EP4267406A1 - Kautschukzusammensetzung - Google Patents
KautschukzusammensetzungInfo
- Publication number
- EP4267406A1 EP4267406A1 EP21835808.3A EP21835808A EP4267406A1 EP 4267406 A1 EP4267406 A1 EP 4267406A1 EP 21835808 A EP21835808 A EP 21835808A EP 4267406 A1 EP4267406 A1 EP 4267406A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubber composition
- phr
- composition according
- copolymer
- units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 229920001971 elastomer Polymers 0.000 title claims abstract description 80
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000005977 Ethylene Substances 0.000 claims abstract description 44
- 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 24
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 17
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000003784 tall oil Substances 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000001993 dienes Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 abstract description 39
- 235000019241 carbon black Nutrition 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000012763 reinforcing filler Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 239000000243 solution Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000000945 filler Substances 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
- 230000002787 reinforcement Effects 0.000 description 5
- 239000003981 vehicle Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- -1 1,2-cyclohexanediyl Chemical group 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 101000582320 Homo sapiens Neurogenic differentiation factor 6 Proteins 0.000 description 2
- 102100030589 Neurogenic differentiation factor 6 Human genes 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 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
- BWRTUFTXSMWLSX-UHFFFAOYSA-N tris(6-methylheptoxy)thallane Chemical compound CC(C)CCCCCO[Tl](OCCCCCC(C)C)OCCCCCC(C)C BWRTUFTXSMWLSX-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- 238000011000 absolute method Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 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
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the field of the present invention is that of rubber compositions reinforced with carbon black and comprising a highly saturated diene elastomer, the rubber compositions being particularly intended for use in a tire, more particularly in a tire sidewall.
- a tire usually comprises 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 sidewall is an elastomer layer placed on the outside of the carcass reinforcement with respect to the internal cavity of the tire, between the crown and the bead so as to totally or partially cover the area of the carcass reinforcement extending from top to bead.
- the various constituent components of the crown, of the carcass reinforcement, of the beads and of the sidewalls are assembled to form a tire tyre.
- the assembly step is followed by a step of shaping the bandage to give the toric shape to the assembly before the step of curing under a press.
- the tires, and in particular the sidewalls, are subjected to numerous mechanical stresses which are repeated cyclically during travel. These stresses, in the form of bending and compressive stresses, test the endurance of the tire and contribute to reducing its lifespan.
- One way to improve the endurance of the tire lies in increasing the fatigue resistance of the rubber compositions which constitute the tire.
- the use of silica with a low specific surface typically less than 125 m 2 /g, or even much less than 100 m 2 /g in a rubber composition is described respectively in patents EP 722 977 B1 and EP 547 344 B1 to improve fatigue resistance.
- tire sidewalls are also exposed to the action of ozone.
- Deformation cycles combined with the action of ozone can cause cracks or cracks in the sidewall, preventing the use of the tire independently of the wear of the tread. Consequently, rubber compositions are sought which are very cohesive for forming tire sidewalls, for example, by virtue of their ability to undergo large deformations without breaking.
- copolymers having less sensitivity to oxidation such as for example highly saturated diene elastomers, elastomers comprising ethylene units at a molar rate greater than 50% by mole of the monomer units of the elastomer.
- the use of such copolymers of ethylene and 1,3-butadiene in a tread of a tire is for example described in document WO 2014114607 A1 and has the effect of conferring good wear resistance properties. and tire rolling resistance.
- the use of copolymers of ethylene and 1,3-diene in a sidewall composition is also described, for example, in document EP 2 682 423 A1 to increase resistance to the action of ozone.
- tall oil ester plasticizer is described in the documents JP2008201933, JP2008201944 and JP2008201945 in various elastomeric matrices and not comprising a highly saturated diene elastomer, with effects that are also varied and depend on the elastomer matrices in which type of plasticizer is used.
- the Applicant has discovered that the use of a specific plasticizer in a rubber composition comprising a copolymer highly saturated based on ethylene units and diene units, makes it possible, in this composition, to improve the balance between the performances of endurance, deformability and hysteresis.
- a first object of the invention is a rubber composition based on at least one elastomer matrix comprising from 45 to 80 phr of at least one polyisoprene and from 20 to 55 phr of at least one highly saturated diene elastomer ; a tall oil ester plasticizer, carbon black, and a crosslinking system; wherein the highly saturated diene elastomer is a copolymer of ethylene and 1,3-diene.
- compositions according to the invention are preferably in at least one sidewall of the pneumatic or non-pneumatic tire.
- composition based on means a composition comprising the mixture and/or the in situ reaction product of the various constituents used, some of these constituents being able to react and/or being intended to react with one another, less partially, during the various phases of manufacture of the composition; the composition thus possibly being in the totally or partially crosslinked state or in the non-crosslinked state.
- part by weight per hundred parts by weight of elastomer (or phr) is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
- any interval of values denoted by the expression "between a and b” represents the range of values going from more than a to 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 (i.e. including the strict limits a and b) .
- the interval represented by the expression “between a and b” is also and preferably designated.
- the term “all of the monomer units of the elastomer” or “all of the monomer units of the elastomer” means all the constituent repeating units of the elastomer which result from the insertion of the monomers in the elastomer chain by polymerization. Unless otherwise indicated, the contents of a monomer unit or repeating unit in the highly saturated diene elastomer are given in molar percentage calculated on the basis of all the monomer units of the elastomer.
- a predominant elastomer is the elastomer representing the greatest mass relative to the total mass of the elastomers in the composition.
- a so-called majority filler is the one representing the greatest mass among the fillers of the composition.
- a "minority” compound is a compound which does not represent the largest mass fraction among compounds of the same type.
- by majority is meant present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
- 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 mentioned compounds can also come from the recycling of already used materials, that is to say they can be, partially or totally, resulting from a recycling process, or obtained from raw materials themselves resulting from a recycling process. This concerns in particular polymers, plasticizers, fillers, etc.
- glass transition temperature “Tg” values described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to standard ASTM D3418 (1999).
- elastomer matrix is meant all of the elastomers of the composition.
- the elastomer matrix comprises from 45 to 80 phr of at least one polyisoprene and from 20 to 55 phr of at least one highly saturated diene elastomer, the latter being a copolymer of ethylene and 1,3- diene (hereinafter referred to as "the copolymer").
- copolymer containing ethylene units and 1,3-diene units is meant any copolymer comprising, within its structure, at least ethylene units and 1,3-diene units.
- the copolymer can thus comprise monomer units other than ethylene units and 1,3-diene units.
- the copolymer can also comprise alpha-olefin units, in particular alpha-olefin units having from 3 to 18 carbon atoms, advantageously having 3 to 6 carbon atoms.
- the alpha-olefin units can be selected from the group consisting of propylene, butene, pentene, hexene or mixtures thereof.
- ethylene unit refers to the —(CH2—CH2)— unit resulting from the insertion of ethylene into the elastomer chain.
- “By 1,3-diene unit” is meant a monomer unit resulting from the insertion of a monomer unit resulting from the polymerization of a 1,3-diene monomer.
- the 1,3-diene units of the copolymer can be 1,3-diene units having 4 to 12 carbon atoms, for example 1,3-butadiene, 2-methyl-1,3-butadiene units.
- the 1,3-diene units are predominantly, or even preferentially exclusively, 1,3-butadiene units.
- the ethylene units advantageously represent between 50% and 95% by mole of the monomer units of the copolymer, that is to say between 50% and 95% by mole of the monomer units of the copolymer.
- the ethylene units in the copolymer represent more than 60%, preferably more than 70%, by mole of the monomer units of the copolymer.
- the ethylene units represent at most 90% by mole, preferably at most 85% by mole, of the monomer units of the copolymer.
- the copolymer (that is to say, as a reminder, the at least one copolymer containing ethylene units and diene units) is a copolymer of ethylene and 1,3-diene (preferably 1,3- butadiene), that is to say, according to the invention, a copolymer consisting exclusively of ethylene units and 1,3-diene units (preferably 1,3-butadiene), more preferably a copolymer of ethylene and random 1,3-diene (preferably 1,3-butadiene).
- 1,3-diene preferably 1,3-butadiene
- the copolymer is a copolymer of ethylene and of a 1,3-diene
- the latter advantageously contains units of formula (I) [Chem 1] and/or (II) [Chem 2].
- the presence of a saturated 6-membered cyclic unit, 1,2-cyclohexanediyl, of formula (I) as a monomer unit in the copolymer can result from a series of very particular insertions of ethylene and 1,3-butadiene in the polymer chain during its growth. [Chem 1]
- the copolymer of ethylene and a 1,3-diene may be devoid of units of formula (I). In this case, it preferably contains units of formula (II).
- the copolymer of ethylene and of a 1,3-diene 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, respectively o and p preferably satisfy the following equation (eq. 1) [Math 1], more preferably equation (eq. 2) [Math 2], and more preferably to equation (eq. 3) [Math 3], o and p being calculated on the basis of all the monomer units of the highly saturated diene elastomer.
- the copolymer preferably the copolymer of ethylene and of a 1,3-diene (preferably of 1,3-butadiene), is a random copolymer.
- the number-average mass (Mn) of the copolymer, preferably of the copolymer of ethylene and of a 1,3-diene (preferably of 1,3-butadiene) is within a range ranging from 100,000 to 300 000 g/mol, preferably from 150,000 to 250,000 g/mol.
- the Mn of the copolymer is determined in a known manner, by steric exclusion chromatography (SEC) as described below:
- the solution is filtered through a 0.45 ⁇ m porosity filter before injection.
- the equipment used is a "WATERS Acquity” or “WATERS Alliance” chromatographic chain.
- the elution solvent is tetrahydrofuran with BHT type antioxidant (butylated hydroxytoluene) at 250 ppm, the flow rate is 1 mL.min-1, the column temperature is 35° C and the analysis time is 40 min. .
- the columns used are a set of three Agilent columns under the trade name "InfinityLab PolyPore".
- the injected volume of the sample solution is 100 pL.
- the detector is an "Acquity refractometer” or “WATERS 2410" differential refractometer and the chromatographic data processing software is the “WATERS EMPOWER” system.
- Molar masses calculated averages relate to a calibration curve produced from standard polystyrene.
- the copolymer can be obtained according to various synthetic methods known to those skilled in the art, in particular depending on the targeted microstructure of the highly saturated diene elastomer. Generally, it can be prepared by copolymerization of at least one diene, preferably a 1,3-diene, more 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 copolymer 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.
- the copolymer can consist of a mixture of copolymers containing ethylene units and diene units which differ from one another by their microstructures and/or by their macrostructures.
- the elastomer matrix of the composition according to the invention also contains a polyisoprene.
- the polyisoprene can be an elastomer of any microstructure.
- the polyisoprene preferably having a mass rate of 1,4-cis bond of at least 90% of the mass of the polyisoprene, is a natural rubber, a synthetic polyisoprene or a mixture thereof. More preferably, the polyisoprene, preferably having a mass content of 1,4-cis bonding of at least 90% of the mass of the polyisoprene, is a natural rubber.
- the level of the copolymer, preferably the copolymer of ethylene and 1,3-diene (preferably 1,3-butadiene), in the composition can be comprised in a range ranging from 20 to 50 phr, preferably comprised in a range ranging from 20 to less than 45 phr, more preferably comprised in a range ranging from 20 to 40 phr.
- the content of polyisoprene, preferably of natural rubber, in the composition can be included in a range ranging from 50 to 80 phr, preferably, included in a range ranging from more than 55 phr to 80 phr, more preferably included in an area ranging from 60 to 80 pce.
- the elastomer matrix can comprise at least one other elastomer, which is not a polyisoprene or a copolymer containing ethylene units and diene units, but this is not necessary.
- the at least one polyisoprene and at least one copolymer containing ethylene units and diene units are the only elastomers of the composition, that is to say they represent 100% by weight of the elastomer matrix .
- the elastomer matrix comprises at least one other elastomer, which is not a polyisoprene or a copolymer containing ethylene units and diene units
- the at least one other elastomer can represent less than 50%, preferably less than 40% , preferably less than 30%, preferably less than 20%, preferably less than 10%, by mass of the elastomeric matrix.
- the other elastomer can be any diene elastomer well known to those skilled in the art which is not a polyisoprene or a copolymer containing ethylene units and diene units. 11-2 Specific plasticizer
- the rubber composition is based on at least one tall oil ester plasticizer (also called “tallate”).
- tall oil ester plasticizer also called “tallate”.
- the tall oil ester plasticizer is present in the composition at a rate comprised in a range ranging from 5 to 50 phr, preferably from 7 to 40 phr and more preferably from 8 to 30 pc.
- the content of tall oil ester plasticizer is within a range ranging from 10 to 25 phr.
- the tall oil ester plasticizer is a compound of formula TI(OR)3 in which R is a linear or branched alkyl and T1 represents tall oil (or tallate).
- R is an alkyl comprising from 4 to 20 carbon atoms, preferably from 6 to 12 carbon atoms and more preferably from 6 to 10 carbon atoms.
- R is a branched alkyl, and very preferably, R is an isooctyl radical.
- the tall oil ester plasticizer is the isooctyl tallate compound, [Chem 3] below. [Chem 3]
- Isooctyl tallate with CAS number 68333-78-8, has a glass transition temperature of ⁇ 110° C. and it is, for example, marketed under the name “Plasthall 100” by the company Hallstar.
- composition according to the invention advantageously does not comprise any plasticizer other than the specific plasticizer above, or contains less than 15 phr thereof, preferably less than 10 phr, preferably less than 5 phr.
- the rubber composition in accordance with the invention has the other essential characteristic of comprising a reinforcing filler comprising carbon black.
- the rubber composition may comprise any other type of so-called reinforcing filler, known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler other than carbon black, an inorganic reinforcing filler such as silica with which a coupling agent is combined in known manner.
- a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
- Suitable carbon blacks are all carbon blacks, in particular the blacks conventionally used in tires or their treads.
- the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series 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.
- the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO97/36724-A2 or WO99/16600-A1).
- the carbon black has a BET specific surface comprised in a range ranging from 30 to 100 m 2 /g, preferably from 33 to 70 m 2 /g, more preferably from 35 to 50 m 2 /g.
- the BET specific surface can be measured according to the ASTM D6556-09 standard [multipoint method (5 points) - gas: nitrogen - relative pressure range P/PO: 0.05 to 0.30].
- the reinforcing filler comprising mainly, preferably exclusively, carbon black.
- the reinforcing filler preferably consists of at least 80% by weight, preferably at least 90% by weight of carbon black.
- the reinforcing filler comprises exclusively, that is to say 100% by weight, of carbon black.
- the content of carbon black, in the composition according to the invention, is preferably within a range ranging from 15 to 65 phr, preferably from 20 to 45 phr.
- the carbon black can be a mixture of different carbon blacks, in which case the carbon black levels relate to all the carbon blacks. 11-4 crosslinking
- the crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions for tires. It may in particular be based on sulfur, and/or peroxide and/or bismaleimides.
- the crosslinking system is sulfur-based, one then speaks of a vulcanization system.
- the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur-donating agent.
- At least one vulcanization accelerator is also preferentially present, and, optionally, also preferentially, various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts can be used. of transition metals, guanidine derivatives (in particular diphenylguanidine), or alternatively known vulcanization retarders.
- the sulfur is used at a preferential rate of between 0.2 phr and 10 phr, more preferentially between 0.3 and 5 phr.
- the primary vulcanization accelerator is used at a preferential rate comprised between 0.5 and 10 phr, more preferentially comprised between 0.5 and 5 phr.
- Any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur can be used as an accelerator, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type.
- MBTS 2-mercaptobenzothiazyl disulphide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N,N-dicyclohexyl-2-benzothiazyl sulfenamide
- TBBS N-ter-butyl-2-benzothiazyl sulfenamide
- TZTD tetrabenzylthiuram disulfide
- ZBEC zinc dibenzyldithiocarbamate
- the rubber compositions according to the invention may also optionally comprise all or part of the usual additives usually used in elastomer compositions for tires, such as, for example, pigments, protective agents such as anti-ozone waxes, anti-ozonants chemicals, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
- additives usually used in elastomer compositions for tires such as, for example, pigments, protective agents such as anti-ozone waxes, anti-ozonants chemicals, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
- composition according to the invention does not comprise any hydrocarbon-based plasticizing resin.
- compositions in accordance with the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:
- thermomechanical mixing (so-called "non-productive" phase), which can be carried out in a single thermomechanical step during which, in a suitable mixer such as a usual internal mixer (for example of the type 'Banbury'), all the necessary constituents, in particular the elastomeric matrix, the reinforcing filler, any other miscellaneous additives, with the exception of the crosslinking system.
- a suitable mixer such as a usual internal mixer (for example of the type 'Banbury')
- all the necessary constituents in particular the elastomeric matrix, the reinforcing filler, any other miscellaneous additives, with the exception of the crosslinking system.
- the incorporation of any charge to the elastomer can be produced in one or more stages by thermomechanical kneading.
- the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch (“masterbatch” in English) as described for example in applications WO 97/36724 or WO 99 /16600, it is the masterbatch which is mixed directly and, if necessary, the other elastomers or fillers present in the composition which are not in the form of the masterbatch are incorporated, as well as any other various additives other than the cross-linking system.
- the non-productive phase can be carried out at high temperature, up to a maximum temperature of between 110° C. and 200° C., preferably between 130° C. and 185° C., for a duration generally of between 2 and 10 minutes.
- a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically below 120° C., for example between 40° C. and 100° C.
- the crosslinking system is then incorporated, and the whole is then mixed for a few minutes, for example between 5 and 15 min.
- the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or else extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profiled) rubber that can be used, for example, as a tire sidewall.
- a semi-finished (or profiled) rubber that can be used, for example, as a tire sidewall.
- the composition can be either in the green state (before crosslinking or vulcanization), or in the cured state (after crosslinking or vulcanization), can be a semi-finished product which can be used in a tire.
- the crosslinking (or curing), where appropriate 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 crosslinking system adopted and the crosslinking kinetics of the composition considered.
- a subject of the present invention is also a tire comprising a rubber composition according to the invention.
- the composition according to the invention is present at least in one sidewall of the tire according to the invention.
- this composition is present exclusively in the sidewalls of the tire.
- the tire according to the invention can be intended to equip motor vehicles of the passenger car type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, "Weight - heavy” - i.e. metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering machinery -, and others.
- SUV Sport Utility Vehicles
- industrial vehicles chosen from vans, "Weight - heavy” - i.e. metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering machinery -, and others.
- the dynamic properties are measured on a viscoanalyzer (Metravib V A4000), according to standard ASTM D5992-96.
- the response of a sample of vulcanized composition (cylindrical test piece 4 mm thick and 400 mm2 cross-section) is recorded, subjected to a sinusoidal stress in simple alternating shear, at a frequency of 10Hz according to standard ASTM D 1349- 99 at a temperature of 23°C.
- a peak-to-peak deformation amplitude scan is performed from 0.1 to 50% (go cycle), then from 50% to 0.1% (return cycle).
- the results used are the measurement, in return cycle, of the moduli G' and G” at 10% strain, at 23°C, representing respectively the stiffness (and therefore the deformability) and the hysteresis of the compositions.
- results are indicated in base 100 (percentage), the value 100 being assigned to the control.
- a result above 100 indicates an improvement in the performance in question.
- a result greater than 100 indicates a reduction in the modulus and therefore better deformability, an important property for endurance in the case of use in tire sidewalls.
- a result greater than 100 indicates a reduction in the hysteresis and therefore better performance in rolling resistance in the case of use in tires.
- the elastomer (EBR) is prepared according to the following procedure:
- metallocene [ ⁇ Me2SiFlu2Nd(p-BH4)2Li(THF) ⁇ 2, the symbol Flu representing the fluorenyl group of formula C13H8] are introduced into a first bottle Steinie in glove box.
- the catalytic solution is then introduced into the polymerization reactor.
- the temperature in the reactor is then increased to 80°C.
- the reaction starts by injecting a gaseous mixture of ethylene and 1,3-butadiene (80/20 mol %) into the reactor.
- the polymerization reaction takes place at a pressure of 8 bars.
- the proportions of metallocene and of co-catalyst are respectively 0.00007 mol/L and 0.0004 mol/L.
- 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 by drying in a vacuum oven.
- butyloctylmagnesium (BOMAG) is added to neutralize the impurities of the reactor, then the catalytic system .
- the reaction temperature is regulated at 80°C and the polymerization reaction starts.
- the polymerization reaction takes place at a constant pressure of 8 bars.
- the reactor is supplied throughout the polymerization with ethylene and butadiene in the proportions 80/20% molar (Ethylene/Butadiene).
- 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 by drying in a vacuum oven to constant mass.
- the catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from a metallocene, [Me2Si(Flu)2Nd(p-BH4)2Li(THF)], a co-catalyst, butyloctylmagnesium (BOMAG), and a monomer of preformation, 1,3-butadiene, in the following contents: metallocene: 0.00007 mol/L, co- catalyst: 0.00036 mol/L. It is prepared according to a preparation method in accordance with paragraph ll.l of patent application WO 2017093654 Al.
- the rubber compositions were produced as described in point 11.6 above.
- the “non-productive” phase was carried out in a 0.4 liter mixer for 6 minutes, for an average paddle speed of 50 revolutions per minute until reaching a maximum drop temperature of 160°C.
- the “productive” phase was carried out in a cylinder tool at 23°C for 10 minutes.
- the crosslinking of the composition was carried out at a temperature of between 130° C. and 200° C., under pressure.
- Table 1 presents the compositions tested (in phr), and Table 2 presents the results obtained, in base 100.
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FR2014026A FR3118045B1 (fr) | 2020-12-23 | 2020-12-23 | Composition de caoutchouc |
PCT/FR2021/052126 WO2022136754A1 (fr) | 2020-12-23 | 2021-11-29 | Composition de caoutchouc |
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US (1) | US20240052142A1 (de) |
EP (1) | EP4267406A1 (de) |
CN (1) | CN116635434A (de) |
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Family Cites Families (23)
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FR2673187B1 (fr) | 1991-02-25 | 1994-07-01 | Michelin & Cie | Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition. |
DE4236218C2 (de) | 1991-12-19 | 2001-08-16 | Degussa | Vulkanisierbare EPDM-Kautschukmischungen |
FR2729671B1 (fr) | 1995-01-20 | 1997-04-18 | Michelin & Cie | Enveloppe de pneumatique a base de silice precipitee presentant une resistance au roulement amelioree |
FR2732351B1 (fr) | 1995-03-29 | 1998-08-21 | Michelin & Cie | Composition de caoutchouc pour enveloppe de pneumatique renfermant de la silice dopee aluminium a titre de charge renforcante |
CA2250774C (en) | 1996-04-01 | 2008-08-05 | Cabot Corporation | Novel elastomer composites, method and apparatus |
FR2749313A1 (fr) | 1996-05-28 | 1997-12-05 | Michelin & Cie | Composition de caoutchouc dienique a base d'alumine en tant que charge renforcante et son utilisation pour la fabrication d'enveloppes de pneumatiques |
CA2305702C (en) | 1997-09-30 | 2008-02-05 | Cabot Corporation | Elastomer composite blends and methods for producing them |
WO2000005301A1 (fr) | 1998-07-22 | 2000-02-03 | Societe De Technologie Michelin | Systeme de couplage (charge blanche/elastomere dienique) a base d'alkoxysilane polysulfure, de dithiophosphate de zinc et de derive guanidique |
WO2000005300A1 (fr) | 1998-07-22 | 2000-02-03 | Societe De Technologie Michelin | Systeme de couplage (charge blanche/elastomere dienique) a base d'alkoxysilane polysulfure, d'enamine et de derive guanidique |
FR2799468B1 (fr) | 1999-10-12 | 2006-04-28 | Michelin Soc Tech | Systeme catalytique utilisable pour la copolymerisation de l'ethylene et d'un diene conjugue, procede de preparation de ce systeme catalytique et d'un copolymere d'ethylene et d'un diene conjugue |
CN1257211C (zh) | 2000-07-31 | 2006-05-24 | 米其林技术公司 | 轮胎胎面 |
RU2312870C2 (ru) | 2002-10-16 | 2007-12-20 | Сосьете Де Текноложи Мишлен | Сополимеры этилена и бутадиена, каталитическая система и способ их синтеза |
FR2893029B1 (fr) | 2005-11-09 | 2009-01-16 | Michelin Soc Tech | Complexe metallocene borohydrure d'un lanthanide, systeme catalytique l'incorporant, procede de polymerisation l'utilisant et copolymere ethylene/butadiene obtenu par ce procede |
FR2893028B1 (fr) | 2005-11-09 | 2008-02-15 | Michelin Soc Tech | Complexe metallocene borohydrure d'un lanthanide, systeme catalytique l'incorporant, procede de polymerisation l'utilisant et copolymere ethylene/butadiene obtenu par ce procede |
JP2008201945A (ja) | 2007-02-21 | 2008-09-04 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物及びそれを用いたタイヤ |
JP2008201933A (ja) | 2007-02-21 | 2008-09-04 | Yokohama Rubber Co Ltd:The | タイヤ用ゴム組成物 |
JP2008201944A (ja) | 2007-02-21 | 2008-09-04 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物及びそれを用いたタイヤ |
WO2012117715A1 (ja) | 2011-03-01 | 2012-09-07 | 株式会社ブリヂストン | ゴム組成物、タイヤサイド用ゴム組成物、架橋ゴム組成物、及びタイヤ |
FR3001223B1 (fr) | 2013-01-22 | 2015-03-06 | Michelin & Cie | Composition de caoutchouc comprenant un elastomere dienique fortement sature |
CN105916949A (zh) * | 2013-09-27 | 2016-08-31 | 阿利桑那化学公司 | 松香酯及其组合物 |
FR3044662B1 (fr) | 2015-12-03 | 2017-12-08 | Michelin & Cie | Systeme catalytique preforme comprenant un metallocene de terre rare |
FR3054220A1 (fr) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | Systeme catalytique preforme comprenant un metallocene de terre rare |
FR3054221A1 (fr) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | Systeme catalytique preforme comprenant un metallocene de terre rare |
-
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2021
- 2021-11-29 WO PCT/FR2021/052126 patent/WO2022136754A1/fr active Application Filing
- 2021-11-29 US US18/268,816 patent/US20240052142A1/en active Pending
- 2021-11-29 EP EP21835808.3A patent/EP4267406A1/de active Pending
- 2021-11-29 CN CN202180085999.2A patent/CN116635434A/zh active Pending
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FR3118045B1 (fr) | 2022-12-30 |
CN116635434A (zh) | 2023-08-22 |
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