CN101148521A - 充气轮胎 - Google Patents
充气轮胎 Download PDFInfo
- Publication number
- CN101148521A CN101148521A CNA2007101543293A CN200710154329A CN101148521A CN 101148521 A CN101148521 A CN 101148521A CN A2007101543293 A CNA2007101543293 A CN A2007101543293A CN 200710154329 A CN200710154329 A CN 200710154329A CN 101148521 A CN101148521 A CN 101148521A
- Authority
- CN
- China
- Prior art keywords
- rubber
- tyre
- copolymer
- isoprene
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 78
- 239000005060 rubber Substances 0.000 claims abstract description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 23
- -1 polyhutadiene Polymers 0.000 claims description 23
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 21
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 241000254043 Melolonthinae Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229920005555 halobutyl Polymers 0.000 claims description 2
- 125000004968 halobutyl group Chemical group 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims 1
- 229920003245 polyoctenamer Polymers 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000002174 Styrene-butadiene Substances 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000006884 silylation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- UQYXGXMHZJMWGH-UHFFFAOYSA-N [1,1,3-trimethoxy-3-[(1,3,3-trimethoxy-3-silylpropyl)tetrasulfanyl]propyl]silane Chemical compound COC(CC([SiH3])(OC)OC)SSSSC(CC(OC)(OC)[SiH3])OC UQYXGXMHZJMWGH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000178 monomer Substances 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VBCFHWSPNHEYGE-UHFFFAOYSA-N 2,3,4-trimethylquinoline Chemical compound C1=CC=C2C(C)=C(C)C(C)=NC2=C1 VBCFHWSPNHEYGE-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-MICDWDOJSA-N 2-deuterioethenylbenzene Chemical compound [2H]C=CC1=CC=CC=C1 PPBRXRYQALVLMV-MICDWDOJSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ABTGGVQYJQKMME-UHFFFAOYSA-N CC(CSSSSCC(C)(OCCCOCC)[SiH3])([SiH3])OCCCOCC Chemical compound CC(CSSSSCC(C)(OCCCOCC)[SiH3])([SiH3])OCCCOCC ABTGGVQYJQKMME-UHFFFAOYSA-N 0.000 description 1
- SXSGKPIKBFCWJT-UHFFFAOYSA-N COC(CC([SiH3])(OC)OC)SSSC(CC(OC)(OC)[SiH3])OC Chemical compound COC(CC([SiH3])(OC)OC)SSSC(CC(OC)(OC)[SiH3])OC SXSGKPIKBFCWJT-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GHCSOVVTQWYFIM-UHFFFAOYSA-N [1,1,3-trimethoxy-3-[(1,3,3-trimethoxy-3-silylpropyl)disulfanyl]propyl]silane Chemical compound COC(CC([SiH3])(OC)OC)SSC(CC(OC)(OC)[SiH3])OC GHCSOVVTQWYFIM-UHFFFAOYSA-N 0.000 description 1
- VNNGGZLEHCTJMS-UHFFFAOYSA-N [1,1,3-trimethoxy-3-[(1,3,3-trimethoxy-3-silylpropyl)hexasulfanyl]propyl]silane Chemical compound COC(CC([SiH3])(OC)OC)SSSSSSC(CC(OC)(OC)[SiH3])OC VNNGGZLEHCTJMS-UHFFFAOYSA-N 0.000 description 1
- XWDUMRTZHYADKZ-UHFFFAOYSA-N [O].CC1CCCCC1 Chemical compound [O].CC1CCCCC1 XWDUMRTZHYADKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- CCUFKANGGGOKMA-UHFFFAOYSA-N cyclohex-2-en-1-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC=C1 CCUFKANGGGOKMA-UHFFFAOYSA-N 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- YACCECLVHQLZQK-UHFFFAOYSA-N methoxyperoxyethane Chemical compound CCOOOC YACCECLVHQLZQK-UHFFFAOYSA-N 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
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 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
- 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
- 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
- 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B60C1/0008—Compositions of the inner liner
-
- 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
- B60C1/0025—Compositions of the sidewalls
-
- 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
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Abstract
本发明涉及具有橡胶部件的充气轮胎,该橡胶部件包括(A)100重量份(phr)含烯属不饱和的橡胶;(B)50至100phr的二氧化硅;(C)1至40phr的聚辛烯。
Description
背景技术
美国专利No.5,430,084公开了一种包含大约10至25重量%的预混二氧化硅和聚辛烯的橡胶组合物和轮胎。
发明内容
本发明涉及具有组成如下的橡胶部件的充气轮胎
(A)100重量份(phr)含烯属不饱和的橡胶;
(B)50至100phr的二氧化硅;
(C)1至40phr的聚辛烯。
具体实施方式
公开了具有组成如下的橡胶部件的充气轮胎
(A)100重量份(phr)含烯属不饱和的橡胶;
(B)50至100phr的二氧化硅;和
(C)1至40phr的聚辛烯。
橡胶组合物的一种组分是聚辛烯。合适的聚辛烯可以包括基于环辛烯的环状或线型大分子,或这类环状和线型大分子的混合物。合适的聚辛烯可作为Vestenamer 8012或V6213购自Degussa AG HighPerformance Polymers。Vestenamer是在环辛烯的复分解(methathesis)反应中产生的聚辛烯。在一个实施方案中,聚辛烯可以具有大约90,000至大约110,000的重均分子量;大约-65℃至大约-75℃的玻璃化转变温度;大约10至大约30重量%的结晶含量;大约36℃至大约54℃的熔点;大约250℃至大约275℃的热分解温度;大约20∶80至大约40∶60的顺式/反式双键比率;和小于10的门尼粘度ML1+4。
在一个实施方案中,聚辛烯以橡胶组合物中所用橡胶或弹性体总重量的大约1至大约40重量%的量添加,或大约1至大约40phr(每百份橡胶中的份数)。例如,1至40phr聚辛烯可以与60至99phr的至少一种其它弹性体一起使用以构成100份的橡胶或弹性体。或者,在橡胶组合物中添加大约5phr至大约30phr的聚辛烯。
橡胶组合物含有含烯属不饱和的橡胶。术语“含烯属不饱和的橡胶或弹性体”旨在包括天然橡胶及其各种原始和再生形式以及各种合成橡胶。在本发明的描述中,术语“橡胶”和“弹性体”可以互换使用,除非另行规定。术语“橡胶组合物”、“复合橡胶”和“橡胶化合物”可互换使用以指已经与各种成分和材料掺合或混合的橡胶,这类术语是橡胶混合或橡胶配混领域技术人员公知的。代表性的合成聚合物是丁二烯及其同系物和衍生物(例如甲基丁二烯、二甲基丁二烯和戊二烯)的均聚产物、共聚物,例如由丁二烯或其同系物或其衍生物与其它不饱和单体构成的共聚物。后者包括乙炔,例如乙烯基乙炔;烯烃,例如异丁烯,其与异戊二烯共聚形成丁基橡胶;乙烯基化合物,例如,丙烯酸、丙烯腈(其与丁二烯聚合形成NBR)、甲基丙烯酸和苯乙烯(后一种化合物与丁二烯聚合形成SBR),以及乙烯基酯和各种不饱和醛、酮和醚,例如丙烯醛、甲基异丙烯酮和乙烯基***。合成橡胶的具体例子包括氯丁橡胶(聚氯丁二烯)、聚丁二烯(包括顺式1,4-聚丁二烯)、聚异戊二烯(包括顺式1,4-聚异戊二烯)、丁基橡胶、卤丁基橡胶(例如氯丁基橡胶或溴丁基橡胶)、苯乙烯/异戊二烯/丁二烯橡胶、1,3-丁二烯或异戊二烯与诸如苯乙烯、丙烯腈和甲基丙烯酸甲酯之类单体的共聚物、以及乙烯/丙烯三元共聚物,也称作乙烯/丙烯/二烯单体(EPDM),特别是乙烯/丙烯/二环戊二烯三元共聚物。可用橡胶的其它例子包括羧化橡胶、硅偶联和锡偶联的星形支化聚合物。优选的橡胶或弹性体是聚丁二烯和SBR。
一方面,橡胶可以是至少两种二烯基橡胶的掺合物。例如,两种或更多种橡胶的掺合物是优选的,例如顺式1,4-聚异戊二烯橡胶(天然或合成的,而天然的是优选的)、3,4-聚异戊二烯橡胶、苯乙烯/异戊二烯/丁二烯橡胶、乳液和溶液聚合衍生的苯乙烯丁二烯橡胶、顺式1,4-聚丁二烯橡胶,和乳液聚合制成的丁二烯/丙烯腈共聚物。
在本发明的一个方面中,可以使用具有大约20至大约28%结合苯乙烯的相对传统苯乙烯含量的乳液聚合衍生的苯乙烯丁二烯(E-SBR),对于某些应用,E-SBR具有中等至相对高的结合苯乙烯含量,即大约30至大约45%的结合苯乙烯含量。
当用在轮胎胎面中时,E-SBR的大约30至大约45的相对较高的苯乙烯含量可以被认为有益于提高牵引力或抗滑力的用途。E-SBR的存在本身被认为有益于提高未硫化弹性体组合物混合物的加工性能的用途,尤其是与溶液聚合制成的SBR(S-SBR)的使用相比。
乳液聚合制成的E-SBR是指苯乙烯和1,3-丁二烯作为水乳液共聚。这些是本领域技术人员公知的。结合苯乙烯含量可以为例如大约5至大约50%。一方面,E-SBR还可以含有丙烯腈以形成三元共聚物橡胶,例如E-SBAR,其中结合丙烯腈在三元共聚物中的量为大约2至大约30重量%。
在共聚物中含有大约2至大约40重量%结合丙烯腈的乳液聚合制成的苯乙烯/丁二烯/丙烯腈共聚物橡胶也被考虑作为本发明中所用的二烯基橡胶。
溶液聚合制成的SBR(S-SBR)通常具有大约5至大约50,优选大约9至大约36%的结合苯乙烯含量。S-SBR可以方便地例如在有机烃溶剂存在下通过有机锂催化制备。
当用在轮胎胎面组合物中时,使用S-SBR的目的是用于由较低的滞后性来改进轮胎滚动阻力。
当用在轮胎胎面组合物中时,3,4-聚异戊二烯橡胶(3,4-PI)被认为有益于提高轮胎牵引力的目的。在经此引用并入本文的美国专利No.5,087,668中更充分描述了3,4-PI及其应用。
顺式1,4-聚丁二烯橡胶(BR)被认为有益于提高胎面耐磨性的目的。这类BR可以例如通过1,3-丁二烯的有机溶液聚合制备。BR可以方便地以例如具有至少90%顺式1,4-含量为特征。
本文所用的和根据常规实践的术语“phr”是指“每一百重量份橡胶或弹性体,各种材料的重量份”。
在轮胎的橡胶部件中,除了聚辛烯和含烯属不饱和的橡胶外,还存在二氧化硅。二氧化硅的量可以为50至120phr。优选地,二氧化硅以60至100phr的量存在。或者,二氧化硅以大约70至大约90phr的量存在。
橡胶化合物中可用的常用硅质颜料包括传统的热解和沉淀硅质颜料(二氧化硅),然而沉淀二氧化硅是优选的。本发明中优选使用的传统硅质颜料是沉淀二氧化硅,例如通过可溶硅酸盐,例如硅酸钠的酸化获得的那些。
这类传统二氧化硅可以例如以具有优选大约40至大约600,更通常大约50至大约300平米/克的使用氮气测得的BET表面积为特征。在Journal of the American Chemical Society,卷60,第304页(1930)中描述了测量表面积的BET法。
传统二氧化硅也可以通常以具有大约100至大约400,更通常大约150至大约300的二丁基邻苯二甲酸酯(DBP)吸收值为特征。
传统二氧化硅可以预计具有通过电子显微镜测得的0.01至0.05微米的平均最终粒度,然而二氧化硅粒子可以在尺寸上更小或可能更大。
可以使用各种市售二氧化硅,例如但不限于,可以以Hi-Sil商标和标号210,243等购自PPG Industries的二氧化硅;可以以例如名称Z1165MP和Z165GR获自Rhone-Poulenc的二氧化硅和可以以例如名称VN2和VN3等获自Degussa AG的二氧化硅。
常用炭黑可以作为常规填料以0至50phr的量使用。这类炭黑的代表性例子包括N110、N115、N121、N134、N220、N231、N234、N242、N293、N299、S315、N326、N330、M332、N339、N343、N347、N351、N358、N375、N539、N550、N582、N630、N642、N650、N660、N683、N754、N762、N765、N774、N787、N907、N908、N990和N991。这些炭黑具有9至170克/千克的碘吸收和34至150立方厘米/100克的DBP No.。
轮胎部件中所用的橡胶组合物优选另外含有传统的含硫有机硅化合物。合适的含硫有机硅化合物的例子是下式的化合物:
Z-Alk-Sn-Alk-Z
其中Z选自
其中R5是含有1至4个碳原子的烷基、环己基或苯基;R6是含有1至8个碳原子的烷氧基,或含有5至8个碳原子的环烷氧基;Alk是含有1至18个碳原子的二价烃,n是2至8的整数。
可以根据本发明使用的含硫有机硅化合物的具体例子包括:3,3′-双(三甲氧基甲硅烷基丙基)二硫化物、3,3’-双(三乙氧基甲硅烷基丙基)二硫化物、3,3′-双(三乙氧基甲硅烷基丙基)四硫化物、3,3′-双(三乙氧基甲硅烷基丙基)八硫化物、3,3′-双(三甲氧基甲硅烷基丙基)四硫化物、2,2′-双(三乙氧基甲硅烷基乙基)四硫化物、3,3′-双(三甲氧基甲硅烷基丙基)三硫化物、3,3′-双(三乙氧基甲硅烷基丙基)三硫化物、3,3′-双(三丁氧基甲硅烷基丙基)二硫化物,3,3′-双(三甲氧基甲硅烷基丙基)六硫化物、3,3′-双(三甲氧基甲硅烷基丙基)八硫化物、3,3′-双(三辛氧基甲硅烷基丙基)四硫化物、3,3′-双(三己氧基甲硅烷基丙基)二硫化物、3,3-双(三-2″-乙基己氧基甲硅烷基丙基)三硫化物、3,3′-双(三异辛氧基甲硅烷基丙基)四硫化物、3,3′-双(三叔丁氧基甲硅烷基丙基)二硫化物、2,2′-双(甲氧基二乙氧基甲硅烷基乙基)四硫化物、2,2′-双(三丙氧基甲硅烷基乙基)五硫化物、3,3′-双(三环己氧基(tricyclonexoxy)甲硅烷基丙基)四硫化物、3,3′-双(三环戊氧基甲硅烷基丙基)三硫化物、2,2′-双(三-2″-甲基环己氧基甲硅烷基乙基)四硫化物、双(三甲氧基甲硅烷基甲基)四硫化物、3-甲氧基乙氧基丙氧基甲硅烷基3′-二乙氧基丁氧基-甲硅烷基丙基四硫化物、2,2′-双(二甲基甲氧基甲硅烷基乙基)二硫化物、2,2′-双(二甲基仲丁氧基甲硅烷基乙基)三硫化物、3,3′-双(甲基丁基乙氧基甲硅烷基丙基)四硫化物、3,3′-双(二叔丁基甲氧基甲硅烷基丙基)四硫化物、2,2′-双(苯基甲基甲氧基甲硅烷基乙基)三硫化物、3,3′-双(二苯基异丙氧基甲硅烷基丙基)四硫化物、3,3′-双(二苯基环己氧基甲硅烷基丙基)二硫化物、3,3′-双(二甲基乙基巯基甲硅烷基丙基)四硫化物、2,2′-双(甲基二甲氧基甲硅烷基乙基)三硫化物、2,2′-双(甲基乙氧基丙氧基甲硅烷基乙基)四硫化物、3,3′-双(二乙基甲氧基甲硅烷基丙基)四硫化物、3,3′-双(乙基二仲丁氧基甲硅烷基丙基)二硫化物、3,3′-双(丙基二乙氧基甲硅烷基丙基)二硫化物、3,3′-双(丁基二甲氧基甲硅烷基丙基)三硫化物、3,3′-双(苯基二甲氧基甲硅烷基丙基)四硫化物、3-苯基乙氧基丁氧基甲硅烷基3′-三甲氧基甲硅烷基丙基四硫化物、4,4′-双(三甲氧基甲硅烷基丁基)四硫化物、6,6′-双(三乙氧基甲硅烷基己基)四硫化物、12,12′-双(三异丙氧基甲硅烷基十二烷基)二硫化物、18,18′-双(三甲氧基甲硅烷基十八烷基)四硫化物、18,18′-双(三丙氧基甲硅烷基十八烯基)四硫化物、4,4′-双(三甲氧基甲硅烷基-丁烯-2-基)四硫化物、4,4′-双(三甲氧基甲硅烷基环己烯)四硫化物、5,5′-双(二甲氧基甲基甲硅烷基戊基)三硫化物、3,3′-双(三甲氧基甲硅烷基-2-甲基丙基)四硫化物、3,3′-双(二甲氧基苯基甲硅烷基-2-甲基丙基)二硫化物。
优选的含硫有机硅化合物是3,3’-双(三甲氧基或三乙氧基甲硅烷基丙基)硫化物。最优选的化合物是3,3’-双(三乙氧基甲硅烷基丙基)二硫化物和3,3’-双(三乙氧基甲硅烷基丙基)四硫化物。因此对于上式,优选地,Z是
其中R6是含有2至4个碳原子的烷氧基,其中2个碳原子特别优选;alk是含有2至4个碳原子的二价烃,其中3个碳原子特别优选;以及n是2至5的整数,其中2和4特别优选。
橡胶组合物中上式的含硫有机硅化合物的量随所用的其它添加剂的量而变。一般而言,上式的化合物的量为0.5至20phr。优选地,该量为1至10phr。
本领域技术人员容易理解的是,通过橡胶配混领域中公知的方法配混橡胶组合物,例如将各种可硫-硫化成分橡胶与各种常用添加剂材料,例如给硫体、固化助剂(例如活化剂和延迟剂)和加工添加剂(例如油,包括增粘树脂在内的树脂、和增塑剂)、填料、颜料、脂肪酸、氧化锌、蜡、抗氧化剂和抗臭氧剂和胶溶剂混合。如本领域技术人员已知的那样,根据可硫-硫化和已硫-硫化材料(橡胶)的预期用途,选择上述添加剂并通常以传统量使用。给硫体的代表性例子包括元素硫(游离硫)、二硫化胺、聚合多硫化物和硫烯烃加合物。优选地,硫-硫化剂是元素硫。硫-硫化剂可以以0.5至8phr的量使用,优选1.5至6phr。如果使用增粘剂树脂,其典型量包括大约0.5至大约10phr,通常大约1至大约5phr。加工助剂的典型量包括大约1至大约50phr。这类加工助剂可以包括,例如,芳族、环烷类和/或链烷类加工助剂。抗氧化剂的典型量包括大约1至大约5phr。代表性的抗氧化剂可以是,例如,二苯基-对苯二胺和其它,例如在The Vanderbilt Rubber Handbook(1978),第344至346页中公开的那些。抗氧化剂的典型量包括大约1至5phr。如果使用脂肪酸(可以包括硬脂酸),其典型量包括大约0.5至大约3phr。氧化锌的典型量包括大约2至大约5phr。蜡的典型量包括大约1至大约5phr。通常使用微晶蜡。胶溶剂的典型量包括大约0.1至大约1phr。典型胶溶剂可以是,例如,五氯苯硫酚和二苯甲酰氨基二苯基二硫化物。
使用促进剂来控制硫化所需的时间和/或温度,和改进硫化产品的性能。在一个实施方案中,可以使用单一促进剂体系,即主促进剂。可以以大约0.5至大约4,优选大约0.8至大约1.5phr的总量使用主促进剂。在另一实施方案中,可以使用主促进剂和辅助促进剂的组合,其中辅助促进剂以较少量,例如大约0.05至大约3phr使用以活化和改进硫化橡胶的性能。这些促进剂的组合预计对最终性能产生协同作用并略好于单独使用任一促进剂产生的那些。此外,可以使用不受正常加工温度影响但在普通硫化温度下产生令人满意的硫化的后效性促进剂。还可以使用硫化延迟剂。本发明中可用的促进剂的合适类型是胺、二硫化物、胍、硫脲、噻唑、秋兰姆、亚磺酰胺、二硫代氨基甲酸酯和黄原酸酯。优选地,主促进剂是亚磺酰胺。如果使用辅助促进剂,辅助促进剂优选为胍、二硫代氨基甲酸酯或秋兰姆化合物。
橡胶组合物的混合可以通过橡胶混合领域技术人员已知的方法实现。例如,各成分通常在至少两个阶段混合,即至少一个非生产性阶段,然后生产性混合阶段。最终的包含硫-硫化剂的固化剂(curative)通常在最后阶段中混合,该阶段传统上被称作“生产性”混合阶段,其中混合通常在低于前一非生产性混合阶段的混合温度的温度或最终温度下进行。橡胶和化合物在一个或多个非生产性混合阶段仲混合。术语“非生产性”和“生产性”混合阶段是橡胶混合领域技术人员公知的。如果橡胶组合物含有含硫有机硅化合物,则可以对橡胶组合物施以热机械混合步骤。热机械混合步骤通常包括在混合机或挤出机中机械加工达到适合产生140℃至190℃的橡胶温度的时间。热机械加工的适当持续时间随操作条件和组分的量和性质而变。例如,热机械加工可以为1至20分钟。
该橡胶组合物可以并入轮胎的各种橡胶部件中。例如,橡胶部件可以是胎面(包括胎冠和胎面基部)、胎侧、三角胶(apex)、胎圈包布、胎侧镶圈(sidewall insert)、线涂层(wirecoat)、气密层(innerliner)、和胎层涂层(ply coat)。优选地,该化合物是胎侧镶圈或胎冠或胎面基部(tread base)。
本发明的充气轮胎可以是乘用车轮胎、摩托车轮胎、飞机轮胎、农用的、推土机、非道路的(off-the-road)、载重汽车轮胎和类似物。术语“载重汽车轮胎”包括轻型载重汽车、中型载重汽车和重型载重汽车。优选地,轮胎是乘用车或载重汽车轮胎。轮胎也可以是子午线或斜交的,其中子午线轮胎是优选的。
本发明的充气轮胎的硫化通常在大约100℃至200℃的常规温度下进行。优选地,硫化在大约110℃至180℃进行。可以使用任何普通硫化方法,例如在压机或模具中加热,用过热蒸汽或热空气加热。
在硫-硫化的组合物硫化后,本发明的橡胶组合物可用于各种用途。例如,硫-硫化的橡胶组合物可以为轮胎、带材或软管形式。在轮胎的情况下,其可用于各种轮胎部件。这类轮胎可以通过本领域技术人员已知和容易想到的各种方法构造、成型、模制和硫化。可以看出,轮胎可以是乘用车(passenger)轮胎、飞机轮胎、载重汽车轮胎和类似物。优选地,轮胎是乘用车轮胎。轮胎也可以是子午线或斜交轮胎,其中子午线轮胎是优选的。
实施例1
在该实施例中,在橡胶组合物中评测聚辛烯。
含有表1中列出的材料的橡胶组合物使用多个添加(混合)阶段制备;至少一个非生产性混合阶段和生产性混合阶段。非生产性阶段在160℃的橡胶温度下混合2分钟。生产性混合阶段的滴落(drop)温度为115℃。
橡胶组合物被标为样品1至样品5。将样品在大约160℃下固化大约14分钟。表2显示了固化样品1至5的物理性能。根据下列规程测试样品:
Zwick回弹:ASTM D1054,DIN 53512
RPA 2000:ASTM D5289
MV2000塑性:ASTM D1646,DIN 53523
转鼓磨损:ASTM D5963,DIN 53516
MDR 2000:ASTM D2084,D5289
表1
橡胶化合物配方(以phr计的量)
非生产性混合
SBR1 30
SBR2 50
顺式-1,4聚丁二烯3 20
二氧化硅4 80
偶联剂5 10
硬脂酸 3
生产性混合
氧化锌 2.5
促进剂6 2
抗氧化剂7 2
硫 2
聚辛烯8 根据表2的变化
1作为SLF30H41来自The Goodyear Tire & Rubber Company的溶液聚合的苯乙烯-丁二烯橡胶
2作为SLF31X22来自The Goodyear Tire & Rubber Company的溶液聚合的苯乙烯-丁二烯橡胶
3Budene 1207,来自The Goodyear Tire & Rubber Company
4Zeosil 1165MP,来自Rhone Poulenc Company
550%有机硅硫化物类型,在炭黑载体上
6亚磺酰胺和秋兰姆类型
7二氢三甲基喹啉类型
8Vestenamer 8012,来自Degussa GmbH
表2
样品 | 1 | 2 | 3 | 4 | 5 |
聚辛烯,phr门尼粘度(ML 1+1.5@100℃) | 050.1 | 547.6 | 1046.6 | 2041.2 | 3036.3 |
RPA2000100C([email protected]) | |||||
G′(15%)Green,MPaG′(1%),MPaG′(15%),MPaG′(50%),MPaG″(10%),MPaTan del(10%) | 0.2542.7151.5190.9970.2260.131 | 0.2452.5021.4570.9660.2080.127 | 0.2492.4861.4700.9760.2080.126 | 0.2332.2371.3850.9340.1900.124 | 0.2172.0451.3290.9160.1740.120 |
MDR2000Light轮胎(150C) | |||||
最大,dN-m量,dN-m焦化1,分钟T25,分钟T90,分钟 | 17.814.73.76.115.1 | 17.414.53.76.315.9 | 17.414.44.16.617.2 | 16.8144.57.219.2 | 16.6144.97.620.7 |
拉伸 | |||||
致断伸长,%模量比率100%模量,MPa300模量,MPa回弹,%肖氏A拉伸强度,MPa | 4015.22.512.8286716.3 | 4145.22.512.7306616.9 | 4294.82.612.3316817.1 | 4564.42.711.7337017 | 4863.92.911.2367117.7 |
MV2000焦化 | |||||
T+5,分钟T+20,分钟 | 29.437.2 | 31.239.2 | 33.040.7 | 37.245.4 | 40.549.2 |
Zwick回弹(100C),% | 60 | 60 | 60 | 60 | 60 |
转鼓磨损 | |||||
损失样品,立方毫米损失标准品,毫克相对体积损失,立方毫米 | 124.3189108.9 | 109.718996.5 | 102.318692.2 | 89.718681.5 | 8118674.5 |
从表2中可以看出,在包含聚辛烯的橡胶组合物中获得物理性能的有利平衡。特别地,含有聚辛烯的化合物的耐磨性于对照物相比极大改进。
尽管已经显示了某些代表性实施方案和细节以例示本发明,本领域技术人员显而易见的是,可以在不背离本发明的精神和范围的情况下对其作出各种变动和修改。
Claims (6)
1.充气轮胎,其特征在于橡胶部件组成如下
(A)100重量份(phr)含烯属不饱和度的橡胶;
(B)50至100phr的二氧化硅;
(C)1至40phr的聚辛烯。
2.权利要求1所述的充气轮胎,其特征在于所述橡胶选自天然橡胶、氯丁橡胶、聚异戊二烯、丁基橡胶、卤丁基橡胶、聚丁二烯、苯乙烯丁二烯共聚物、苯乙烯/异戊二烯/丁二烯橡胶、甲基丙烯酸甲酯-丁二烯共聚物、异戊二烯-苯乙烯共聚物、甲基丙烯酸甲酯-异戊二烯共聚物、丙烯腈-异戊二烯共聚物、丙烯腈-丁二烯共聚物、羧化橡胶、EPDM、硅偶联的星形支化聚合物、锡偶联的星形支化聚合物和它们的混合物。
4.前述权利要求任一项所述的充气轮胎,其特征在于将所述组合物在140℃至190℃的橡胶温度下热机械混合1至20分钟的总混合时间。
5.前述权利要求任一项所述的充气轮胎,其特征在于所述轮胎选自乘用车轮胎、摩托车轮胎、飞机轮胎、农用的、推土机、非道路的和载重汽车轮胎。
6.前述权利要求任一项所述的充气轮胎,其特征在于所述橡胶部件选自胎冠、胎面基部、胎侧、三角胶、胎圈包布、胎侧镶圈、气密层、线涂层和胎层涂层。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102558633A (zh) * | 2011-12-05 | 2012-07-11 | 莱芜固可力轮胎有限公司 | 摩托车胎冠配方 |
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100078110A1 (en) * | 2008-09-30 | 2010-04-01 | Paul Harry Sandstrom | Pneumatic tire |
US8357756B2 (en) | 2008-12-23 | 2013-01-22 | Taylor Made Golf Company, Inc. | Compositions for sports equipment |
IT1400743B1 (it) * | 2010-06-30 | 2013-07-02 | Dow Global Technologies Inc | Composizioni polimeriche |
US20120123018A1 (en) * | 2010-11-17 | 2012-05-17 | Carlo Kanz | Pneumatic tire |
FR2967679B1 (fr) * | 2010-11-23 | 2012-12-21 | Michelin Soc Tech | Elastomere dienique a ip faible fonctionnel a fluage a froid ameliore et composition de caoutchouc le contenant |
US8905097B2 (en) | 2012-02-01 | 2014-12-09 | Bridgestone Americas Tire Operations, Llc | Agricultural tire tread |
JP6557087B2 (ja) * | 2015-08-05 | 2019-08-07 | Toyo Tire株式会社 | スチールコードトッピングゴムおよびタイヤ |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4898223A (en) * | 1989-01-30 | 1990-02-06 | The Goodyear Tire & Rubber Company | Stiff rubber composition and articles having components thereof |
DE3920745A1 (de) * | 1989-06-24 | 1991-01-03 | Bayer Ag | Kautschukmischungen enthaltend schwefel-modifizierte polychloroprengel |
US5087668A (en) * | 1990-10-19 | 1992-02-11 | The Goodyear Tire & Rubber Company | Rubber blend and tire with tread thereof |
US5430084A (en) | 1992-06-15 | 1995-07-04 | The Goodyear Tire & Rubber Company | Rubber containing silica and tire and tread thereof |
DE4220563A1 (de) * | 1992-06-24 | 1994-01-13 | Bayer Ag | Kautschukmischungen enthaltend Polybutadien-Gel |
DE19503779C2 (de) | 1995-02-04 | 2000-05-11 | Degussa | Chemicalienbatch mit Trans-Polyoctenamer als Trägermaterial für polymergebundene flüssige Kautschukchemikalien und Verfahren zu seiner Herstellung |
US5672639A (en) * | 1996-03-12 | 1997-09-30 | The Goodyear Tire & Rubber Company | Starch composite reinforced rubber composition and tire with at least one component thereof |
DE19701488A1 (de) * | 1997-01-17 | 1998-07-23 | Bayer Ag | SBR-Kautschukgele enthaltende Kautschukmischungen |
DE19701489A1 (de) * | 1997-01-17 | 1998-07-23 | Bayer Ag | Modifizierte Kautschukgele enthaltende Kautschukmischungen |
DE19834803A1 (de) * | 1998-08-01 | 2000-02-03 | Continental Ag | Kautschukmischung |
DE19834804A1 (de) * | 1998-08-01 | 2000-02-03 | Continental Ag | Kautschukmischung |
DE19834802A1 (de) * | 1998-08-01 | 2000-02-03 | Continental Ag | Kautschukmischung |
EP1063259A1 (de) * | 1999-06-26 | 2000-12-27 | Bayer Ag | Mikrogelhaltige Kautschukcompounds mit schwefelhaltigen Organosiliciumverbindungen |
DE19939865A1 (de) * | 1999-08-23 | 2001-03-01 | Bayer Ag | Agglomerierte Kautschukgele enthaltende Kautschukmischungen und Vulkanisate |
DE19942620A1 (de) * | 1999-09-07 | 2001-03-08 | Bayer Ag | Mikrogelhaltige Kautschukmischungen mit verkappten bifunktionellen Mercaptanen und hieraus hergestellte Vulkanisate |
US6527022B2 (en) * | 2000-03-10 | 2003-03-04 | The Goodyear Tire & Rubber Company | Pneumatic tire having a tread containing a metal oxide aerogel |
DE10038488A1 (de) * | 2000-08-08 | 2002-02-21 | Bayer Ag | Isocyanatosilan- und mikrogelhaltige Kautschukmischungen |
DE10052287A1 (de) * | 2000-10-20 | 2002-04-25 | Bayer Ag | Kautschukgele und Phenolharzedukte enthaltende Kautschukmischungen |
DE10056311A1 (de) | 2000-11-14 | 2002-05-16 | Bayer Ag | Gelhaltige Kautschukmischungen mit anorganischen Peroxiden |
DE10057508A1 (de) * | 2000-11-21 | 2002-05-23 | Bayer Ag | Polyether/Diolefin-Kautschuke enthaltende Kautschukmischungen und deren Verwendung zur Herstellung von insbesondere rollwiderstandsarmen Reifen |
DE10061174A1 (de) * | 2000-12-07 | 2002-06-20 | Bayer Ag | NBR-Gele in Butylkautschukcompounds |
US6807994B2 (en) | 2001-03-13 | 2004-10-26 | The Goodyear Tire & Rubber Company | Pneumatic tire having a rubber component containing a rubber gel and syndiotatic 1,2-polybutadiene |
BR0210300B1 (pt) | 2001-06-15 | 2012-01-24 | processos para produzir e armazenar um produto semi-acabado em forma de tira produzido de material elastomérico reticulável e para produzir pneus para rodas de veìculo, e, pneu para rodas de veìculo. | |
DE10129058A1 (de) * | 2001-06-15 | 2002-12-19 | Bayer Ag | Kieselsäure-, Ruß- und Kautschukgel enthaltende Kautschukmischungen |
JP2004535319A (ja) | 2001-07-25 | 2004-11-25 | ピレリ・プネウマティチ・ソチエタ・ペル・アツィオーニ | エラストマー性組成物を連続的に製造するための方法および装置 |
AU2003258013A1 (en) | 2002-08-01 | 2004-02-23 | California Institute Of Technology | Synthesis of macrocyclic polymers by ring insertion polymerization of cyclic olefin monomers |
US6749708B2 (en) * | 2002-08-22 | 2004-06-15 | Goodyear Tire & Rubber | Method for splicing a conveyor belt |
US6848487B2 (en) * | 2002-12-19 | 2005-02-01 | The Goodyear Tire & Rubber Company | Pneumatic tire having a rubber component containing a rubber gel and starch composite |
-
2006
- 2006-09-21 US US11/524,634 patent/US7629409B2/en active Active
-
2007
- 2007-09-10 BR BRPI0703893-3A patent/BRPI0703893A/pt active Search and Examination
- 2007-09-21 CN CN2007101543293A patent/CN101148521B/zh active Active
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN110372931A (zh) * | 2019-08-02 | 2019-10-25 | 中策橡胶集团有限公司 | 一种橡胶组合物及炼胶方法和采用该组合物的低轮胎滚动阻力轮胎 |
CN112778595A (zh) * | 2019-11-11 | 2021-05-11 | 固特异轮胎和橡胶公司 | 轮胎 |
CN112778595B (zh) * | 2019-11-11 | 2023-08-25 | 固特异轮胎和橡胶公司 | 轮胎 |
US11851549B2 (en) | 2019-11-11 | 2023-12-26 | The Goodyear Tire & Rubber Company | Tire |
CN115362205A (zh) * | 2020-03-31 | 2022-11-18 | Nok株式会社 | Nbr组合物及使用其的缓冲材料 |
CN115362205B (zh) * | 2020-03-31 | 2023-07-11 | Nok株式会社 | Nbr组合物及使用其的缓冲材料 |
CN111944213A (zh) * | 2020-08-22 | 2020-11-17 | 青岛励扬橡胶科技有限公司 | 适用于挤出法的半钢子午线轮胎冠带条胶料及其制备工艺 |
CN111944213B (zh) * | 2020-08-22 | 2022-08-16 | 青岛励扬橡胶科技有限公司 | 适用于挤出法的半钢子午线轮胎冠带条胶料及其制备工艺 |
CN114479222A (zh) * | 2020-11-13 | 2022-05-13 | 固特异轮胎和橡胶公司 | 橡胶组合物和轮胎 |
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US20080076867A1 (en) | 2008-03-27 |
CN101148521B (zh) | 2012-02-08 |
US7629409B2 (en) | 2009-12-08 |
BRPI0703893A (pt) | 2008-05-13 |
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