1.4 1.4 1.4 Accelerators 2.4 2.4 2.4 2.4 Zinc Oxide 3 3 3 3 Physical Properties ML1+4 @ 100° C. 93.7 84.7 93.3 88.8 Tensile (psi) @ 23° C. 2913 2216 2476 2834 Tensile (psi) @ 1239 954 1122 1294 100° C. % Elong. at break, 444 603 504 551 23° C. % Elong. at break, 262 407 342 365 100° C. Ring Tear (lb/in) @ 191 198 179 223 100° C. Dispersion Index, % 72.9 76.1 84 84.3 - Test results for the Control, C-B, using the Si69 processing aid only, and Examples 4-7, using silane processing aids according to the invention in Formulation B, are reported in Table III.
TABLE III Formulation B for the Partial Replacement of Si69 and Physical Test Results Material Amount (phr) Example No. C-B 4 5 6 7 SBR 75 75 75 75 75 BR 25 25 25 25 25 Oil 41.25 41.25 41.25 41.25 41.25 Silica 80 80 80 80 80 Carbon Black 8 8 8 8 8 Stearic Acid 1 1 1 1 1 Wax 1.5 1.5 1.5 1.5 1.5 Si-69 7.2 0.8 0.8 0.8 0.8 Silane (Type) — Propyl 3- Octyl i-Butyl Triethoxy Chloropropyl Triethoxy Triethoxy Triethoxy Silane 0 5.5 6.42 7.39 5.88 (Amount) Tackifier 3 3 3 3 3 Antioxidant 1.17 1.17 1.17 1.17 1.17 Sulfur 2.8 2.8 2.8 2.8 2.8 Accelerators 2.4 2.4 2.4 2.4 2.4 Zinc Oxide 1.7 1.7 1.7 1.7 1.7 Physical Properties ML1+4 @ 64.8 69.2 96.1 53.8 93.9 100° C. Tensile (psi) @ 2497 2268 2566 2400 2513 23 ° C. Tensile (psi) @ 1453 1278 1693 1280 1379 100° C. % Elong. at 487 614 544 612 649 break, 23° C. % Elong. at 386 486 487 467 499 break, 100° C. Ring Tear (lb/ 190 270 245 262 298 in) @ 100° C. Dispersion 93.1 80.5 95.7 87.9 93.3 Index, % - A series of tests were conducted, in which the Si69 processing aid was omitted and insoluble sulfur was added, while processing Formulation B with 2 phr octyl-triethoxy silane, and 4 phr sorbitan oleate. Test conditions and results are reported for Examples 8-17 and the Control (no added insoluble sulfur), C-C, in Table IV, below.
TABLE IV Physical Properties of Formulation B with 2 phr Octyl-Triethoxy Silane, 4 phr Sorbitan Monooleate, and Insoluble Sulfur without Si69 Sample 8 9 10 11 12 13 14 15 16 17 C-C Insoluble S (phr) 1.4 1.7 2 2.3 2.6 2.9 3.3 3.7 4.1 4.5 0 Total S (phr) 2.8 3.1 3.4 3.7 4 4.3 4.7 5.1 5.5 5.9 1.4 Physical Test Results ML1+4/100° C. 84 81.9 80.7 78.9 78.5 103.6 101.8 99.5 99.8 101.7 75.7 Monsanto Cure @ 171° C. ML 13.6 14.7 13.4 13 12.8 18 18.2 18 17.8 18.2 116 MH 33.4 34.8 37.1 37 38.3 46.5 48.3 50.6 50.8 53.9 37.37 ts2 2:54 2:48 2:41 2:47 2:44 2:42 2:34 2:30 2:28 2:29 2:30 tc90 10:51 9:50 9:42 9:28 9:15 12:05 11:36 11:11 10:29 11:11 10:01 Ring Tensile @ 24° C. 100% Modulus, 188 184 209 194 227 212 267 256 284 326 318 psi 300% Modulus, 494 485 592 556 667 670 792 765 872 988 1150 psi Tensile str, psi 1798 1550 1814 1548 1769 1842 2120 1757 1925 2076 2809 % Elongation 724 657 641 613 594 601 591 538 527 510 556 Break energy, 5273 4203 4835 4000 4445 4569 5196 4034 4343 4580 6596 lbs/in2 Ring Tensile @ 100° C. 100% Modulus, 131 151 191 215 187 210 231 255 286 292 268 psi 300% Modulus, 333 381 519 566 532 621 656 730 846 833 661 psi Tensile str, psi 905 1062 1233 1162 983 1156 1017 878 1079 1042 1263 % Elongation 649 652 592 529 500 500 441 340 375 364 364 Break Energy, 2612 3070 3306 2850 2310 2849 2172 1565 1984 1906 2092 lbs/in2 Ring Tear 250 217 228 230 201 247 216 201 192 221 276 @ 171° C., ppi Pendulum Re- 33.6 35 32.4 37.6 40.2 37.2 40.2 37.6 41.2 41.4 53.6 bound 65° C. Wet Stanley 56/53 54/53 56/53 53/53 57/53 60/54 62/54 63/54 64/54 63/54 London,(#/std) Shore A 68 67 68 68 69 71 71 73 73 72 65 @ 24° C. Dispersion 85.6 85.5 86.5 87.1 88 59.4 Index #1 Specific Gravity 1.184 1.186 1.189 1.188 1.189 1.195 1.197 1.199 1.199 1.21 1.202 Rheometries @ 7% strain tan δ @ 65° C. .1978 .1924 .1807 .1858 .1789 .1697 .1662 .158 .1583 .1503 .1839 Δ G′ @ 65° C., 4.884 6.201 6.133 5.937 6.117 7.747 8.845 9.295 9.552 10.041 6.88 MPa Tensile Retraction Mc × 10−3 g/mol 20.9 20.0 17.5 17.4 16.3 15.4 13.2 12.3 12.2 - A further series of tests were conducted, in which Formulation B, described in Table III, was processed with added sulfur and a processing aid comprising 1.5 phr octyl-triethoxy silane, 0.5 phr Si69, and 4 phr sorbitan oleate. Test conditions and results are reported for Examples 18-22 in Table V, below.
TABLE V Physical Properties of Formulation B with 1.5 phr Octyl-triethoxysilane, 4 phr Sorbitan, 0.5 Si69 and Insoluble Sulfur Sample 18 19 20 21 22 Insoluble S (phr) 2.8 3.2 3.6 4 4.4 Total S (phr) 4.2 4.6 5 5.4 5.8 Physical Test Results ML1+4/100° C. 81.9 83.6 84.2 86.3 80.8 Monsanto Cure @ 171° C. ML 13.15 13.2 13.15 13.82 12.48 MH 41.84 44.62 44.62 46.58 46.98 ts2 2:50 2:44 2:43 2:35 2:38 tc90 10:15 10:12 9:12 9:24 8:59 Ring Tensile @ 24° C. 100% Modulus, psi 273 291 326 341 408 300% Modulus, psi 935 994 1112 1158 1452 Tensile str, psi 2323 2183 2112 2012 2497 % Elongation 582 537 483 461 460 Break Energy,lbs/in2 5760 5099 4545 4164 5130 Ring Tensile @ 100° C. 100% Modulus, psi 251 251 287 307 311 300% Modulus, psi 826 798 933 1030 998 Tensile str, psi 1326 1215 1255 1229 1113 % Elongation 444 428 388 350 329 Break Energy, lbs/in2 2720 2439 2306 2069 1800 Ring Tear @ 171° C., 240 230 201 219 206 psi Pendulum Rebound 37.2 39 42.8 39.4 42.4 65° C. Wet Stanley London 64/53 61/53 64/53 65/53 65/53 (#/std) Shore A, @ RT 72 71 72 74 73 Specific Gravity 1.195 1.196 1.197 1.197 1.202 Rheometries @ 7% strain tan δ @ 65° C. 0.1577 0.1528 0.1444 0.1384 0.1533 Δ G′ @ 65° C., MPa 6.89 6.798 6.676 6.285 7.789 Tensile Retraction 12.6 12.4 11.1 10.4 9.7 Mc, × 10−3 g/mol - The present invention can thus further utilize the presence of an ester of a fatty acid or an ester of a polyol as a processing aid to replace the silane Si69 to give equal processability of the vulcanizable compound, and better hot tear strength and lower hysteresis of the vulcanized rubber stock, without loss of the other measured physical properties.
- The further processing aid, such as the preferred sorbitan oleate, is air stable and does not decompose. The sorbitan oleate is lower in cost and more storage stable than Si69, and when used with a silica filler and a silane terminated polymer, gives similar reduction of ML4, and tan δ with an increase in tear strength.
- The additional processing aids useful according to the present invention include esters of fatty acids or esters of polyols. Representative examples include the sorbitan oleates, such as sorbitan monooleate, dioleate, trioleate and sesquioleate, as well as sorbitan esters of laurate, palmate and stearate fatty acids, and the polyoxyethylene derivatives of each, and other polyols, including glycols such as polyhydroxy compounds and the like. Of these, sorbitan monooleate is preferred.
- It is therefore demonstrated that the present invention provides a means for improving the processability of formulations of diene polymer elastomers with silica-filler, reducing the viscosity of silica-filled elastomeric vulcanizable compounds. It is further demonstrated that the present invention provides vulcanizable silica-filled elastomeric compounds having enhanced physical properties.
- It should be appreciated that the present invention is not limited to the specific embodiments described above, but includes variations, modifications and equivalent embodiments defined by the following claims.
Claims (30)
1. A process for the preparation of a silica-filled, vulcanized elastomeric compound comprising:
mixing an elastomer with an amorphous silica filler, 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide, an alkylalkoxysilane and a cure agent; and,
effecting vulcanization.
2. The process as in claim 1 wherein the elastomer is a diene monomer homopolymer or a copolymer of a diene monomer and a monomer selected from the group consisting of monovinyl aromatic monomers and triene monomers.
3. The process as in claim 1 wherein the alkylalkoxysilane is represented by the formula (R1)2Si(OR2)2 or R1Si(OR2)3,
wherein each R1 independently is selected from the group consisting of C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, and about C6 to about C18 aromatic; and,
wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
4. The process as in claim 1 wherein the alkylalkoxysilane is represented by the formula (R1)2Si(OR2)2 or R1Si(OR2)3,
wherein each R1 independently is selected from the group consisting of C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, and about C6 to about C12 aromatic; and,
wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
5. The process as in claim 1 wherein the alkylalkoxysilane is selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropylrimethoxy silane, (3-glycidoxypropylriethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacroyltrimethoxy silane, and i-butyltriethoxy silane.
6. The process as in claim 1 wherein the alkylalkoxysilane is octyltriethoxysilane.
7. The process as in claim 1 , including mixing prior to vulcanizing, a processing aid comprising at least one of an ester of a fatty acid or an ester of a polyol.
8. The process as in claim 7 wherein the processing aid is selected from the group consisting of at least one sorbitan ester of an oleate, laurate, palmate and stearate fatty acids, polyoxyethylene derivatives thereof, at least one ester of a polyhydroxy compound, and mixtures thereof.
9. The process as in claim 7 wherein the processing aid is sorbitan monooleate.
10. The process as in claim 1 wherein the elastomer is styrene butadiene rubber.
11. The process as in claim 1 wherein the elastomer is a copolymer of styrene butadiene rubber and butyl rubber.
12. The process as in claim 1 including mixing the elastomer with carbon black.
13. The process as in claim 1 including mixing insoluble sulfur prior to vulcanizing.
14. A vulcanizable silica-filled compound comprising an elastomer, a silica filler, from 0 to less than about 1% by weight based on said silica filler of bis[3-(triethoxysilylropyl]tetrasulfide, an alkylalkoxysilane and a cure agent.
15. The compound as in claim 14 wherein the alkylalkoxysilane is represented by the formula (R1)2Si(OR2)2 or R1Si(OR2)3,
wherein each R1 independently is selected from the group consisting of C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, and about C6 to about C18 aromatic; and,
wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
16. The compound as in claim 14 wherein the alkylalkoxysilane is represented by the formula (R1)2Si(OR2)2 or R1Si(OR2)3,
wherein each R1 independently is selected from the group consisting of C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, and about C6 to about C12 aromatic; and,
wherein the alkoxy groups are the same or are different, each R2 independently containing from one to about 6 carbon atoms.
17. The compound as in claim 14 wherein the alkylalkoxysilane is selected from the group consisting of octyltriethoxy silane, octyltrimethyloxy silane, (3-glycidoxypropylrimethoxy silane, (3-glycidoxypropylriethoxy silane, hexyltrimethoxy silane, ethyltrimethyoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethyoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy silane, methacryoltrimethoxy silane, and i-butyltriethoxy silane.
18. The compound as in claim 14 wherein the alkylalkoxysilane is octyltriethoxysilane.
19. The compound as in claim 14 , including a processing aid comprising at least one of an ester of a fatty acid or an ester of a polyol.
20. The compound as in claim 19 wherein the processing aid is selected from the group consisting of at least one sorbitan ester of an oleate, laurate, palmate and stearate fatty acid, their polyoxyethylene derivatives, at least one ester of a polylhydroxy compound, and mixtures thereof.
21. The compound as in claim 19 wherein the processing aid is sorbitan monooleate.
22. The compound of claim 14 wherein the elastomer is a diene monomer homopolymer or a copolymer of at least one diene and at least one monomer selected from the group consisting of monovinyl aromatic monomers and triene monomers.
23. The compound of claim 22 wherein the elastomer is styrene butadiene rubber.
24. The compound as in claim 23 wherein the elastomer is a copolymer of styrene butadiene rubber and butyl rubber.
25. The compound of claim 14 further containing a carbon black filler.
26. The compound of claim 14 further containing a natural rubber. ?
27. The compound of claim 19 further containing a carbon black filler. ?
27. The compound of claim 19 further containing a natural rubber.
28. A pneumatic tire comprising tread stock vulcanized from the vulcanizable silica-filled compound of claim 14 .
29. A pneumatic tire comprising tread stock vulcanized from the vulcanizable silica-filled compound of claim 19.
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US09/961,710 Expired - Lifetime US6384118B1 (en) | 1997-07-11 | 2001-09-24 | Processability of silica-filled rubber stocks |
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-
1997
- 1997-07-11 US US08/893,864 patent/US6221943B1/en not_active Expired - Lifetime
-
1998
- 1998-07-06 EP EP98112481A patent/EP0890606B1/en not_active Expired - Lifetime
- 1998-07-06 DE DE69811436T patent/DE69811436T2/en not_active Expired - Lifetime
- 1998-07-06 ES ES98112481T patent/ES2193443T3/en not_active Expired - Lifetime
- 1998-07-10 CA CA002243091A patent/CA2243091A1/en not_active Abandoned
- 1998-07-10 JP JP10210258A patent/JPH11130874A/en active Pending
-
2000
- 2000-11-28 US US09/724,130 patent/US6348531B1/en not_active Expired - Lifetime
-
2001
- 2001-09-24 US US09/961,710 patent/US6384118B1/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10526475B2 (en) | 2014-09-24 | 2020-01-07 | Bridgestone Americas Tire Operations, Llc | Silica-containing rubber compositions containing specified coupling agents and related methods |
US11028256B2 (en) | 2014-09-24 | 2021-06-08 | Bridgestone Americas Tire Operations, Llc | Silica-containing rubber compositions containing specified coupling agents and related methods |
Also Published As
Publication number | Publication date |
---|---|
US6384118B1 (en) | 2002-05-07 |
DE69811436D1 (en) | 2003-03-27 |
DE69811436T2 (en) | 2003-11-20 |
JPH11130874A (en) | 1999-05-18 |
EP0890606B1 (en) | 2003-02-19 |
EP0890606A1 (en) | 1999-01-13 |
CA2243091A1 (en) | 1999-01-11 |
US6221943B1 (en) | 2001-04-24 |
US6348531B1 (en) | 2002-02-19 |
ES2193443T3 (en) | 2003-11-01 |
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