WO2021205108A1 - Rubber composition comprising low melting point polyethylene - Google Patents
Rubber composition comprising low melting point polyethylene Download PDFInfo
- Publication number
- WO2021205108A1 WO2021205108A1 PCT/FR2021/050596 FR2021050596W WO2021205108A1 WO 2021205108 A1 WO2021205108 A1 WO 2021205108A1 FR 2021050596 W FR2021050596 W FR 2021050596W WO 2021205108 A1 WO2021205108 A1 WO 2021205108A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyethylene
- phr
- silica
- composition according
- carbon black
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 150
- -1 polyethylene Polymers 0.000 title claims abstract description 74
- 229920001971 elastomer Polymers 0.000 title claims abstract description 71
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 69
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 67
- 239000005060 rubber Substances 0.000 title claims abstract description 54
- 238000002844 melting Methods 0.000 title claims abstract description 33
- 230000008018 melting Effects 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000006229 carbon black Substances 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 229920001195 polyisoprene Polymers 0.000 claims description 48
- 238000006735 epoxidation reaction Methods 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000000806 elastomer Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 13
- 229920003052 natural elastomer Polymers 0.000 claims description 13
- 229920001194 natural rubber Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 229920003051 synthetic elastomer Polymers 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000001747 exhibiting effect Effects 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000019241 carbon black Nutrition 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 15
- 150000001993 dienes Chemical class 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000000463 material Substances 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
- 239000003921 oil Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000016571 aggressive behavior Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- 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 2
- 125000002897 diene group Chemical group 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 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
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000005372 silanol group Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- JOXQUHMJFUINQP-UHFFFAOYSA-N 2-(2-methylpentan-2-yl)-4-n-phenylbenzene-1,4-diamine Chemical compound C1=C(N)C(C(C)(C)CCC)=CC(NC=2C=CC=CC=2)=C1 JOXQUHMJFUINQP-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000005065 mining 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
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000012991 xanthate 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
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- 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
Definitions
- TITLE RUBBER COMPOSITION INCLUDING POEYETHYEENE AT LOW MELTING TEMPERATURE
- the present invention relates to rubber compositions exhibiting a good performance compromise between resistance to mechanical attack and hysteresis. It is particularly interested in rubber articles such as pneumatic tires, non-pneumatic tires, caterpillars, conveyor belts or any other rubber article for which the aforementioned performance compromise would be interesting.
- the rubber compositions of the invention are of great interest when used in tire treads for civil engineering vehicles.
- these tires must have very different technical characteristics from the tires intended for vehicles running exclusively on the road (that is to say a bituminous ground), because the nature of the off-road soils on which they mainly operate is very. different, and in particular much more aggressive, by its stony nature.
- the tires for passenger vehicles for example the tires for large civil engineering machines must be able to withstand a load which can be extremely heavy. Therefore, the known solutions for tires rolling on bituminous ground are not directly applicable to off-road tires such as tires for civil engineering vehicles.
- a tread is subjected to mechanical stresses and attacks resulting from direct contact with the ground.
- the mechanical stresses and the attacks undergone by the tire are amplified under the effect of the weight it supports.
- the tires for mining vehicles in particular are subjected to strong stresses, both at the local level: rolling on the macro-indenters represented by the pebbles which constitute the tracks (crushed rock), and at the global level: passage of significant torque because the slopes of the tracks to enter or leave the "pits", or open-pit mines, are of the order 10%, and heavy stress on the tires during vehicle U-turns for loading and unloading maneuvers.
- the subject of the invention is a rubber composition based on at least one diene elastomer, from 10 to 60 phr of carbon black, from 5 to 30 phr of silica, a polyethylene having a melting point of between 120 ° C and 160 ° C, and a crosslinking system, in which the carbon black represents from 50% to 95% by weight relative to the total weight of carbon black and silica.
- composition based on is meant 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 may thus be in the fully or partially crosslinked state or in the non-crosslinked state.
- part by weight per hundred parts by weight of elastomer (or phr), it is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
- any interval of values designated by the expression “between a and b” represents the domain of values going from more than a to less than b (that is to say limits a and b excluded) while any range of values designated 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 interval represented by the expression “between a and b” is also and preferably designated.
- a “majority” compound it is understood, within the meaning of the present invention, that this compound is the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest amount by mass among compounds of the same type.
- a major 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 that 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.
- the term “majority” is understood to mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
- the compounds comprising carbon mentioned in the description can be of fossil origin or biobased. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
- Tg glass transition temperature values described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to the ASTM D3418 (1999) standard.
- composition according to the invention may contain a single diene elastomer or a mixture of several diene elastomers.
- elastomer or indistinctly rubber
- diene monomer units monomers carrying two carbon-carbon double bonds, conjugated or not.
- diene elastomers can be classified into two categories: "essentially unsaturated” or “essentially saturated”.
- essentially unsaturated is understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); it is thus that diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the preceding definition and can in particular be qualified as "essentially saturated” diene elastomers (content of units of weak or very weak diene origin, always less than 15%).
- the diene elastomer is a substantially unsaturated diene elastomer.
- iene elastomer capable of being used in the context of the present invention is particularly understood to mean: a) any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms, b) any copolymer of a diene , conjugated or not, having 4 to 18 carbon atoms and at least one other monomer.
- the other monomer can be ethylene, an olefin or a diene, conjugated or not.
- Suitable conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
- Suitable olefins are vinyl aromatic compounds having from 8 to 20 carbon atoms and aliphatic ⁇ -monoolefins having from 3 to 12 carbon atoms.
- Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture “vinyl-toluene” and para-tert-butylstyrene.
- Suitable aliphatic ⁇ -monoolefins are in particular acyclic aliphatic ⁇ -monoolefins having from 3 to 18 carbon atoms.
- the diene elastomer is chosen from the group consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures thereof.
- the diene elastomer is chosen from the group consisting of synthetic polyisoprenes, natural rubber and mixtures thereof.
- the butadiene copolymers are preferably chosen from the group consisting of butadiene-styrene (SBR) copolymers.
- SBR can be prepared in emulsion (ESBR) or in solution (SSBR). Whether it's ESBR or SSBR.
- ESBR emulsion
- SSBR solution
- the copolymers based on styrene and on butadiene there may be mentioned in particular those having a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (molar%) in -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) of trans-1,4 bonds of between 10% and 80%.
- the butadiene-styrene copolymer is an SBR prepared in solution and has a styrene content of between 5% and 60%, preferably from 6% to 30%, by weight relative to the total weight of the copolymer, and a content ( mol%) in -1.2 bonds of the butadiene part of between 4% and 75%, preferably between 15% and 30%.
- the diene elastomer comprises predominantly, preferably exclusively, at least one polyisoprene, preferably at least one epoxidized polyisoprene.
- polyisoprene is understood to mean any polyisoprene, whether or not it is epoxidized.
- the polyisoprene is a non-epoxidized polyisoprene chosen from the group consisting of natural rubber, a synthetic polyisoprene and one of their mixtures.
- the non-epoxidized polyisoprene has a molar ratio of 1,4-cis bond of at least 90%.
- epoxidized polyisoprene means a polyisoprene which has undergone an epoxidation step.
- the epoxidized polyisoprene can be an epoxidized natural rubber, an epoxidized synthetic polyisoprene having a molar ratio of 1,4-cis bond of at least 90% before epoxidation, or a mixture thereof.
- Epoxidized polyisoprene used in the context of the present invention is an elastomer and is not to be confused with an epoxidized polyisoprene of low molar mass generally used as a plasticizer which is not an elastomer given its low molar mass.
- Epoxidized polyisoprene as an elastomer generally has a high raw Mooney viscosity.
- the Mooney viscosities (ML 1 + 4) at 100 ° C. of the epoxidized polyisoprenes which can be used in the context of the present invention are preferably from 30 to 150, more preferably from 40 to 150, even more preferably from 50 to 140.
- Epoxidized polyisoprene whether epoxidized natural rubber or epoxidized synthetic polyisoprene, can be obtained in a known manner by epoxidation of polyisoprene, for example by processes based on chlorohydrin or bromohydrin or processes based on peroxides. hydrogen, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid). Epoxidized polyisoprenes are commercially available.
- the molar rate of epoxidation which is a supplier data, corresponds to the ratio of the number of moles of epoxidized isoprene unit to the number of moles of isoprene unit in the polyisoprene before epoxidation.
- epoxidation rate expressed in molar percentage (mol%) is understood to mean the number of moles of cis-1,4-epoxy-polyisoprene units present in the rubber polymer per 100 moles of total monomer units in this same polymer.
- the rate of epoxidation can be measured in particular by 1 H NMR analysis.
- Epoxyprene 25 and Epoxyprene 50 from the company Guthrie or Ekoprena 25 and Ekoprena 50 from the company Felda.
- the expression "at least one epoxidized polyisoprene” should be understood as one or more epoxidized polyisoprenes which can be differentiated either by their microstructure, their macrostructure or their rate of epoxidation.
- the reference to the amount of epoxidized polyisoprene of the polyisoprene applies to the total mass of the epoxidized polyisoprene of the polyisoprene.
- the characteristic according to which the epoxidized polyisoprene is present in the rubber composition at a level greater than 50 phr means that in the case of a mixture of epoxidized polyisoprenes, the total mass of epoxidized polyisoprenes is greater than 50 phr.
- the epoxidized polyisoprene is a mixture of epoxidized polyisoprenes which can be differentiated from each other by their molar rate of epoxidation
- the at least one epoxidized polyisoprene advantageously exhibits a molar rate of epoxidation ranging from 5% to 85%, preferably from 10% to less than 80%, preferably from 15% to 75%.
- the molar rate of epoxidation of the at least one epoxidized polyisoprene can be within a range ranging from 40% to 80%, preferably from 45% to 75%. This rate of epoxidation is particularly advantageous for improving the reinforcement of the rubber composition.
- the molar rate of epoxidation of the at least one epoxidized polyisoprene can be within a range ranging from 10% to less than 49%, preferably from 15% to less than 40%.
- the content of diene elastomer, preferably polyisoprene, preferably epoxidized polyisoprene, in the composition according to the invention is advantageously within a range ranging from 50 to 100 phr, preferably from 75 to 100 phr, more preferably still it is 100 pce.
- the composition is based on a filler comprising from 10 to 60 phr of carbon black and from 5 to 30 phr of silica, the carbon black representing from 50% to 95% by weight relative to the total weight carbon black and silica.
- the blacks that can be used in the context of the present invention can be any black conventionally used in pneumatic or non-pneumatic tires or their treads (so-called black tire grade).
- black tire grade there will be mentioned more particularly the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM grades), such as for example the blacks NI 15, NI 34, N234, N326. , N330, N339, N347, N375, N550, N683, N772).
- These carbon blacks can be used in the isolated state, as available commercially, or in any other form, for example as a support 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 WO 97/36724 or WO 99/16600). Mixtures of several carbon blacks can also be used in prescribed rates.
- organic fillers other than carbon blacks mention may be made of organic fillers of functionalized polyvinyl as described in applications WO 2006/069792, WO 2006/069793, WO 2008/003434 and WO 2008/003435.
- the BET specific surface area of the carbon black is at least 90 m 2 / g, preferably between 100 and 150 m 2 / g.
- the BET specific surface area of carbon blacks is measured according to standard ASTM D6556-10 [multipoint method (at least 5 points)
- the carbon black advantageously has a COAN oil absorption index greater than or equal to 90 mL / 100 g. COAN, or Compressed Oil Absorption Number, of carbon blacks, is measured according to ASTM D3493-16.
- the level of carbon black (whether there is one or more) in the composition according to the invention is within a range ranging from 15 to 55 phr, preferably from 30 to 50 phr.
- the silicas which can be used in the context of the present invention can be any silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface as well as a CTAB specific surface both less than 450 m 2 / g, of preferably from 30 to 400 m 2 / g. It can also be a mixture of several silicas, as long as they are used in the prescribed rates.
- the BET specific surface area of silica 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 NE ISO 5794-1, annex E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160 ° C
- CT AB specific surface area values of silica 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-N, N, N bromide -trimethylammonium) on the “external” surface of the reinforcing filler.
- the silicas which can be used in the context of the present invention advantageously exhibit a BET specific surface area of less than 250 m 2 / g and / or a CTAB specific surface area of less than 220 m 2 / g, preferably a BET specific surface area within a range ranging from 125 to 200 m 2 / g and / or a CTAB specific surface area within a range from 140 to 170 m 2 / g.
- silicas which can be used in the context of the present invention mention will be made, for example, of the highly dispersible precipitated silicas (called “HDS”) “Ultrasil 7000” and “Ultrasil 7005” from the company Evonik, the silicas “Zeosil 1165MP, 1135MP and 1115MP “from the company Rhodia, the silica” Hi-Sil EZ150G “from the company PPG, the silicas” Zeopol 8715, 8745 and 8755 "from the company Huber, silicas with a high specific surface as described in application WO 03 / 016387.
- HDS highly dispersible precipitated silicas
- the level of silica (whether there is one or more) in the composition according to the invention is within a range ranging from 5 to 25 phr, preferably from 6 to 20 phr.
- an at least bifunctional coupling agent intended to ensure a sufficient connection, of a chemical and / or physical nature, between the silica ( surface of its particles) and the diene elastomer (hereinafter simply referred to as “coupling agent”).
- 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, the said first functional group being suitable interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being able to interact with the diene elastomer.
- the content of coupling agent, in the composition according to the invention is advantageously less than 6% by weight relative to the weight of silica, preferably less than 2%, preferably less than 1% by weight per relative to the weight of silica. More preferably, the composition according to the invention does not include a coupling agent.
- the composition according to the invention comprises silica
- the composition advantageously comprises a silica covering agent.
- silica covering agents mention may be made, for example, of hydroxysilanes or hydrolyzable silanes such as hydroxysilanes (see for example WO 2009/062733), alkylalkoxy silanes, in particular alkyltriethoxysilanes such as, for example, 1 - octyl-tri -ethoxysilane, polyols (eg diols or triols), polyethers (eg polyethylene glycols), primary, secondary or tertiary amines (eg trialkanol amines), an optionally substituted guanidine, in particular diphenylguanidine, hydroxylated or hydrolyzable polyorganosiloxanes (for example a, w -dihydroxy-poly-organosilanes (in particular a, w-dihydroxy-poly
- the silica covering agent is a polyethylene glycol.
- covering the silica, preferably polyethylene glycol, in the composition according to the invention is advantageously included in a range ranging from 1 to 6 phr, preferably from 1.5 to 4 phr.
- the total level of carbon black and silica in the composition according to the invention is within a range ranging from 15 to 90 phr, preferably from 20 to 70 phr.
- the carbon black represents from 60% to 90% by weight, preferably from 65% to 80% by weight, relative to the total weight of carbon black and silica.
- composition according to the invention also has the essential characteristic of comprising a polyethylene having a melting point of between 120 ° C and 160 ° C, hereinafter referred to as "polyethylene” for the sake of drafting simplicity.
- polyethylene having a melting point of between 120 ° C and 160 ° C
- the melting temperature is measured in a well-known manner by DSC according to the standard ASTM D3418 (2015).
- polyethylene is understood to mean a polymer predominantly comprising ethylene units.
- the polyethylene that is to say the polyethylene having a melting point of between 120 ° C and 160 ° C
- the polyethylene comprises more than 50% by mole, preferably more than 75% by mole, more preferably more than 90 mol% of ethylene unit.
- the polyethylene does not comprise a polypropylene unit or comprises less than 10% thereof by weight relative to the total weight of the polyethylene.
- the polyethylene does not include a polypropylene unit.
- the polyethylene is chosen from the group consisting of high density polyethylenes, low density polyethylenes, linear low density polyethylenes, medium density polyethylenes, very high molecular weight polyethylenes, very low density polyethylenes and mixtures of these polyethylenes.
- the polyethylene has a density within a range ranging from 910 to 970 kg / m 3 , more preferably in a range ranging from 940 to 965 kg / m 3 .
- the polyethylene has a melt index at 190 ° C. at 2.16 kg within a range ranging from 0.1 to 25 g / 10 min, preferably within a range ranging from 1 to 15 g / 10 min.
- the melt index can be measured according to ISO 1133.
- the polyethylene can be a functionalized polyethylene comprising at least one functional group comprising at least one heteroatom chosen from the group consisting of Si, N, O, S and Cl.
- the polyethylene when functionalized, it is a polyethylene functionalized by a function chosen from the group consisting of maleic anhydride, epoxy, amines and acid functions, preferably by a maleic anhydride function.
- the level of polyethylene having a melting point of between 120 ° C. and 160 ° C. may be within a range ranging from 3 to 40 phr, preferably from 5 to 30 phr.
- the total level of carbon black, silica and polyethylene having a melting point of between 120 ° C and 160 ° C is within a range ranging from 20 to 90 phr, preferably from 30 to 80 phr.
- the volume fraction of the set of carbon black, silica and polyethylene is within a range ranging from 10% to 40%, preferably from 15% to 35%.
- the total level of thermoplastic polymer that is to say the sum of the thermoplastic polymers including polyethylene, is within a range ranging from 3 to 40 phr, preferably from 5 to 30 phr.
- the The composition does not include any thermoplastic polymer other than polyethylene having a melting point of between 120 ° C and 160 ° C.
- the polyethylene which can be used can be obtained by the conventional known processes, such as in particular polymerization in the presence of metallocene catalysts. At the end of the polymerization, the polyethylene is granulated without any crosslinking reaction.
- Non-functionalized and non-crosslinked polyethylenes are commercially available from suppliers such as Dow Global Technologies, EXXONMOBIL, Silon, ENI.
- polyethylene which can be used commercially, mention may be made of polyethylene “ERACLENE MP90U” from the company ENI or “B5206” from the company SABIC, and by way of example of functionalized polyethylene, mention may be made of “Exxelor”. TM PE 1040 ”from ExxonMobil or“ OREVAC 18302 ”from ARKEMA.
- 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 can in particular be based on sulfur, and / or peroxide and / or bismaleimides.
- the crosslinking system is sulfur-based, this is called a vulcanization system.
- the sulfur can be provided in any form, in particular in the form of molecular sulfur and / or of sulfur donor.
- At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, one can use various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as salts of stearic acid and salts. transition metals, guanide derivatives (in particular diphenylguanidine), or else known vulcanization retarders.
- Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
- the vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N-dicyclohexyl- 2-Benzothiazyl sulfenamide
- TBBS N-ter-butyl-2-benzothiazyl sulfenamide
- TZTD tetrabenzylthiuram disulfide
- ZBEC zinc dibenzyldithiocarbamate
- the rubber compositions may optionally also include all or part of the usual additives usually used in elastomer compositions for tires, such as, for example, plasticizers (such as plasticizing oils and / or plasticizing resins), pigments, conditioning agents. protection such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins (such as described for example in application WO 02/10269). It may further be preferable that the composition according to the invention does not include certain ingredients which could compromise the performance of the composition.
- the composition according to the invention does not include a foaming agent (or "foaming agent" in English) which could penalize the endurance of the composition, degrade the properties of resistance to attack of the composition, etc. II-B Preparation process
- a subject of the present invention is also a process for preparing a composition for the manufacture of the rubber composition according to the invention, characterized in that it comprises the following steps: a) bringing into contact and mixing, concomitantly or successively, in one or more installments, at least one diene elastomer, a filler comprising carbon black and silica, the carbon black representing from 50% to 95% by weight relative to the total weight of carbon black and of silica, and a polyethylene having a melting temperature between 120 ° C and 160 ° C, thermomechanically mixing everything until a maximum temperature Tl greater than or equal to the melting point of the polyethylene is reached, b) reduce the temperature of the mixture obtained at step (a) up to a maximum temperature T2 below the melting point of the polyethylene, then incorporate a crosslinking system into the mixture and mix everything together.
- diene elastomer of carbon black, of silica, of any coupling agent, of polyethylene having a melting point of between 120 ° C and 160 ° C, of the crosslinking system are as defined in point II-A above in their general embodiments, and advantageously in their preferred embodiments.
- step (a) then constitutes a first thermo-mechanical working or mixing phase (sometimes referred to as non-productive phase) at high temperature, up to a maximum temperature between 130 ° C and 190 ° C, preferably between 140 ° C and 180 ° C, followed by a second mechanical work phase (sometimes qualified as “productive” phase) (step (b) of the process according to the invention) at a lower temperature, typically less than 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
- Such phases have been described for example in applications EP 0 501 227 A, EP 0 735 088 A, EP 0 810258 A, WO 2000/05300 or WO 2000/05301.
- the first phase can preferably be carried out in several thermomechanical steps.
- a first step at least one diene elastomer, at least one polyethylene having a melting point of between 120 ° C and 160 ° C, black of carbon, silica, at a temperature between 20 ° C and 100 ° C and, preferably, between 25 ° C and 100 ° C.
- the other ingredients i.e. ie, those which remain if all have not been put at the start
- the total mixing time, in this non-productive phase is preferably between 2 and 10 minutes at a temperature less than or equal to 180 ° C, and preferably less than or equal to 170 ° C.
- the crosslinking system preferably the vulcanization system
- the vulcanization system is then incorporated at low temperature (typically less than 100 ° C.), generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) 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 of a plate, in particular for a characterization in the laboratory, or else extruded, to form for example a rubber profile used for the manufacture of semi- finished in order to obtain products such as a tire tread.
- These products can then be used for the manufacture of tires, according to techniques known to those skilled in the art.
- the crosslinking (or curing) is carried out in a known manner at a temperature generally between 100 ° C and 200 ° C, for example between 130 ° C and 200 ° C, under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the baking temperature, on the crosslinking system adopted, on the crosslinking kinetics of the composition considered.
- the crosslinking is carried out at a temperature between 110 ° C and 160 ° C, preferably between 120 ° C and 150 ° C.
- Polyethylene (whose melting point is between 120 ° C and 160 ° C) can be introduced in the solid state, as sold commercially, or in the liquid state. When the polyethylene is introduced in liquid form, it is then necessary to carry out an additional step of heating the polyethylene to a temperature above its temperature. melting temperature, before being brought into contact with the other constituents of step (a). However, it is preferable to introduce the polyethylene in the solid state.
- the maximum temperature Tl is preferably at least 1 ° C, preferably 2 ° C, preferably 3 ° C, preferably 4 ° C, preferably 5 ° C above the temperature of the polyethylene.
- the maximum temperature T1 is 5 to 20 ° C. higher than the temperature of the polyethylene.
- the maximum temperature T2 is preferably less than 120 ° C, preferably less than 100 ° C, more preferably less than 90 ° C. Preferably, the maximum temperature T2 is within a range from 20 to 90 ° C.
- a subject of the present invention is also a rubber composition capable of being obtained by a process according to the invention.
- a subject of the present invention is also a rubber article comprising a composition according to the invention or a composition obtainable by the process according to the invention.
- the rubber article is advantageously chosen from the group consisting of pneumatic tires, non-pneumatic tires, tracks and conveyor belts.
- a subject of the invention is also a pneumatic or non-pneumatic tire provided with a tread comprising a composition according to the invention or a composition capable of being obtained by the process according to the invention.
- the tread has a tread surface provided with a pattern formed by a plurality of grooves delimiting elements in relief (blocks, ribs) so as to generate material ridges as well as hollows.
- These grooves represent a volume of hollows which, in relation to the total volume of the tread (including both the volume of elements in relief and that of all the grooves) is expressed by a percentage designated herein by "rate. of volume hollow ".
- a volume void ratio of zero indicates a tread without grooves or valleys.
- the present invention is particularly well suited to tire treads intended to equip civil engineering, agricultural and heavy goods vehicles, more particularly civil engineering vehicles whose tires are subjected to very specific stresses, in particular soils. stony on which they roll.
- the pneumatic or non-pneumatic tire provided with a tread comprising a composition according to the invention or with a composition capable of being obtained by the method according to the invention is a tire for a civil engineering vehicle, agricultural or heavy goods vehicles, preferably civil engineering.
- These tires are provided with treads which have, compared with the thicknesses of the treads of tires for light vehicles, in particular for passenger vehicles or vans, large thicknesses of rubber material.
- the wearing part of the tread of a tire for heavy goods vehicles has a thickness of at least 15 mm, that of a civil engineering vehicle at least 30 mm, or even up to 120 mm.
- the tread of the tire according to the invention advantageously has one or more grooves, the average depth of which ranges from 15 to 120 mm, preferably 65 to 120 mm.
- the pneumatic tires according to the invention can have a diameter ranging from 20 to 63 inches, preferably from 35 to 63 inches.
- the average volume void rate over the whole of the tread of the tire according to the invention may be within a range ranging from 5 to 40%, preferably from 5 to 25%.
- a subject of the invention is also a rubber track comprising at least one rubber element comprising a composition according to the invention or a composition capable of being obtained by the process according to the invention, the at least one rubber element being preferably an endless rubber belt or a plurality of rubber pads, as well as a rubber conveyor belt comprising a composition according to the invention or a composition obtainable by the process according to the invention.
- the invention relates to the tires and semi-finished products for tires described above, to rubber articles, both in the raw state (that is to say, before curing) and in the cured state (that is to say , after crosslinking or vulcanization).
- Rubber composition based on at least one diene elastomer from 10 to
- composition according to embodiment 1 in which the diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers, preferably chosen from the group consisting of synthetic polyisoprenes, natural rubber and mixtures thereof.
- the diene elastomer predominantly comprises at least one polyisoprene, preferably at least one epoxidized polyisoprene.
- composition according to embodiment 1 in which the diene elastomer predominantly comprises at least one epoxidized polyisoprene having a molar rate of epoxidation ranging from 5% to 85%. 5. Composition according to embodiment 4, in which the at least one epoxidized polyisoprene has a molar rate of epoxidation ranging from 40% to 80%, preferably from 45% to 75%.
- composition according to embodiment 4 in which at least one epoxidized polyisoprene has a molar rate of epoxidation ranging from 10% to less than 49%, preferably from 15% to less than 40%.
- Mooney viscosity ML 1 + 4
- the level of carbon black is within a range ranging from 15 to 55 phr, preferably from 30 to 50 phr.
- composition according to any one of the preceding embodiments in which the level of silica is within a range ranging from 5 to 25 phr, preferably from 6 to 20 phr.
- composition according to any one of the preceding embodiments not comprising a coupling agent or comprising less than 6% by weight relative to the weight of silica, preferably less than 2% by weight relative to the weight of silica. .
- composition according to any one of the preceding embodiments not comprising a coupling agent.
- composition according to any one of the preceding embodiments in which the total level of carbon black and of silica is within a range ranging from 15 to 90 phr, preferably from 20 to 70 phr.
- composition according to any one of the preceding embodiments in which the carbon black represents from 60% to 90% by weight, preferably from 65% to 80% by weight, relative to the total weight of carbon black and of silica.
- the polyethylene is functionalized by a function chosen from the group consisting of maleic anhydride, epoxy, amines and acids, preferably by a maleic anhydride function.
- the polyethylene does not comprise a polypropylene unit or comprises less than 10% thereof by weight relative to the total weight of the polyethylene.
- composition according to any one of the preceding embodiments in which the level of polyethylene having a melting point of between 120 ° C and 160 ° C is within a range ranging from 3 to 40 phr, preferably from 5 to 30 pc.
- composition according to any one of the preceding embodiments in which the total content of carbon black, of silica and of polyethylene having a melting point of between 120 ° C and 160 ° C, is within a range ranging from 20. to 90 phr, preferably 30 to 80 phr. 19. Composition according to any one of the preceding embodiments, in which the volume fraction of the whole of carbon black, silica and polyethylene is within a range ranging from 10% to 40%, preferably from 15% to 35%.
- thermoplastic polymer in which the total level of thermoplastic polymer is within a range ranging from 3 to 40 phr, preferably from 5 to 30 phr.
- composition according to any one of the preceding embodiments in which the composition does not comprise a thermoplastic polymer other than polyethylene having a melting point of between 120 ° C and 160 ° C.
- Rubber article comprising a composition as defined in any one of embodiments 1 to 21 or 26.
- Pneumatic or non-pneumatic tire provided with a tread comprising a composition as defined in any one of embodiments 1 to 21 or 26.
- Tire according to embodiment 29, being a tire for a civil engineering vehicle, agricultural or heavy goods vehicles, preferably of civil engineering.
- Track comprising at least one rubber element comprising a composition as defined in any one of embodiments 1 to 21 or 26.
- the at least one rubber element is an endless rubber belt or a plurality of rubber pads.
- Rubber conveyor belt comprising a composition as defined in any one of embodiments 1 to 21 or 26.
- results of hysteretic performance are expressed as a percentage base 100 relative to the control composition T1.
- a result greater than 100 indicates an improvement in the hysteretic performance, ie a decrease in thysteresis.
- Track test This test is representative of resistance to attack. It consists in rolling a metal caterpillar mounted on a pneumatic tire mounted on a wheel and vehicle, and inflated, on which rubber pads of a given composition are fixed, on a track filled with stones for a certain time. At the end of the ride, the pads are removed and the number of cuts visible to the naked eye on the surface is counted. The lower the number, the better the aggression resistance performance. To carry out this test, pads of different compositions (see Table 1 below) were manufactured according to the method described in point Vl above.
- the non-crosslinked composition obtained at point Vl was calendered to a thickness of 5.5 mm, cut from the plates (2 of 260x120 mm, 2 of 250x100 mm and 2 of 235x90 mm) which were then stacked. in a pyramidal fashion.
- This block of 6 plates was then inserted into a pyramid-shaped mold with a rectangular base of 260x120 mm and a flat top of 235x90 mm in area, and baked at a temperature of 120 ° C for 300 minutes at a pressure of 180 bars, thus allowing crosslinking of the composition.
- the pads were then mounted on two X-TRACK10 metal tracks from the Caterpillar company, which were themselves mounted on two MICHELIN XMINE D2 12.00R24 tires on the rear axle of a SCANIA R410 truck.
- the tires have been recut to support the tracks.
- the tires were inflated to a pressure of 7 bars and carried a load of 4250 kg per tire.
- the truck drove on a slope without slope covered with porphyry pebbles of size 30/60 obtained from SONVOLES Murcia, Spain, for 5 hours at a speed of 5 km / h.
- the density of pebbles on the track was around 1,000 to 1,500 pebbles per square meter.
- the rubber compositions were produced as described in point II-B above.
- the “non-productive” phase was carried out in a 0.4 liter mixer for 8 minutes, for an average pallet speed of 50 revolutions per minute until a maximum drop temperature of 165 ° C. was reached.
- the "productive” phase was carried out in a cylinder tool at 23 ° C for 5 minutes.
- the crosslinking of the composition was carried out at a temperature between 130 ° C and 200 ° C, under pressure.
- witness T1 is a composition conventionally used in tire treads for civil engineering vehicles.
- Compositions C1 and C2 differ from control T2 only by the presence of polyethylene exhibiting a melting point between 120 ° C and 160 ° C.
- Composition C3 makes it possible to study the impact of the nature of the diene elastomer on the aforementioned performance compromise. [Table 1]
- Epoxidized natural rubber at 50% molar (“Epoxyprene 50” from the company Gurthrie)
Abstract
Description
Claims
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CN202180025033.XA CN115427236A (en) | 2020-04-07 | 2021-04-06 | Rubber composition comprising low-melting polyethylene |
BR112022016180A BR112022016180A2 (en) | 2020-04-07 | 2021-04-06 | RUBBER COMPOSITION COMPRISING POLYETHYLENE WITH LOW MELTING TEMPERATURE |
CA3167814A CA3167814A1 (en) | 2020-04-07 | 2021-04-06 | Rubber composition comprising low melting point polyethylene |
AU2021251445A AU2021251445A1 (en) | 2020-04-07 | 2021-04-06 | Rubber composition comprising low melting point polyethylene |
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PCT/FR2021/050596 WO2021205108A1 (en) | 2020-04-07 | 2021-04-06 | Rubber composition comprising low melting point polyethylene |
Country Status (6)
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CN (1) | CN115427236A (en) |
AU (1) | AU2021251445A1 (en) |
BR (1) | BR112022016180A2 (en) |
CA (1) | CA3167814A1 (en) |
FR (1) | FR3108910B1 (en) |
WO (1) | WO2021205108A1 (en) |
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Also Published As
Publication number | Publication date |
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FR3108910A1 (en) | 2021-10-08 |
BR112022016180A2 (en) | 2022-10-25 |
FR3108910B1 (en) | 2023-06-02 |
CN115427236A (en) | 2022-12-02 |
CA3167814A1 (en) | 2021-10-14 |
AU2021251445A1 (en) | 2022-09-01 |
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