CN112980063A - 充气轮胎 - Google Patents
充气轮胎 Download PDFInfo
- Publication number
- CN112980063A CN112980063A CN202011487394.XA CN202011487394A CN112980063A CN 112980063 A CN112980063 A CN 112980063A CN 202011487394 A CN202011487394 A CN 202011487394A CN 112980063 A CN112980063 A CN 112980063A
- Authority
- CN
- China
- Prior art keywords
- phr
- rubber
- functionalized
- styrene
- butadiene
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 80
- 239000005060 rubber Substances 0.000 claims abstract description 59
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000000806 elastomer Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000009477 glass transition Effects 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 6
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 239000002174 Styrene-butadiene Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- -1 sulfanyl (sulfanyl) groups Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 150000003961 organosilicon compounds Chemical class 0.000 description 8
- 125000005370 alkoxysilyl group Chemical group 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 3
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 150000007970 thio esters Chemical class 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- TUHNTFBFUHRNMN-UHFFFAOYSA-N (2,2-dimethoxyazasilolidin-1-yl)-trimethylsilane Chemical compound CO[Si]1(OC)CCCN1[Si](C)(C)C TUHNTFBFUHRNMN-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- RKNURYVWLFJIMO-UHFFFAOYSA-N 3-[methoxy-methyl-(trimethylsilylmethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](C)(OC)OC[Si](C)(C)C RKNURYVWLFJIMO-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
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 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 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003999 initiator 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
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 125000004001 thioalkyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LLMLGZUZTFMXSA-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzenethiol Chemical compound SC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LLMLGZUZTFMXSA-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OWBQIMXHFSSKPH-UHFFFAOYSA-N 2-[diethoxy(1-trimethylsilylethoxy)silyl]ethanamine Chemical compound CCO[Si](CCN)(OCC)OC(C)[Si](C)(C)C OWBQIMXHFSSKPH-UHFFFAOYSA-N 0.000 description 1
- JIDHFKQYRQEGCQ-UHFFFAOYSA-N 2-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)ethanamine Chemical compound CCO[Si](C)(OCC)CCN([Si](C)(C)C)[Si](C)(C)C JIDHFKQYRQEGCQ-UHFFFAOYSA-N 0.000 description 1
- BOJVBHJRCWEKHP-UHFFFAOYSA-N 2-[dimethoxy(trimethylsilylmethoxy)silyl]ethanamine Chemical compound NCC[Si](OC)(OC)OC[Si](C)(C)C BOJVBHJRCWEKHP-UHFFFAOYSA-N 0.000 description 1
- YWHLEHJNQVBIRD-UHFFFAOYSA-N 2-[methoxy-methyl-(trimethylsilylmethoxy)silyl]ethanamine Chemical compound NCC[Si](C)(OC)OC[Si](C)(C)C YWHLEHJNQVBIRD-UHFFFAOYSA-N 0.000 description 1
- ITTUZXHSAMIHEK-UHFFFAOYSA-N 3-[diethoxy(1-trimethylsilylethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)[Si](C)(C)C ITTUZXHSAMIHEK-UHFFFAOYSA-N 0.000 description 1
- DIGKGWWSMMWBIZ-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C DIGKGWWSMMWBIZ-UHFFFAOYSA-N 0.000 description 1
- NOOCTNSDRIEGBC-UHFFFAOYSA-N 3-[dimethoxy(trimethylsilylmethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](OC)(OC)OC[Si](C)(C)C NOOCTNSDRIEGBC-UHFFFAOYSA-N 0.000 description 1
- VOSGLHJWGFISCM-UHFFFAOYSA-N 3-[ethoxy-methyl-(1-trimethylsilylethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](C)(OCC)OC(C)[Si](C)(C)C VOSGLHJWGFISCM-UHFFFAOYSA-N 0.000 description 1
- SLSKAIZCBJQHFI-UHFFFAOYSA-N 3-triethoxysilyl-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C SLSKAIZCBJQHFI-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- JYGLAHSAISAEAL-UHFFFAOYSA-N Diphenadione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C(=O)C(C=1C=CC=CC=1)C1=CC=CC=C1 JYGLAHSAISAEAL-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 241000254043 Melolonthinae Species 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
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- 229920000026 Si 363 Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 238000003754 machining Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000010618 wire wrap Methods 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
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Abstract
本发明涉及一种充气轮胎,其包含可硫化橡胶组合物,所述可硫化橡胶组合物包含:30至90 phr的具有‑70至‑50℃的玻璃化转变温度Tg1的第一官能化苯乙烯‑丁二烯橡胶;10至50 phr的具有‑110至‑70℃的玻璃化转变温度Tg2的第二官能化苯乙烯‑丁二烯橡胶;其中Tg2–Tg1为至少10℃;0至40 phr的至少一种附加弹性体;50至150 phr的二氧化硅;0至50 phr的烃树脂;和10至50 phr的油。
Description
技术领域
本发明涉及一种包含可硫化橡胶组合物的充气轮胎。
背景技术
非常期望轮胎具有良好的抗湿滑性、低滚动阻力和良好的磨损特性。传统上已很难在不牺牲轮胎抗湿滑性和牵引力特性的情况下改进轮胎的磨损特性。这些性质在很大程度上取决于用于制造轮胎的橡胶的动态粘弹性性质。
为了降低滚动阻力和改进轮胎的胎面磨耗特性,传统上使用具有高回弹率的橡胶制造轮胎胎面橡胶胶料。另一方面,为了提高轮胎的抗湿滑性,通常在轮胎胎面中使用经历大能量损失的橡胶。为了平衡这两个在粘弹性上不一致的性质,一般在轮胎胎面中使用各种类型的合成和天然橡胶的混合物。
有时期望轮胎具有增进在有雪表面上的牵引力的胎面。可为轮胎胎面提议各种橡胶组合物。当意图将胎面用于低温冬季条件,特别是用于车辆雪地驾驶时,此处的挑战在于降低此类胎面橡胶组合物的固化刚度(cured stiffness),如通过在-20℃下具有较低储能模量G’表明。
认为存在提供既保持轮胎胎面橡胶组合物的湿地牵引力,同时增进低温(例如冬季)性能的此类轮胎胎面橡胶组合物的重大挑战。
发明内容
本发明涉及一种充气轮胎,其包含可硫化橡胶组合物,所述可硫化橡胶组合物包含:30至90 phr的具有-70至-50℃的玻璃化转变温度Tg1的第一官能化苯乙烯-丁二烯橡胶;10至50 phr的具有-110至-70℃的玻璃化转变温度Tg2的第二官能化苯乙烯-丁二烯橡胶;其中Tg2 – Tg1为至少10℃;0至40 phr的至少一种附加弹性体;50至150 phr的二氧化硅;0至50 phr的烃树脂;和10至50 phr的油。
详细描述
公开了一种充气轮胎,其包含可硫化橡胶组合物,所述可硫化橡胶组合物包含:30至90 phr的具有-70至-50℃的玻璃化转变温度Tg1的第一官能化苯乙烯-丁二烯橡胶;10至50 phr的具有-110至-70℃的玻璃化转变温度Tg2的第二官能化苯乙烯-丁二烯橡胶;其中Tg2 – Tg1为至少10℃;0至40 phr的至少一种附加弹性体;50至150 phr的二氧化硅;0至50phr的烃树脂;和10至50 phr的油。
可硫化橡胶组合物包含30至90 phr的具有-70至-50℃的玻璃化转变温度Tg1的第一官能化苯乙烯-丁二烯橡胶,和10至50 phr的具有-110至-70℃的玻璃化转变温度Tg2的第二官能化苯乙烯-丁二烯橡胶。在一个实施方案中,Tg2 – Tg1为至少10℃;或者,Tg2 –Tg1为至少15℃,或者,Tg2 – Tg1为至少20℃。
可用各种官能团官能化作为第一和第二官能化苯乙烯-丁二烯橡胶的合适苯乙烯-丁二烯橡胶。在一个实施方案中,苯乙烯-丁二烯橡胶可用烷氧基硅烷基团和选自含硫官能团和氨基官能团的官能团进行官能化。合适的含硫基团包括硫醇、硫醚、硫酯、硫化物(sulfide)或硫烷基(sulfanyl)基团。合适的氨基官能团包括伯、仲和叔氨基。可用橡胶的另外实例包括用以下基团官能化的溶液聚合苯乙烯-丁二烯,所述基团如:烷氧基,包括单烷氧基、二烷氧基和三烷氧基、甲硅烷基、硫醇基团、硫酯基团、硫醚基团、硫烷基、巯基、硫化物基团(sulfide group)及其组合。这样官能化的溶液聚合的聚合物可例如借助官能引发剂或终止剂在聚合物链末端被官能化,或例如借助官能单体在聚合物链内被官能化,或为链内和链末端官能化的组合。合适的官能化的溶液聚合的聚合物的具体实例包括美国专利No. 8,217,103和美国专利No. 8,569,409中描述的具有烷氧基甲硅烷基和硫化物(即硫醚)官能的那些。这样的硫醇官能包括来自化合物加工过程中的含硫基团裂解,例如来自硫酯和硫醚的硫醇或硫烷基官能。在一个实施方案中,苯乙烯-丁二烯橡胶用伯胺基和硫醇基团中的至少一种和烷氧基硅烷基团官能化。在一个实施方案中,苯乙烯-丁二烯橡胶通过苯乙烯和丁二烯的共聚获得,并且其特征在于苯乙烯-丁二烯橡胶具有键合到聚合物链上的伯氨基和/或硫醇基团与烷氧基甲硅烷基。在一个实施方案中,烷氧基甲硅烷基是乙氧基甲硅烷基。
一个或多个官能团可键合到聚合起始端、聚合终止端、苯乙烯-丁二烯橡胶的主链和侧链中的任一,只要其键合到苯乙烯-丁二烯橡胶链上。但是,优选将一个或多个官能团引入聚合起始端或聚合终止端,从而抑制在聚合物端处的能量消失以改进滞后损失特性。因此,在一个实施方案中,第一和第二官能化的苯乙烯-丁二烯橡胶是末端官能化并且不是链内官能化的。
苯乙烯-丁二烯橡胶可以通过以下生产:在烃溶剂中通过使用有机碱金属和/或有机碱土金属作为引发剂的阴离子聚合使苯乙烯和丁二烯聚合,加入具有由保护基团保护的官能团的终止剂化合物,使其在聚合已基本完成时与活性聚合物链端进行反应,并然后例如通过水解或其它适当程序进行脱保护(deblocking)。在一个实施方案中,可以如U.S. 7,342,070中所公开生产苯乙烯-丁二烯橡胶。在另一实施方案中,可以如WO 2007/047943中所公开生产苯乙烯-丁二烯橡胶。
在一个实施方案中,具有受保护的伯氨基和烷氧基甲硅烷基的终止剂化合物可为如本领域中已知的各种化合物的任何。在一个实施方案中,具有受保护的伯氨基和烷氧基甲硅烷基的化合物可包括例如N,N-双(三甲基甲硅烷基)氨基丙基甲基二甲氧基硅烷、1-三甲基甲硅烷基-2,2-二甲氧基-1-氮杂-2-硅杂环戊烷、N,N-双(三甲基甲硅烷基)氨基丙基三甲氧基硅烷、N,N-双(三甲基甲硅烷基)氨基丙基三乙氧基硅烷、N,N-双(三甲基甲硅烷基)氨基丙基甲基二乙氧基硅烷、N,N-双(三甲基甲硅烷基)氨基乙基三甲氧基硅烷、N,N-双(三甲基甲硅烷基)-氨基乙基三乙氧基硅烷、N,N-双(三甲基甲硅烷基)氨基乙基甲基二甲氧基硅烷、N,N-双(三甲基甲硅烷基)氨基乙基甲基二乙氧基硅烷等,并且优选的是1-三甲基甲硅烷基-2,2-二甲氧基-1-氮杂-2-硅杂环戊烷、N,N-双(三甲基甲硅烷基)氨基丙基甲基二甲氧基硅烷和N,N-双(三甲基甲硅烷基)氨基丙基甲基二乙氧基硅烷。在一个实施方案中,具有受保护的伯氨基和烷氧基甲硅烷基的化合物是N,N-双(三甲基甲硅烷基)氨基丙基三乙氧基硅烷。
第一和第二溶液聚合的苯乙烯-丁二烯橡胶分别具有在-70℃至-50℃范围内的玻璃化转变温度Tg1和在-110℃至-70℃范围内的Tg2。在一个实施方案中,Tg2 – Tg1为至少10℃;或者,Tg2 – Tg1为至少15℃,或者,Tg2 – Tg1为至少20℃。在本文中涉及时,提到弹性体或弹性体组合物的玻璃化转变温度或Tg代表各个弹性体或弹性体组合物在其未固化状态下或在弹性体组合物的情况下可能在固化状态下的一个或多个玻璃化转变温度。Tg可以通过差示扫描量热仪(DSC)在10℃/分钟的升温速率下作为峰值中点被合适地测定,例如根据ASTM D7426或等同物。
橡胶组合物可包括0至40 phr的一种或多种含有烯属不饱和的附加橡胶或弹性体。术语“含有烯属不饱和的橡胶或弹性体”或“基于二烯的弹性体”旨在包括天然橡胶及其各种生胶和再生橡胶形式,以及各种合成橡胶二者。在本发明的说明书中,除非另行规定,术语“橡胶”和“弹性体”可互换使用。术语“橡胶组合物”、“配混橡胶”和“橡胶胶料”可互换使用,以指已与各种成分和材料共混或混合的橡胶,并且这样的术语是橡胶混合或橡胶配混领域的技术人员所公知的。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,以及共聚物,如由丁二烯或其同系物或衍生物与其它不饱和单体形成的那些。其它不饱和单体之中的为乙炔,例如乙烯基乙炔;烯烃,例如异丁烯,其与异戊二烯共聚以形成丁基橡胶;乙烯基化合物,例如丙烯酸、丙烯腈(其与丁二烯聚合以形成NBR)、甲基丙烯酸和苯乙烯(后一化合物与丁二烯聚合以形成SBR)、以及乙烯基酯和各种不饱和醛、酮和醚,例如丙烯醛、甲基异丙烯基酮和乙烯基乙醚。合成橡胶的具体实例包括氯丁橡胶(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、卤化丁基橡胶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单体如苯乙烯、丙烯腈和甲基丙烯酸甲酯的共聚物、以及乙烯/丙烯三元共聚物,也称为乙烯/丙烯/二烯单体(EPDM),且特别是乙烯/丙烯/二环戊二烯三元共聚物。可用橡胶的另外实例包括烷氧基-甲硅烷基末端官能化的溶液聚合的聚合物(SBR、PBR、IBR和SIBR)、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异戊二烯(天然或合成)、聚丁二烯和SBR。
在一个方面中,至少一种附加橡胶优选为基于二烯的橡胶中的至少两种。例如,两种或更多种橡胶的组合是优选的,如顺式1,4-聚异戊二烯橡胶(天然或合成,尽管天然是优选的)、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备的丁二烯/丙烯腈共聚物。
在本发明的一个方面中,可使用具有大约20至大约28%结合苯乙烯的相对常规苯乙烯含量的乳液聚合衍生的苯乙烯/丁二烯(E-SBR),或(对于一些应用)具有中等至相对高的结合苯乙烯含量,即大约30至大约45%的结合苯乙烯含量的E-SBR。
通过乳液聚合制备的E-SBR是指苯乙烯和1,3-丁二烯作为水性乳液共聚。这是本领域技术人员所公知的。结合苯乙烯含量可以为例如大约5至大约50%不等。在一个方面中,E-SBR还可含有丙烯腈以形成E-SBAR形式的三元共聚物橡胶,该三元共聚物中的结合丙烯腈的量为例如大约2至大约30重量%。
在共聚物中含有大约2至大约40重量%的结合丙烯腈的乳液聚合制备的苯乙烯/丁二烯/丙烯腈共聚物橡胶也被考虑作为用于本发明的基于二烯的橡胶。
溶液聚合制备的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的存在下通过有机锂催化制备。
在一个实施方案中,可使用顺式1,4-聚丁二烯橡胶(BR)。可以例如通过1,3-丁二烯的有机溶液聚合制备这样的BR。所述BR可方便地例如通过具有至少90%的顺式-1,4-含量为特征。
合成顺式1,4-聚异戊二烯和天然橡胶是橡胶领域的技术人员众所公知的。
在一个实施方案中,附加弹性体是10至30 phr的具有在-20至-40℃范围内的Tg的苯乙烯-丁二烯橡胶。在一个实施方案中,附加弹性体是具有-20至-40℃的Tg的末端官能化苯乙烯-丁二烯橡胶。
本文中所用的和根据常规实践的术语“phr”是指“各材料的重量份/每100重量份橡胶或弹性体”。
橡胶组合物还包含10至50 phr的加工油。加工油可作为通常用于填充弹性体的填充油包含在橡胶组合物中。加工油也可通过在橡胶配混过程中直接加入该油而包含在橡胶组合物中。所用加工油可包含存在于弹性体中的填充油和在配混过程中加入的操作油二者。合适的操作油包括本领域中已知的各种油,包括芳族油、石蜡油、环烷油、植物油和低PCA油,如MES、TDAE、SRAE和重环烷油。合适的低PCA油包括具有通过IP346方法测定的小于3重量%的多环芳族含量的那些。IP346方法的程序可见于Standard Methods for Analysis& Testing of Petroleum and Related Products和British Standard 2000 Parts,2003, 第62版, the Institute of Petroleum, United Kingdom出版。
橡胶组合物包含0至50 phr的具有大于30℃的Tg的烃树脂。
代表性的烃树脂包括香豆酮-茚树脂、石油树脂、C5、C9、C5/C9树脂、DCPD和改性DCPD树脂、萜烯树脂、α甲基苯乙烯树脂及其混合物和/或改性和/或氢化。
橡胶组合物可包含大约50至大约150 phr的二氧化硅。在另一实施方案中,可使用80至130 phr的二氧化硅。
可用于橡胶胶料的常采用硅质颜料包括常规的热解和沉淀硅质颜料(二氧化硅)。在一个实施方案中,使用沉淀二氧化硅。本发明中采用的常规硅质颜料是沉淀二氧化硅如,例如通过可溶硅酸盐,例如硅酸钠的酸化获得的那些。
这样的常规二氧化硅可例如通过得到如使用氮气测得的BET表面积进行表征。在一个实施方案中,BET表面积可在大约40至大约600平方米/克的范围内。在另一实施方案中,BET表面积可在大约80至大约300平方米/克的范围内。在Journal of the AmericanChemical Society, 第60卷, 第304页(1930)中描述了测量表面积的BET方法。
常规二氧化硅也可以具有大约100至大约400,或大约150至大约300的邻苯二甲酸二丁酯(DBP)吸收值为特性。
常规二氧化硅可预计具有如通过电子显微镜测得的例如在0.01至0.05微米范围内的平均最终粒度,尽管二氧化硅粒子的尺寸可更小或可能更大。
可使用各种市售二氧化硅,如(在本文中仅举例且非限制性地),可在Hi-Sil商标下以标号210、243等购自PPG Industries的二氧化硅;可以例如名称Z1165MP和Z165GR获自Solvan的二氧化硅,和可以例如名称VN2和VN3获自Evonik的二氧化硅,等等。
可以以至多10 phr的量使用通常采用的炭黑作为常规填料。在另一实施方案中,可使用至多5 phr的炭黑。此类炭黑的代表性实例包括N110、N121、N134、N220、N231、N234、N242、N293、N299、N315、N326、N330、N332、N339、N343、N347、N351、N358、N375、N539、N550、N582、N630、N642、N650、N683、N754、N762、N765、N774、N787、N907、N908、N990和N991。这些炭黑具有9至145 g/kg范围内的碘吸收和在34至150 cm3/100 g范围内的DBP值。
在一个实施方案中,橡胶组合物可含有常规含硫有机硅化合物。在一个实施方案中,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)多硫化物。在一个实施方案中,含硫有机硅化合物是3,3'-双(三乙氧基甲硅烷基丙基)二硫化物和/或3,3'-双(三乙氧基甲硅烷基丙基)四硫化物。
在另一实施方案中,合适的含硫有机硅化合物包括美国专利No. 6,608,125中公开的化合物。在一个实施方案中,含硫有机硅化合物包括3-(辛酰基硫基)-1-丙基三乙氧基硅烷,CH3(CH2)6C(=O) ―S―CH2CH2CH2Si(OCH2CH3)3,其可作为NXT™购自MomentivePerformance Materials。
在另一实施方案中,合适的含硫有机硅化合物包括美国专利公开No. 2003/0130535中公开的那些。在一个实施方案中,含硫有机硅化合物是来自Evonik的Si-363。
含硫有机硅化合物在橡胶组合物中的量将根据所用的其它添加剂的含量而变。一般而言,化合物的量将在0.5至20 phr内变化。在一个实施方案中,量将在1至10 phr内变化。
本领域技术人员容易理解的是,橡胶组合物将通过橡胶配混领域中公知的方法配混,如将各种硫-可硫化成分橡胶与各种常用添加剂材料如,例如给硫体、固化助剂(如活化剂和延迟剂)和加工添加剂,如油、树脂(包括增粘性树脂)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,根据硫可硫化和硫-已硫化材料(橡胶)的预期用途,选择上述添加剂并通常以常规量使用。给硫体的代表性实例包括元素硫(游离硫)、胺二硫化物、聚合多硫化物和硫烯烃加合物。在一个实施方案中,硫-硫化剂是元素硫。硫-硫化剂可以0.5至8 phr范围内的量使用,或以1.5至6 phr范围内。如果使用增粘性树脂,其典型量包括大约0.5至大约10 phr,通常大约1至大约5 phr。加工助剂的典型量包括大约1至大约50 phr。抗氧化剂的典型量包括大约1至大约5 phr。代表性的抗氧化剂可为例如二苯基-对苯二胺及其他,如,例如The Vanderbilt Rubber Handbook(1978), 第344至346页中公开的那些。抗臭氧剂的典型量包括大约1至5 phr。如果使用脂肪酸(其可包括硬脂酸),其典型量包括大约0.5至大约3 phr。氧化锌的典型量包括大约2至大约5 phr。蜡的典型量包括大约1至大约5 phr。通常使用微晶蜡。胶溶剂的典型量包括大约0.1至大约1 phr。典型胶溶剂可为例如五氯苯硫酚和二苯甲酰氨基二苯基二硫。
使用促进剂控制硫化所需的时间和/或温度并改进硫化橡胶的性质。在一个实施方案中,可使用单一促进剂体系,即主促进剂。一种或多种主促进剂可以大约0.5至大约4、或大约0.8至大约1.5 phr的总量使用。在另一实施方案中,可使用主促进剂和辅促进剂的组合,其中辅促进剂以较少量,如大约0.05至大约3 phr使用,以活化和改进硫化橡胶的性质。这些促进剂的组合可预计对最终性质产生协同效应,并一定程度好于通过单独使用任一促进剂所产生的那些。此外,可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固化的迟效性促进剂。也可使用硫化延迟剂。可用于本发明的合适类型的促进剂是胺类、二硫化物类、胍类、硫脲类、噻唑类、秋兰姆类、亚磺酰胺类、二硫代氨基甲酸盐类和黄原酸盐/酯类。在一个实施方案中,主促进剂是亚磺酰胺。如果使用辅促进剂,则辅促进剂可为胍类、二硫代氨基甲酸盐或秋兰姆类化合物。
可以通过橡胶混合领域中技术人员已知的方法实现橡胶组合物的混合。例如,成分通常在至少两个阶段中混合,即至少一个非生产性阶段,然后生产性混合阶段。包含硫-硫化剂的最终固化剂(curative)通常在最后阶段中混入,所述最后阶段通常被称为“生产性”混合阶段,其中混合通常在比先前的一个或多个非生产性混合阶段的一个或多个混合温度更低的温度或最终温度下进行。术语“非生产性”和“生产性”混合阶段是橡胶混合领域的技术人员所公知的。可对橡胶组合物施以热机械混合步骤。所述热机械混合步骤通常包括在混合机或挤出机中机械加工一段适合时间,从而产生在140℃至190℃的橡胶温度。热机械加工的适当持续时间随操作条件以及组分的体积和性质而变化。例如,热机械加工可为1至20分钟。
橡胶组合物可并入轮胎的各种橡胶组件中。例如,该橡胶组件可为胎面(包括胎面冠部和胎面基部)、胎侧、三角胶芯、胎圈包布、胎侧插入物(sidewall insert)、钢丝包胶(wirecoat)或内衬(innerliner)。在一个实施方案中,组件是胎面。
或者,橡胶组合物可用于各种制品,包括但不限于轮胎胎面、鞋、鞋底、传动带、软管、空气弹簧、输送带、履带(track belts)和减震器。
本发明的充气轮胎可为赛车轮胎、轿车轮胎、飞机轮胎、农用、推土机、越野、载重汽车轮胎等。在一个实施方案中,轮胎是轿车或载重汽车轮胎。该轮胎也可为子午线或斜交轮胎。
本发明的充气轮胎的硫化通常在大约100℃至200℃范围内的常规温度下进行。在一个实施方案中,在大约110℃至180℃范围内的温度下进行硫化。可使用任何常用硫化方法,如在压机或模具中加热、用过热蒸汽或热空气加热。此类轮胎可以通过本领域技术人员已知和对其而言易于显而易见的各种方法构造、成型、模制和固化。
通过下列实施例举例说明本发明,所述实施例仅用于举例说明的目的且不应被视为限制本发明的范围或其可以实践的方式。除非明确地另行指明,份数和百分比按重量计。
实施例
在这一实施例中,举例说明了组合不同Tg的官能化苯乙烯-丁二烯橡胶的效果。根据表1中给出的组成在多步混合程序中混合橡胶胶料,所有的量按phr计。测试固化样品的物理性质,结果在表2中给出。为了比较的目的而制造样品C1至C4,以含有1) 高和低Tg的官能化SBR的组合和2) 100 phr的低Tg官能化SBR。另一方面,本发明的实施例含有两种低Tg官能化SBR的组合。
观察到两种都具有低于-50℃的Tg的官能化聚合物的组合提供与1) 高和低Tg的官能化SBR的组合和2) 100 phr的低Tg官能化SBR相比类似或更好的湿地、RR和雪地预测性质。
表1
C-1 C-2 C-3 C-4 I-1 I-2
SBR1 (官能化的,Tg -23℃)1 30 0 0 40 0 0
SBR2 (官能化的,Tg -73℃)2 70 0 0 0 30 0
SBR3 (官能化的,Tg -60℃)3 0 100 0 0 0 0
SBR4 (官能化的,Tg -60℃)4 0 0 100 0 0 0
SBR5 (官能化的,Tg -80℃)5 0 0 0 60 0 20
SBR6 (官能化的,Tg -55℃)6 0 0 0 0 70 80
烃牵引树脂 10 10 10 10 10 10
石油油料 28 28 28 28 28 28
沉淀二氧化硅 90 90 90 90 90 90
硅烷偶联剂 9 9 9 9 9 9
抗降解剂 4.8 4.8 4.8 4.8 4.8 4.8
硬脂酸 5 5 5 5 5 5
硫 1.3 1.3 1.3 1.3 1.3 1.3
氧化锌 1.8 1.8 1.8 1.8 1.8 1.8
固化促进剂 4.8 4.8 4.8 4.8 4.8 4.8
1 溶液聚合的苯乙烯-丁二烯橡胶,Tg = -23℃,用硫化物和烷氧基硅烷基团末端官能化的,作为来自Trinseo的SE SLR 4602
2 溶液聚合的苯乙烯-丁二烯橡胶,Tg= -73℃,官能化的,作为来自LG Chem的F1810
3 溶液聚合的苯乙烯-丁二烯橡胶,Tg = -60℃,用硫化物和烷氧基硅烷基团末端官能化的,作为来自Trinseo的SE SLR 3402
4 溶液聚合的苯乙烯-丁二烯橡胶,Tg= -60℃,用氨基烷氧基硅烷基团末端官能化的,来自Goodyear
5 溶液聚合的苯乙烯-丁二烯橡胶,Tg= -80℃,用氨基烷氧基硅烷基团末端官能化的,来自Goodyear
6 溶液聚合的苯乙烯-丁二烯橡胶,Tg= -55℃,用氨基烷氧基硅烷基团末端官能化的,来自Goodyear。
表2
C-1 C-2 C-3 C-4 I-1 I-2
SBR1 (官能化的,Tg -23℃) 30 0 0 40 0 0
SBR2 (官能化的,Tg -73℃) 70 0 0 0 30 0
SBR3 (官能化的,Tg -60℃) 0 100 0 0 0 0
SBR4 (官能化的,Tg -60℃) 0 0 100 0 0 0
SBR5 (官能化的,Tg -80℃) 0 0 0 60 0 20
SBR6 (官能化的,Tg -55℃) 0 0 0 0 70 80
湿地预测性质
在0℃下的回弹率(越低越好)1 22 26 26 21 24 24
在0℃下的Tanδ(越高越好)2 0.31 0.28 0.27 0.32 0.28 0.27
RR预测性质
在100℃下的回弹率(越高越好)1 64 64 66 65 67 68
在30℃下的Tanδ(越低越好)2 0.18 0.20 0.18 0.19 0.16 0.16
冬季预测性质2
在-20℃下的G’ (MPa)(越低越好) 6.2 8.4 7.0 8.7 6.3 6.6
拉伸性质3
致断应力(MPa) 18.4 17.6 20.7 16.8 21.2 20.2
致断应变(%) 485 470 510 442 506 506
1回弹率是如通过ASTM D1054测得的胶料在经受荷载时的滞后现象的量度。通常,在0℃下测得的回弹率越低,湿抓地力性质越好。通常,在100℃下测得的回弹率越高,滚动阻力越低。
2 借助ARES动态机械分析仪可以容易地测得在各种温度下的tanδ和G'模量。在10Hz下对测试样本施以大约3%正弦形变并改变温度。试验方法被理解为类似于ISO 6721。
3依据Instron Corporation的自动化测试系统(Automated Testing System)仪器的数据。通过在室温下运行哑铃形样本至拉伸破裂,生成表中报道的数据。
Claims (6)
1.一种充气轮胎,其特征在于可硫化橡胶组合物,所述可硫化橡胶组合物包含:
30至90 phr的具有-70至-50℃的玻璃化转变温度Tg1的第一官能化苯乙烯-丁二烯橡胶;
10至50 phr的具有-110至-70℃的玻璃化转变温度Tg2的第二官能化苯乙烯-丁二烯橡胶;
其中Tg2 – Tg1为至少10℃;
0至40 phr的至少一种附加弹性体;
50至150 phr的二氧化硅;
0至50 phr的烃树脂;和
10至50 phr的油。
2.权利要求1所述的充气轮胎,其特征在于所述第一和第二官能化苯乙烯丁二烯橡胶是末端官能化的。
3.权利要求1所述的充气轮胎,其特征在于Tg2 – Tg1为至少15℃。
4.权利要求1所述的充气轮胎,其特征在于Tg2 – Tg1为至少20℃。
5.权利要求1所述的充气轮胎,其特征在于所述附加弹性体是10至30 phr的具有-20至-40℃的Tg的苯乙烯-丁二烯橡胶。
6.权利要求1所述的充气轮胎,其特征在于所述附加弹性体是10至30 phr的具有-20至-40℃的Tg的末端官能化苯乙烯-丁二烯橡胶。
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2019
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- 2020-12-16 CN CN202011487394.XA patent/CN112980063A/zh active Pending
- 2020-12-16 JP JP2020208033A patent/JP2021095571A/ja active Pending
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JP2021095571A (ja) | 2021-06-24 |
EP3838983A1 (en) | 2021-06-23 |
US20210179822A1 (en) | 2021-06-17 |
US11884823B2 (en) | 2024-01-30 |
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