WO2023088822A1 - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- WO2023088822A1 WO2023088822A1 PCT/EP2022/081718 EP2022081718W WO2023088822A1 WO 2023088822 A1 WO2023088822 A1 WO 2023088822A1 EP 2022081718 W EP2022081718 W EP 2022081718W WO 2023088822 A1 WO2023088822 A1 WO 2023088822A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber composition
- composition according
- highly saturated
- diene
- diene elastomer
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 141
- 229920001971 elastomer Polymers 0.000 title claims abstract description 131
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 114
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 114
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005977 Ethylene Substances 0.000 claims abstract description 48
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- -1 N-substituted imidazole function Chemical group 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 21
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 239000000470 constituent Substances 0.000 claims abstract description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000004073 vulcanization Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 150000002825 nitriles Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002883 imidazolyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001993 dienes Chemical group 0.000 claims description 5
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 5
- 150000007855 nitrilimines Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 125000002897 diene group Chemical group 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 10
- 235000019241 carbon black Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 5
- 230000000930 thermomechanical effect Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- BIYYMYUSXQGRMI-UHFFFAOYSA-N 2,2-bis(sulfanylidene)-1,3,2-dioxathionane;sodium Chemical compound [Na].[Na].S=S1(=S)OCCCCCCO1 BIYYMYUSXQGRMI-UHFFFAOYSA-N 0.000 description 2
- KKEYUDYQGXPKQW-UHFFFAOYSA-N 2,4,6-trimethyl-3-[(2-methylimidazol-1-yl)methyl]benzonitrile oxide Chemical compound CC1=C(C#[N+][O-])C(=CC(=C1CN1C(=NC=C1)C)C)C KKEYUDYQGXPKQW-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000035508 accumulation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011903 deuterated solvents Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 238000001208 nuclear magnetic resonance pulse sequence Methods 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
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 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
- 229960002447 thiram Drugs 0.000 description 2
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 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
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical group NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000007872 degassing Methods 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004008 high resolution magic-angle spinning Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000019612 pigmentation Effects 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
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response 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
- 239000011265 semifinished product Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000012936 vulcanization activator Substances 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Definitions
- the field of the present invention is that of rubber compositions which comprise a silica and a highly saturated diene elastomer and which are in particular intended for use in the manufacture of tires.
- a tire must comply in a known manner with a large number of often conflicting technical requirements, including low rolling resistance, high wear resistance, as well as high grip on both dry and wet roads.
- This compromise of properties, in particular from the point of view of rolling resistance and resistance to wear, has been improved in recent years on "Green Tires” with low energy consumption, intended in particular for passenger cars.
- new low-hysteretic rubber compositions having the characteristic of being reinforced mainly with highly dispersible silicas called "HDS" (Highly Dispersible Silica), capable of competing, from the point of view of the reinforcing power, with the conventional tire grade carbon blacks. Since fuel savings and the need to preserve the environment have also become a priority, it is desirable to further reduce the hysteresis of rubber compositions.
- the highly saturated diene elastomers which contain more than 50% by mole of ethylene unit have the particularity of vulcanizing according to a slower kinetics than the highly unsaturated diene elastomers which contain more than 50% by mole of diene units. Longer residence times in the curing presses are therefore necessary to vulcanize the rubber compositions containing the highly saturated diene elastomers, which results in a longer press occupation time per rubber composition which has the consequence of reduce the productivity of tire manufacturing sites.
- the inventors have discovered a solution for reducing both the press time and the hysteresis of a rubber composition which is preserved from premature vulcanization.
- the invention relates to a rubber composition which comprises:
- the invention also relates to a tire which comprises a rubber composition in accordance with the invention, preferably in its tread.
- any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and less than “b” (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” means the range of values going from “a” to “b” (that is to say including the strict limits a and b).
- the abbreviation "phr” means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present).
- the compounds mentioned in the description can be of fossil origin or biosourced. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. In the same way, the compounds mentioned can also come from the recycling of materials already used, that is to say they can be, partially or totally, from a recycling process, or obtained from materials raw materials themselves from a recycling process.
- tire is understood to mean a pneumatic or non-pneumatic tire.
- a pneumatic tire usually has two beads intended to come into contact with a rim, a crown composed of at least one crown reinforcement and a tread, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads.
- a non-pneumatic tire for its part, usually comprises a base, designed for example for mounting on a rigid rim, a crown reinforcement, ensuring the connection with a tread and a deformable structure, such as spokes, ribs or cells, this structure being arranged between the base and the top.
- Such non-pneumatic tires do not necessarily include a sidewall.
- Non-pneumatic bandages are described for example in documents WO 03/018332 and FR2898077.
- the tire according to the invention is preferably a pneumatic tire.
- the levels of the units in a polymer such as the highly saturated functional diene elastomer useful in the invention are expressed in molar percentage relative to all of the constitutive repeating units (in English “constitutional repeating unit”, also designated by the abbreviation CRU by IUPAC) of the polymer.
- the elastomer useful for the purposes of the invention is a highly saturated functional diene elastomer, preferably random, which comprises ethylene units resulting from the polymerization of ethylene.
- ethylene unit refers to the —(CH2—CH2)— unit resulting from the insertion of ethylene into the elastomer chain.
- the functional highly saturated diene elastomer is rich in ethylene units, since the ethylene units represent more than 50% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- the functional highly saturated diene elastomer comprises at least 60% molar of ethylene units, preferably at least 65% molar of ethylene units, more preferably at least 70% molar of ethylene units.
- the functional highly saturated diene elastomer comprises at most 90% molar of ethylene unit. More preferably, it comprises at most 85% molar ethylene unit. Even more preferentially, it comprises at most 80 molar % of ethylene unit.
- the highly saturated functional diene elastomer comprises from 60% to 90% molar of ethylene unit, particularly from 60% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 60% to 80% molar of ethylene unit.
- the functional highly saturated diene elastomer comprises from 65% to 90% molar of ethylene unit, particularly from 65% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 65% to 80% molar of ethylene unit. According to yet another advantageous embodiment of the invention, the functional highly saturated diene elastomer comprises from 70% to 90% molar of ethylene unit, particularly from 70% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 70% to 80% molar of ethylene unit.
- the functional highly saturated diene elastomer contains units of a 1,3 diene.
- the expression "unit of a 1,3-diene” or “diene unit” refers to the units resulting from the insertion of the 1,3-diene by a 1,4 addition, a 1,2 or a 3,4 addition in the case of isoprene for example.
- the units of a 1,3-diene are those for example of a 1,3-diene having 4 to 12 carbon atoms, such as 1,3-butadiene, isoprene, 1,3-pentadiene, an aryl-1,3-butadiene.
- the 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene. More preferably, the 1,3-diene is 1,3-butadiene
- the highly saturated functional diene elastomer preferably contains units of formula (I) or units of formula (II).
- the presence of a saturated 6-membered ring unit, 1,2-cyclohexanediyl, of formula (I) in the functional highly saturated diene elastomer may result from a series of very particular insertions of ethylene and 1,3- butadiene in the polymer chain during its growth.
- the functional highly saturated diene elastomer comprises units of formula (I) or units of formula (II)
- the molar percentages of the units of formula (I) and of the units of formula (II) in the highly saturated diene elastomer functional, respectively o and p preferably satisfy the following equation (eq. 1) or the equation (eq. 2), o and p being calculated on the basis of the totality of the repeating units constituting the functional highly saturated diene elastomer.
- the highly saturated functional diene elastomer comprises units of formula (I) according to a molar rate greater than 0% and less than 15%, more preferably less than 10% molar, molar percentage calculated on the basis of all of the constituent repeating units of the functional highly saturated diene elastomer.
- These beaches preferential molar ratios of the units of formula (I) can be applied to any one of the embodiments of the invention.
- the highly saturated functional diene elastomer also has the further characteristic of carrying pendant groups containing an N-substituted imidazole function.
- the pendant groups containing the imidazole function according to the invention are preferably pendant groups randomly distributed in the functional highly saturated diene elastomer.
- the level of the imidazole function in the functional highly saturated diene elastomer is less than 3% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- molar percentage calculated on the basis of all the units constituent repeats of the functional highly saturated diene elastomer.
- the N-substituted imidazole function is preferably a group of formula (1) in which the symbol Yi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Y? denotes an attachment to a diene unit of the highly saturated functional diene elastomer, the symbols Y3 and Y4 are each a hydrogen atom.
- the alkyl represented by Yi contains 1 to 3 carbon atoms, preferably is methyl.
- Attachment to a diene unit of the highly saturated functional diene elastomer is understood to mean a bond or a group which makes it possible to covalently link the 5-membered ring of the imidazole function to said unit.
- the unit attached to the N-substituted imidazole function is a diene unit modified by reaction of a modifying agent containing a group reactive with respect to diene units.
- Y2 denotes in formula (1) an attachment to a unit of the highly saturated functional diene elastomer which is a diene unit modified by reaction of a modifying agent containing a group reactive with screw of diene units.
- the functional highly saturated diene elastomer is obtained by modification of a highly saturated diene elastomer, called the starting highly saturated diene elastomer , by a grafting reaction of the modifying agent onto units of the starting highly saturated diene elastomer 1,3-diene, which results in the presence of unmodified 1,3-diene units and units 1,3-diene modified into the functional highly saturated diene elastomer.
- the reactive group of the modifier can be a dipole capable of reacting with carbon-carbon double bonds such as units of a 1,3-diene.
- the dipole can be a nitrile, nitrone or nitrile imine oxide group.
- the modifying agent is preferably a 1,3-dipolar compound, more preferably a nitrile oxide, a nitrone or a nitrile imine, even more preferably a nitrile oxide.
- 1,3-di polar compound is understood according to the definition given by IUPAC.
- the 1,3-dipolar compound has the characteristic of comprising a dipole such as a nitrile, nitrone or nitrile imine oxide, and the imidazole function.
- the dipole constitutes the reactive group of the modifying agent with respect to the diene units.
- the dipole typically reacts with diene units, notably by [3+2] cycloaddition reaction,
- the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, a compound comprising a benzene ring substituted by a nitrile oxide dipole and substituted by a group containing an imidazole function of formula ( 2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 designates an attachment to the dipole, the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
- Aromatic nitrile monooxide compound means an aromatic compound which contains a single nitrile oxide dipole and in which the benzene ring is substituted by the nitrile oxide dipole, which means that the carbon atom of the dipole is bonded directly by a covalent bond to a carbon atom of the benzene ring.
- the benzene ring substituted by the nitrile oxide dipole is also substituted by a group containing the imidazole function.
- the benzene ring is also substituted ortho to the dipole.
- the 1,3-dipolar compound contains a unit of formula (3) in which Ri represents the nitrile oxide dipole, one of the symbols R2 to Re represents a saturated group having 1 to 6 carbon atoms and covalently bonded to one of the nitrogen atoms of the 5-membered ring of the imidazole function of formula (2), the other symbols, identical or different, representing a hydrogen atom or a substituent.
- the substituent can be any group as long as it does not react with the dipole.
- the substituent can form a ring with the substituent on the neighboring carbon.
- the substituent is an alkyl having 1 to 3 carbon atoms, preferably methyl or ethyl, more preferably methyl.
- the saturated group in formula (3) makes it possible to covalently link the imidazole function to the benzene ring substituted in particular by the nitrile oxide dipole. It may contain one or more heteroatoms. It preferably contains 1 to 3 carbon atoms.
- the saturated group of formula (3) is preferably an alkanediyl, more preferably an alkanediyl having 1 to 3 carbon atoms, even more preferably methanediyl.
- R2 and Re are preferably different from a hydrogen atom.
- R2, R4 and Re are all different from a hydrogen atom and are identical.
- the synthesis of the 1,3-dipolar compound can be carried out using a relatively easy synthetic route from a commercially available precursor, for example mesitylene, as described in particular in document WO 2015059269.
- the 1,3-dipolar compound is the 2,4,6-trimethyl-3-((2-methyl-1/7-imidazol-1-yl)methyl)benzo-nitrile oxide compound of formula (4) or the 2,4,6-triethyl-3-((2-methyl-1/7-imidazol-1-yl)methyl)benzonitrile oxide compound of formula (5), more advantageously the compound of formula (4).
- the functional highly saturated diene elastomer is a modified highly saturated diene elastomer, since it can be obtained by modifying a starting highly saturated diene elastomer, part of the diene units of which are modified by grafting of a modifying agent as described above.
- the modification can be carried out in bulk or in solution.
- the highly saturated functional diene elastomer is preferably a modified copolymer of ethylene and a 1,3-diene or a copolymer of ethylene and several 1,3-dienes, the 1,3-diene being advantageously 1, 3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene.
- the highly saturated functional diene elastomer is more preferably a modified copolymer of ethylene and 1,3-butadiene.
- the functional highly saturated diene elastomer is a modified random copolymer.
- the starting highly saturated diene elastomer can be obtained according to various synthetic methods known to those skilled in the art, in particular depending on the targeted microstructure of the functional highly saturated diene elastomer. Generally, it can be prepared by copolymerization of at least one 1,3-diene, preferably 1,3-butadiene, and ethylene and according to known synthetic methods, in particular in the presence of a catalytic system comprising a metallocene complex. Mention may be made in this respect of catalytic systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731, WO 2004035639, WO 2007054223 and WO 2007054224 in the name of the Applicant.
- the starting highly saturated diene elastomer can also be prepared by a process using a catalytic system of the preformed type such as those described in the documents WO 2017093654 A1, WO 2018020122 A1 and WO 2018020123 A1.
- the starting highly saturated diene elastomer is random and is preferably prepared according to a semi-continuous or continuous process as described in documents WO 2017103543 A1, WO 201713544 A1, WO 2018193193 and WO 2018193194.
- the rubber composition may contain in addition to the functional highly saturated diene elastomer a second diene elastomer.
- diene elastomer is meant an elastomer consisting at least in part (i.e., a homopolymer or a copolymer) of diene monomer units (monomers carrying two carbon-carbon double bonds, conjugated or not).
- the second elastomer can be chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof.
- a highly unsaturated elastomer is called an elastomer which contains more than 50% by mole of diene unit.
- the level of functional highly saturated diene elastomer in the rubber composition is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr). More preferably, the rate of the functional highly saturated diene elastomer in the rubber composition varies within a range of 80 to 100 phr. Even more preferably, it varies within a range ranging from 90 to 100 phr. It is advantageously 100 pce.
- the functional highly saturated diene elastomer can be a single functional highly saturated diene elastomer or else a mixture of several functional highly saturated diene elastomers which differ from one another by their microstructures or by their macrostructures.
- the level of the functional highly saturated diene elastomer in the rubber composition relates to the mixture of functional highly saturated diene elastomers.
- the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area as well as a CTAB specific surface area, both of which are less than 450 m 2 /g, preferably comprised in a range ranging from 30 to 400 m 2 /g, in particular from 60 to 300 m 2 /g.
- BET surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” (Vol.
- CTAB N-hexadecyl-bromide N,N,N-trimethylammonium
- Non-HDS silica the following commercial silicas can be used: “Ultrasil ® VN2GR” and “Ultrasil ® VN3GR” silicas from Evonik, “Zeosil® 175GR” silica from Solvay, “Hi -Sil EZ120G(-D)", “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210", “Hi-Sil HDP 320G” from PPG.
- the reinforcing filler can comprise any type of so-called reinforcing filler other than silica, known for its ability to reinforce a rubber composition that can be used in particular for the manufacture of tires, for example a carbon black.
- carbon blacks are suitable for all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, mention will be made more particularly of the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772.
- carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
- the carbon black is used in the rubber composition, it is preferably used at a level less than or equal to 10 phr (for example the level of carbon black can be included in a range ranging from 1 to 10 phr) .
- the content of carbon black in the rubber composition is less than or equal to 5 phr.
- the coloring (black pigmentation agent) and anti-UV properties of carbon blacks are benefited, without penalizing the typical performance provided by silica.
- the silica preferably represents more than 50% by mass of the reinforcing filler.
- the proportion of silica in the reinforcing filler is greater than 50% by weight of the total weight of the reinforcing filler. More preferably, the silica represents more than 85% by mass of the reinforcing filler.
- the total amount of reinforcing filler can vary within a wide range, for example from 30 phr to 150 phr.
- the total rate of reinforcing filler varies within a range ranging from 30 phr to 60 phr.
- the total rate of reinforcing filler varies within a range ranging from more than 60 phr to 150 phr.
- the first embodiment is preferred to the second embodiment for use of the rubber composition in a tread having very low rolling resistance. Any of these ranges of total level of reinforcing filler can be applied to any of the embodiments of the invention.
- a coupling agent or bonding agent
- a silane at least bifunctional intended to ensure a sufficient connection, of a chemical and/or physical nature, is used in a well-known manner.
- at least bifunctional organosilanes or polyorganosiloxanes are used.
- bifunctional is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer.
- such a bifunctional compound can comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.
- the organosilanes are chosen from the group consisting of polysulphide organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilyl propyl) tetrasulphide, abbreviated as TESPT marketed under the name “Si69” by the company Evonik, or bis(3-triethoxysilyl propyl) tetrasulphide.
- TESPD bis-(triethoxysilylpropyl), abbreviated as TESPD marketed under the name "Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”, the oligomers having at least one blocked mercaptosilane unit, at least one mercaptosilane unit and at least one cyclic hydroxyalkoxysilyl or dia Icoxysilyl group marketed by the company Momentive under the name “NXT-Z”.
- NXT Silane the oligomers having at least one blocked mercaptosilane unit, at least one mercaptosilane unit and at least one cyclic hydroxyalkoxysilyl or dia Icoxysilyl group marketed by the
- Polysulphurized silanes called “symmetrical” or “asymmetrical” according to their particular structure, are for example described in applications W003/002648 (or US 2005/016651) and W003/002649 (or US 2005/016650).
- - x is an integer from 2 to 8, preferably from 2 to 5;
- the symbols A 1 which are identical or different, represent a divalent hydrocarbon radical (preferably a Ci-Ci alkylene group or a Cg-C arylene group, more particularly a Ci-Cio alkylene, in particular in
- radicals R 1 substituted or unsubstituted, identical or different from each other, represent a C1-C18 alkyl group, C5-C18 cycloalkyl group, or Cg-Ci8 aryl group (preferably Ci-Cg alkyl groups, cyclohexyl or phenyl , in particular C1-C4 alkyl groups, more particularly methyl and/or ethyl),
- the radicals R 2 substituted or unsubstituted, identical or different from each other, represent a Ci-Cis alkoxyl group or a C5-C18 cycloalkoxyl group (preferably a group chosen from Ci-Cs alkoxyls and C 5 -Cs cycloalkoxyls, more preferably still a group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
- the denomination in C n -C m qualifying a group refers to the number of carbon atoms constituting the group which contains n to m carbon atoms, n and m being whole numbers with m greater than n.
- polysulphide silanes examples include the polysulphides (in particular disulphides, trisulphides or tetrasulphides) of bis-(alcoxyl(Ci-C4)-a I kyl(Ci-C4)silyl-alkyl(Ci-C4 )), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilyl propyl) polysulfides.
- TESPT bis(3-triethoxysilylpropyl) tetrasulfide
- TESPD bis(triethoxysilyl propyl) disulfide
- Bifunctional POSS polyorganosiloxanes
- hydroxysilane polysulphides are for example described in patent applications WO 02/30939 (or US 6,774,255), WO 02/31041 (or US 2004/051210).
- the rate of the silane coupling agent is adjusted by the person skilled in the art according to the chemical structure of the coupling agent, according to the specific surface area of the silica used in the composition. of rubber and according to the level of silica in the rubber composition. It is preferentially included in a range ranging from 1 to 15 phr, more preferentially from 1.5 to 10 phr, even more preferentially from 2 to 5 phr.
- the hydrate of a thiosulfate salt is inorganic in the sense that it does not contain carbon atoms.
- the hydrate of an inorganic thiosulfate salt is a thiosulfate hydrate of an alkali metal such as lithium, sodium, potassium, or of an alkaline-earth metal such as magnesium, calcium, barium.
- the hydrate of an inorganic thiosulfate salt is more preferably sodium thiosulfate pentahydrate, Na2S2O3 5H2O.
- the level of the hydrate of an inorganic thiosulphate salt in the rubber composition is adjusted by those skilled in the art according to the desired impact on the hysteresis properties and, where appropriate, on the stiffness properties, being understood that it is generally desirable to use as little as possible.
- Its content is preferably greater than 0.5 phr, more preferably greater than 1 phr, and is preferably less than 10 phr, more preferably less than 5 phr. It advantageously varies within a range ranging from 0.5 phr to 10 phr, more advantageously within a range ranging from del phr to 5 phr.
- the rubber composition in accordance with the invention has the other essential characteristic of containing a vulcanization system, that is to say a sulfur-based crosslinking system.
- the sulfur is typically provided in the form of molecular sulfur or a sulfur-donating agent, preferably in molecular form. Sulfur in molecular form is also referred to as molecular sulfur.
- sulfur donor is meant any compound which releases sulfur atoms, combined or not in the form of a polysulphide chain, capable of being inserted into the polysulphide chains formed during vulcanization and bridging the elastomer chains.
- vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc.
- the sulfur content is preferably between 0.5 and 4 phr, that of the primary accelerator is preferably between 0.5 and 5 phr.
- vulcanization accelerator primary or secondary any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide type with regard to primary accelerators, of the thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthates type as far as secondary accelerators are concerned.
- primary accelerators examples include sulfenamide compounds such as N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N,N-dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”) , N-tert-butyl-2-benzothiazyl sulfenamide (“TBBS”), and mixtures of these compounds.
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N,N-dicyclohexyl-2-benzothiazyl sulfenamide
- TBBS N-tert-butyl-2-benzothiazyl sulfenamide
- the primary accelerator is preferably a sulfenamide, more preferably N-cyclohexyl-2-benzothiazyl sulfenamide.
- secondary accelerators By way of example of secondary accelerators, mention may in particular be made of thiuram disulphides such as tetraethylthiuram disulphide, tetrabutylthiuram disulphide (“TBTD”), tetrabenzylthiuram disulphide (“TBZTD”) and mixtures of these compounds .
- the secondary accelerator is preferably a thiuram disulphide, more preferably tetrabenzylthiuram disulphide.
- the vulcanization is carried out in a known manner at a temperature generally between 130° C. and 200° C., for a sufficient time which can vary for example between 5 and 90 min depending in particular on the curing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition under consideration.
- the rubber composition in accordance with the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, in particular pigments, protective agents such as anti-ozone waxes, anti- chemical ozonants, anti-oxidants, plasticizers such as plasticizing oils or resins.
- the rubber composition, before vulcanization, can be manufactured in suitable mixers, using two successive preparation phases according to a procedure well known to those skilled in the art: a first working phase or thermo-mechanical mixing (sometimes referred to as “non-productive") at high temperature, up to a maximum temperature between 110°C and 190°C, preferably between 130°C and 180°C, followed by a second phase of mechanical work (sometimes called “productive" phase) at lower temperature, typically below 110°C, for example between 40°C and 100°C, finishing phase during which the sulfur or the sulfur donor and the vulcanization accelerator are incorporated .
- a first working phase or thermo-mechanical mixing sometimes referred to as "non-productive”
- a second phase of mechanical work sometimes called “productive” phase
- the first phase (non-productive) is carried out in a single thermomechanical step during which all the necessary constituents, any setting agents implements and other miscellaneous additives, with the exception of the vulcanization system.
- the total mixing time, in this non-productive phase is preferably between 1 and 15 min.
- the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roller mixer, the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
- the functional highly saturated diene elastomer is prepared by modifying a starting highly saturated diene elastomer.
- a modifying agent as described above is incorporated into a starting highly saturated diene elastomer by thermomechanical mixing in an internal mixer before the introduction of the other constituents of the rubber composition.
- the contact time between the starting highly saturated diene elastomer and the thermomechanically kneaded modifying agent is adjusted according to the conditions of the thermomechanical kneading, in particular according to the temperature. The higher the mixing temperature, the shorter this contact time. Typically it is 1 to 5 minutes for a temperature of 100 to 130°C.
- the non-productive phase is preceded by a step during which the functional highly saturated diene elastomer is prepared on an external mixer.
- a modifying agent as described above is incorporated into a starting highly saturated diene elastomer on a roller mixer (known as an external mixer) to form a mixture which is homogenized for example by several passages over the rollers.
- the mixture undergoes a heat treatment to graft the modifying agent onto the diene elastomer, for example in a press at a temperature of at least 100° C., before being introduced into the internal mixer to proceed to the phase non-productive with the incorporation of the other constituents of the rubber composition.
- the rubber composition can be calendered or extruded in the form of a sheet or a plate, in particular for characterization in the laboratory, or else in the form of a semi-finished (or profiled) rubber that can be used in a tire. .
- the composition can be either in the raw state (before crosslinking or vulcanization), or in the cured state after crosslinking or vulcanization). It may constitute all or part of a semi-finished article, in particular intended for use in a pneumatic or non-pneumatic tire which comprises a tread, in particular in the tread of the tire.
- Rubber composition which comprises: a functional highly saturated diene elastomer, copolymer which contains ethylene units, units of a 1,3-diene and which carries pendant groups containing an N-substituted imidazole function, the ethylene units representing more than 50 mol% of the constituent repeating units of the functional highly saturated diene elastomer
- Mode 2 A rubber composition according to Mode 1 wherein the functional highly saturated diene elastomer is a modified copolymer of ethylene and a 1,3-diene.
- Mode 3 Rubber composition according to mode 1 or 2 in which the 1,3-diene is the
- 1,3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene.
- Mode 4 Rubber composition according to any one of modes 1 to 3 in which the
- 1.3-diene is 1,3-butadiene.
- Mode 5 A rubber composition according to any one of modes 1 to 4 in which the ethylene units in the functional highly saturated diene elastomer represent at least 60% by mole of the constituent repeating units of the functional highly saturated diene elastomer.
- Mode 6 Rubber composition according to any one of Modes 1 to 5 in which the ethylene units in the functional highly saturated diene elastomer represent at least 65% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- Mode 7 Rubber composition according to any one of Modes 1 to 6 in which the ethylene units in the functional highly saturated diene elastomer represent at least 70% by mole of the constituent repeating units of the functional highly saturated diene elastomer.
- Mode 8 Rubber composition according to any one of Modes 1 to 7 in which the ethylene units in the functional highly saturated diene elastomer represent at most 90% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- Mode 9 Rubber composition according to any one of Modes 1 to 8 in which the ethylene units in the functional highly saturated diene elastomer represent at most 85% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- Mode 10 Rubber composition according to any one of Modes 1 to 9 in which the ethylene units in the functional highly saturated diene elastomer represent at most 80% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- Mode 11 Rubber composition according to any one of modes 1 to 10 in which the functional highly saturated diene elastomer is a random copolymer.
- Mode 12 Rubber composition according to any one of modes 1 to 11 in which the N-substituted imidazole function is a group of formula (1) in which the symbol Yi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Y? denotes an attachment to a diene unit of the highly saturated functional diene elastomer, the symbols Y3 and Y4 are each a hydrogen atom.
- Mode 13 Rubber composition according to mode 12 in which the alkyl represented by Yi contains 1 to 3 carbon atoms.
- Mode 14 Rubber composition according to mode 12 or 13 in which the alkyl represented by Yi is methyl.
- Mode 15 Rubber composition according to any one of modes 12 to 14 in which the unit attached to the N-substituted imidazole function is a diene unit modified by reacting a modifying agent containing a group reactive with diene units.
- Mode 16 A rubber composition according to Mode 15 wherein the modifier is a 1,3-dipolar compound.
- Mode 17 Rubber composition according to mode 15 or 16 in which the modifying agent is a nitrile oxide, a nitrone or a nitrile imine.
- Mode 18 Rubber composition according to any one of modes 15 to 17 in which the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, compound comprising a benzene ring substituted by a dipole nitrile and by a group containing an imidazole function of formula (2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 denotes an attachment to the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
- the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, compound comprising a benzene ring substituted by a dipole nitrile and by a group containing an imidazole function of formula (2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 denotes an attachment to the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
- Mode 19 Rubber composition according to mode 18 in which the 1,3-dipolar compound contains a unit of formula (3) in which Ri represents the nitrile oxide dipole, one of the symbols R2 to Re represents a saturated group having 1 to 6 carbon atoms and covalently bonded to one of the nitrogen atoms of the 5-membered ring of the imidazole function of formula (2), the other symbols, identical or different, representing a hydrogen atom or a substituent .
- Mode 20 Rubber composition according to mode 19 in which the saturated group is an alkanediyl.
- Mode 21 Rubber composition according to mode 19 or 20 in which the saturated group is an alkanediyl having 1 to 3 carbon atoms.
- Mode 22 A rubber composition according to any of Modes 19 to 21 wherein the saturated group is methanediyl.
- Mode 23 A rubber composition according to any of Modes 19 to 22 wherein the substituent is an alkyl having 1 to 3 carbon atoms.
- Mode 24 A rubber composition according to any of Modes 19 to 23 wherein the substituent is methyl or ethyl.
- Mode 25 A rubber composition according to any one of Modes 19 to 24 in which Fu and Re are different from a hydrogen atom.
- Mode 26 Rubber composition according to any one of modes 19 to 25 in which R2, R4 and Re are all different from a hydrogen atom and are identical.
- Mode 27 Rubber composition according to any one of modes 1 to 26 in which the level of the imidazole function in the functional highly saturated diene elastomer is greater than 0% and less than 3% by mole of the repeating units constituting the functional highly saturated diene elastomer.
- Mode 28 Rubber composition according to any one of modes 1 to 27 in which the content of the functional highly saturated diene elastomer is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr ).
- Mode 29 Rubber composition according to any one of modes 1 to 28 in which the content of the highly saturated functional diene elastomer varies within a range ranging from 80 to 100 phr.
- Mode 30 Rubber composition according to any one of modes 1 to 29 in which the total content of reinforcing filler varies within a range ranging from 30 to 150 phr.
- Mode 31 Rubber composition according to any one of modes 1 to 30 in which the total content of reinforcing filler varies within a range ranging from 30 phr to 60 phr.
- Mode 32 Rubber composition according to any one of modes 1 to 31 in which the silica represents more than 50% by mass of the reinforcing filler.
- Mode 33 Rubber composition according to any one of modes 1 to 32 in which the silica represents more than 85% by mass of the reinforcing filler.
- Mode 34 A rubber composition according to any of Modes 1 to 33 wherein the inorganic thiosulfate salt hydrate is an alkali metal or alkaline earth metal thiosulfate hydrate.
- Mode 35 A rubber composition according to any of Modes 1 to 34 wherein the hydrate of an inorganic thiosulfate salt is sodium thiosulfate pentahydrate, NazSzO1 5H2O.
- Mode 36 Rubber composition according to any one of Modes 1 to 35 in which the level of the hydrate of an inorganic thiosulfate salt is greater than 0.5 phr and is less than 10 phr.
- Mode 37 Rubber composition according to any one of modes 1 to 36 in which the level of the hydrate of an inorganic thiosulphate salt is greater than 1 phr.
- Mode 38 Rubber composition according to any one of modes 1 to 37 in which the level of the hydrate of an inorganic thiosulphate salt is less than 5 phr.
- Mode 39 A rubber composition according to any of modes 1 to 38, which composition contains a silane coupling agent.
- the dynamic properties G* and tanô(max) are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 5992-96.
- the response of a sample of vulcanized composition (cylindrical test piece 4 mm thick and 400 mm 2 in section) subjected to a sinusoidal stress in alternating simple shearing, at a frequency of 10Hz at 60°C, is recorded.
- a deformation amplitude scan is performed from 0.1% to 100% (go cycle), then from 100% to 0.1% (return cycle) and the loss factor tanô is measured.
- the maximum value of tanô observed, denoted tanô(max) is indicated.
- results are expressed in base 100 relative to a control.
- a value greater than that of the control arbitrarily set at 100, indicates a quantity measured greater than that of the control.
- the measurements are carried out at 150° C. with an oscillating chamber rheometer, according to standard DIN 53529 - part 3 (June 1983).
- the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
- the measurements are processed according to DIN 53529 - part 2 (March 1983).
- Ti is the induction time, ie the time required for the start of the vulcanization reaction.
- Ta (for example T95) is the time required to reach a conversion of a%, that is to say a% (for example 95%) of the difference between the minimum and maximum torques.
- the microstructure of the elastomers is determined by 1 H NMR analysis, supplemented by 13 C NMR analysis when the resolution of the 1 H NMR spectra does not allow the attribution and quantification of all the species.
- the measurements are carried out using a BRUKER 500 MHz NMR spectrometer at frequencies of 500.43 MHz for the observation of the proton and 125.83 MHz for the observation of the carbon.
- a 4mm z-grad HRMAS probe is used to observe the proton and carbon in proton-decoupled mode.
- the spectra are acquired at rotation speeds of 4000Hz to 5000Hz.
- a liquid NMR probe is used to observe the proton and carbon in proton-decoupled mode.
- insoluble samples are done in rotors filled with the material analyzed and a deuterated solvent allowing swelling, generally deuterated chloroform (CDCI3).
- the solvent used must always be deuterated and its chemical nature can be adapted by those skilled in the art.
- the quantities of material used are adjusted so as to obtain spectra with sufficient sensitivity and resolution.
- Soluble samples are dissolved in a deuterated solvent (approximately 25mg of elastomer in 1 mL), generally deuterated chloroform (CDCI3).
- the solvent or solvent mixture used must always be deuterated and its chemical nature can be adapted by those skilled in the art.
- a single 30° pulse sequence is used.
- the spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules.
- the number of accumulations is adjusted in order to obtain a sufficient signal-to-noise ratio for the quantification of each pattern.
- the recycling time between each pulse is adapted to obtain a quantitative measurement.
- a simple 30° pulse sequence is used with proton decoupling only during acquisition to avoid “Nuclear Overhauser” (NOE) effects and remain quantitative.
- the spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules.
- the number of accumulations is adjusted in order to obtain a sufficient signal-to-noise ratio for the quantification of each pattern.
- the recycling time between each pulse is adapted to obtain a quantitative measurement.
- the NMR measurements are carried out at 25°C.
- the glass transition temperature (Tg) is measured by means of a differential calorimeter (“Differential Scanning Calorimeter”) according to standard ASTM D3418 (1999).
- Elastomer El is a highly saturated diene elastomer, a copolymer of ethylene and 1,3-butadiene prepared according to the following procedure:
- a 70 L reactor containing methylcyclohexane (64 L), ethylene (5600 g) and 1,3-butadiene (2948 g), butyloctylmagnesium (BOMAG) is added in solution in methylcyclohexane and the catalytic system .
- the Mg/Nd ratio is 6.2.
- the volume of catalytic system introduced is 840 mL, the concentration of the solution of the catalytic system in Nd being 0.0065 M.
- the reaction temperature is regulated at a temperature of 80° C. and the polymerization reaction starts.
- the polymerization reaction takes place at a constant pressure of 8.3 bars.
- the reactor is fed throughout the polymerization with ethylene and 1,3-butadiene in molar proportions.
- the polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol. An antioxidant is added to the polymer solution.
- the copolymer is recovered after steam stripping and drying to constant mass.
- the polymerization time is 225 minutes.
- the weighed mass (6.206 kg) makes it possible to determine the average catalytic activity of the catalytic system expressed in kilogram of polymer synthesized per mole of neodymium metal and per hour (kg/mol.h).
- the copolymer has an ML value of 62.
- the catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from a metallocene, [Me2Si(Flu)2Nd(p-BH4)2Li(TH F)] at 0.0065 mol/L, from a co-catalyst, butyloctylmagnesium (BOMAG) whose the BOMAG/Nd molar ratio is equal to 2.2, and of a preformation monomer, 1,3-butadiene whose 1,3-butadiene/Nd molar ratio is equal to 90.
- the medium is heated to 80° C. on a duration of 5 hours. It is prepared according to a preparation method in accordance with paragraph 11.1 of patent application WO 2017093654 Al.
- the starting highly saturated diene elastomer is the elastomer El.
- rubber composition C4 contains a modified highly saturated diene elastomer, the El elastomer modified by the grafting reaction of a modifying agent, the 1,3-dipolar compound, a silica, a hydrate of a thiosulfate salt, sodium thiosulfate pentahydrate, NazSzCh 5H2O.
- Composition C1 is a control composition: it contains neither the highly saturated functional diene elastomer nor a hydrate of a thiosulphate salt.
- Compositions C2 and C3 are comparative compositions. C2 and C3 are distinguished from C4 by the respective absence of the functional highly saturated diene elastomer and the hydrate.
- compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin sheets of rubber, for the measurement of their physical or mechanical properties after vulcanization at 150° C. (cured state) , or in the form of sections which can be used directly, after cutting and/or assembly to the desired dimensions, for example as semi-finished products for tires.
- the properties of the comparative composition C3 show that the use of the highly saturated functional diene elastomer is accompanied by a strong reduction in the hysteresis, but does not make it possible to reduce the curing time under the press, in particular because of a high induction time (Ti) which is even greater than that of the control composition C1.
- the comparison of the induction times of the compositions C3 and C1 and the comparison of their T90 show that the use of the highly saturated functional diene elastomer does not make it possible to increase the speed of vulcanization either.
- the properties of the comparative composition C2 show that the use of the hydrate of an inorganic thiosulfate salt accelerates the rate of vulcanization while ensuring scorch safety with an induction time of 4 minutes without substantial modification of the hysteresis, relative to composition C1.
- the rubber composition C4 has a hysteresis as low as that of C3, an induction time as low as that of C2 and surprisingly a T90 lower than that of C2. We therefore observe for the composition C4 an acceleration of the vulcanization rate.
- the combined use of the functional highly saturated diene elastomer and the hydrate of an inorganic thiosulfate salt gives the best compromise between hysteresis properties and press cook time without compromising scorch safety. Table 1
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Abstract
The invention relates to a rubber composition that comprises a functional, highly saturated diene elastomer, the elastomer being a copolymer that contains ethylene units, units of a 1,3-diene and bears pendant groups containing an N-substituted imidazole function, the ethylene units representing more than 50 mol % of the constituent repeat units of the functional highly saturated diene elastomer, a vulcanizing system, a reinforcing filler that contains a silica, and a hydrate of an inorganic thiosulphate salt. Such a composition has improved hysteresis and curing properties.
Description
Composition de caoutchouc Rubber composition
Le domaine de la présente invention est celui des compositions de caoutchouc qui comprennent une silice et un élastomère diénique fortement saturé et qui sont notamment destinées à être utilisées dans la fabrication de pneumatique. The field of the present invention is that of rubber compositions which comprise a silica and a highly saturated diene elastomer and which are in particular intended for use in the manufacture of tires.
Un pneumatique doit obéir de manière connue à un grand nombre d'exigences techniques, souvent antinomiques, parmi lesquelles une faible résistance au roulement, une résistance élevée à l'usure, ainsi qu'une adhérence élevée sur route sèche comme mouillée. Ce compromis de propriétés, en particulier du point de vue de la résistance au roulement et de la résistance à l'usure, a pu être amélioré ces dernières années sur les « Pneus Verts » à faible consommation d'énergie, destinés notamment aux véhicules tourisme, grâce notamment à l'emploi de nouvelles compositions de caoutchouc faiblement hystérétiques ayant pour caractéristique d'être renforcées majoritairement de silices hautement dispersibles dites "HDS" (Highly Dispersible Silica), capables de rivaliser, du point de vue du pouvoir renforçant, avec les noirs de carbone conventionnels de grade pneumatique. Depuis que les économies de carburant et la nécessité de préserver l'environnement sont aussi devenues une priorité, il est souhaitable de réduire toujours plus l'hystérèse des compositions de caoutchouc. A tire must comply in a known manner with a large number of often conflicting technical requirements, including low rolling resistance, high wear resistance, as well as high grip on both dry and wet roads. This compromise of properties, in particular from the point of view of rolling resistance and resistance to wear, has been improved in recent years on "Green Tires" with low energy consumption, intended in particular for passenger cars. , thanks in particular to the use of new low-hysteretic rubber compositions having the characteristic of being reinforced mainly with highly dispersible silicas called "HDS" (Highly Dispersible Silica), capable of competing, from the point of view of the reinforcing power, with the conventional tire grade carbon blacks. Since fuel savings and the need to preserve the environment have also become a priority, it is desirable to further reduce the hysteresis of rubber compositions.
L'utilisation d'élastomères diéniques fortement saturés dans une composition de caoutchouc pour une bande de roulement pour pneumatique est décrite dans le document WO 2014114607 Al pour améliorer encore le compromis de performance entre la résistance au roulement et la résistance à l'usure d'un pneumatique. The use of highly saturated diene elastomers in a rubber composition for a tire tread is described in document WO 2014114607 A1 to further improve the performance trade-off between rolling resistance and tire wear resistance. a tire.
Les élastomères diéniques fortement saturés qui contiennent plus de 50% en mole d'unité éthylène ont la particularité de vulcaniser selon une cinétique plus lente que les élastomères diéniques fortement insaturés qui contiennent plus de 50% en moles d'unités diéniques. Des temps de séjour plus longs dans les presses de cuisson sont donc nécessaires pour vulcaniser les compositions de caoutchouc contenant les élastomères diéniques fortement saturés, ce qui se traduit par un temps d'occupation des presses plus long par composition de caoutchouc qui a pour conséquence de diminuer la productivité des sites de fabrication de pneumatiques. The highly saturated diene elastomers which contain more than 50% by mole of ethylene unit have the particularity of vulcanizing according to a slower kinetics than the highly unsaturated diene elastomers which contain more than 50% by mole of diene units. Longer residence times in the curing presses are therefore necessary to vulcanize the rubber compositions containing the highly saturated diene elastomers, which results in a longer press occupation time per rubber composition which has the consequence of reduce the productivity of tire manufacturing sites.
Pour diminuer le temps sous presse, il a été proposé dans le document WO 2018189455 Al d'introduire dans de telles compositions de caoutchouc des additifs comme la diphénylguanidine et l'hexaméthylène bisthiosulfate de disodium. L'utilisation de la diphénylguanidine qui réduit fortement le temps d'induction augmente aussi le risque de vulcanisation prématurée (ou grillage) de la composition de caoutchouc. Ce phénomène de vulcanisation prématurée, s'il se produit, est pénalisant dans les étapes de préparation et de mise en forme de la composition de caoutchouc, en particulier le calandrage ou l'extrusion, étapes qui précèdent généralement l'étape de vulcanisation de la composition de
caoutchouc diénique. En effet, le grillage peut conduire à de fortes élévations de viscosité des compositions de caoutchouc qui deviennent alors beaucoup plus difficiles à travailler et à mettre en œuvre industriellement. L'utilisation d'hexaméthylène bisthiosulfate de disodium assure une bien meilleure sécurité au grillage, mais elle ne permet pas de réduire davantage l'hystérèse de la composition de caoutchouc. To reduce the press time, it has been proposed in document WO 2018189455 A1 to introduce additives such as diphenylguanidine and disodium hexamethylene bisthiosulfate into such rubber compositions. The use of diphenylguanidine which greatly reduces the induction time also increases the risk of premature vulcanization (or scorching) of the rubber composition. This phenomenon of premature vulcanization, if it occurs, is penalizing in the stages of preparation and shaping of the rubber composition, in particular calendering or extrusion, stages which generally precede the stage of vulcanization of the composition of diene rubber. Indeed, the scorch can lead to strong increases in viscosity of the rubber compositions which then become much more difficult to work and to implement industrially. The use of disodium hexamethylene bisthiosulfate provides much better scorch safety, but does not further reduce the hysteresis of the rubber composition.
Il existe donc un besoin de fournir une composition de caoutchouc à base d'un élastomère diénique fortement saturé qui ne présente pas les inconvénients susmentionnés. There is therefore a need to provide a rubber composition based on a highly saturated diene elastomer which does not have the aforementioned drawbacks.
Les inventeurs ont découvert une solution pour réduire à la fois le temps sous presse et l'hystérèse d'une composition de caoutchouc qui est préservée d'une vulcanisation prématurée. The inventors have discovered a solution for reducing both the press time and the hysteresis of a rubber composition which is preserved from premature vulcanization.
Ainsi, l'invention concerne une composition de caoutchouc qui comprend : Thus, the invention relates to a rubber composition which comprises:
- un élastomère diénique fortement saturé fonctionnel, copolymère qui contient des unités éthylène, des unités d'un 1,3-diène et qui porte des groupes pendants contenant une fonction imidazole N-substituée, les unités éthylène représentant plus de 50% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel,- a highly saturated functional diene elastomer, copolymer which contains ethylene units, units of a 1,3-diene and which bears pendant groups containing an N-substituted imidazole function, the ethylene units representing more than 50% by mole of the constituent repeating units of the functional highly saturated diene elastomer,
- un système de vulcanisation, - a vulcanization system,
- une charge renforçante qui contient une silice, - a reinforcing filler which contains a silica,
- et un hydrate d'un sel de thiosulfate inorganique. - and a hydrate of an inorganic thiosulfate salt.
L'invention concerne également un pneumatique qui comprend une composition de caoutchouc conforme à l'invention, préférentiellement dans sa bande de roulement. The invention also relates to a tire which comprises a rubber composition in accordance with the invention, preferably in its tread.
Description Description
Tout intervalle de valeurs désigné par l'expression "entre a et b" représente le domaine de valeurs supérieur à "a" et inférieur à "b" (c'est-à-dire bornes a et b exclues) tandis que tout intervalle de valeurs désigné par l'expression "de a à b" signifie le domaine de valeurs allant de "a" jusqu'à "b" (c'est-à-dire incluant les bornes strictes a et b). Any interval of values denoted by the expression "between a and b" represents the range of values greater than "a" and less than "b" (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” means the range of values going from “a” to “b” (that is to say including the strict limits a and b).
L'abréviation "pce" signifie parties en poids pour cent parties d'élastomère (du total des élastomères si plusieurs élastomères sont présents). The abbreviation "phr" means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present).
Les composés mentionnés dans la description peuvent être d'origine fossile ou biosourcés. Dans ce dernier cas, ils peuvent être, partiellement ou totalement, issus de la biomasse ou obtenus à partir de matières premières renouvelables issues de la biomasse. De la même manière, les composés mentionnés peuvent également provenir du recyclage de matériaux déjà utilisés, c'est-à-dire qu'ils peuvent être, partiellement ou totalement, issus d'un procédé de recyclage, ou encore obtenus à partir de matières premières elles-mêmes issues d'un procédé de recyclage. The compounds mentioned in the description can be of fossil origin or biosourced. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. In the same way, the compounds mentioned can also come from the recycling of materials already used, that is to say they can be, partially or totally, from a recycling process, or obtained from materials raw materials themselves from a recycling process.
Dans la présente invention, on entend par pneumatique (en anglais « tyre ») un bandage pneumatique ou non pneumatique. Un bandage pneumatique comporte usuellement deux
bourrelets destinés à entrer en contact avec une jante, un sommet composé d'au moins une armature de sommet et une bande de roulement, deux flancs, le pneumatique étant renforcé par une armature de carcasse ancrée dans les deux bourrelets. Un bandage non- pneumatique, quant à lui, comporte usuellement une base, conçue par exemple pour le montage sur une jante rigide, une armature de sommet, assurant la liaison avec une bande de roulement et une structure déformable, tels que des rayons, nervures ou alvéoles, cette structure étant disposée entre la base et le sommet. De tels bandages non-pneumatiques ne comprennent pas nécessairement de flanc. Des bandages non-pneumatiques sont décrits par exemples dans les documents WO 03/018332 et FR2898077. Selon l'un quelconque des modes de réalisation de l'invention, le pneumatique selon l'invention est préférentiellement un bandage pneumatique. In the present invention, tire is understood to mean a pneumatic or non-pneumatic tire. A pneumatic tire usually has two beads intended to come into contact with a rim, a crown composed of at least one crown reinforcement and a tread, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads. A non-pneumatic tire, for its part, usually comprises a base, designed for example for mounting on a rigid rim, a crown reinforcement, ensuring the connection with a tread and a deformable structure, such as spokes, ribs or cells, this structure being arranged between the base and the top. Such non-pneumatic tires do not necessarily include a sidewall. Non-pneumatic bandages are described for example in documents WO 03/018332 and FR2898077. According to any one of the embodiments of the invention, the tire according to the invention is preferably a pneumatic tire.
Sauf indication contraire, les taux des unités dans un polymère tel que l'élastomère diénique fortement saturé fonctionnel utile à l'invention sont exprimés en pourcentage molaire par rapport à la totalité des unités de répétition constitutives (en anglais « constitutional repeating unit », également désignée sous l'abréviation CRU par IUPAC) du polymère. Unless otherwise indicated, the levels of the units in a polymer such as the highly saturated functional diene elastomer useful in the invention are expressed in molar percentage relative to all of the constitutive repeating units (in English “constitutional repeating unit”, also designated by the abbreviation CRU by IUPAC) of the polymer.
L'élastomère utile aux besoins de l'invention est un élastomère diénique fortement saturé fonctionnel, de préférence statistique, qui comprend des unités éthylène résultant de la polymérisation d'éthylène. De manière connue, l'expression « unité éthylène » fait référence au motif -(CH2-CH2)- résultant de l'insertion de l'éthylène dans la chaîne élastomère. L'élastomère diénique fortement saturé fonctionnel est riche en unité éthylène, puisque les unités éthylène représentent plus de 50% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. The elastomer useful for the purposes of the invention is a highly saturated functional diene elastomer, preferably random, which comprises ethylene units resulting from the polymerization of ethylene. In a known manner, the expression “ethylene unit” refers to the —(CH2—CH2)— unit resulting from the insertion of ethylene into the elastomer chain. The functional highly saturated diene elastomer is rich in ethylene units, since the ethylene units represent more than 50% by mole of the repeating units constituting the functional highly saturated diene elastomer.
De préférence, l'élastomère diénique fortement saturé fonctionnel comprend au moins 60% molaire d'unité éthylène, préférentiellement au moins 65% molaire d'unité éthylène, plus préférentiellement au moins 70% molaire d'unités éthylène. Preferably, the functional highly saturated diene elastomer comprises at least 60% molar of ethylene units, preferably at least 65% molar of ethylene units, more preferably at least 70% molar of ethylene units.
De préférence, l'élastomère diénique fortement saturé fonctionnel comprend au plus 90% molaire d'unité éthylène. De manière plus préférentielle, il comprend au plus 85% molaire d'unité éthylène. De manière encore plus préférentielle, il comprend au plus 80% molaire d'unité éthylène. Preferably, the functional highly saturated diene elastomer comprises at most 90% molar of ethylene unit. More preferably, it comprises at most 85% molar ethylene unit. Even more preferentially, it comprises at most 80 molar % of ethylene unit.
Selon un mode de réalisation avantageux, l'élastomère diénique fortement saturé fonctionnel comprend de 60% à 90% molaire d'unité éthylène, particulièrement de 60% à 85% molaire d'unité éthylène. Plus avantageusement, l'élastomère diénique fortement saturé fonctionnel comprend de 60% à 80% molaire d'unité éthylène. According to an advantageous embodiment, the highly saturated functional diene elastomer comprises from 60% to 90% molar of ethylene unit, particularly from 60% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 60% to 80% molar of ethylene unit.
Selon un autre mode de réalisation avantageux, l'élastomère diénique fortement saturé fonctionnel comprend de 65% à 90% molaire d'unité éthylène, particulièrement de 65% à 85% molaire d'unité éthylène. Plus avantageusement, l'élastomère diénique fortement saturé fonctionnel comprend de 65% à 80% molaire d'unité éthylène.
Selon encore un autre mode de réalisation avantageux de l'invention, l'élastomère diénique fortement saturé fonctionnel comprend de 70% à 90% molaire d'unité éthylène, particulièrement de 70% à 85% molaire d'unité éthylène. Plus avantageusement, l'élastomère diénique fortement saturé fonctionnel comprend de 70% à 80% molaire d'unité éthylène. According to another advantageous embodiment, the functional highly saturated diene elastomer comprises from 65% to 90% molar of ethylene unit, particularly from 65% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 65% to 80% molar of ethylene unit. According to yet another advantageous embodiment of the invention, the functional highly saturated diene elastomer comprises from 70% to 90% molar of ethylene unit, particularly from 70% to 85% molar of ethylene unit. More advantageously, the functional highly saturated diene elastomer comprises from 70% to 80% molar of ethylene unit.
L'élastomère diénique fortement saturé fonctionnel contient des unités d'un 1,3 diène. De manière connue, l'expression « unité d'un 1,3-diène » ou « unité diénique » fait référence aux unités résultant de l'insertion du 1,3-diène par une addition 1,4, une addition 1,2 ou une addition 3,4 dans le cas de l'isoprène par exemple. Les unités d'un 1,3-diène sont celles par exemple d'un 1,3-diène ayant 4 à 12 atomes de carbone, tels que le 1,3-butadiène, l'isoprène, le 1,3-pentadiène, un aryl-l,3-butadiène. De préférence, le 1,3-diène est le 1,3- butadiène ou un mélange de 1,3-diènes dont un est le 1,3-butadiène. De manière plus préférentielle, le 1,3-diène est le 1,3-butadiène The functional highly saturated diene elastomer contains units of a 1,3 diene. In a known manner, the expression "unit of a 1,3-diene" or "diene unit" refers to the units resulting from the insertion of the 1,3-diene by a 1,4 addition, a 1,2 or a 3,4 addition in the case of isoprene for example. The units of a 1,3-diene are those for example of a 1,3-diene having 4 to 12 carbon atoms, such as 1,3-butadiene, isoprene, 1,3-pentadiene, an aryl-1,3-butadiene. Preferably the 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene. More preferably, the 1,3-diene is 1,3-butadiene
L'élastomère diénique fortement saturé fonctionnel contient de préférence des unités de formule (I) ou des unités de formule (II).
The highly saturated functional diene elastomer preferably contains units of formula (I) or units of formula (II).
-CH2-CH(CH=CH2)- (II) -CH2-CH(CH=CH 2 )- (II)
La présence de motif cyclique saturé à 6 membres, 1,2-cyclohexanediyle, de formule (I) dans l'élastomère diénique fortement saturé fonctionnel peut résulter d'une série d'insertions très particulières de l'éthylène et du 1,3-butadiène dans la chaîne polymère au cours de sa croissance. Lorsque l'élastomère diénique fortement saturé fonctionnel comprend des unités de formule (I) ou des unités de formule (II), les pourcentages molaires des unités de formule (I) et des unités de formule (II) dans l'élastomère diénique fortement saturé fonctionnel, respectivement o et p, satisfont de préférence à l'équation suivante (eq. 1) ou à l'équation (eq. 2), o et p étant calculés sur la base de la totalité des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. The presence of a saturated 6-membered ring unit, 1,2-cyclohexanediyl, of formula (I) in the functional highly saturated diene elastomer may result from a series of very particular insertions of ethylene and 1,3- butadiene in the polymer chain during its growth. When the functional highly saturated diene elastomer comprises units of formula (I) or units of formula (II), the molar percentages of the units of formula (I) and of the units of formula (II) in the highly saturated diene elastomer functional, respectively o and p, preferably satisfy the following equation (eq. 1) or the equation (eq. 2), o and p being calculated on the basis of the totality of the repeating units constituting the functional highly saturated diene elastomer.
0 < o+p < 30 (eq. 1) 0 < o+p < 30 (eq. 1)
0 < o+p < 25 (eq. 2) 0 < o+p < 25 (eq. 2)
De préférence, l'élastomère diénique fortement saturé fonctionnel comprend des unités de formule (I) selon un taux molaire supérieur à 0% et inférieur à 15%, plus préférentiellement inférieur à 10% molaire, pourcentage molaire calculé sur la base de la totalité des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Ces plages
préférentielles de taux molaire des unités de formule (I) peuvent s'appliquer à l'un quelconque des modes de réalisation de l'invention. Preferably, the highly saturated functional diene elastomer comprises units of formula (I) according to a molar rate greater than 0% and less than 15%, more preferably less than 10% molar, molar percentage calculated on the basis of all of the constituent repeating units of the functional highly saturated diene elastomer. These beaches preferential molar ratios of the units of formula (I) can be applied to any one of the embodiments of the invention.
L'élastomère diénique fortement saturé fonctionnel a aussi pour autre caractéristique de porter des groupes pendants contenant une fonction imidazole N-substituée. L'homme du métier comprend que les groupes pendants sont rattachés à l'élastomère par liaison covalente. Les groupes pendants contenant la fonction imidazole selon l'invention sont de préférence des groupes pendants répartis de façon statistique dans l'élastomère diénique fortement saturé fonctionnel. De préférence, le taux de la fonction imidazole dans l'élastomère diénique fortement saturé fonctionnel est inférieur à 3% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Typiquement il est supérieur à 0% et préférentiellement inférieur à 3%, plus préférentiellement supérieur à 0.02% et inférieur à 2%, encore plus préférentiellement supérieur à 0.07% et inférieur à 0.7%, pourcentage molaire calculé sur la base de la totalité des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Ces plages préférentielles de la teneur molaire de la fonction imidazole peuvent s'appliquer à l'un quelconque des modes de réalisation de l'invention. The highly saturated functional diene elastomer also has the further characteristic of carrying pendant groups containing an N-substituted imidazole function. A person skilled in the art understands that the pendant groups are attached to the elastomer by a covalent bond. The pendant groups containing the imidazole function according to the invention are preferably pendant groups randomly distributed in the functional highly saturated diene elastomer. Preferably, the level of the imidazole function in the functional highly saturated diene elastomer is less than 3% by mole of the repeating units constituting the functional highly saturated diene elastomer. Typically it is greater than 0% and preferably less than 3%, more preferably greater than 0.02% and less than 2%, even more preferably greater than 0.07% and less than 0.7%, molar percentage calculated on the basis of all the units constituent repeats of the functional highly saturated diene elastomer. These preferential ranges of the molar content of the imidazole function can be applied to any one of the embodiments of the invention.
La fonction imidazole N-substituée est préférentiellement un groupe de formule (1) dans laquelle le symbole Yi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Y? désigne un rattachement à une unité diénique de l'élastomère diénique fortement saturé fonctionnel, les symboles Y3 et Y4 sont chacun un atome d'hydrogène.
The N-substituted imidazole function is preferably a group of formula (1) in which the symbol Yi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Y? denotes an attachment to a diene unit of the highly saturated functional diene elastomer, the symbols Y3 and Y4 are each a hydrogen atom.
Avantageusement, elle est de formule (1) dans laquelle l'alkyle représenté par Yi contient 1 à 3 atomes de carbone, de préférence est méthyle. Advantageously, it is of formula (1) in which the alkyl represented by Yi contains 1 to 3 carbon atoms, preferably is methyl.
On entend par rattachement à une unité diénique de l'élastomère diénique fortement saturé fonctionnel une liaison ou un groupe qui permet de relier de façon covalente le cycle à 5 membres de la fonction imidazole à ladite unité. Attachment to a diene unit of the highly saturated functional diene elastomer is understood to mean a bond or a group which makes it possible to covalently link the 5-membered ring of the imidazole function to said unit.
Selon un mode de réalisation de l'invention, l'unité rattachée à la fonction imidazole N- substituée est une unité diénique modifiée par réaction d'un agent de modification contenant un groupe réactif vis à vis d'unités diéniques. Autrement dit, selon ce mode de réalisation, Y2 désigne dans la formule (1) un rattachement à une unité de l'élastomère diénique fortement saturé fonctionnel qui est une unité diénique modifiée par réaction d'un agent de modification contenant un groupe réactif vis à vis d'unités diéniques.
Autrement dit, dans cette variante préférentielle selon laquelle le rattachement se fait à une unité diénique modifiée par un agent de modification, l'élastomère diénique fortement saturé fonctionnel est obtenu par modification d'un élastomère diénique fortement saturé, dit élastomère diénique fortement saturé de départ, par une réaction de greffage de l'agent de modification sur des unités du 1,3-diène de élastomère diénique fortement saturé de départ, ce qui se traduit par la présence d'unités du 1,3-diène non modifiées et des unités du 1,3-diène modifiées dans l'élastomère diénique fortement saturé fonctionnel. According to one embodiment of the invention, the unit attached to the N-substituted imidazole function is a diene unit modified by reaction of a modifying agent containing a group reactive with respect to diene units. In other words, according to this embodiment, Y2 denotes in formula (1) an attachment to a unit of the highly saturated functional diene elastomer which is a diene unit modified by reaction of a modifying agent containing a group reactive with screw of diene units. In other words, in this preferential variant according to which the attachment is made to a diene unit modified by a modifying agent, the functional highly saturated diene elastomer is obtained by modification of a highly saturated diene elastomer, called the starting highly saturated diene elastomer , by a grafting reaction of the modifying agent onto units of the starting highly saturated diene elastomer 1,3-diene, which results in the presence of unmodified 1,3-diene units and units 1,3-diene modified into the functional highly saturated diene elastomer.
Le groupe réactif de l'agent de modification peut être un dipôle susceptible de réagir avec des doubles liaisons carbone-carbone telles que des unités d'un 1,3-diène. Le dipôle peut être un groupe oxyde de nitrile, nitrone ou nitrile imine. The reactive group of the modifier can be a dipole capable of reacting with carbon-carbon double bonds such as units of a 1,3-diene. The dipole can be a nitrile, nitrone or nitrile imine oxide group.
L'agent de modification est préférentiellement un composé 1,3-di polai re, plus préférentiellement un oxyde de nitrile, une nitrone ou un nitrile imine, encore plus préférentiellement un oxyde de nitrile. Le terme composé 1,3-di polai re est compris selon la définition donnée par IUPAC. Le composé 1,3-dipolaire a pour caractéristique de comprendre un dipôle tel qu'un oxyde de nitrile, nitrone ou nitrile imine, et la fonction imidazole. Le dipôle constitue le groupe réactif de l'agent de modification vis-à-vis des unités diéniques. Le dipôle réagit typiquement avec les unités diéniques, notamment par réaction de cycloaddition [3+2], The modifying agent is preferably a 1,3-dipolar compound, more preferably a nitrile oxide, a nitrone or a nitrile imine, even more preferably a nitrile oxide. The term 1,3-di polar compound is understood according to the definition given by IUPAC. The 1,3-dipolar compound has the characteristic of comprising a dipole such as a nitrile, nitrone or nitrile imine oxide, and the imidazole function. The dipole constitutes the reactive group of the modifying agent with respect to the diene units. The dipole typically reacts with diene units, notably by [3+2] cycloaddition reaction,
De manière plus préférentielle, l'agent de modification est un composé 1,3-dipolaire qui est un monooxyde de nitrile aromatique, composé comprenant un noyau benzénique substitué par un dipôle oxyde de nitrile et substitué par un groupe contenant une fonction imidazole de formule (2) dans laquelle le symbole Zi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Z2 désigne un rattachement au dipôle, le groupe réactif, les symboles Z3 et Z4 sont chacun un atome d'hydrogène.
More preferably, the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, a compound comprising a benzene ring substituted by a nitrile oxide dipole and substituted by a group containing an imidazole function of formula ( 2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 designates an attachment to the dipole, the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
On entend par composé monooxyde de nitrile aromatique un composé aromatique qui contient un seul dipôle oxyde de nitrile et dans lequel le noyau benzénique est substitué par le dipôle oxyde de nitrile, ce qui signifie que l'atome de carbone du dipôle est lié directement par une liaison covalente à un atome de carbone du noyau benzénique. Le noyau benzénique substitué par le dipôle oxyde de nitrile est aussi substitué par un groupe contenant la fonction imidazole. De préférence, le noyau benzénique est aussi substitué en ortho du dipôle.
Avantageusement, le composé 1,3-dipolaire contient un motif de formule (3) dans laquelle Ri représente le dipôle oxyde de nitrile, un des symboles R2 à Re représente un groupe saturé ayant 1 à 6 atomes de carbone et lié de façon covalente à l'un des atomes d'azote du cycle à 5 membres de la fonction imidazole de formule (2), les autres symboles, identiques ou différents, représentant un atome d'hydrogène ou un substituant.
Aromatic nitrile monooxide compound means an aromatic compound which contains a single nitrile oxide dipole and in which the benzene ring is substituted by the nitrile oxide dipole, which means that the carbon atom of the dipole is bonded directly by a covalent bond to a carbon atom of the benzene ring. The benzene ring substituted by the nitrile oxide dipole is also substituted by a group containing the imidazole function. Preferably, the benzene ring is also substituted ortho to the dipole. Advantageously, the 1,3-dipolar compound contains a unit of formula (3) in which Ri represents the nitrile oxide dipole, one of the symbols R2 to Re represents a saturated group having 1 to 6 carbon atoms and covalently bonded to one of the nitrogen atoms of the 5-membered ring of the imidazole function of formula (2), the other symbols, identical or different, representing a hydrogen atom or a substituent.
Le substituant peut être tout groupe tant qu'il ne réagit pas avec le dipôle. Le substituant peut former avec le substituant du carbone voisin un cycle. De préférence, le substituant est un alkyle ayant 1 à 3 atomes de carbone, préférentiellement méthyle ou éthyle, plus préférentiellement méthyle. The substituent can be any group as long as it does not react with the dipole. The substituent can form a ring with the substituent on the neighboring carbon. Preferably, the substituent is an alkyl having 1 to 3 carbon atoms, preferably methyl or ethyl, more preferably methyl.
Le groupe saturé dans la formule (3) permet de lier de façon covalente la fonction imidazole au noyau benzénique substitué notamment par le dipôle oxyde de nitrile. Il peut contenir un ou plusieurs hétéroatomes. Il contient préférentiellement 1 à 3 atomes de carbone. Le groupe saturé de la formule (3) est de préférence un alcanediyle, de manière plus préférentielle un alcanediyle ayant 1 à 3 atomes de carbone, de manière encore plus préférentielle méthanediyle. The saturated group in formula (3) makes it possible to covalently link the imidazole function to the benzene ring substituted in particular by the nitrile oxide dipole. It may contain one or more heteroatoms. It preferably contains 1 to 3 carbon atoms. The saturated group of formula (3) is preferably an alkanediyl, more preferably an alkanediyl having 1 to 3 carbon atoms, even more preferably methanediyl.
Dans la formule (3), R2 et Re sont préférentiellement différents d'un atome d'hydrogène. De préférence, R2 , R4 et Re sont tous différents d'un atome d'hydrogène et sont identiques.In formula (3), R2 and Re are preferably different from a hydrogen atom. Preferably, R2, R4 and Re are all different from a hydrogen atom and are identical.
La synthèse du composé 1,3-dipolaire peut être réalisée à partir d'une voie de synthèse relativement aisée à partir d'un précurseur commercialement disponible, par exemple le mésitylène, comme cela est décrit notamment dans le document WO 2015059269. The synthesis of the 1,3-dipolar compound can be carried out using a relatively easy synthetic route from a commercially available precursor, for example mesitylene, as described in particular in document WO 2015059269.
Avantageusement, le composé 1,3-dipolaire est le composé 2,4,6-triméthyl-3-((2-méthyl-l/7- imidazol-l-yl)méthyl)benzo-nitrile oxyde de formule (4) ou le composé 2,4,6-triéthyl-3-((2- méthyl-l/7-imidazol-l-yl)méthyl)benzo-nitrile oxyde de formule (5), plus avantageusement le composé de formule (4).
Selon une variante préférentielle de l'invention, l'élastomère diénique fortement saturé fonctionnel est un élastomère diénique fortement saturé modifié, puisqu'il peut être obtenu par modification d'un élastomère diénique fortement saturé de départ dont une partie des unités diéniques sont modifiées par greffage d'un agent de modification tel que décrit précédemment. La modification peut être réalisée en masse ou en solution. L'élastomère diénique fortement saturé fonctionnel est préférentiellement un copolymère modifié d'éthylène et d'un 1,3-diène ou un copolymère d'éthylène et de plusieurs 1,3-diènes, le 1,3- diène étant avantageusement le 1,3-butadiène ou un mélange de 1,3-diènes dont un est le 1,3-butadiène. L'élastomère diénique fortement saturé fonctionnel est plus préférentiellement un copolymère modifié d'éthylène et de 1,3-butadiène. Advantageously, the 1,3-dipolar compound is the 2,4,6-trimethyl-3-((2-methyl-1/7-imidazol-1-yl)methyl)benzo-nitrile oxide compound of formula (4) or the 2,4,6-triethyl-3-((2-methyl-1/7-imidazol-1-yl)methyl)benzonitrile oxide compound of formula (5), more advantageously the compound of formula (4). According to a preferred variant of the invention, the functional highly saturated diene elastomer is a modified highly saturated diene elastomer, since it can be obtained by modifying a starting highly saturated diene elastomer, part of the diene units of which are modified by grafting of a modifying agent as described above. The modification can be carried out in bulk or in solution. The highly saturated functional diene elastomer is preferably a modified copolymer of ethylene and a 1,3-diene or a copolymer of ethylene and several 1,3-dienes, the 1,3-diene being advantageously 1, 3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene. The highly saturated functional diene elastomer is more preferably a modified copolymer of ethylene and 1,3-butadiene.
Avantageusement, l'élastomère diénique fortement saturé fonctionnel est un copolymère statistique modifié. Advantageously, the functional highly saturated diene elastomer is a modified random copolymer.
L'élastomère diénique fortement saturé de départ peut être obtenu selon différentes méthodes de synthèse connues de l'homme du métier, notamment en fonction de la microstructure visée de l'élastomère diénique fortement saturé fonctionnel. Généralement, il peut être préparé par copolymérisation au moins d'un 1,3-diène, de préférence le 1,3- butadiène, et d'éthylène et selon des méthodes de synthèse connues, en particulier en présence d'un système catalytique comprenant un complexe métallocène. On peut citer à ce titre les systèmes catalytiques à base de complexes métallocènes, lesquels systèmes catalytiques sont décrits dans les documents EP 1 092 731, WO 2004035639, WO 2007054223 et WO 2007054224 au nom de la Demanderesse. L'élastomère diénique fortement saturé de départ, y compris lorsqu'il est statistique, peut être préparé aussi par un procédé utilisant un système catalytique de type préformé comme ceux décrits dans les documents WO 2017093654 Al, WO 2018020122 Al et WO 2018020123 Al. The starting highly saturated diene elastomer can be obtained according to various synthetic methods known to those skilled in the art, in particular depending on the targeted microstructure of the functional highly saturated diene elastomer. Generally, it can be prepared by copolymerization of at least one 1,3-diene, preferably 1,3-butadiene, and ethylene and according to known synthetic methods, in particular in the presence of a catalytic system comprising a metallocene complex. Mention may be made in this respect of catalytic systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731, WO 2004035639, WO 2007054223 and WO 2007054224 in the name of the Applicant. The starting highly saturated diene elastomer, including when it is random, can also be prepared by a process using a catalytic system of the preformed type such as those described in the documents WO 2017093654 A1, WO 2018020122 A1 and WO 2018020123 A1.
Avantageusement, l'élastomère diénique fortement saturé de départ est statistique et est préparé préférentiellement selon un procédé semi continu ou continu tel que décrit dans les documents WO 2017103543 Al, WO 201713544 Al, WO 2018193193 et WO 2018193194.Advantageously, the starting highly saturated diene elastomer is random and is preferably prepared according to a semi-continuous or continuous process as described in documents WO 2017103543 A1, WO 201713544 A1, WO 2018193193 and WO 2018193194.
La composition de caoutchouc peut contenir en plus de l'élastomère diénique fortement saturé fonctionnel un deuxième élastomère diénique. On entend par élastomère diénique un élastomère constitué au moins en partie (i.e., un homopolymère ou un copolymère) d'unités monomères diènes (monomères porteurs de deux doubles liaisons carbone- carbone, conjuguées ou non). Le deuxième élastomère peut être choisi dans le groupe des élastomères diéniques fortement insaturés constitué par les polybutadiènes, les polyisoprènes, les copolymères de butadiène, les copolymères d'isoprène et leur mélange. On appelle un élastomère fortement insaturé un élastomère qui contient plus de 50% en mole d'unité diénique. The rubber composition may contain in addition to the functional highly saturated diene elastomer a second diene elastomer. By diene elastomer is meant an elastomer consisting at least in part (i.e., a homopolymer or a copolymer) of diene monomer units (monomers carrying two carbon-carbon double bonds, conjugated or not). The second elastomer can be chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof. A highly unsaturated elastomer is called an elastomer which contains more than 50% by mole of diene unit.
De préférence, le taux de l'élastomère diénique fortement saturé fonctionnel dans la composition de caoutchouc est d'au moins 50 parties en poids pour cent parties d'élastomère de la composition de caoutchouc (pce). De manière plus préférentielle, le taux
de l'élastomère diénique fortement saturé fonctionnel dans la composition de caoutchouc varie dans un domaine allant de 80 à 100 pce. De manière encore plus préférentielle, il varie dans un domaine allant de 90 à 100 pce. Il est avantageusement de 100 pce. L'élastomère diénique fortement saturé fonctionnel peut être un seul élastomère diénique fortement saturé fonctionnel ou bien un mélange de plusieurs élastomères diéniques fortement saturés fonctionnels qui se différencient les uns des autres par leurs microstructures ou par leurs macrostructures. Dans le cas où la composition de caoutchouc contient plusieurs élastomères diéniques fortement saturés fonctionnels qui se différencient les uns des autres par leurs microstructures ou par leurs macrostructures, le taux de l'élastomère diénique fortement saturé fonctionnel dans la composition de caoutchouc se rapporte au mélange d'élastomères diéniques fortement saturés fonctionnels. Preferably, the level of functional highly saturated diene elastomer in the rubber composition is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr). More preferably, the rate of the functional highly saturated diene elastomer in the rubber composition varies within a range of 80 to 100 phr. Even more preferably, it varies within a range ranging from 90 to 100 phr. It is advantageously 100 pce. The functional highly saturated diene elastomer can be a single functional highly saturated diene elastomer or else a mixture of several functional highly saturated diene elastomers which differ from one another by their microstructures or by their macrostructures. In the case where the rubber composition contains several functional highly saturated diene elastomers which differ from one another by their microstructures or by their macrostructures, the level of the functional highly saturated diene elastomer in the rubber composition relates to the mixture of functional highly saturated diene elastomers.
La silice utilisée peut être toute silice renforçante connue de l'homme du métier, notamment toute silice précipitée ou pyrogénée présentant une surface spécifique BET ainsi qu'une surface spécifique CTAB toutes deux inférieures à 450 m2/g, de préférence comprises dans un domaine allant de 30 à 400 m2/g, notamment de 60 à 300 m2/g. Dans le présent exposé, la surface spécifique BET est déterminée par adsorption de gaz à l'aide de la méthode de Brunauer-Emmett-Teller décrite dans « The Journal of the American Chemical Society » (Vol. 60, page 309, février 1938), et plus précisément selon une méthode adaptée de la norme NF ISO 5794-1, annexe E de juin 2010 [méthode volumétrique multipoints (5 points) - gaz: azote - dégazage sous vide: une heure à 160°C - domaine de pression relative p/po : 0.05 à 0.17], Les valeurs de surface spécifique CTAB ont été déterminées selon la norme NF ISO 5794-1, annexe G de juin 2010. Le procédé est basé sur l'adsorption du CTAB (bromure de N-hexadécyl-N,N,N-triméthylammonium) sur la surface « externe » de la charge renforçante. The silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area as well as a CTAB specific surface area, both of which are less than 450 m 2 /g, preferably comprised in a range ranging from 30 to 400 m 2 /g, in particular from 60 to 300 m 2 /g. In this disclosure, BET surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (Vol. 60, page 309, February 1938) , and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160°C - relative pressure range p/po: 0.05 to 0.17], The CTAB specific surface values were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-bromide N,N,N-trimethylammonium) on the "external" surface of the reinforcing filler.
On peut utiliser tout type de silice précipitée, notamment des silices précipitées hautement dispersibles (dites « HDS » pour « highly dispersible » ou « highly dispersible silica »). Ces silices précipitées, hautement dispersibles ou non, sont bien connues de l'homme du métier. On peut citer, par exemple, les silices décrites dans les demandes W003/016215-A1 et W003/016387-A1. Parmi les silices HDS commerciales, on peut notamment utiliser les silices « Ultrasil ® 5000GR », « Ultrasil ® 7000GR » de la société Evonik, les silices « Zeosil ® 1085GR », « Zeosil® 1115 MP », « Zeosil® 1165MP », « Zeosil® Premium 200MP », « Zeosil® HRS 1200 MP » de la Société Solvay. À titre de silice non HDS, les silices commerciales suivantes peuvent être utilisées : les silices « Ultrasil ® VN2GR », « Ultrasil ® VN3GR » de la société Evonik, la silice « Zeosil® 175GR » » de la société Solvay, les silices « Hi-Sil EZ120G(- D) », « Hi-Sil EZ160G(-D) », « Hi-Sil EZ200G(-D) », « Hi-Sil 243LD », « Hi-Sil 210 », « Hi-Sil HDP 320G » de la société PPG. It is possible to use any type of precipitated silica, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”). These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications WO03/016215-A1 and WO03/016387-A1. Among the commercial HDS silicas, it is possible in particular to use the “Ultrasil® 5000GR”, “Ultrasil® 7000GR” silicas from the company Evonik, the “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “Zeosil® 1165MP” silicas, Zeosil® Premium 200MP”, “Zeosil® HRS 1200 MP” from Solvay. As non-HDS silica, the following commercial silicas can be used: “Ultrasil ® VN2GR” and “Ultrasil ® VN3GR” silicas from Evonik, “Zeosil® 175GR” silica from Solvay, “Hi -Sil EZ120G(-D)", "Hi-Sil EZ160G(-D)", "Hi-Sil EZ200G(-D)", "Hi-Sil 243LD", "Hi-Sil 210", "Hi-Sil HDP 320G" from PPG.
La charge renforçante peut comprendre tout type de charge dite renforçante autre que la silice, connue pour ses capacités à renforcer une composition de caoutchouc utilisable notamment pour la fabrication de pneumatiques, par exemple un noir de carbone. Comme
noirs de carbone conviennent tous les noirs de carbone, notamment les noirs conventionnellement utilisés dans les pneumatiques ou leurs bandes de roulement. Parmi ces derniers, on citera plus particulièrement les noirs de carbone renforçants des séries 100, 200, 300, ou les noirs de série 500, 600 ou 700 (grades ASTM D-1765-2017), comme par exemple les noirs N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772. Ces noirs de carbone peuvent être utilisés à l'état isolé, tels que disponibles commercialement, ou sous tout autre forme, par exemple comme support de certains des additifs de caoutchouterie utilisés. Lorsque le noir de carbone est utilisé dans la composition de caoutchouc, il l'est de préférence à un taux inférieur ou égal à 10 pce (par exemple le taux de noir de carbone peut être compris dans un domaine allant de 1 à 10 pce). The reinforcing filler can comprise any type of so-called reinforcing filler other than silica, known for its ability to reinforce a rubber composition that can be used in particular for the manufacture of tires, for example a carbon black. As carbon blacks are suitable for all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, mention will be made more particularly of the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772. These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used. When the carbon black is used in the rubber composition, it is preferably used at a level less than or equal to 10 phr (for example the level of carbon black can be included in a range ranging from 1 to 10 phr) .
Avantageusement, le taux de noir de carbone dans la composition de caoutchouc est inférieur ou égal à 5 pce. Dans les intervalles indiqués, on bénéficie des propriétés colorantes (agent de pigmentation noir) et anti-UV des noirs de carbone, sans pénaliser par ailleurs les performances typiques apportées par la silice. Advantageously, the content of carbon black in the rubber composition is less than or equal to 5 phr. Within the ranges indicated, the coloring (black pigmentation agent) and anti-UV properties of carbon blacks are benefited, without penalizing the typical performance provided by silica.
La silice représente préférentiellement plus de 50% en masse de la charge renforçante. En d'autres termes, la proportion de silice dans la charge renforçante est supérieure à 50% en poids du poids total de la charge renforçante. De manière plus préférentielle, la silice représente plus de 85% en masse de la charge renforçante. The silica preferably represents more than 50% by mass of the reinforcing filler. In other words, the proportion of silica in the reinforcing filler is greater than 50% by weight of the total weight of the reinforcing filler. More preferably, the silica represents more than 85% by mass of the reinforcing filler.
Le taux total de charge renforçante peut varier dans un large domaine, par exemple de 30 pce à 150 pce. Selon un premier mode de réalisation, le taux total de charge renforçante varie dans un domaine allant de 30 pce à 60 pce. Selon un deuxième mode de réalisation, le taux total de charge renforçante varie dans un domaine allant de plus de 60 pce à 150 pce. Le premier mode de réalisation est préféré au deuxième mode de réalisation pour un usage de la composition de caoutchouc dans une bande de roulement ayant une très faible résistance au roulement. L'une quelconque de ces plages de taux total de charge renforçante peut s'appliquer à l'un quelconque des modes de réalisation de l'invention.The total amount of reinforcing filler can vary within a wide range, for example from 30 phr to 150 phr. According to a first embodiment, the total rate of reinforcing filler varies within a range ranging from 30 phr to 60 phr. According to a second embodiment, the total rate of reinforcing filler varies within a range ranging from more than 60 phr to 150 phr. The first embodiment is preferred to the second embodiment for use of the rubber composition in a tread having very low rolling resistance. Any of these ranges of total level of reinforcing filler can be applied to any of the embodiments of the invention.
Pour coupler la silice à l'élastomère diénique fortement saturé fonctionnel, on utilise de manière bien connue un agent de couplage (ou agent de liaison), un silane, au moins bifonctionnel destiné à assurer une connexion suffisante, de nature chimique et/ou physique, entre la silice et l'élastomère diénique. On utilise en particulier des organosilanes ou des polyorganosiloxanes au moins bifonctionnels. Par « bifonctionnel », on entend un composé possédant un premier groupe fonctionnel capable d'interagir avec la charge inorganique et un second groupe fonctionnel capable d'interagir avec l'élastomère diénique. Par exemple, un tel composé bifonctionnel peut comprendre un premier groupe fonctionnel comprenant un atome de silicium, le dit premier groupe fonctionnel étant apte à interagir avec les groupes hydroxyles d'une charge inorganique et un second groupe fonctionnel comprenant un atome de soufre, le dit second groupe fonctionnel étant apte à interagir avec l'élastomère diénique.
Préférentiellement, les organosilanes sont choisis dans le groupe constitué par les organosilanes polysulfurés (symétriques ou asymétriques) tels que le tétrasulfure de bis(3- triéthoxysilyl propyl), en abrégé TESPT commercialisé sous la dénomination « Si69 » par la société Evonik ou le disulfure de bis-(triéthoxysilylpropyle), en abrégé TESPD commercialisé sous la dénomination « Si75 » par la société Evonik, les polyorganosiloxanes, les mercaptosilanes, les mercaptosilanes bloqués, tels que l'octanethioate de S-(3- (triéthoxysilyl)propyle) commercialisé par la société Momentive sous la dénomination « NXT Silane », les oligomères ayant au moins un motif mercaptosilane bloqué, au moins un motif mercaptosilane et au moins un groupe hydroxyalcoxysilyle ou dia Icoxysilyle cyclique commercialisés par la société Momentive sous la dénomination « NXT-Z » . Bien entendu pourraient être également utilisés des mélanges des agents de couplage précédemment décrits. To couple the silica to the highly saturated functional diene elastomer, a coupling agent (or bonding agent), a silane, at least bifunctional intended to ensure a sufficient connection, of a chemical and/or physical nature, is used in a well-known manner. , between the silica and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By “bifunctional”, is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound can comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer. Preferably, the organosilanes are chosen from the group consisting of polysulphide organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilyl propyl) tetrasulphide, abbreviated as TESPT marketed under the name “Si69” by the company Evonik, or bis(3-triethoxysilyl propyl) tetrasulphide. bis-(triethoxysilylpropyl), abbreviated as TESPD marketed under the name "Si75" by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”, the oligomers having at least one blocked mercaptosilane unit, at least one mercaptosilane unit and at least one cyclic hydroxyalkoxysilyl or dia Icoxysilyl group marketed by the company Momentive under the name “NXT-Z”. Of course, mixtures of the coupling agents described above could also be used.
Les silanes polysulfurés, dits "symétriques" ou "asymétriques" selon leur structure particulière, sont par exemple décrits dans les demandes W003/002648 (ou US 2005/016651) et W003/002649 (ou US 2005/016650). Conviennent en particulier, sans que la définition ci-après soit limitative, des silanes polysulfurés répondant à la formule générale (6) Z - A1 - Sx - A1 - Z (6) dans laquelle : Polysulphurized silanes, called “symmetrical” or “asymmetrical” according to their particular structure, are for example described in applications W003/002648 (or US 2005/016651) and W003/002649 (or US 2005/016650). Suitable in particular, without the definition below being limiting, are polysulphide silanes corresponding to the general formula (6) Z - A 1 - Sx - A 1 - Z (6) in which:
- x est un entier de 2 à 8, de préférence de 2 à 5 ; - x is an integer from 2 to 8, preferably from 2 to 5;
- les symboles A1, identiques ou différents, représentent un radical hydrocarboné divalent (de préférence un groupement alkylène en Ci-Cisou un groupement arylène en Cg-C , plus particulièrement un alkylène en Ci-Cio, notamment en - the symbols A 1 , which are identical or different, represent a divalent hydrocarbon radical (preferably a Ci-Ci alkylene group or a Cg-C arylene group, more particularly a Ci-Cio alkylene, in particular in
C1-C4, en particulier le propylène) ; C1-C4, in particular propylene);
- les symboles Z, identiques ou différents, répondent à l'une des trois formules ci-après: - the Z symbols, identical or different, correspond to one of the three formulas below:
R1 R1 R2 R1 R1 R2
— Si— R1 ; — Si— R2 ; — Si— R2 2 R2 R2 dans lesquelles — Si— R1; — Si—R2; — If— R2 2 R2 R2 in which
- les radicaux R1, substitués ou non substitués, identiques ou différents entre eux, représentent un groupe alkyle en C1-C18, cycloalkyle en C5-C18OU aryle en Cg-Ci8 (de préférence des groupes alkyle en Ci-Cg, cyclohexyle ou phényle, notamment des groupes alkyle en C1-C4, plus particulièrement le méthyle et/ou l'éthyle), - the radicals R 1 , substituted or unsubstituted, identical or different from each other, represent a C1-C18 alkyl group, C5-C18 cycloalkyl group, or Cg-Ci8 aryl group (preferably Ci-Cg alkyl groups, cyclohexyl or phenyl , in particular C1-C4 alkyl groups, more particularly methyl and/or ethyl),
- les radicaux R2, substitués ou non substitués, identiques ou différents entre eux, représentent un groupe alcoxyle en Ci-Cisou cycloalcoxyle en C5-C18 (de préférence un groupe choisi parmi alcoxyles en Ci-Cs et cycloalcoxyles en C5-Cs, plus préférentiellement encore un groupe choisi parmi alcoxyles en C1-C4, en particulier méthoxyle et éthoxyle). - the radicals R 2 , substituted or unsubstituted, identical or different from each other, represent a Ci-Cis alkoxyl group or a C5-C18 cycloalkoxyl group (preferably a group chosen from Ci-Cs alkoxyls and C 5 -Cs cycloalkoxyls, more preferably still a group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
La dénomination en Cn-Cm qualifiant un groupe fait référence au nombre d'atomes de carbone constitutifs du groupe qui contient n à m atomes de carbone, n et m étant des nombres entiers avec m supérieur à n.
Dans le cas d'un mélange d'alcoxysilanes polysulfurés répondant à la formule (6) ci-dessus, notamment des mélanges usuels disponibles commercialement, la valeur moyenne des "x" est un nombre fractionnaire de préférence compris entre 2 et 5, plus préférentiellement proche de 4. Mais l'invention peut être aussi avantageusement mise en œuvre par exemple avec des alcoxysilanes disulfurés (x = 2). The denomination in C n -C m qualifying a group refers to the number of carbon atoms constituting the group which contains n to m carbon atoms, n and m being whole numbers with m greater than n. In the case of a mixture of polysulphurized alkoxysilanes corresponding to formula (6) above, in particular the usual commercially available mixtures, the average value of the "x" is a fractional number preferably between 2 and 5, more preferably close to 4. But the invention can also be advantageously implemented, for example with disulfurized alkoxysilanes (x=2).
A titre d'exemples de silanes polysulfurés, on citera plus particulièrement les polysulfurés (notamment disulfures, trisulfures ou tétrasulfures) de bis-(a lcoxyl(Ci-C4)-a I kyl(Ci-C4)silyl- alkyl(Ci-C4)), comme par exemple les polysulfurés de bis(3-triméthoxysilylpropyl) ou de bis(3-triéthoxysilyl propyl). Parmi ces composés, on utilise en particulier le tétrasulfure de bis(3-triéthoxysi lylpropyl), en abrégé TESPT, de formule [(CzHsO SifCHzhSzh ou le disulfure de bis-(triéthoxysilyl propyle), en abrégé TESPD, de formule [(CzHsO SifCHzhS . As examples of polysulphide silanes, mention will be made more particularly of the polysulphides (in particular disulphides, trisulphides or tetrasulphides) of bis-(alcoxyl(Ci-C4)-a I kyl(Ci-C4)silyl-alkyl(Ci-C4 )), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilyl propyl) polysulfides. Among these compounds, use is made in particular of bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(CzHsO SifCHzhSzh) or bis-(triethoxysilyl propyl) disulfide, abbreviated TESPD, of formula [(CzHsO SifCHzhS .
Les POSS (polyorganosiloxanes) bifonctionnels ou encore les polysulfurés d'hydroxysilane sont par exemple décrits dans les demandes de brevets WO 02/30939 (ou US 6,774,255), WO 02/31041 (ou US 2004/051210). Bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulphides are for example described in patent applications WO 02/30939 (or US 6,774,255), WO 02/31041 (or US 2004/051210).
Les mercaptosilanes, bloqués ou non, sont par exemple décrits dans les brevets ou demandes de brevet US 6 849 754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2010/072685 et WO 2008/055986. Mercaptosilanes, blocked or not, are for example described in US patents or patent applications 6,849,754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2010/072685 and WO 2008/055986.
Dans la composition de caoutchouc conforme à l'invention, le taux de l'agent de couplage silane est ajusté par l'homme du métier selon la structure chimique de l'agent de couplage, selon la surface spécifique de la silice utilisée dans la composition de caoutchouc et selon le taux de silice dans la composition de caoutchouc. Il est préférentiellement compris dans un domaine allant de 1 à 15 pce, plus préférentiellement de 1.5 à 10 pce, encore plus préférentiellement de 2 à 5 pce. In the rubber composition in accordance with the invention, the rate of the silane coupling agent is adjusted by the person skilled in the art according to the chemical structure of the coupling agent, according to the specific surface area of the silica used in the composition. of rubber and according to the level of silica in the rubber composition. It is preferentially included in a range ranging from 1 to 15 phr, more preferentially from 1.5 to 10 phr, even more preferentially from 2 to 5 phr.
L'hydrate d'un sel de thiosulfate (ou sel de thiosufate hydraté) est inorganique dans le sens où il ne contient pas d'atomes de carbone. Préférentiellement l'hydrate d'un sel de thiosulfate inorganique est un hydrate de thiosulfate d'un métal alcalin comme le lithium, le sodium, le potassium, ou d'un métal alcalino-terreux comme le magnésium, le calcium, le baryum. A ce titre conviennent par exemple BaSzCh H2O, K2S2O3 1.5 H2O, CaS2Û3 6H2O, MgS2Û3 6H2O, Na2S2O35H2O, U2S2O3 3H2 O. L'hydrate d'un sel de thiosulfate inorganique est plus préférentiellement le pentahydrate de thiosulfate de sodium, Na2S2Û3 5H2O. The hydrate of a thiosulfate salt (or hydrated thiosulfate salt) is inorganic in the sense that it does not contain carbon atoms. Preferably, the hydrate of an inorganic thiosulfate salt is a thiosulfate hydrate of an alkali metal such as lithium, sodium, potassium, or of an alkaline-earth metal such as magnesium, calcium, barium. BaSzCh H2O, K2S2O3 1.5 H2O, CaS2O3 6H2O, MgS2O3 6H2O, Na2S2O35H2O, U2S2O3 3H2O, for example, are suitable for this purpose. The hydrate of an inorganic thiosulfate salt is more preferably sodium thiosulfate pentahydrate, Na2S2O3 5H2O.
Le taux de l'hydrate d'un sel de thiosulfate inorganique dans la composition de caoutchouc est ajusté par l'homme du métier en fonction de l'impact recherché sur les propriétés d'hystérèse et le cas échéant sur les propriétés de rigidité, étant entendu qu'il est en général souhaitable d'en utiliser le moins possible. Son taux est préférentiellement supérieur à 0.5 pce, plus préférentiellement supérieur à 1 pce, et est préférentiellement inférieur à 10 pce, plus préférentiellement inférieur à 5 pce. Il varie avantageusement dans un domaine allant de 0.5 pce à 10 pce, plus avantageusement dans un domaine allant del pce à 5 pce.
La composition de caoutchouc conforme à l'invention a pour autre caractéristique essentielle de contenir un système de vulcanisation, c'est-à-dire un système de réticulation à base de soufre. Le soufre est typiquement apporté sous forme de soufre moléculaire ou d'un agent donneur de soufre, de préférence sous forme moléculaire. Le soufre sous forme moléculaire est aussi désigné sous l'appellation de soufre moléculaire. On entend par donneur de soufre tout composé qui libère des atomes de soufre, combinés ou pas sous la forme d'une chaîne polysulfure, aptes à s'insérer dans les chaînes polysulfures formés au cours de la vulcanisation et pontant les chaînes élastomères. Au système de vulcanisation viennent s'ajouter, incorporés au cours de la première phase non-productrice et/ou au cours de la phase productive, divers accélérateurs secondaires ou activateurs de vulcanisation connus tels qu'oxyde de zinc, acide stéarique, dérivés guanidiques (en particulier diphénylguanidine), etc. Le taux de soufre est de préférence compris entre 0.5 et 4 pce, celui de l'accélérateur primaire est de préférence compris entre 0.5 et 5 pce. Ces taux préférentiels peuvent s'appliquer à l'un quelconque des modes de réalisation de l'invention.The level of the hydrate of an inorganic thiosulphate salt in the rubber composition is adjusted by those skilled in the art according to the desired impact on the hysteresis properties and, where appropriate, on the stiffness properties, being understood that it is generally desirable to use as little as possible. Its content is preferably greater than 0.5 phr, more preferably greater than 1 phr, and is preferably less than 10 phr, more preferably less than 5 phr. It advantageously varies within a range ranging from 0.5 phr to 10 phr, more advantageously within a range ranging from del phr to 5 phr. The rubber composition in accordance with the invention has the other essential characteristic of containing a vulcanization system, that is to say a sulfur-based crosslinking system. The sulfur is typically provided in the form of molecular sulfur or a sulfur-donating agent, preferably in molecular form. Sulfur in molecular form is also referred to as molecular sulfur. By sulfur donor is meant any compound which releases sulfur atoms, combined or not in the form of a polysulphide chain, capable of being inserted into the polysulphide chains formed during vulcanization and bridging the elastomer chains. Added to the vulcanization system, incorporated during the first non-productive phase and/or during the productive phase, are various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives ( especially diphenylguanidine), etc. The sulfur content is preferably between 0.5 and 4 phr, that of the primary accelerator is preferably between 0.5 and 5 phr. These preferential rates can apply to any of the embodiments of the invention.
On peut utiliser comme accélérateur de vulcanisation (primaire ou secondaire) tout composé susceptible d'agir comme accélérateur de vulcanisation des élastomères diéniques en présence de soufre, notamment des accélérateurs du type thiazoles ainsi que leurs dérivés, des accélérateurs de types sulfénamides pour ce qui est des accélérateurs primaires, du type thiurames, dithiocarbamates, dithiophosphates, thiourées et xanthates pour ce qui est des accélérateurs secondaires. A titre d'exemples d'accélérateurs primaires, on peut citer notamment les composés sulfénamides tels que la N-cyclohexyl-2-benzothiazyle sulfénamide ("CBS"), la N,N-dicyclohexyl-2-benzothiazyle sulfénamide ("DCBS"), la N-ter- butyl-2-benzothiazyle sulfénamide ("TBBS"), et les mélanges de ces composés. L'accélérateur primaire est préférentiellement une sulfénamide, plus préférentiellement la N-cyclohexyl-2-benzothiazyle sulfénamide. A titre d'exemple d'accélérateurs secondaires, on peut citer notamment les disulfures de thiurame tels que le disulfure de tétraéthylthiurame, le disulfure de tétrabutylthiurame ("TBTD"), le disulfure de tétrabenzylthiurame ("TBZTD") et les mélanges de ces composés. L'accélérateur secondaire est préférentiellement un disulfure de thiurame, plus préférentiellement le disulfure de tétrabenzylthiurame. It is possible to use as vulcanization accelerator (primary or secondary) any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide type with regard to primary accelerators, of the thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthates type as far as secondary accelerators are concerned. As examples of primary accelerators, mention may in particular be made of sulfenamide compounds such as N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS") , N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), and mixtures of these compounds. The primary accelerator is preferably a sulfenamide, more preferably N-cyclohexyl-2-benzothiazyl sulfenamide. By way of example of secondary accelerators, mention may in particular be made of thiuram disulphides such as tetraethylthiuram disulphide, tetrabutylthiuram disulphide ("TBTD"), tetrabenzylthiuram disulphide ("TBZTD") and mixtures of these compounds . The secondary accelerator is preferably a thiuram disulphide, more preferably tetrabenzylthiuram disulphide.
La vulcanisation est conduite de manière connue à une température généralement comprise entre 130°C et 200°C, pendant un temps suffisant qui peut varier par exemple entre 5 et 90 min en fonction notamment de la température de cuisson, du système de vulcanisation adopté et de la cinétique de vulcanisation de la composition considérée. The vulcanization is carried out in a known manner at a temperature generally between 130° C. and 200° C., for a sufficient time which can vary for example between 5 and 90 min depending in particular on the curing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition under consideration.
La composition de caoutchouc conforme à l'invention peut comporter également tout ou partie des additifs usuels habituellement utilisés dans les compositions d'élastomères destinées à la fabrication de pneumatiques, notamment des pigments, des agents de protection tels que cires anti-ozone, anti-ozonants chimiques, anti-oxydants, des plastifiants tels que des huiles ou des résines plastifiantes.
La composition de caoutchouc, avant vulcanisation, peut être fabriquée dans des mélangeurs appropriés, en utilisant deux phases de préparation successives selon une procédure bien connue de l'homme du métier : une première phase de travail ou malaxage thermo-mécanique (parfois qualifiée de phase "non-productive") à haute température, jusqu'à une température maximale comprise entre 110°C et 190°C, de préférence entre 130°C et 180°C, suivie d'une seconde phase de travail mécanique (parfois qualifiée de phase "productive") à plus basse température, typiquement inférieure à 110°C, par exemple entre 40°C et 100°C, phase de finition au cours de laquelle est incorporé le soufre ou le donneur de soufre et l'accélérateur de vulcanisation. The rubber composition in accordance with the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, in particular pigments, protective agents such as anti-ozone waxes, anti- chemical ozonants, anti-oxidants, plasticizers such as plasticizing oils or resins. The rubber composition, before vulcanization, can be manufactured in suitable mixers, using two successive preparation phases according to a procedure well known to those skilled in the art: a first working phase or thermo-mechanical mixing (sometimes referred to as "non-productive") at high temperature, up to a maximum temperature between 110°C and 190°C, preferably between 130°C and 180°C, followed by a second phase of mechanical work (sometimes called "productive" phase) at lower temperature, typically below 110°C, for example between 40°C and 100°C, finishing phase during which the sulfur or the sulfur donor and the vulcanization accelerator are incorporated .
A titre d'exemple, la première phase (non-productive) est conduite en une seule étape thermomécanique au cours de laquelle on introduit, dans un mélangeur approprié tel qu'un mélangeur interne usuel, tous les constituants nécessaires, les éventuels agents de mise en œuvre complémentaires et autres additifs divers, à l'exception du système de vulcanisation. La durée totale du malaxage, dans cette phase non-productive, est de préférence comprise entre 1 et 15 min. Après refroidissement du mélange ainsi obtenu au cours de la première phase non-productive, on incorpore alors le système de vulcanisation à basse température, généralement dans un mélangeur externe tel qu'un mélangeur à cylindres, le tout est alors mélangé (phase productive) pendant quelques minutes, par exemple entre 2 et 15 min.By way of example, the first phase (non-productive) is carried out in a single thermomechanical step during which all the necessary constituents, any setting agents implements and other miscellaneous additives, with the exception of the vulcanization system. The total mixing time, in this non-productive phase, is preferably between 1 and 15 min. After cooling the mixture thus obtained during the first non-productive phase, the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roller mixer, the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
Selon une première variante du procédé de préparation de la composition de caoutchouc, dans le mélangeur interne de la phase non productive, il est procédé à la préparation de l'élastomère diénique fortement saturé fonctionnel par modification d'un élastomère diénique fortement saturé de départ. Typiquement, un agent de modification tel que décrit précédemment est incorporé à un élastomère diénique fortement saturé de départ par un malaxage thermomécanique dans un mélangeur interne avant l'introduction des autres constituants de la composition de caoutchouc. Le temps de contact entre l'élastomère diénique fortement saturé de départ et l'agent de modification malaxés thermomécaniquement est ajusté en fonction des conditions du malaxage thermomécanique, notamment en fonction de la température. Plus la température du malaxage est élevée, plus ce temps de contact est court. Typiquement il est de 1 à 5 minutes pour une température de 100 à 130°C. According to a first variant of the process for preparing the rubber composition, in the internal mixer of the non-productive phase, the functional highly saturated diene elastomer is prepared by modifying a starting highly saturated diene elastomer. Typically, a modifying agent as described above is incorporated into a starting highly saturated diene elastomer by thermomechanical mixing in an internal mixer before the introduction of the other constituents of the rubber composition. The contact time between the starting highly saturated diene elastomer and the thermomechanically kneaded modifying agent is adjusted according to the conditions of the thermomechanical kneading, in particular according to the temperature. The higher the mixing temperature, the shorter this contact time. Typically it is 1 to 5 minutes for a temperature of 100 to 130°C.
Selon une deuxième variante, la phase non-productive est précédée d'une étape au cours de laquelle est préparé l'élastomère diénique fortement saturé fonctionnel sur un mélangeur externe. Typiquement, un agent de modification tel que décrit précédemment est incorporé à un élastomère diénique fortement saturé de départ sur un mélangeur à cylindres (dit mélangeur externe) pour former un mélange qui est homogénéisé par exemple par plusieurs passages sur les cylindres. Le mélange subit un traitement thermique pour greffer l'agent de modification sur l'élastomère diénique, par exemple dans une presse à une température d'au moins 100°C, avant d'être introduit dans le mélangeur interne pour procéder à la phase
non productive avec l'incorporation des autres constituants de la composition de caoutchouc. According to a second variant, the non-productive phase is preceded by a step during which the functional highly saturated diene elastomer is prepared on an external mixer. Typically, a modifying agent as described above is incorporated into a starting highly saturated diene elastomer on a roller mixer (known as an external mixer) to form a mixture which is homogenized for example by several passages over the rollers. The mixture undergoes a heat treatment to graft the modifying agent onto the diene elastomer, for example in a press at a temperature of at least 100° C., before being introduced into the internal mixer to proceed to the phase non-productive with the incorporation of the other constituents of the rubber composition.
La composition de caoutchouc peut être calandrée ou extrudée sous la forme d'une feuille ou d'une plaque, notamment pour une caractérisation au laboratoire, ou encore sous la forme d'un semi-fini (ou profilé) de caoutchouc utilisable dans un pneumatique. The rubber composition can be calendered or extruded in the form of a sheet or a plate, in particular for characterization in the laboratory, or else in the form of a semi-finished (or profiled) rubber that can be used in a tire. .
La composition peut être soit à l'état cru (avant réticulation ou vulcanisation), soit à l'état cuit après réticulation ou vulcanisation). Elle peut constituer tout ou partie d'un article semi- fini, en particulier destiné à être utilisé dans un bandage pneumatique ou non pneumatique qui comporte une bande de roulement, notamment dans la bande de roulement du bandage. The composition can be either in the raw state (before crosslinking or vulcanization), or in the cured state after crosslinking or vulcanization). It may constitute all or part of a semi-finished article, in particular intended for use in a pneumatic or non-pneumatic tire which comprises a tread, in particular in the tread of the tire.
En résumé, l'invention est mise en œuvre avantageusement selon l'un quelconque des modes de réalisation suivants 1 à 40 : In summary, the invention is advantageously implemented according to any one of the following embodiments 1 to 40:
Mode 1 : Composition de caoutchouc qui comprend : un élastomère diénique fortement saturé fonctionnel, copolymère qui contient des unités éthylène, des unités d'un 1,3-diène et qui porte des groupes pendants contenant une fonction imidazole N-substituée, les unités éthylène représentant plus de 50% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnelMode 1: Rubber composition which comprises: a functional highly saturated diene elastomer, copolymer which contains ethylene units, units of a 1,3-diene and which carries pendant groups containing an N-substituted imidazole function, the ethylene units representing more than 50 mol% of the constituent repeating units of the functional highly saturated diene elastomer
- un système de vulcanisation, - a vulcanization system,
- une charge renforçante qui contient une silice, - a reinforcing filler which contains a silica,
- et un hydrate d'un sel de thiosulfate inorganique. - and a hydrate of an inorganic thiosulfate salt.
Mode 2 : Composition de caoutchouc selon le mode 1 dans laquelle l'élastomère diénique fortement saturé fonctionnel est un copolymère modifié d'éthylène et d'un 1,3-diène. Mode 2: A rubber composition according to Mode 1 wherein the functional highly saturated diene elastomer is a modified copolymer of ethylene and a 1,3-diene.
Mode 3 : Composition de caoutchouc selon le mode 1 ou 2 dans laquelle le 1,3-diène est leMode 3: Rubber composition according to mode 1 or 2 in which the 1,3-diene is the
1.3-butadiène ou un mélange de 1,3-diènes dont un est le 1,3-butadiène. 1,3-butadiene or a mixture of 1,3-dienes one of which is 1,3-butadiene.
Mode 4 : Composition de caoutchouc selon l'un quelconque des modes 1 à 3 dans laquelle leMode 4: Rubber composition according to any one of modes 1 to 3 in which the
1.3-diène est le 1,3-butadiène. 1.3-diene is 1,3-butadiene.
Mode 5 : Composition de caoutchouc selon l'un quelconque des modes 1 à 4 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au moins 60% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 5: A rubber composition according to any one of modes 1 to 4 in which the ethylene units in the functional highly saturated diene elastomer represent at least 60% by mole of the constituent repeating units of the functional highly saturated diene elastomer.
Mode 6 : Composition de caoutchouc selon l'un quelconque des modes 1 à 5 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au moins 65% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel.
Mode 7 : Composition de caoutchouc selon l'un quelconque des modes 1 à 6 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au moins 70% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 6: Rubber composition according to any one of Modes 1 to 5 in which the ethylene units in the functional highly saturated diene elastomer represent at least 65% by mole of the repeating units constituting the functional highly saturated diene elastomer. Mode 7: Rubber composition according to any one of Modes 1 to 6 in which the ethylene units in the functional highly saturated diene elastomer represent at least 70% by mole of the constituent repeating units of the functional highly saturated diene elastomer.
Mode 8 : Composition de caoutchouc selon l'un quelconque des modes 1 à 7 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au plus 90% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 8: Rubber composition according to any one of Modes 1 to 7 in which the ethylene units in the functional highly saturated diene elastomer represent at most 90% by mole of the repeating units constituting the functional highly saturated diene elastomer.
Mode 9 : Composition de caoutchouc selon l'un quelconque des modes 1 à 8 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au plus 85% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 9: Rubber composition according to any one of Modes 1 to 8 in which the ethylene units in the functional highly saturated diene elastomer represent at most 85% by mole of the repeating units constituting the functional highly saturated diene elastomer.
Mode 10 : Composition de caoutchouc selon l'un quelconque des modes 1 à 9 dans laquelle les unités éthylène dans l'élastomère diénique fortement saturé fonctionnel représentent au plus 80% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 10: Rubber composition according to any one of Modes 1 to 9 in which the ethylene units in the functional highly saturated diene elastomer represent at most 80% by mole of the repeating units constituting the functional highly saturated diene elastomer.
Mode 11 : Composition de caoutchouc selon l'un quelconque des modes 1 à 10 dans laquelle l'élastomère diénique fortement saturé fonctionnel est un copolymère statistique. Mode 11: Rubber composition according to any one of modes 1 to 10 in which the functional highly saturated diene elastomer is a random copolymer.
Mode 12 : Composition de caoutchouc selon l'un quelconque des modes 1 à 11 dans laquelle la fonction imidazole N-substituée est un groupe de formule (1) dans laquelle le symbole Yi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Y? désigne un rattachement à une unité diénique de l'élastomère diénique fortement saturé fonctionnel, les symboles Y3 et Y4 sont chacun un atome d'hydrogène.
Mode 12: Rubber composition according to any one of modes 1 to 11 in which the N-substituted imidazole function is a group of formula (1) in which the symbol Yi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Y? denotes an attachment to a diene unit of the highly saturated functional diene elastomer, the symbols Y3 and Y4 are each a hydrogen atom.
Mode 13 : Composition de caoutchouc selon le mode 12 dans laquelle l'alkyle représenté par Yi contient 1 à 3 atomes de carbone. Mode 13: Rubber composition according to mode 12 in which the alkyl represented by Yi contains 1 to 3 carbon atoms.
Mode 14 : Composition de caoutchouc selon le mode 12 ou 13 dans laquelle l'alkyle représenté par Yi est méthyle. Mode 14: Rubber composition according to mode 12 or 13 in which the alkyl represented by Yi is methyl.
Mode 15 : Composition de caoutchouc selon l'un quelconque des modes 12 à 14 dans laquelle l'unité rattachée à la fonction imidazole N-substituée est une unité diénique
modifiée par réaction d'un agent de modification contenant un groupe réactif vis à vis d'unités diéniques. Mode 15: Rubber composition according to any one of modes 12 to 14 in which the unit attached to the N-substituted imidazole function is a diene unit modified by reacting a modifying agent containing a group reactive with diene units.
Mode 16 : Composition de caoutchouc selon le mode 15 dans laquelle l'agent de modification est un composé 1,3-dipolaire. Mode 16: A rubber composition according to Mode 15 wherein the modifier is a 1,3-dipolar compound.
Mode 17 : Composition de caoutchouc selon le mode 15 ou 16 dans laquelle l'agent de modification est un oxyde de nitrile, une nitrone ou un nitrile imine. Mode 17: Rubber composition according to mode 15 or 16 in which the modifying agent is a nitrile oxide, a nitrone or a nitrile imine.
Mode 18 : Composition de caoutchouc selon l'un quelconque des modes 15 à 17 dans laquelle l'agent de modification est un composé 1,3-dipolaire qui est un monooxyde de nitrile aromatique, composé comprenant un noyau benzénique substitué par un dipôle oxyde de nitrile et par un groupe contenant une fonction imidazole de formule (2)
dans laquelle le symbole Zi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Z2 désigne un rattachement au groupe réactif, les symboles Z3 et Z4 sont chacun un atome d'hydrogène. Mode 18: Rubber composition according to any one of modes 15 to 17 in which the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, compound comprising a benzene ring substituted by a dipole nitrile and by a group containing an imidazole function of formula (2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 denotes an attachment to the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
Mode 19 : Composition de caoutchouc selon le mode 18 dans laquelle le composé 1,3- dipolaire contient un motif de formule (3) dans laquelle Ri représente le dipôle oxyde de nitrile, un des symboles R2 à Re représente un groupe saturé ayant 1 à 6 atomes de carbone et lié de façon covalente à l'un des atomes d'azote du cycle à 5 membres de la fonction imidazole de formule (2), les autres symboles, identiques ou différents, représentant un atome d'hydrogène ou un substituant.
Mode 19: Rubber composition according to mode 18 in which the 1,3-dipolar compound contains a unit of formula (3) in which Ri represents the nitrile oxide dipole, one of the symbols R2 to Re represents a saturated group having 1 to 6 carbon atoms and covalently bonded to one of the nitrogen atoms of the 5-membered ring of the imidazole function of formula (2), the other symbols, identical or different, representing a hydrogen atom or a substituent .
Mode 20 : Composition de caoutchouc selon le mode 19 dans laquelle le groupe saturé est un alcanediyle. Mode 20: Rubber composition according to mode 19 in which the saturated group is an alkanediyl.
Mode 21 : Composition de caoutchouc selon le mode 19 ou 20 dans laquelle le groupe saturé est un alcanediyle ayant 1 à 3 atomes de carbone. Mode 21: Rubber composition according to mode 19 or 20 in which the saturated group is an alkanediyl having 1 to 3 carbon atoms.
Mode 22 : Composition de caoutchouc selon l'un quelconque des modes 19 à 21 dans laquelle le groupe saturé est méthanediyle.
Mode 23 : Composition de caoutchouc selon l'un quelconque des modes 19 à 22 dans laquelle le substituant est un alkyle ayant 1 à 3 atomes de carbone. Mode 22: A rubber composition according to any of Modes 19 to 21 wherein the saturated group is methanediyl. Mode 23: A rubber composition according to any of Modes 19 to 22 wherein the substituent is an alkyl having 1 to 3 carbon atoms.
Mode 24 : Composition de caoutchouc selon l'un quelconque des modes 19 à 23 dans laquelle le substituant est méthyle ou éthyle. Mode 24: A rubber composition according to any of Modes 19 to 23 wherein the substituent is methyl or ethyl.
Mode 25 : Composition de caoutchouc selon l'un quelconque des modes 19 à 24 dans laquelle Fù et Re sont différents d'un atome d'hydrogène. Mode 25: A rubber composition according to any one of Modes 19 to 24 in which Fu and Re are different from a hydrogen atom.
Mode 26 : Composition de caoutchouc selon l'un quelconque des modes 19 à 25 dans laquelle R2, R4 et Re sont tous différents d'un atome d'hydrogène et sont identiques. Mode 26: Rubber composition according to any one of modes 19 to 25 in which R2, R4 and Re are all different from a hydrogen atom and are identical.
Mode 27 : Composition de caoutchouc selon l'un quelconque des modes 1 à 26 dans laquelle le taux de la fonction imidazole dans l'élastomère diénique fortement saturé fonctionnel est supérieur à 0% et inférieur à 3% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel. Mode 27: Rubber composition according to any one of modes 1 to 26 in which the level of the imidazole function in the functional highly saturated diene elastomer is greater than 0% and less than 3% by mole of the repeating units constituting the functional highly saturated diene elastomer.
Mode 28 : Composition de caoutchouc selon l'un quelconque des modes 1 à 27 dans laquelle le taux de l'élastomère diénique fortement saturé fonctionnel est d'au moins 50 parties en poids pour cent parties d'élastomère de la composition de caoutchouc (pce). Mode 28: Rubber composition according to any one of modes 1 to 27 in which the content of the functional highly saturated diene elastomer is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr ).
Mode 29 : Composition de caoutchouc selon l'un quelconque des modes 1 à 28 dans laquelle le taux de l'élastomère diénique fortement saturé fonctionnel varie dans un domaine allant de 80 à 100 pce. Mode 29: Rubber composition according to any one of modes 1 to 28 in which the content of the highly saturated functional diene elastomer varies within a range ranging from 80 to 100 phr.
Mode 30 : Composition de caoutchouc selon l'un quelconque des modes 1 à 29 dans laquelle le taux total de charge renforçante varie dans un domaine allant de 30 à 150 pce. Mode 30: Rubber composition according to any one of modes 1 to 29 in which the total content of reinforcing filler varies within a range ranging from 30 to 150 phr.
Mode 31 : Composition de caoutchouc selon l'un quelconque des modes 1 à 30 dans laquelle le taux total de charge renforçante varie dans un domaine allant de 30 pce à 60 pce. Mode 31: Rubber composition according to any one of modes 1 to 30 in which the total content of reinforcing filler varies within a range ranging from 30 phr to 60 phr.
Mode 32 : Composition de caoutchouc selon l'un quelconque des modes 1 à 31 dans laquelle la silice représente plus de 50% en masse de la charge renforçante. Mode 32: Rubber composition according to any one of modes 1 to 31 in which the silica represents more than 50% by mass of the reinforcing filler.
Mode 33 : Composition de caoutchouc selon l'un quelconque des modes 1 à 32 dans laquelle la silice représente plus de 85% en masse de la charge renforçante. Mode 33: Rubber composition according to any one of modes 1 to 32 in which the silica represents more than 85% by mass of the reinforcing filler.
Mode 34 : Composition de caoutchouc selon l'un quelconque des modes 1 à 33 dans laquelle l'hydrate d'un sel de thiosulfate inorganique est un hydrate de thiosulfate d'un métal alcalin ou d'un métal alcalino-terreux. Mode 34: A rubber composition according to any of Modes 1 to 33 wherein the inorganic thiosulfate salt hydrate is an alkali metal or alkaline earth metal thiosulfate hydrate.
Mode 35 : Composition de caoutchouc selon l'un quelconque des modes 1 à 34 dans laquelle l'hydrate d'un sel de thiosulfate inorganique est le pentahydrate de thiosulfate de sodium, NazSzOî 5H2O.
Mode 36 : Composition de caoutchouc selon l'un quelconque des modes 1 à 35 dans laquelle le taux de l'hydrate d'un sel de thiosulfate inorganique est supérieur à 0.5 pce et est inférieur à 10 pce. Mode 35: A rubber composition according to any of Modes 1 to 34 wherein the hydrate of an inorganic thiosulfate salt is sodium thiosulfate pentahydrate, NazSzO1 5H2O. Mode 36: Rubber composition according to any one of Modes 1 to 35 in which the level of the hydrate of an inorganic thiosulfate salt is greater than 0.5 phr and is less than 10 phr.
Mode 37 : Composition de caoutchouc selon l'un quelconque des modes 1 à 36 dans laquelle le taux de l'hydrate d'un sel de thiosulfate inorganique est supérieur à 1 pce. Mode 37: Rubber composition according to any one of modes 1 to 36 in which the level of the hydrate of an inorganic thiosulphate salt is greater than 1 phr.
Mode 38 : Composition de caoutchouc selon l'un quelconque des modes 1 à 37 dans laquelle le taux de l'hydrate d'un sel de thiosulfate inorganique est inférieur à 5 pce. Mode 38: Rubber composition according to any one of modes 1 to 37 in which the level of the hydrate of an inorganic thiosulphate salt is less than 5 phr.
Mode 39 : Composition de caoutchouc selon l'un quelconque des modes 1 à 38, laquelle composition contient un agent de couplage silane. Mode 39: A rubber composition according to any of modes 1 to 38, which composition contains a silane coupling agent.
Mode 40 : Pneumatique qui comprend une composition de caoutchouc définie à l'un quelconque des modes 1 à 39, préférentiellement dans sa bande de roulement. Mode 40: Tire which comprises a rubber composition defined in any one of modes 1 to 39, preferably in its tread.
Les caractéristiques précitées de la présente invention, ainsi que d'autres, seront mieux comprises à la lecture de la description suivante de plusieurs exemples de réalisation de l'invention, donnés à titre illustratif et non limitatif. The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of non-limiting illustration.
Exemples Examples
Propriétés dynamiques Dynamic properties
Les propriétés dynamiques G* et tanô(max) sont mesurées sur un viscoanalyseur (Metravib VA4000), selon la norme ASTM D 5992-96. On enregistre la réponse d'un échantillon de composition vulcanisée (éprouvette cylindrique de 4 mm d'épaisseur et de 400 mm2 de section), soumis à une sollicitation sinusoïdale en cisaillement simple alterné, à la fréquence de 10Hz à 60°C. On effectue un balayage en amplitude de déformation de 0.1% à 100% (cycle aller), puis de 100% à 0.1% (cycle retour) et on mesure le facteur de perte tanô. Pour le cycle retour, on indique la valeur maximale de tanô observée, noté tanô(max). The dynamic properties G* and tanô(max) are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical test piece 4 mm thick and 400 mm 2 in section) subjected to a sinusoidal stress in alternating simple shearing, at a frequency of 10Hz at 60°C, is recorded. A deformation amplitude scan is performed from 0.1% to 100% (go cycle), then from 100% to 0.1% (return cycle) and the loss factor tanô is measured. For the return cycle, the maximum value of tanô observed, denoted tanô(max), is indicated.
Les résultats sont exprimés en base 100 par rapport à un témoin. Une valeur supérieure à celle du témoin, arbitrairement fixée à 100, indique une grandeur mesurée supérieure à celle du témoin. The results are expressed in base 100 relative to a control. A value greater than that of the control, arbitrarily set at 100, indicates a quantity measured greater than that of the control.
Propriétés de vulcanisation : Vulcanization properties:
Les mesures sont effectuées à 150°C avec un rhéomètre à chambre oscillante, selon la norme DIN 53529 - partie 3 (juin 1983). L'évolution du couple rhéométrique en fonction du temps décrit l'évolution de la rigidification de la composition par suite de la réaction vulcanisation. Les mesures sont traitées selon la norme DIN 53529 - partie 2 (mars 1983). Ti est le délai d'induction, c'est-à-dire le temps nécessaire au début de la réaction de vulcanisation. Ta (par exemple T95) est le temps nécessaire pour atteindre une conversion de a%, c'est-à-dire a% (par exemple 95%) de l'écart entre les couples minimum et maximum.The measurements are carried out at 150° C. with an oscillating chamber rheometer, according to standard DIN 53529 - part 3 (June 1983). The evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to DIN 53529 - part 2 (March 1983). Ti is the induction time, ie the time required for the start of the vulcanization reaction. Ta (for example T95) is the time required to reach a conversion of a%, that is to say a% (for example 95%) of the difference between the minimum and maximum torques.
Microstructure des élastomères par analyse de résonance magnétique nucléaire (RM Microstructure of elastomers by nuclear magnetic resonance (MR) analysis
La microstructure des élastomères est déterminée par analyse RMN 1H, suppléée par
l'analyse RMN 13C lorsque la résolution des spectres RMN du 1H ne permet pas l'attribution et la quantification de toutes les espèces. Les mesures sont réalisées à l'aide d'un spectromètre RMN BRUKER 500MHz à des fréquences de 500.43 MHz pour l'observation du proton et 125.83MHz pour l'observation du carbone. The microstructure of the elastomers is determined by 1 H NMR analysis, supplemented by 13 C NMR analysis when the resolution of the 1 H NMR spectra does not allow the attribution and quantification of all the species. The measurements are carried out using a BRUKER 500 MHz NMR spectrometer at frequencies of 500.43 MHz for the observation of the proton and 125.83 MHz for the observation of the carbon.
Pour les élastomères non solubles mais ayant la capacité de gonfler dans un solvant, est utilisée une sonde HRMAS 4mm z-grad permettant d'observer le proton et le carbone en mode découplé du proton. Les spectres sont acquis à des vitesses de rotation de 4000Hz à 5000Hz. For elastomers that are not soluble but have the ability to swell in a solvent, a 4mm z-grad HRMAS probe is used to observe the proton and carbon in proton-decoupled mode. The spectra are acquired at rotation speeds of 4000Hz to 5000Hz.
Pour les mesures sur des élastomères solubles, est utilisée une sonde RMN liquide permettant d'observer le proton et le carbone en mode découplé du proton. For measurements on soluble elastomers, a liquid NMR probe is used to observe the proton and carbon in proton-decoupled mode.
La préparation des échantillons non solubles est faite dans des rotors remplis avec le matériau analysé et un solvant deutéré permettant le gonflement, en général du chloroforme deutéré (CDCI3). Le solvant utilisé doit toujours être deutéré et sa nature chimique peut être adaptée par l'homme du métier. Les quantités de matériau utilisées sont ajustées de façon à obtenir des spectres avec une sensibilité et une résolution suffisante. Les échantillons solubles sont mis en solution dans un solvant deutéré (environ 25mg d'élastomère dans lmL), en général du chloroforme deutéré (CDCI3). Le solvant ou coupage de solvant utilisé doit toujours être deutéré et sa nature chimique peut être adaptée par l'homme du métier. The preparation of insoluble samples is done in rotors filled with the material analyzed and a deuterated solvent allowing swelling, generally deuterated chloroform (CDCI3). The solvent used must always be deuterated and its chemical nature can be adapted by those skilled in the art. The quantities of material used are adjusted so as to obtain spectra with sufficient sensitivity and resolution. Soluble samples are dissolved in a deuterated solvent (approximately 25mg of elastomer in 1 mL), generally deuterated chloroform (CDCI3). The solvent or solvent mixture used must always be deuterated and its chemical nature can be adapted by those skilled in the art.
Dans les deux cas (échantillon soluble ou échantillon gonflé): In both cases (soluble sample or swollen sample):
Pour la RMN du proton est utilisée une séquence simple impulsion de 30°. La fenêtre spectrale est réglée pour observer l'ensemble des raies de résonances appartenant aux molécules analysées. Le nombre d'accumulation est réglé afin d'obtenir un rapport signal sur bruit suffisant pour la quantification de chaque motif. Le délai de recyclage entre chaque impulsion est adapté pour obtenir une mesure quantitative. For proton NMR, a single 30° pulse sequence is used. The spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules. The number of accumulations is adjusted in order to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling time between each pulse is adapted to obtain a quantitative measurement.
Pour la RMN du carbone est utilisée une séquence simple impulsion 30° avec un découplage du proton uniquement pendant l'acquisition pour éviter les effets « Overhauser Nucléaire » (NOE) et rester quantitatif. La fenêtre spectrale est réglée pour observer l'ensemble des raies de résonances appartenant aux molécules analysées. Le nombre d'accumulation est réglé afin d'obtenir un rapport signal sur bruit suffisant pour la quantification de chaque motif. Le délai de recyclage entre chaque impulsion est adapté pour obtenir une mesure quantitative. For carbon NMR, a simple 30° pulse sequence is used with proton decoupling only during acquisition to avoid “Nuclear Overhauser” (NOE) effects and remain quantitative. The spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules. The number of accumulations is adjusted in order to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling time between each pulse is adapted to obtain a quantitative measurement.
Les mesures de RMN sont réalisées à 25°C. The NMR measurements are carried out at 25°C.
Température de transition vitreuse des polymères : Glass transition temperature of polymers:
La température de transition vitreuse (Tg) est mesurée au moyen d'un calorimètre différentiel ("Differential Scanning Calorimeter") selon la norme ASTM D3418 (1999). The glass transition temperature (Tg) is measured by means of a differential calorimeter (“Differential Scanning Calorimeter”) according to standard ASTM D3418 (1999).
Viscosité Mooney : Mooney Viscosity:
La viscosité Mooney est mesurée à l'aide d'un consistomètre oscillant tel que décrit dans la norme ASTM D1646 (1999). La mesure se fait selon le principe suivant : l'échantillon analysé à l'état cru (i.e., avant cuisson) est moulé (mis en forme) dans une enceinte cylindrique
chauffée à une température donnée (100°C). Après 1 minute de préchauffage, le rotor tourne au sein de l'éprouvette à 2 tours/minute et on mesure le couple utile pour entretenir ce mouvement après 4 minutes de rotation. La viscosité Mooney (ML) est exprimée en "unité Mooney" (UM, avec 1 UM=0.83 Newton. mètre). The Mooney viscosity is measured using an oscillating consistometer as described in standard ASTM D1646 (1999). The measurement is made according to the following principle: the sample analyzed in the raw state (ie, before cooking) is molded (shaped) in a cylindrical enclosure heated to a given temperature (100°C). After 1 minute of preheating, the rotor rotates within the specimen at 2 revolutions/minute and the useful torque is measured to maintain this movement after 4 minutes of rotation. The Mooney viscosity (ML) is expressed in "Mooney units" (UM, with 1 UM=0.83 Newton. meter).
Préparation d'un élastomère diénique fortement saturé de départ, El : Preparation of a starting highly saturated diene elastomer, El:
L'élastomère El est un élastomère diénique fortement saturé, copolymère d'éthylène et de 1,3-butadiène préparé selon le mode opératoire suivant : Elastomer El is a highly saturated diene elastomer, a copolymer of ethylene and 1,3-butadiene prepared according to the following procedure:
Dans un réacteur de 70 L contenant du méthylcyclohexane (64 L), de l'éthylène (5600 g) et du 1,3-butadiène (2948 g), on ajoute du butyloctylmagnésium (BOMAG) en solution dans le méthylcyclohexane et le système catalytique. Le ratio Mg/Nd est de 6.2. Le volume de système catalytique introduit est de 840 mL, la concentration de la solution du système catalytique en Nd étant 0.0065 M. La température de réaction est régulée à une température de 80°C et la réaction de polymérisation démarre. La réaction de polymérisation se déroule à une pression constante de 8.3 bars. Le réacteur est alimenté tout au long de la polymérisation en éthylène et en 1,3-butadiène dans les proportions molaires . La réaction de polymérisation est stoppée par refroidissement, dégazage du réacteur et ajout d'éthanol. Un anti-oxydant est ajouté à la solution de polymère. Le copolymère est récupéré après un stripping à la vapeur d'eau et séchage jusqu'à masse constante. La durée de polymérisation est de 225 minutes. La masse pesée (6.206 kg) permet de déterminer l'activité catalytique moyenne du système catalytique exprimée en kilogramme de polymère synthétisé par mole de métal néodyme et par heure (kg/mol.h). Le copolymère possède une valeur de ML égale à 62. In a 70 L reactor containing methylcyclohexane (64 L), ethylene (5600 g) and 1,3-butadiene (2948 g), butyloctylmagnesium (BOMAG) is added in solution in methylcyclohexane and the catalytic system . The Mg/Nd ratio is 6.2. The volume of catalytic system introduced is 840 mL, the concentration of the solution of the catalytic system in Nd being 0.0065 M. The reaction temperature is regulated at a temperature of 80° C. and the polymerization reaction starts. The polymerization reaction takes place at a constant pressure of 8.3 bars. The reactor is fed throughout the polymerization with ethylene and 1,3-butadiene in molar proportions. The polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered after steam stripping and drying to constant mass. The polymerization time is 225 minutes. The weighed mass (6.206 kg) makes it possible to determine the average catalytic activity of the catalytic system expressed in kilogram of polymer synthesized per mole of neodymium metal and per hour (kg/mol.h). The copolymer has an ML value of 62.
Le système catalytique est un système catalytique préformé. Il est préparé dans le méthylcyclohexane à partir d'un métallocène, le [Me2Si(Flu)2Nd(p-BH4)2Li(TH F)] à 0.0065 mol/L, d'un co-catalyseur, le butyloctylmagnésium (BOMAG) dont le ratio molaire BOMAG/Nd est égal à 2.2, et d'un monomère de préformation, le 1,3-butadiène dont le ratio molaire 1,3-butadiène/Nd est égal à 90. Le milieu est chauffé à 80°C sur une durée de 5h. Il est préparé selon une méthode de préparation conforme au paragraphe 11.1 de la demande de brevet WO 2017093654 Al. The catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from a metallocene, [Me2Si(Flu)2Nd(p-BH4)2Li(TH F)] at 0.0065 mol/L, from a co-catalyst, butyloctylmagnesium (BOMAG) whose the BOMAG/Nd molar ratio is equal to 2.2, and of a preformation monomer, 1,3-butadiene whose 1,3-butadiene/Nd molar ratio is equal to 90. The medium is heated to 80° C. on a duration of 5 hours. It is prepared according to a preparation method in accordance with paragraph 11.1 of patent application WO 2017093654 Al.
Préparation des compositions de caoutchouc : Preparation of rubber compositions:
On utilise comme agent de modification un composé 1,3-di polai re, le 2,4,6-tri méthyl-3-((2- méthyl-lH-imidazol-l-yl)méthyl)benzonitrile oxyde dont la synthèse est décrite dans la demande de brevet WO 2015059274. A 1,3-dipolar compound, 2,4,6-trimethyl-3-((2-methyl-1H-imidazol-1-yl)methyl)benzonitrile oxide, the synthesis of which is described in patent application WO 2015059274.
On utilise comme élastomère diénique fortement saturé de départ l'élastomère El. The starting highly saturated diene elastomer is the elastomer El.
Quatre compositions de caoutchouc Cl à C4 sont préparées. On procède pour la fabrication de ces compositions de la manière suivante : Four rubber compositions C1 to C4 are prepared. The procedure for the manufacture of these compositions is as follows:
On introduit dans un mélangeur interne de 400 mL (taux de remplissage final : environ 70% en volume), dont la température initiale de cuve est d'environ 80°C, l'élastomère diénique fortement saturé de départ El, le cas échéant l'agent de modification qui est malaxé seul avec l'élastomère pendant environ 1 minutes à 120°C, puis la silice, l'agent de couplage
silane, le cas échéant le sel de thiosulfate inorganique hydraté, ainsi que les divers autres ingrédients à l'exception du système de vulcanisation. On conduit alors un travail thermomécanique (phase non-productive) en une étape, qui dure environ 5 min à 6 minutes pour une vitesse moyenne de palette de 100 tours/minute, jusqu'à atteindre une température maximale de « tombée » de 160°C. On récupère le mélange ainsi obtenu, on le refroidit puis on incorpore du soufre et un accélérateur type sulfénamide sur un mélangeur (homo-finisseur) à 23°C, en mélangeant le tout (phase productive) pendant 5 minutes. Is introduced into a 400 mL internal mixer (final filling rate: approximately 70% by volume), whose initial tank temperature is approximately 80° C., the highly saturated starting diene elastomer El, if necessary l modifying agent which is kneaded alone with the elastomer for approximately 1 minute at 120° C., then the silica, the coupling agent silane, optionally the hydrated inorganic thiosulfate salt, as well as the various other ingredients with the exception of the vulcanization system. Thermomechanical work is then carried out (non-productive phase) in one step, which lasts approximately 5 min to 6 minutes for an average paddle speed of 100 rpm, until a maximum "drop" temperature of 160° is reached. vs. The mixture thus obtained is recovered, cooled and then sulfur and a sulfenamide type accelerator are incorporated on a mixer (homo-finisher) at 23° C., while mixing the whole (productive phase) for 5 minutes.
Seule la composition de caoutchouc C4 est conforme à l'invention, puisqu'elle contient un élastomère diénique fortement saturé modifié, l'élastomère El modifié par réaction de greffage d'un agent de modification, le composé 1,3-di polaire, une silice, un hydrate d'un sel de thiosulfate, le thiosulfate de sodium pentahydraté, NazSzCh 5H2O. Only rubber composition C4 is in accordance with the invention, since it contains a modified highly saturated diene elastomer, the El elastomer modified by the grafting reaction of a modifying agent, the 1,3-dipolar compound, a silica, a hydrate of a thiosulfate salt, sodium thiosulfate pentahydrate, NazSzCh 5H2O.
La composition Cl est une composition témoin : elle contient ni l'élastomère diénique fortement saturé fonctionnel, ni un hydrate d'un sel de thiosulfate. Les compositions C2 et C3 sont des compositions comparatives. C2 et C3 se distinguent de C4 par l'absence respective de l'élastomère diénique fortement saturé fonctionnel et de l'hydrate. Composition C1 is a control composition: it contains neither the highly saturated functional diene elastomer nor a hydrate of a thiosulphate salt. Compositions C2 and C3 are comparative compositions. C2 and C3 are distinguished from C4 by the respective absence of the functional highly saturated diene elastomer and the hydrate.
A ces différences près, la formulation des compositions de caoutchouc préparées est identique. Les formulations (en pce) des compositions de caoutchouc Cl à C4 sont décrites dans le tableau 1 (table 1). Apart from these differences, the formulation of the rubber compositions prepared is identical. The formulations (in phr) of the rubber compositions C1 to C4 are described in table 1 (table 1).
Les compositions ainsi obtenues sont ensuite calandrées, soit sous forme de plaques (d'une épaisseur allant de 2 à 3 mm) ou fines feuilles de caoutchouc, pour la mesure de leurs propriétés physiques ou mécaniques après vulcanisation à 150°C (état cuit), soit sous la forme de profilés directement utilisables, après découpage et/ou assemblage aux dimensions souhaitées, par exemple comme produits semi-finis pour pneumatiques. The compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin sheets of rubber, for the measurement of their physical or mechanical properties after vulcanization at 150° C. (cured state) , or in the form of sections which can be used directly, after cutting and/or assembly to the desired dimensions, for example as semi-finished products for tires.
Les résultats des propriétés de cuisson et des propriétés à l'état cuit des compositions de caoutchouc sont aussi consignés dans le tableau 1. The results of the cure properties and cured properties of the rubber compositions are also shown in Table 1.
Les propriétés de la composition C3 comparative montrent que l'utilisation de l'élastomère diénique fortement saturé fonctionnel s'accompagne d'une forte diminution de l'hystérèse, mais ne permet pas de diminuer le temps de cuisson sous presse, notamment à cause d'un temps d'induction élevé (Ti) qui est même supérieur à celui de la composition Cl témoin. La comparaison des temps d'induction des compositions C3 et Cl et la comparaison de leur T90 montrent que l'utilisation de l'élastomère diénique fortement saturé fonctionnel ne permet pas non plus d'augmenter la vitesse de vulcanisation. Les propriétés de la composition C2 comparative montrent que l'utilisation de l'hydrate d'un sel de thiosulfate inorganique accélère la vitesse de vulcanisation tout en assurant une sécurité au grillage avec un temps d'induction de 4 minutes sans modification substantielle de l'hystérèse, par rapport à la composition Cl. La composition de caoutchouc C4 a une hystérèse aussi faible que celle de C3, un temps d'induction aussi faible que celle de C2 et de manière surprenante un T90 plus faible que celui de C2. On observe donc pour la composition C4 une accélération de la
vitesse de vulcanisation. L'utilisation combinée de l'élastomère diénique fortement saturé fonctionnel et de l'hydrate d'un sel de thiosulfate inorganique donne le meilleur compromis entre les propriétés d'hystérèse et le temps de cuisson sous presse sans compromettre la sécurité au grillage. Tableau 1
The properties of the comparative composition C3 show that the use of the highly saturated functional diene elastomer is accompanied by a strong reduction in the hysteresis, but does not make it possible to reduce the curing time under the press, in particular because of a high induction time (Ti) which is even greater than that of the control composition C1. The comparison of the induction times of the compositions C3 and C1 and the comparison of their T90 show that the use of the highly saturated functional diene elastomer does not make it possible to increase the speed of vulcanization either. The properties of the comparative composition C2 show that the use of the hydrate of an inorganic thiosulfate salt accelerates the rate of vulcanization while ensuring scorch safety with an induction time of 4 minutes without substantial modification of the hysteresis, relative to composition C1. The rubber composition C4 has a hysteresis as low as that of C3, an induction time as low as that of C2 and surprisingly a T90 lower than that of C2. We therefore observe for the composition C4 an acceleration of the vulcanization rate. The combined use of the functional highly saturated diene elastomer and the hydrate of an inorganic thiosulfate salt gives the best compromise between hysteresis properties and press cook time without compromising scorch safety. Table 1
(1) Copolymère d'éthylène et de 1,3-butadiène contenant 74% en mole de d'unité éthylène, 19% d'unité butadiène sous la forme de motifs 1,2 et 1,4 et 7% en mole de motif 1,2- cyclohexanediyle, de Tg -44°C (2) Noir de carbone grade N234 (1) Copolymer of ethylene and 1,3-butadiene containing 74% by mole of ethylene unit, 19% of butadiene unit in the form of 1,2 and 1,4 units and 7% by mole of unit 1,2- cyclohexanediyl, of Tg -44°C (2) Carbon black grade N234
(3) "Zeosil 1165 MP" de Solvay-Rhodia sous forme de microperles (3) "Zeosil 1165 MP" from Solvay-Rhodia in the form of microbeads
(4) Silane liquide triéthoxysilylpropyltétrasulfure (TESPT) « Si69 » de la société Evonik(4) Triethoxysilylpropyltetrasulfide (TESPT) “Si69” liquid silane from Evonik
(5) Diphénylguanidine « Perkacit DPG » de la société Flexsys (5) Diphenylguanidine “Perkacit DPG” from Flexsys
(6) Cire anti-ozone « VARAZON 4959 » de la société Sasol Wax
(7) N-(l,3-diméthylbutyl)-N'-phényl-p-phenylènediamine « Santoflex 6PPD » de la société Flexys (6) “VARAZON 4959” anti-ozone wax from Sasol Wax (7) N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine “Santoflex 6PPD” from the company Flexys
(8) Acide stéarique « Pristerene 4931 » de la société Uniqema (8) “Pristerene 4931” stearic acid from Uniqema
(9) Oxyde de Zinc de grade industriel de la société Umicore (10) Thiosulfate de sodium pentahydrate - CAS 10102-17-7 (9) Industrial Grade Zinc Oxide from Umicore (10) Sodium Thiosulfate Pentahydrate - CAS 10102-17-7
(11) Composé 1,3-dipolaire (2,4,6-triméthyl-3-((2-méthyl-IH-imidazol-l- yl)méthyl)benzonitrile oxyde) (11) 1,3-dipolar compound (2,4,6-trimethyl-3-((2-methyl-1H-imidazol-1-yl)methyl)benzonitrile oxide)
(12) N-cyclohexyl-2-benzothiazol-sulfénamide « Santocure CBS » de la société Flexsys
(12) N-cyclohexyl-2-benzothiazol-sulfenamide “Santocure CBS” from Flexsys
Claims
1. Composition de caoutchouc qui comprend : 1. Rubber composition which includes:
- un élastomère diénique fortement saturé fonctionnel, copolymère qui contient des unités éthylène, des unités d'un 1,3-diène et qui porte des groupes pendants contenant une fonction imidazole N-substituée, les unités éthylène représentant plus de 50% en mole des unités de répétition constitutives de l'élastomère diénique fortement saturé fonctionnel - a highly saturated functional diene elastomer, copolymer which contains ethylene units, units of a 1,3-diene and which bears pendant groups containing an N-substituted imidazole function, the ethylene units representing more than 50% by mole of the constituent repeating units of the functional highly saturated diene elastomer
- un système de vulcanisation, - a vulcanization system,
- une charge renforçante qui contient une silice, - a reinforcing filler which contains a silica,
- et un hydrate d'un sel de thiosulfate inorganique. - and a hydrate of an inorganic thiosulfate salt.
2. Composition de caoutchouc selon la revendication 1 dans laquelle l'élastomère diénique fortement saturé fonctionnel est un copolymère modifié d'éthylène et d'un 1,3-diène. 2. A rubber composition according to claim 1 wherein the functional highly saturated diene elastomer is a modified copolymer of ethylene and a 1,3-diene.
3. Composition de caoutchouc selon la revendication 1 ou 2 dans laquelle le 1,3-diène est le 1,3-butadiène ou un mélange de 1,3-diènes dont un est le 1,3-butadiène, de préférence le 1,3-butadiène. 3. Rubber composition according to claim 1 or 2 in which the 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes, one of which is 1,3-butadiene, preferably 1, 3-butadiene.
4. Composition de caoutchouc selon l'une quelconque des revendications 1 à 3 dans laquelle la fonction imidazole N-substituée est un groupe de formule (1) dans laquelle le symbole Yi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Y? désigne un rattachement à une unité diénique de l'élastomère diénique fortement saturé fonctionnel, les symboles Y3 et Y4 sont chacun un atome d'hydrogène.
4. Rubber composition according to any one of claims 1 to 3, in which the N-substituted imidazole function is a group of formula (1) in which the symbol Yi represents a hydrogen atom or an alkyl having 1 to 6 atoms. of carbon, the symbol Y? denotes an attachment to a diene unit of the highly saturated functional diene elastomer, the symbols Y3 and Y4 are each a hydrogen atom.
5. Composition de caoutchouc selon la revendication 4 dans laquelle l'alkyle représenté par Yi contient 1 à 3 atomes de carbone, de préférence est méthyle. 5. A rubber composition according to claim 4 wherein the alkyl represented by Yi contains 1 to 3 carbon atoms, preferably is methyl.
6. Composition de caoutchouc selon la revendication 4 ou 5 dans laquelle l'unité rattachée à la fonction imidazole N-substituée est une unité diénique modifiée par réaction d'un agent de modification contenant un groupe réactif vis à vis d'unités diéniques, l'agent de modification étant préférentiellement un composé 1,3-dipolaire, plus préférentiellement un oxyde de nitrile, une nitrone ou un nitrile imine. 6. Rubber composition according to claim 4 or 5 wherein the unit attached to the N-substituted imidazole function is a diene unit modified by reaction of a modifying agent containing a group reactive with respect to diene units, the the modifying agent preferably being a 1,3-dipolar compound, more preferably a nitrile oxide, a nitrone or a nitrile imine.
7. Composition de caoutchouc selon la revendication 6 dans laquelle l'agent de modification est un composé 1,3-dipolaire qui est un monooxyde de nitrile aromatique, composé comprenant un noyau benzénique substitué par un dipôle oxyde de nitrile et par un groupe contenant une fonction imidazole de formule (2)
dans laquelle le symbole Zi représente un atome d'hydrogène ou un alkyle ayant 1 à 6 atomes de carbone, le symbole Z2 désigne un rattachement au groupe réactif, les symboles Z3 et Z4 sont chacun un atome d'hydrogène. 7. Rubber composition according to Claim 6, in which the modifying agent is a 1,3-dipolar compound which is an aromatic nitrile monooxide, a compound comprising a benzene ring substituted by a nitrile oxide dipole and by a group containing a imidazole function of formula (2) in which the symbol Zi represents a hydrogen atom or an alkyl having 1 to 6 carbon atoms, the symbol Z2 denotes an attachment to the reactive group, the symbols Z3 and Z4 are each a hydrogen atom.
8. Composition de caoutchouc selon la revendication 7 dans laquelle le composé 1,3- dipolaire contient un motif de formule (3) dans laquelle Ri représente le dipôle oxyde de nitrile, un des symboles R2 à Re représente un groupe saturé ayant 1 à 6 atomes de carbone et lié de façon covalente à l'un des atomes d'azote du cycle à 5 membres de la fonction imidazole de formule (2), les autres symboles, identiques ou différents, représentant un atome d'hydrogène ou un substituant.
8. Rubber composition according to Claim 7, in which the 1,3-dipolar compound contains a unit of formula (3) in which R represents the nitrile oxide dipole, one of the symbols R2 to Re represents a saturated group having 1 to 6 carbon atoms and covalently bonded to one of the nitrogen atoms of the 5-membered ring of the imidazole function of formula (2), the other symbols, identical or different, representing a hydrogen atom or a substituent.
9. Composition de caoutchouc selon la revendication 8 dans laquelle le groupe saturé est un alcanediyle, de préférence un alcanediyle ayant 1 à 3 atomes de carbone, de manière plus préférentielle méthanediyle. 9. Rubber composition according to claim 8 in which the saturated group is an alkanediyl, preferably an alkanediyl having 1 to 3 carbon atoms, more preferably methanediyl.
10. Composition de caoutchouc selon l'une quelconque des revendications 8 à 9 dans laquelle le substituant est un alkyle ayant 1 à 3 atomes de carbone, plus préférentiellement méthyle ou éthyle. 10. Rubber composition according to any one of claims 8 to 9, in which the substituent is an alkyl having 1 to 3 carbon atoms, more preferably methyl or ethyl.
11. Composition de caoutchouc selon l'une quelconque des revendications 1 à 10 dans laquelle le taux de l'élastomère diénique fortement saturé fonctionnel est d'au moins 50 parties en poids pour cent parties d'élastomère de la composition de caoutchouc (pce), préférentiellement varie dans un domaine allant de 80 à 100 pce. 11. Rubber composition according to any one of claims 1 to 10, in which the content of the highly saturated functional diene elastomer is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr) , preferably varies within a range ranging from 80 to 100 pce.
12. Composition de caoutchouc selon l'une quelconque des revendications 1 à 11 dans laquelle la silice représente plus de 50% en masse de la charge renforçante, préférentiellement plus de 85% en masse de la charge renforçante. 12. Rubber composition according to any one of claims 1 to 11, in which the silica represents more than 50% by weight of the reinforcing filler, preferably more than 85% by weight of the reinforcing filler.
13. Composition de caoutchouc selon l'une quelconque des revendications 1 à 12 dans laquelle l'hydrate d'un sel de thiosulfate inorganique est un hydrate de thiosulfate d'un métal alcalin ou d'un métal alcalino-terreux, de préférence le pentahydrate de thiosulfate de sodium, Na2S2Û3 5H2O. 13. A rubber composition according to any one of claims 1 to 12 wherein the hydrate of an inorganic thiosulfate salt is a thiosulfate hydrate of an alkali metal or an alkaline earth metal, preferably the pentahydrate sodium thiosulfate, Na2S2O3 5H2O.
14. Composition de caoutchouc selon l'une quelconque des revendications 1 à 13 dans laquelle le taux de l'hydrate d'un sel de thiosulfate inorganique est supérieur à 0.5 pce,
préférentiellement supérieur à 1 pce, et est inférieur à 10 pce, préférentiellement inférieur à 5 pce. Pneumatique qui comprend une composition de caoutchouc définie à l'une quelconque des revendications 1 à 14, préférentiellement dans sa bande de roulement.
14. Rubber composition according to any one of claims 1 to 13, in which the level of the hydrate of an inorganic thiosulphate salt is greater than 0.5 phr, preferably greater than 1 phr, and is less than 10 phr, preferably less than 5 phr. A tire which comprises a rubber composition defined in any one of Claims 1 to 14, preferably in its tread.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2112332A FR3129400B1 (en) | 2021-11-22 | 2021-11-22 | Rubber composition |
| FRFR2112332 | 2021-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023088822A1 true WO2023088822A1 (en) | 2023-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2022/081718 WO2023088822A1 (en) | 2021-11-22 | 2022-11-14 | Rubber composition |
Country Status (2)
| Country | Link |
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| FR (1) | FR3129400B1 (en) |
| WO (1) | WO2023088822A1 (en) |
Citations (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999009036A1 (en) | 1997-08-21 | 1999-02-25 | Osi Specialties, Inc. | Blocked mercaptosilane coupling agents for filled rubbers |
| EP1092731A1 (en) | 1999-10-12 | 2001-04-18 | Société de Technologie Michelin | Catalytic system, process for its preparation and that of an ethylene-conjugated diene copolymer |
| WO2002031041A1 (en) | 2000-10-13 | 2002-04-18 | Societe De Technologie Michelin | Rubber composition comprising as coupling agent a polyfunctional organosilane |
| WO2002030939A1 (en) | 2000-10-13 | 2002-04-18 | Societe De Technologie Michelin | Polyfunctional organosilane for use as coupling agent and method for obtaining same |
| WO2003002648A1 (en) | 2001-06-28 | 2003-01-09 | Societe De Technologie Michelin | Tyre tread reinforced with silica having a low specific surface area |
| WO2003002649A1 (en) | 2001-06-28 | 2003-01-09 | Societe De Technologie Michelin | Tyre tread reinforced with silica having a very low specific surface area |
| WO2003016215A1 (en) | 2001-08-13 | 2003-02-27 | Rhodia Chimie | Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution and the use thereof, in particular for reinforcing polymers |
| WO2003016387A1 (en) | 2001-08-13 | 2003-02-27 | Societe De Technologie Michelin | Diene rubber composition for tyres comprising a specific silicon as a reinforcing filler |
| WO2003018332A1 (en) | 2001-08-24 | 2003-03-06 | Societe De Technologie Michelin | Non-pneumatic tire |
| WO2004035639A1 (en) | 2002-10-16 | 2004-04-29 | Societe De Technologie Michelin | Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers |
| US6849754B2 (en) | 2001-08-06 | 2005-02-01 | Degussa Ag | Organosilicon compounds |
| WO2006023815A2 (en) | 2004-08-20 | 2006-03-02 | General Electric Company | Cyclic diol-derived blocked mercaptofunctional silane compositions |
| WO2007054223A2 (en) | 2005-11-09 | 2007-05-18 | Societe De Technologie Michelin | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method |
| WO2007054224A2 (en) | 2005-11-09 | 2007-05-18 | Societe De Technologie Michelin | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method |
| WO2007098080A2 (en) | 2006-02-21 | 2007-08-30 | Momentive Performance Materials Inc. | Free flowing filler composition based on organofunctional silane |
| FR2898077A1 (en) | 2006-03-01 | 2007-09-07 | Peugeot Citroen Automobiles Sa | Non pneumatic tire for use in motor vehicle wheel, has tire ribs cooperating with pockets introducing damping in case of deformation of ribs, where pockets are formed of walls delimiting volume filled with compressible material |
| WO2008055986A2 (en) | 2006-11-10 | 2008-05-15 | Rhodia Operations | Method for production of (poly)thio alkoxysilanes and novel intermediates for said method |
| WO2010072685A1 (en) | 2008-12-22 | 2010-07-01 | Societe De Technologie Michelin | Blocked mercaptosilane coupling agent |
| WO2014114607A1 (en) | 2013-01-22 | 2014-07-31 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
| WO2015059269A1 (en) | 2013-10-25 | 2015-04-30 | Compagnie Generale Des Etablissements Michelin | 1,3-dipolar compound bearing an imidazole function |
| WO2015059274A1 (en) | 2013-10-25 | 2015-04-30 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a 1,3-dipolar compound additive having an imidazole function |
| WO2017013544A1 (en) | 2015-07-17 | 2017-01-26 | Orlando Lozzi | Mechanical speed variator for large inertial flywheels |
| WO2017093654A1 (en) | 2015-12-03 | 2017-06-08 | Compagnie Generale Des Etablissements Michelin | Catalytic preform system comprising a rare earth metallocene |
| WO2017103543A1 (en) | 2015-12-17 | 2017-06-22 | Compagnie Generale Des Etablissements Michelin | Ethylene/butadiene copolymer of homogeneous microstructure |
| WO2018020123A1 (en) | 2016-07-25 | 2018-02-01 | Compagnie Generale Des Etablissements Michelin | Preformed catalytic system comprising a rare-earth metallocene |
| WO2018020122A1 (en) | 2016-07-25 | 2018-02-01 | Compagnie Generale Des Etablissements Michelin | Preformed catalytic system comprising a rare-earth metallocene |
| WO2018189455A1 (en) | 2017-04-10 | 2018-10-18 | Compagnie Generale Des Etablissements Michelin | Tyre tread based on a highly saturated diene elastomer |
| WO2018189456A1 (en) * | 2017-04-10 | 2018-10-18 | Compagnie Generale Des Etablissements Michelin | Rubber composition made from a highly saturated diene elastomer and a dithiosulfate salt |
| WO2018193193A1 (en) | 2017-04-18 | 2018-10-25 | Compagnie Generale Des Etablissements Michelin | Continuous synthesis of an ethylene and butadiene copolymer |
| WO2018193194A1 (en) | 2017-04-18 | 2018-10-25 | Compagnie Generale Des Etablissements Michelin | Continuous synthesis of an ethylene and butadiene copolymer |
| WO2018224776A1 (en) * | 2017-06-08 | 2018-12-13 | Compagnie Generale Des Etablissements Michelin | Rubber composition |
-
2021
- 2021-11-22 FR FR2112332A patent/FR3129400B1/en active Active
-
2022
- 2022-11-14 WO PCT/EP2022/081718 patent/WO2023088822A1/en unknown
Patent Citations (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999009036A1 (en) | 1997-08-21 | 1999-02-25 | Osi Specialties, Inc. | Blocked mercaptosilane coupling agents for filled rubbers |
| EP1092731A1 (en) | 1999-10-12 | 2001-04-18 | Société de Technologie Michelin | Catalytic system, process for its preparation and that of an ethylene-conjugated diene copolymer |
| US20040051210A1 (en) | 2000-10-13 | 2004-03-18 | Jean-Claude Tardivat | Rubber composition comprising a polyfunctional organosilane as coupling agent |
| WO2002031041A1 (en) | 2000-10-13 | 2002-04-18 | Societe De Technologie Michelin | Rubber composition comprising as coupling agent a polyfunctional organosilane |
| WO2002030939A1 (en) | 2000-10-13 | 2002-04-18 | Societe De Technologie Michelin | Polyfunctional organosilane for use as coupling agent and method for obtaining same |
| US6774255B1 (en) | 2000-10-13 | 2004-08-10 | Michelin Recherche Et Technique, S.A. | Polyfunctional organosilane usable as a coupling agent and process for the obtainment thereof |
| US20050016651A1 (en) | 2001-06-28 | 2005-01-27 | Michelin Recherche Et Technique S.A. | Tire tread reinforced with a silica of low specific surface area |
| WO2003002649A1 (en) | 2001-06-28 | 2003-01-09 | Societe De Technologie Michelin | Tyre tread reinforced with silica having a very low specific surface area |
| WO2003002648A1 (en) | 2001-06-28 | 2003-01-09 | Societe De Technologie Michelin | Tyre tread reinforced with silica having a low specific surface area |
| US20050016650A1 (en) | 2001-06-28 | 2005-01-27 | Michelin Recherche Et Technique S.A. | Tire tread reinforced with a silica of very low specific surface area |
| US6849754B2 (en) | 2001-08-06 | 2005-02-01 | Degussa Ag | Organosilicon compounds |
| WO2003016387A1 (en) | 2001-08-13 | 2003-02-27 | Societe De Technologie Michelin | Diene rubber composition for tyres comprising a specific silicon as a reinforcing filler |
| WO2003016215A1 (en) | 2001-08-13 | 2003-02-27 | Rhodia Chimie | Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution and the use thereof, in particular for reinforcing polymers |
| WO2003018332A1 (en) | 2001-08-24 | 2003-03-06 | Societe De Technologie Michelin | Non-pneumatic tire |
| WO2004035639A1 (en) | 2002-10-16 | 2004-04-29 | Societe De Technologie Michelin | Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers |
| WO2006023815A2 (en) | 2004-08-20 | 2006-03-02 | General Electric Company | Cyclic diol-derived blocked mercaptofunctional silane compositions |
| WO2007054223A2 (en) | 2005-11-09 | 2007-05-18 | Societe De Technologie Michelin | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method |
| WO2007054224A2 (en) | 2005-11-09 | 2007-05-18 | Societe De Technologie Michelin | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method |
| WO2007098080A2 (en) | 2006-02-21 | 2007-08-30 | Momentive Performance Materials Inc. | Free flowing filler composition based on organofunctional silane |
| FR2898077A1 (en) | 2006-03-01 | 2007-09-07 | Peugeot Citroen Automobiles Sa | Non pneumatic tire for use in motor vehicle wheel, has tire ribs cooperating with pockets introducing damping in case of deformation of ribs, where pockets are formed of walls delimiting volume filled with compressible material |
| WO2008055986A2 (en) | 2006-11-10 | 2008-05-15 | Rhodia Operations | Method for production of (poly)thio alkoxysilanes and novel intermediates for said method |
| WO2010072685A1 (en) | 2008-12-22 | 2010-07-01 | Societe De Technologie Michelin | Blocked mercaptosilane coupling agent |
| WO2014114607A1 (en) | 2013-01-22 | 2014-07-31 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a highly saturated diene elastomer |
| WO2015059269A1 (en) | 2013-10-25 | 2015-04-30 | Compagnie Generale Des Etablissements Michelin | 1,3-dipolar compound bearing an imidazole function |
| WO2015059274A1 (en) | 2013-10-25 | 2015-04-30 | Compagnie Generale Des Etablissements Michelin | Rubber composition comprising a 1,3-dipolar compound additive having an imidazole function |
| WO2017013544A1 (en) | 2015-07-17 | 2017-01-26 | Orlando Lozzi | Mechanical speed variator for large inertial flywheels |
| WO2017093654A1 (en) | 2015-12-03 | 2017-06-08 | Compagnie Generale Des Etablissements Michelin | Catalytic preform system comprising a rare earth metallocene |
| WO2017103543A1 (en) | 2015-12-17 | 2017-06-22 | Compagnie Generale Des Etablissements Michelin | Ethylene/butadiene copolymer of homogeneous microstructure |
| WO2018020123A1 (en) | 2016-07-25 | 2018-02-01 | Compagnie Generale Des Etablissements Michelin | Preformed catalytic system comprising a rare-earth metallocene |
| WO2018020122A1 (en) | 2016-07-25 | 2018-02-01 | Compagnie Generale Des Etablissements Michelin | Preformed catalytic system comprising a rare-earth metallocene |
| WO2018189455A1 (en) | 2017-04-10 | 2018-10-18 | Compagnie Generale Des Etablissements Michelin | Tyre tread based on a highly saturated diene elastomer |
| WO2018189456A1 (en) * | 2017-04-10 | 2018-10-18 | Compagnie Generale Des Etablissements Michelin | Rubber composition made from a highly saturated diene elastomer and a dithiosulfate salt |
| WO2018193193A1 (en) | 2017-04-18 | 2018-10-25 | Compagnie Generale Des Etablissements Michelin | Continuous synthesis of an ethylene and butadiene copolymer |
| WO2018193194A1 (en) | 2017-04-18 | 2018-10-25 | Compagnie Generale Des Etablissements Michelin | Continuous synthesis of an ethylene and butadiene copolymer |
| WO2018224776A1 (en) * | 2017-06-08 | 2018-12-13 | Compagnie Generale Des Etablissements Michelin | Rubber composition |
Non-Patent Citations (2)
| Title |
|---|
| CAS, no. 10102-17-7 |
| THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, February 1938 (1938-02-01), pages 309 |
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| FR3129400A1 (en) | 2023-05-26 |
| FR3129400B1 (en) | 2023-11-10 |
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