EP3619050A1 - Rubber composition comprising a polyfunctional acrylate incorporated from a masterbatch - Google Patents
Rubber composition comprising a polyfunctional acrylate incorporated from a masterbatchInfo
- Publication number
- EP3619050A1 EP3619050A1 EP18725287.9A EP18725287A EP3619050A1 EP 3619050 A1 EP3619050 A1 EP 3619050A1 EP 18725287 A EP18725287 A EP 18725287A EP 3619050 A1 EP3619050 A1 EP 3619050A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubber composition
- composition according
- group
- elastomer
- peroxide
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 224
- 229920001971 elastomer Polymers 0.000 title claims abstract description 170
- 239000005060 rubber Substances 0.000 title claims abstract description 79
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 66
- 239000000806 elastomer Substances 0.000 claims abstract description 91
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 56
- 150000002978 peroxides Chemical class 0.000 claims abstract description 55
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical class [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 57
- 239000012763 reinforcing filler Substances 0.000 claims description 42
- 229920001577 copolymer Polymers 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 244000043261 Hevea brasiliensis Species 0.000 claims description 24
- 229920003052 natural elastomer Polymers 0.000 claims description 24
- 229920001194 natural rubber Polymers 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- -1 polybutylene succinate Polymers 0.000 claims description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 16
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 15
- 229920003051 synthetic elastomer Polymers 0.000 claims description 15
- 125000004429 atom Chemical group 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229920003049 isoprene rubber Polymers 0.000 claims description 12
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 125000006574 non-aromatic ring group Chemical group 0.000 claims description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims description 10
- 150000001451 organic peroxides Chemical class 0.000 claims description 10
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 7
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 6
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 6
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 5
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 5
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 claims description 5
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 5
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 5
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920002961 polybutylene succinate Polymers 0.000 claims description 5
- 239000004631 polybutylene succinate Substances 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 claims description 4
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 4
- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 claims description 4
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 claims description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 4
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 claims description 3
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 3
- QYFYJZXZGZFAJC-UHFFFAOYSA-N 2-tert-butylperoxypentanoic acid Chemical compound CCCC(C(O)=O)OOC(C)(C)C QYFYJZXZGZFAJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229960002479 isosorbide Drugs 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- UAXOELSVPTZZQG-UHFFFAOYSA-N trimethyl acrylic acid Chemical compound CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007688 edging Methods 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 239000005061 synthetic rubber Substances 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 230000003014 reinforcing effect Effects 0.000 description 21
- 239000011256 inorganic filler Substances 0.000 description 20
- 229910003475 inorganic filler Inorganic materials 0.000 description 19
- 150000001993 dienes Chemical class 0.000 description 18
- 238000004073 vulcanization Methods 0.000 description 17
- 235000019241 carbon black Nutrition 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 13
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000007822 coupling agent Substances 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000010411 cooking Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 239000012933 diacyl peroxide Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000002897 diene group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WKKRYWQLVOISAU-UHFFFAOYSA-N 1,3,5-tris(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC(C(C)(C)OOC(C)(C)C)=CC(C(C)(C)OOC(C)(C)C)=C1 WKKRYWQLVOISAU-UHFFFAOYSA-N 0.000 description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 2
- TUAPLLGBMYGPST-UHFFFAOYSA-N 2,5-dimethyl-2,5-bis(2-methylbutan-2-ylperoxy)hexane Chemical compound CCC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)CC TUAPLLGBMYGPST-UHFFFAOYSA-N 0.000 description 2
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 2
- PHIGUQOUWMSXFV-UHFFFAOYSA-N 2-methyl-2-[2-(2-methylbutan-2-ylperoxy)propan-2-ylperoxy]butane Chemical compound CCC(C)(C)OOC(C)(C)OOC(C)(C)CC PHIGUQOUWMSXFV-UHFFFAOYSA-N 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- DALNRYLBTOJSOH-UHFFFAOYSA-N 3,3,5,7,7-pentamethyl-1,2,4-trioxepane Chemical compound CC1CC(C)(C)OOC(C)(C)O1 DALNRYLBTOJSOH-UHFFFAOYSA-N 0.000 description 2
- KVWLLOIEGKLBPA-UHFFFAOYSA-N 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane Chemical compound CCC1(C)OOC(C)(CC)OOC(C)(CC)OO1 KVWLLOIEGKLBPA-UHFFFAOYSA-N 0.000 description 2
- CCOJJJCQUHWYAT-UHFFFAOYSA-N 4-methyl-4-(2-methylbutan-2-ylperoxy)pentan-2-ol Chemical compound CCC(C)(C)OOC(C)(C)CC(C)O CCOJJJCQUHWYAT-UHFFFAOYSA-N 0.000 description 2
- JNSWFNBIZLIBPH-UHFFFAOYSA-N 4-tert-butylperoxy-4-methylpentan-2-ol Chemical compound CC(O)CC(C)(C)OOC(C)(C)C JNSWFNBIZLIBPH-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- BRQMAAFGEXNUOL-LLVKDONJSA-N [(2R)-2-ethylhexyl] (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCC[C@@H](CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-LLVKDONJSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 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
- 239000006185 dispersion Substances 0.000 description 2
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical class [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical group NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 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
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- HMWCQCYUKQZPRA-UHFFFAOYSA-N 2,4-dimethyl-3-methylidenepent-1-ene Chemical compound CC(C)C(=C)C(C)=C HMWCQCYUKQZPRA-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical group CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical class COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- PJXJBPMWCKMWLS-UHFFFAOYSA-N 2-methyl-3-methylidenepent-1-ene Chemical compound CCC(=C)C(C)=C PJXJBPMWCKMWLS-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
- OAOZZYBUAWEDRA-UHFFFAOYSA-N 3,4-dimethylidenehexane Chemical compound CCC(=C)C(=C)CC OAOZZYBUAWEDRA-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
- YMLZEXWXVILHEH-UHFFFAOYSA-N 5-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCCCOC(=O)C=C YMLZEXWXVILHEH-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- WVMOOZCJXLDWNG-UHFFFAOYSA-N [2-ethyl-1-[(2-methylpropan-2-yl)oxy]hexyl] hydroxy carbonate Chemical compound CCCCC(CC)C(OC(=O)OO)OC(C)(C)C WVMOOZCJXLDWNG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007767 bonding 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
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- NICWAKGKDIAMOD-UHFFFAOYSA-N ethyl 3,3-bis(2-methylbutan-2-ylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)CC)OOC(C)(C)CC NICWAKGKDIAMOD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- GQDMHTPNJOBEKD-UHFFFAOYSA-N hydroxy 2-[(2-methylpropan-2-yl)oxy]propan-2-yl carbonate Chemical compound CC(C)(C)OC(C)(C)OC(=O)OO GQDMHTPNJOBEKD-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 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
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene 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
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 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
- 239000000725 suspension Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012936 vulcanization activator 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
-
- 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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
- C08J2409/04—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
Definitions
- the invention relates to rubber compositions comprising a polyfunctional acrylate, preferably a zinc diacrylate derivative, and a peroxide, especially for the manufacture of tires or semi-finished products for tires.
- compositions are described in certain documents of the state of the art, for objects which are not tires or do not enter into their composition.
- US 2003/0065076 discloses military tank track compositions comprising an elastomer, a reinforcing filler, zinc diacrylate or zinc dimethacrylate, and a peroxide; with the effect of improving the resistance to abrasion.
- US 2005/0084638 discloses coating mix compositions of an air sleeve for suspensions, also comprising an elastomer, a reinforcing filler, zinc diacrylate and a peroxide.
- compositions comprising a derivative of zinc diacrylate, a peroxide and a low level of reinforcing filler to improve both the resistance rolling and resistance to aging in thermal and thermo-oxidative conditions.
- the Applicant has surprisingly discovered that the use of a polyfunctional acrylate incorporated in a diene elastomeric matrix in the form of a masterbatch, in combination with a peroxide, makes it possible to improve the rigidity of the compositions for pneumatic tires without penalizing cohesion.
- the subject of the present invention is in particular a rubber composition based on at least:
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a linear, branched or cyclic C 1 -C 3 hydrocarbon group,
- R, R 2 and R 3 independently represent a hydrogen atom or a hydrocarbon group -C 8 selected from the group consisting of linear alkyl groups, branched or cyclic, alkylaryl groups, aryl groups and aralkyl, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- ⁇ (*) represents the point of attachment of the radical of formula (II) A
- the polyfunctional acrylate being advantageously a derivative of zinc diacrylate in the form of a zinc salt of formula (III)
- R 1, R 2 and R 3 represent, independently of one another, a hydrogen atom or a C 1 -C 7 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups; and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring.
- composition according to the invention for reasons of simplification of writing.
- the present invention furthermore relates to a process for obtaining a rubber composition based on at least one diene elastomer, a peroxide, and a masterbatch comprising an elastomer and a polyfunctional acrylate of formula (I).
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a linear, branched or cyclic C1-C13 hydrocarbon group,
- R- ⁇ , R 2 and R 3 independently represent a hydrogen atom or a hydrocarbon group -C 8 selected from the group consisting of linear alkyl groups, branched or cyclic, alkylaryl groups, aryl groups and aralkyl, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- ⁇ (*) represents the point of attachment of the radical of formula (II) A
- the polyfunctional acrylate being advantageously a derivative of zinc diacrylate in the form of a zinc salt of formula (III)
- R 1, R 2 and R 3 independently of one another are a hydrogen atom or a C 7 hydrocarbon group selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- said method comprising the following steps:
- step (b) contacting and mixing, concomitantly or sequentially, the masterbatch obtained in step (a), a diene elastomer and a peroxide.
- This object is also referred to herein as the "method according to the invention of the reasons for simplification of writing.
- the present invention also relates to:
- a finished or semi-finished rubber article comprising a composition according to the invention or a rubber composition obtainable by the process according to the invention, and
- a tire comprising a composition according to the invention, a rubber composition obtainable by the process according to the invention, or a semi-finished rubber article according to the invention.
- the expression "part by weight per hundred parts by weight of elastomer” (or phr) is meant for the purposes of the present invention, the part, by mass per hundred parts by weight of elastomer or rubber.
- the elastomer mass includes the mass of the diene elastomer and the mass of the elastomer of the masterbatch defined below.
- any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range 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 designated and preferentially.
- composition based on is understood to mean a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react between they, at least in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
- a composition based on an elastomeric matrix and sulfur comprises the elastomeric matrix and the sulfur before cooking, whereas after cooking the sulfur is no longer detectable because it has reacted with the elastomeric matrix forming sulfur bridges (polysulfides, disulfides, mono-sulfide).
- a majority compound in the sense of the present invention, it is understood that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the largest amount by mass among the compounds of the same type, for example more than 50%, 60%, 70%, 80%, 90% or even 100% by weight relative to the total weight of the type of compound.
- a majority reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.
- a “minor” compound is a compound that does not represent the largest mass fraction among compounds of the same type.
- the carbonaceous products mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. These include polymers, plasticizers, fillers, etc. II- DESCRIPTION OF THE INVENTION
- composition according to the invention may contain a single diene elastomer or a mixture of several diene elastomers.
- elastomer or "rubber”, the two terms being considered synonymous
- diene monomers monomers bearing two carbon-carbon double bonds, conjugated or otherwise
- diene elastomers can be classified into two categories “essentially unsaturated” or “essentially saturated”.
- the term "essentially unsaturated” is generally 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% (mole%);
- diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
- the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
- the term “diene elastomer” can be understood more particularly to be used in the compositions according to the invention:
- diene elastomer any type of diene elastomer
- the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
- conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as for example 2, are particularly suitable.
- Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostoises, vinylmesitylene, divinylbenzene, vinylnaphthalene.
- the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
- the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
- the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
- alkoxysilane groups as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445).
- polyether groups as described for example in EP 1 127 909 or US 6,503,973, WO 2009/000750 and WO 2009/000752).
- elastomers such as SBR, BR, NR or IR of the epoxidized type.
- the diene elastomer of the composition according to the invention can be chosen, for example, from the group of highly unsaturated diene elastomers, preferably from the group comprising or consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
- BR polybutadienes
- IR synthetic polyisoprenes
- NR natural rubber
- butadiene copolymers butadiene copolymers
- isoprene copolymers and mixtures of these elastomers.
- Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene styrene (SBIR), butadiene-acrylonitrile copolymers (NBR), butadiene-styrene-acrylonitrile copolymers (NSBR) or a mixture of two or more of these compounds.
- the diene elastomer comprises predominantly at least one isoprene elastomer.
- isoprene elastomer in known manner a homopolymer or copolymer of isoprene, in other words an isoprene elastomer chosen from the group comprising or consisting of natural rubber (NR), which can be plasticized or peptized, the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers.
- NR natural rubber
- IR synthetic polyisoprenes
- the isoprene elastomer is preferably selected from the group consisting of natural rubber, synthetic polyisoprenes and mixtures thereof. Among these synthetic polyisoprenes, polyisoprenes having a level (mol%) of cis 1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used. More preferably, the diene elastomer is natural rubber.
- the level of diene elastomer preferably of isoprene elastomer, preferably natural rubber
- the rubber composition according to the invention may also contain, in a minority manner, any type of synthetic elastomer other than diene, or even with polymers other than elastomers, by example of thermoplastic polymers.
- the rubber composition according to the invention contains no synthetic elastomer other than diene or polymer other than elastomers or contains less than 10 phr, preferably less than 5 phr.
- composition according to the invention further comprises a masterbatch comprising an elastomer and a polyfunctional acrylate, preferably a zinc diacrylate derivative.
- masterbatch (commonly referred to by its English name “masterbatch”) is well known to those skilled in the art. It is an elastomer-based composite in which one or more additives, for example a filler, have been introduced or, in the context of the present invention, a polyfunctional acrylate, preferably a zinc diacrylate derivative.
- a polyfunctional acrylate preferably a zinc diacrylate derivative.
- the Applicant has found, surprisingly, that the incorporation of polyfunctional acrylate, preferably of zinc diacrylate derivative, in the form of a masterbatch makes it possible to increase the modulus of the composition with respect to the incorporation of the same polyfunctional acrylate, preferably of the same derivative of zinc diacrylate, directly in the composition, in powder form in particular.
- the masterbatch of the composition according to the invention comprises a polyfunctional acrylate of formula (I)
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a linear, branched or cyclic C1-C13 hydrocarbon group,
- R, R 2 and R 3 independently represent a hydrogen atom or a hydrocarbon group -C 8 selected from the group consisting of linear alkyl groups, branched or cyclic, alkylaryl groups, aryl groups and aralkyl, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- ⁇ (*) represents the point of attachment of the radical of formula (II) A
- the polyfunctional acrylate being advantageously a derivative of zinc diacrylate in the form of a zinc salt of formula (III)
- R 1, R 2 and R 3 independently represent a hydrogen atom or a C 1 -C 7 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring.
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, it may be for example an atom selected from the group consisting of Zn and Mg.
- A represents a hydrocarbon group C1-C13, it can be for example a hydrocarbon group C1-C1 0, preferably -C 8, preferably C 1 -C 5.
- A represents a cyclic hydrocarbon group, it may be a nonaromatic or aromatic cyclic hydrocarbon group, preferably non-aromatic.
- the C1-C13 hydrocarbon group is chosen from the consti group.
- m is an integer from 1 to 13, preferably from 6 to 10, and ( * ) represents the point of attachment of A to the radical of formula (II).
- valence p depends on the nature of the radical A. According to the invention, p can 2, 3 or 4. For example, p can be 2 or 3, for example 2.
- the bond between X and A may be an ionic bond or a covalent bond.
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, especially Zn or Mg
- the bond between X and A is an ionic bond.
- A represents a carbon atom or a C1-C13 hydrocarbon group
- the bond between X and A is a covalent bond.
- cyclic alkyl group is meant an alkyl group comprising one or more rings.
- group or hydrocarbon chain (e) interrupted by one or more heteroatoms is meant a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of said group or said chain, or between an atom carbon of said group or said chain and another heteroatom of said group or said chain or between two other hetero atoms of said group or said chain.
- the heteroatom (s) may be a nitrogen, sulfur or oxygen atom.
- R 1, R 2 and R 3 independently represent a hydrogen atom, a methyl group or an ethyl group. More preferably, R 2 and R 3 each represent a hydrogen atom and according to a very preferred alternative, R 1 represents a methyl group. Alternatively, R 1, R 2 and R 3 may each represent a hydrogen atom.
- the polyfunctional acrylate is chosen from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate, trimethylopropane trimethylacrylate, trimethylolpropane triacrylate, 1,6-hexanbediol diacrylate, and the like.
- zinc diacrylate derivatives such as zinc diacrylate (ZDA) "Dymalink 633” from Cray Valley or zinc dimethacrylate (ZDMA) "Dymalink 634" from the company Cray Valley
- ZDA zinc diacrylate
- ZDMA zinc dimethacrylate
- other polyfunctional acrylates such as those of the company SARTOMER: trimethylolpropane trimethacrylate (TMPTMA) "SR351", 1,6-hexanbediol diacrylate (HDDA) "SR238”, 3-methyl-1,5 -pentanediol diacrylate (MPDA) "SR341", 1, 10-decanediol diacrylate (DDDA) "SR595", tricyclodecanedimethanol diacrylate (TCDDMDA) "SR833", pentaerythritol tetraacrylate (PETTA) "SR295", trimethylolpropane triacrylate (TMPTA) "SR351", e
- the masterbatch of the composition according to the invention advantageously comprises from 55 to 85% by weight of the polyfunctional acrylate of formula (I), preferably the zinc diacrylate derivative. More preferably, it comprises from 60 to 80% by weight, preferably from 65 to 80% by weight.
- the amount of polyfunctional acrylate of formula (I), preferably a zinc diacrylate derivative in the masterbatch, the amount of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the composition according to the invention is preferably in a range from 5 to 40 phr, preferably from 5 to 35 phr, preferably from 5 to 30 phr, preferably from 10 to 25 phr. Beyond a rate of 40 phr, the properties of the composition may degrade while below a level of 5 phr, the effect of the polyfunctional acrylate is less noticeable on stiffening and reinforcement.
- the masterbatch of the composition according to the invention comprises an elastomer.
- This elastomer may be chosen from the group comprising or consisting of diene elastomers, thermoplastic elastomers and mixtures of these elastomers.
- the elastomer of the masterbatch may be of the same nature or of a different nature from the diene elastomer of the composition according to the invention.
- the elastomer of the masterbatch may be a diene elastomer as defined above. It can also act of a thermoplastic elastomer as defined in WO 201 1/0861 19, WO 2012/152686 or WO 2016/202645 for example.
- the elastomer of the masterbatch may be chosen from the group comprising or consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene-styrene copolymers, isoprene copolymers, copolymers ethylene-propylene, ethylene-propylene-diene copolymers, styrene-butadiene-methacrylate terpolymers and mixtures of these elastomers.
- the elastomer of the masterbatch mainly comprises, preferably exclusively, a polar elastomer.
- the polar elastomer may thus be chosen from the group comprising or consisting of a polar diene elastomer, a polar thermoplastic elastomer or a mixture thereof.
- the Applicant has in fact unexpectedly realized that the incorporation of polyfunctional acrylate of formula (I) in the form of a masterbatch comprising a polar elastomer makes it possible to further increase the modulus of the composition by in relation to the incorporation of the same polyfunctional acrylate of formula (I) in the form of a masterbatch comprising a non-polar elastomer.
- polar elastomer is understood to mean a diene or thermoplastic elastomer having a net dipole resulting from opposite charges (that is to say having negative partial and positive partial charges) from polar bonds. arranged asymmetrically.
- the polar bonds in the polar elastomer may be, for example, bonds between carbon atoms and other atoms having a relatively high electronegativity, such as O, N, F and Cl.
- the polar elastomer is chosen from the group consisting of or consisting of epoxidized natural rubbers (ENR), synthetic epoxidized rubber, styrene-butadiene-methyl methacrylate copolymers (SBM), non-hydrogenated nitrile rubbers (NBR).
- ERR epoxidized natural rubbers
- SBM styrene-butadiene-methyl methacrylate copolymers
- NBR non-hydrogenated nitrile rubbers
- HNBR hydrogenated nitrile rubbers
- EVA copolymers of ethylene and vinyl acetate
- PVA polylactic acid
- PHA polyhydroxyalkanoates
- PB polyhydroxybutyrates
- PV polyhydroxyvalerate
- PHBV polyhydroxybutyrate-co-hydroxyvalerate
- PCL polycaprolactone
- PBS polybutylene succinate
- PES polyethylene succinate
- PBIT polybutylene-co-isosorbide terephthalate
- PEBAX polyamide-polyether copolymers
- the polar elastomer is selected from the group comprising or consisting of epoxidized natural rubbers, styrene-butadiene-methyl methacrylate copolymers and mixtures of these polar elastomers.
- the masterbatch of the composition according to the invention advantageously comprises from 15 to 45% by weight of elastomer. More preferably, it comprises from 20 to 40% by weight, preferably from 20 to 35% by weight.
- composition according to the invention also comprises a peroxide, which may be any peroxide known to those skilled in the art.
- a peroxide which may be any peroxide known to those skilled in the art.
- an organic peroxide it is preferable to use in the context of the present invention.
- organic peroxide is meant an organic compound, that is to say containing carbon, having a group -O-O- (two oxygen atoms linked by a single covalent bond). During the crosslinking process, the organic peroxide decomposes at its unstable 0-0 bond in free radicals. These free radicals allow the creation of crosslinking bonds
- the organic peroxide is preferably selected from the group consisting of or consisting of dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals or peroxyesters.
- the dialkyl peroxides are selected from the group consisting of or consisting of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di -butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-amylperoxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane dimethyl-2,5-di (t-amylperoxy) hexyne-3, n, (x'-di - [(t-butyl-peroxy) isopropyl] benzene, cc, (x'-di - [(t- amylperoxy) isopropyl] benzene,
- a mixture of dicumyl peroxide and 1,3 and 1,4-isopropylcumyl cumyl peroxide (sold for example by Arkema under the trade name Luperox® DC60) is also of interest.
- Certain monoperoxycarbonates such as O-tert-butyl-O- (2-ethylhexyl) monoperoxycarbonate, O-tert-butyl-O-isopropyl monoperoxycarbonate and OO-tert-amyl-O-2-ethyl hexyl monoperoxycarbonate may also be used.
- the preferred peroxide is benzoyl peroxide.
- the preferred peroxides are selected from the group consisting of or consisting of 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 4,4-di- (t-butylperoxy) valerate n-butyl, ethyl 3,3-di- (t-butylperoxy) butyrate, 2,2-di- (t-amylperoxy) -propane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or cyclic methyl ethyl ketone peroxide), the 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 4,4-bis (t-amylperoxy) n-butyl valerate, 3,3-di (t-amylperoxy) butyrate ethyl, 1,1-di (t-butylperoxy)
- the peroxyesters are selected from the group consisting of tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxy-3,5,5-trimethylhexanoate.
- the organic peroxide is particularly preferably selected from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, peroxide.
- the amount of peroxide to be used in the composition according to the invention is less than or equal to 3 phr.
- the amount of peroxide in the composition according to the invention is in a range from 0.1 to 3 phr.
- the amount of peroxide in the composition is in a range from 0.2 to 2.5 phr, preferably from 0.25 to 1.8 phr.
- the ratio of the peroxide content to the level of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the composition according to the invention is less than or equal to 0.09.
- the ratio of the peroxide content to the level of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the composition according to the invention is between 0.01 and 0.09; preferably between 0.03 and 0.09 and more preferably between 0.05 and 0.08.
- the composition of the tire according to the invention may comprise a reinforcing filler known for its ability to reinforce a rubber composition.
- a reinforcing filler typically consists of particles whose average size (in 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.
- the composition contains no reinforcing filler or contains less than 80 phr, preferably less than 65 phr.
- the level of reinforcing filler in the composition according to the invention is preferably in a range from 5 to 60 phr, preferably from 10 to 50 phr.
- the reinforcing filler when present in the composition according to the invention, is advantageously mainly composed of carbon black.
- the reinforcing filler may comprise, for example, from 50 to 100% by weight of carbon black, preferably from 55 to 90% by weight, preferably from 60 to 80% by weight.
- the reinforcing filler comprises exclusively carbon black.
- the reinforcing filler may also further comprise a reinforcing inorganic filler.
- the reinforcing inorganic filler is silica.
- the blacks that can be used in the context of the present invention may be all black conventionally used in tires or their treads (so-called pneumatic grade blacks).
- the reinforcing carbon blacks of the series 100, 200, 300, or the series blacks 500, 600 or 700 will be mentioned more particularly. 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 WO 97/36724 or WO 99/16600).
- the BET surface area of the carbon blacks is measured according to the D6556-10 standard [multipoint method (at least 5 points) - gas: nitrogen - relative pressure range ⁇ / ⁇ 0: 0.1 to 0.3].
- Reinforcing inorganic filler means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or even “non-black” filler. as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words able to replace, in its function of reinforcement, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
- the inorganic filler does not make it possible to reinforce or not sufficiently the composition and is therefore not included in the definition of "reinforcing inorganic filler".
- Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferentially silica (SiO 2 ).
- the silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or fumed silica having a BET surface and a specific surface area CTAB both less than 450 m 2 / g, preferably 30 to 400 m 2 / g, especially between 60 and 300 m 2 / g.
- HDS highly dispersible precipitated silicas
- the BET surface area is determined in a known manner by gas adsorption using the method of Brunauer-Emmett-Teller described in "The Journal of the American Chemical Society” Flight . 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C. - relative pressure range p / po: 0.05 to 0.17).
- the CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
- Reinforcing inorganic fillers are also suitable for mineral fillers of the aluminous type, in particular alumina (Al 2 O 3 ) or aluminum (oxide) hydroxides, or reinforcing titanium oxides, for example described in US Pat. No. 6,610,261 and US Pat. US 6,747,087.
- the physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
- the term "reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described above.
- Those skilled in the art will understand that, as the equivalent filler of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler, since this reinforcing filler would be covered with a filler.
- inorganic layer such as silica
- inorganic layer such as silica
- an at least bifunctional coupling agent or bonding agent
- organosilanes or at least bifunctional polyorganosiloxanes are used.
- the content of coupling agent is advantageously less than 10 phr, it being understood that it is generally desirable to use as little as possible.
- the level of coupling agent is from 0.5% to 15% by weight based on the amount of inorganic filler. Its level is preferably in a range from 0.5 to 7.5 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition.
- the rubber composition according to the invention may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents which can be used in known manner, thanks to to improve the dispersion of the filler in the rubber matrix and to lower the viscosity of the compositions, to improve their ability to use in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes (in particular alkyltriethoxysilanes), polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol amines), hydroxylated or hydrolyzable POSs, for example ⁇ , ⁇ -dihydroxy- polyorganosiloxanes (especially ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes), fatty acids such as stearic acid.
- hydrolysable silanes such as alkylalkoxys
- the ratio of the filler content to the level of the polyfunctional acrylate of formula (I), preferably the zinc diacrylate derivative, in the composition according to the invention is preferably less than or equal to 4.
- the ratio of the degree of charge to the level of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the composition according to the invention is preferably The invention is in a range from 0.15 to 3, preferably from 1.5 to 3.
- the composition of the tire according to the invention does not require a vulcanization system, which is one of its advantages since it simplifies the formula and the preparation of the composition. If however a vulcanization system is present in the composition, it is preferably in small amounts.
- the vulcanization system itself is usually based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the production phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide. stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine).
- Molecular sulfur (or equivalently the molecular sulfur donor agents), when it is used, is at a preferential rate of less than 0.5 phr,
- the composition does not contain molecular sulfur or sulfur-donor agent as vulcanizing agent or contains less than 0.5 phr, preferably less than 0.3 phr, preferably still less than 0.1 phr. More preferably, the composition of the tire according to the invention does not contain molecular sulfur or sulfur-donor agent as vulcanizing agent.
- the vulcanization system of the composition according to the invention may also comprise one or more additional accelerators, for example the compounds of the thiuram family, the zinc dithiocarbamate derivatives, the sulfenamides, the guanidines or thiophosphates.
- additional accelerators for example the compounds of the thiuram family, the zinc dithiocarbamate derivatives, the sulfenamides, the guanidines or thiophosphates.
- any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur in particular thiazole type accelerators and their derivatives, thiuram type accelerators, zinc dithiocarbamates, may be used in particular.
- accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulphenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated “TBBS”), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated “TBSI”), zinc dibenzyldithiocarbamate (in abbreviated “ZBEC”) and mixtures of these compounds.
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N-dicyclohexy
- composition of the tire according to the invention is preferably devoid of any vulcanization accelerator.
- composition according to the invention may optionally comprise all or part of the usual additives usually used in tire elastomer compositions, such as, for example, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, chemical agents and the like.
- plasticizers such as a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both), anti-fatigue agents, reinforcing resins, acceptors (for example resin phenolic novolak) or methylene donors (eg HMT or H3M).
- the composition according to the invention may also advantageously comprise a metal oxide.
- the metal oxide may be selected from the group consisting of or consisting of the oxides of Group II, IV, V, VI, VII and VII metals, and mixtures thereof.
- the metal oxide is selected from the group comprising or consisting of oxides of zinc, magnesium, cobalt, nickel and mixtures thereof. More preferably, the metal oxide is a zinc oxide.
- the level of metal oxide in the composition of the tire according to the invention is advantageously greater than 5 phr. Preferably, this rate is included in a area ranging from 5 to 20 phr, preferably from 7 to 15 phr.
- industrial grade zinc or magnesium oxides from Umicore.
- compositions according to the invention may be prepared for example by any method according to the invention described below.
- the present invention also relates to a process for obtaining a rubber composition based on at least one diene elastomer, a peroxide, and a masterbatch comprising an elastomer and a polyfunctional acrylate of formula (I)
- A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a linear, branched or cyclic C1-C13 hydrocarbon group,
- R, R 2 and R 3 independently represent a hydrogen atom or a hydrocarbon group -C 8 selected from the group consisting of linear alkyl groups, branched or cyclic alkylaryl groups, groups aryls and aralkyls, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- the polyfunctional acrylate being advantageously a derivative of zinc diacrylate in the form of a zinc salt of formula (III)
- R 1, R 2 and R 3 represent independently of each other a hydrogen atom or a C 7 hydrocarbon group selected from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by one or more heteroatoms, R 2 and R 3 may together form a non-aromatic ring,
- said method comprising the following steps:
- step (b) contacting and mixing, concomitantly or sequentially, the masterbatch obtained in step (a), a diene elastomer and a peroxide.
- Step (a) comprises steps of contacting and mixing the polyfunctional acrylate of formula (I), preferably the zinc diacrylate derivative, and the elastomer.
- step (a) comprises a step of incorporating the polyfunctional acrylate of formula (I), preferably zinc diacrylate derivative, into the elastomer of the masterbatch.
- Step (a) may be carried out in any suitable mixer well known to those skilled in the art, as described for example in WO 97/36724 or WO 99/16600. It may for example be carried out at a temperature ranging from 60 ° C to 200 ° C, preferably at a maximum falling temperature of between 130 ° C and 200 ° C, preferably 130 ° C to 165 ° C.
- Step (a) may be carried out, for example, for a period of from 2 to 7 minutes, preferably from 3 to 6 minutes.
- the zinc diacrylate derivative is brought into contact with the elastomer fractionally, that is to say in several times, preferably in 2 to 5 times.
- the elastomer of the masterbatch can be introduced into a mixer, and a fraction of the polyfunctional acrylate of formula (I), preferably zinc diacrylate derivative, for example a third, can be introduced into the mixer 1 minute after the introduction of the elastomer, then another fraction, for example a third, 1 to 2 minutes later, and a final fraction, for example a third, 1 to 2 minutes later.
- the polyfunctional acrylate of formula (I), preferably the zinc diacrylate derivative, may be as defined above for the composition according to the invention.
- R 1 , R 2 and R 3 preferably represent, independently, a hydrogen atom or a methyl group. More preferably, R 2 and R 3 each represent a hydrogen atom. More preferably, R 1 represents a methyl group. Even more advantageously, R 2 and R 3 each represent a hydrogen atom, and R 1 represents a methyl group.
- A may represent an atom belonging to the group consisting of alkaline earth metals or transition metals, preferably an atom selected from the group consisting of Zn and Mg.
- A may represent a hydrocarbon group C1-C13, preferably a hydrocarbon group C1-C10, preferably -C 8, preferably C 1 -C 5.
- the hydrocarbon group in Ci C 3 may be selected from the group consisting of the following radicals:
- n is an integer from 1 to 13, preferably from 6 to 10
- ( * ) represents the point of attachment of A to the radical of formula (II).
- the number of valence p depends on the nature of the radical A. According to the invention, p may be 2, 3 or 4. For example, p may be 2 or 3 for example 2.
- the polyfunctional acrylate is selected from the group consisting of zinc dimethacrylate, magnesium dimethacrylate, zinc diacrylate, magnesium diacrylate, trimethylopropane trimethylacrylate, trimethylolpropane triacrylate, 1,6-hexanbediol diacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 10-decanediol diacrylate, tricyclodecanedimethanol diacrylate, pentaerythritol tetraacrylate, the ethlyene giycoi dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6- hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, tricyclodecanedimethanol dimethacrylate and mixtures thereof, preferably in the group consisting of zinc dimethacrylate, magnesium acrylate, tri
- the masterbatch of the process according to the invention advantageously comprises from 55 to 85% by weight of the polyfunctional acrylate of formula (I), preferably from zinc diacrylate. More preferably, it comprises from 60 to 80% by weight, preferably from 65 to 80% by weight.
- the amount of polyfunctional acrylate of formula (I), preferably a zinc diacrylate derivative, in the masterbatch is preferably in a range from 5 to 40 phr, preferably from 5 to 35 phr, preferably from 5 to 30 phr, preferably from 10 to 25 phr.
- the amount of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the composition obtainable by the process according to the invention is preferably in a range from 5 to 40 phr, preferably from 5 to 35 phr, preferably from 5 to 30 phr, preferably from 10 to 25 phr.
- the elastomer of the masterbatch may be as defined above for the composition according to the invention.
- the elastomer of the masterbatch may be chosen from the group comprising or consisting of diene elastomers, thermoplastic elastomers and mixtures of these elastomers.
- the elastomer of the masterbatch may be a diene elastomer as defined above. It can also act of a thermoplastic elastomer as defined in WO 201 1/0861 19, WO 2012/152686 or WO 2016/202645 for example.
- the elastomer of the masterbatch may be chosen from the group comprising or consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene-styrene copolymers, isoprene copolymers, copolymers ethylene-propylene, ethylene-propylene-diene copolymers, styrene-butadiene-methacrylate terpolymers and mixtures of these elastomers.
- the elastomer of the masterbatch mainly comprises, preferably exclusively, a polar elastomer.
- the polar elastomer may thus be chosen from the group comprising or consisting of a polar diene elastomer, a polar thermoplastic elastomer or a mixture thereof.
- the polar elastomer is chosen from the group comprising or consisting of epoxidized natural rubbers (ENR), synthetic epoxidized rubber, styrene-butadiene-methyl methacrylate copolymers (SBM), non-hydrogenated nitrile rubbers (NBR).
- HNBR hydrogenated nitrile rubbers
- EVA hydrogenated nitrile rubbers
- PBS polyhydroxyalkanoates
- PVB polyhydroxybutyrates
- PV polyhydroxyvalerate
- PHBV polyhydroxybutyrate-co-hydroxyvalerate
- PCL polycaprolactone
- PBS polybutylene succinate
- PES polyethylene succinate
- PBIT polybutylene-co-isosorbide terephthalate
- PEBAX polyamide-polyether copolymers
- the polar elastomer is selected from the group comprising or consisting of epoxidized natural rubbers, styrene-butadiene-methyl methacrylate copolymers and mixtures of these polar elastomers.
- the masterbatch of the process according to the invention advantageously comprises from 15 to 45% by weight of elastomer. More preferably, it comprises from 20 to 40% by weight, preferably from 20 to 35% by weight.
- Step (b) comprises steps of contacting and mixing, concomitantly or sequentially, the masterbatch obtained in step (a), the diene elastomer and the peroxide.
- step (b) comprises the steps of concomitantly or successively incorporating the masterbatch obtained in step (a) and the peroxide into the diene elastomer.
- Step (b) can be carried out in any suitable mixer well known to those skilled in the art.
- This step can be carried out using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as a "non-productive" phase) at high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C., followed by a second mechanical working phase (sometimes referred to as a "productive" phase) at a lower temperature , typically below 1 10 ° 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 the applications EP 0 501 227 A, EP 0 735 088 A, EP 0 810 258 A, WO 2000/05300 or WO 2000/05301.
- the first (non-productive) phase is preferably carried out in several thermomechanical steps.
- a suitable mixer such as a conventional internal mixer, the diene elastomer, the masterbatch obtained in step (a), optionally one or more reinforcing filler (s) different from the polymeric reinforcing filler, optionally plasticizers (and optionally the coupling agents and / or other ingredients with the exception of the crosslinking system), at a temperature between 20 ° C and 100 ° C and preferably between 25 ° C and 100 ° C.
- the other ingredients ie, those that remain if all were not put initially
- the total mixing time is preferably between 2 and 10 minutes at a temperature of less than or equal to 180 ° C, and preferably less than or equal to 170 ° C.
- the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or extruded, to form for example a rubber profile used for the manufacture of semi-finished products. finished in order to obtain products such as an inner layer of tire. These products can then be used for the manufacture of tires, according to the techniques known to those skilled in the art.
- the crosslinking (or baking) is conducted in a known manner at a temperature generally 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 cooking temperature , the crosslinking system adopted, the kinetics of crosslinking of the composition in question or the size of the tire.
- the diene elastomer of the process according to the invention may be as defined above for the composition according to the invention. It may be of the same or different nature of the elastomer of the masterbatch of the process according to the invention.
- the diene elastomer of the process according to the invention may be chosen, for example, from the group of highly unsaturated diene elastomers, preferably from the group comprising or consisting of polybutadienes, synthetic polyisoprenes, natural rubber, copolymers of butadiene, isoprene copolymers and mixtures of these elastomers.
- the diene elastomer comprises predominantly at least one isoprene elastomer, preferably an isoprene elastomer chosen from the group comprising or consisting of natural rubber, which can be plasticized or peptized, synthetic polyisoprenes, different isoprene copolymers and mixtures of these elastomers.
- the level of diene elastomer preferably of isoprene elastomer, preferably natural rubber
- the rubber composition obtainable by the process according to the invention may also contain, in a minority manner, any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
- the rubber composition obtainable by the process according to the invention does not contain any synthetic elastomer other than diene or polymer other than elastomers or contains less than 10 phr, preferably less than 5 phr. . ll-B-2-b Peroxide
- the peroxide used in the process according to the invention may be any peroxide known to those skilled in the art.
- peroxides well known to those skilled in the art, it is preferable to use in the context of the present invention an organic peroxide.
- the organic peroxide is preferably selected from the group consisting of or consisting of dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals or peroxyesters.
- the dialkyl peroxides are selected from the group consisting of or consisting of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di -butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-amylperoxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane dimethyl-2,5-di (t-amylperoxy) hexyne-3, n, (x'-di - [(t-butyl-peroxy) isopropyl] benzene, cc, (x'-di - [(t- amylperoxy) isopropyl] benzene,
- a mixture of dicumyl peroxide and 1,3 and 1,4-isopropylcumyl cumyl peroxide (sold for example by Arkema under the trade name Luperox® DC60) is also of interest.
- Certain monoperoxycarbonates such as 00-tert-butyl-O- (2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate and OO-tert-amyl-O-2-ethyl hexyl monoperoxycarbonate may also be used.
- the preferred peroxide is benzoyl peroxide.
- the preferred peroxides are selected from the group consisting of or consisting of 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 4,4-di- (t-butylperoxy) valerate n-butyl, ethyl 3,3-di- (t-butylperoxy) butyrate, 2,2-di- (t-amylperoxy) -propane, 3,6,9-triethyl-3,6, 9-trimethyl-1, 4,7-triperoxynonane (or cyclic methyl ethyl ketone peroxide), 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 4,4-bis ( t-amylperoxy) n-butyl valerate, ethyl 3,3-di (t-amylperoxy) butyrate, 1,1-di (t-butylperoxy)
- the peroxyesters are selected from the group consisting of tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxy-3,5,5-trimethylhexanoate.
- the organic peroxide is particularly preferably selected from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, peroxide.
- the amount of peroxide to be used for the purposes of the invention is less than or equal to 3 phr.
- the amount of peroxide in the composition is in a range from 0.1 to 3 phr. More preferably, the amount of peroxide in the composition is in a range from 0.2 to 2.5 phr, preferably from 0.25 to 1.8 phr.
- the ratio of the peroxide content to the level of polyfunctional acrylate of formula (I) preferably zinc diacrylate derivative in the rubber composition is less than or equal to 0.09.
- the ratio of the peroxide content to the level of polyfunctional acrylate of formula (I), preferably of zinc diacrylate derivative, in the rubber composition is between 0.01 and 0.09; preferably between 0.03 and 0.09 and more preferably between 0.05 and 0.08.
- the method according to the invention may comprise a step of incorporating reinforcing filler but this is not mandatory. Thus, the method according to the invention can not to include reinforcing charge incorporation step. If the process according to the invention comprises a step of incorporating reinforcing filler, the level of reinforcing filler incorporated to obtain the rubber composition is advantageously less than 80 phr, preferably less than 65 phr, preferably included in a range of from 5 to 60 phr, preferably from 10 to 50 phr.
- the process according to the invention comprises a step of incorporation of reinforcing filler
- the reinforcing filler is advantageously mainly composed of carbon black.
- the reinforcing filler may comprise, for example, from 50 to 100% by weight of carbon black, preferably from 55 to 90% by weight, preferably from 60 to 80% by weight.
- the reinforcing filler comprises exclusively carbon black.
- the reinforcing filler may also further comprise a reinforcing inorganic filler.
- the reinforcing inorganic filler is silica.
- the ratio of the filler content to the level of the polyfunctional acrylate of formula (I), preferably the zinc diacrylate derivative, in the rubber composition is less than or equal to 4.
- the ratio of the filler content and the polyfunctional acrylate of formula (I), preferably the level of zinc diacrylate derivative, in the rubber composition is in a range from 0.15 to 3, preferably from 1, 5 to 3.
- the step of incorporating reinforcing filler may advantageously comprise or consist of a step of contacting and mixing the diene elastomer and the reinforcing filler. This step may be carried out previously, concomitantly or successively in step (b) of the process according to the invention.
- the process according to the invention comprises a reinforcing filler incorporation step
- the reinforcing filler can be incorporated into the diene elastomer independently before, at the same time or after the masterbatch obtained at the same time.
- the process according to the invention may comprise a step of incorporating molecular sulfur or sulfur donor agent as a vulcanizing agent but this is not mandatory.
- the process according to the invention does not comprise a step of incorporation of molecular sulfur or of sulfur donor agent as vulcanizing agent.
- the process according to the invention comprises a step of incorporating molecular sulfur or sulfur-donor agent as vulcanizing agent, the level of molecular sulfur or of sulfur-donor agent as vulcanizing agent incorporated to obtain the rubber composition is advantageously less than 0.5 phr, preferably less than 0.3 phr, more preferably less than 0.1 phr.
- the step of incorporating the vulcanization system may advantageously comprise or consist of a step of contacting and mixing the diene elastomer and the vulcanization system. This step may be carried out previously, concomitantly or successively in step (b) of the process according to the invention.
- the method according to the invention comprises a step of incorporating the vulcanization system
- the vulcanization system can be incorporated in the diene elastomer independently before, at the same time or after the masterbatch obtained at step (a) and the peroxide, and optionally the reinforcing filler.
- the vulcanization system is incorporated after step (b) of the method according to the invention.
- the method according to the invention may comprise a step of incorporating usual additives usually used in tire elastomer compositions, for example pigments, protective agents such as anti-ozone waxes, chemical antiozonants, plasticizing agents (such as a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both), anti-fatigue agents, reinforcing resins, acceptors (for example novolac phenolic resin) or methylene donors (eg HMT or H3M).
- protective agents such as anti-ozone waxes, chemical antiozonants, plasticizing agents (such as a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both), anti-fatigue agents, reinforcing resins, acceptors (for example novolac phenolic resin) or methylene donors (eg HMT or H3M).
- plasticizing agents such as a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil
- the process according to the invention may also advantageously comprise a step of incorporating a metal oxide.
- the metal oxide can be chosen in the group consisting of or consisting of the oxides of Group II, IV, V, VI, VII and VIII metals, and mixtures thereof.
- the metal oxide is selected from the group comprising or consisting of oxides of zinc, magnesium, cobalt, nickel and mixtures thereof. More preferably, the metal oxide is a zinc oxide.
- the level of metal oxide incorporated is advantageously greater than 5 phr. Preferably, this level is in a range from 5 to 20 phr, preferably from 7 to 15 phr.
- the present invention also relates to a rubber composition that can be obtained by a method according to the invention.
- the present invention also relates to a finished or semi-finished rubber article comprising a composition according to the invention or a composition obtainable by the process according to the invention. It also relates to a tire comprising a composition according to the invention, a composition obtainable by the process according to the invention or a semi-finished rubber article according to the invention.
- the invention particularly relates to tires intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or planes, or industrial vehicles chosen from light trucks, "Poids- "heavy” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery, and others.
- SUV Sport Utility Vehicles
- industrial vehicles chosen from light trucks, "Poids- "heavy” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery, and others.
- the composition defined in the present description is particularly well suited to the inner layers of tire.
- the composition may be present in at least one inner layer of the tire.
- the inner layer may be chosen from the group consisting of carcass plies, crown plies, bead-knuckles, toe feet, decoupling layers, edging gums, tamping gums, the sub-ply tread layer and combinations of these inner layers.
- the inner layer is selected from the group consisting of carcass plies, crown plies, bead fences, toe feet, decoupling layers and combinations of these inner layers.
- the invention relates to tires and semi-finished products for tires previously described, rubber articles, both in the raw state (that is to say, before cooking) and in the cooked state (that is to say, before cooking). after crosslinking or vulcanization).
- the module used here is the nominal secant modulus (or apparent) measured in first elongation, calculated by reducing to the initial section of the specimen.
- the nominal secant modulus (or apparent stresses, in MPa) is measured at first elongation at 23 ° C. at 10% and 100% elongation respectively denoted M10 and M100.
- the rigidity results M 10 and M 100 are presented in "base 100" with respect to the composition Control A. The higher the value, the more rigid the composition.
- the rupture stress (CR) tests are based on the NF ISO 37 standard of December 2005 on a dumbbell test tube type H2 and are measured at a pulling speed of 500 mm / min. The breaking stress is measured in MPa. The results of CR are presented in "base 100" with respect to the control composition A. The higher the value, the more the composition is cohesive.
- the masterbatches were prepared in a "Banbury" type internal vane mixer with a working volume of 3.3 liters set to have a tank temperature of 70 ° C, a 75% filling, a rotation pallets of 50 revolutions per minute, for a duration of about 4 minutes to a maximum temperature of 140 ° C.
- the rubber compositions tested were prepared by introducing the diene elastomer into a "Banbury” type internal mixer with a working volume of 3.3 liters, and then incorporating the zinc diacrylate derivative in the form of a powder (control). ) in the form of a masterbatch (compositions according to the invention) and the reinforcing filler (carbon black), at a temperature of about 90 ° C and a rotation of the pallets of 50 revolutions per minute. After 2 minutes and a rise in temperature to about 110 ° C, the metal oxide (ZnO) was incorporated. The total mixing time was about 4 minutes to reach a maximum temperature of 160 ° C. After cooling the mixture thus obtained to a temperature of 40 ° C, the crosslinking system (peroxide) was incorporated; the whole is then mixed for about 5 minutes.
- the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory.
- the crosslinking was then carried out at a temperature of about 160 ° C, under pressure, for 30 minutes.
- Table 1 The examples presented in Table 1 are intended to compare the different properties of compositions according to the invention (C1 to C5) with a control composition T which differs from the compositions according to the present invention in that the zinc diacrylate derivative is incorporated in powder form not in the form of a masterbatch.
- compositions in accordance with the invention all make it possible to improve the rigidity of the compositions, while maintaining a satisfactory level of cohesion, whatever the nature of the elastomer of the masterbatch.
- the compositions according to the invention and using a polar elastomer (ENR, SBM in particular) in the masterbatch show particularly remarkable levels of rigidity.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1753927A FR3065959A1 (en) | 2017-05-04 | 2017-05-04 | RUBBER COMPOSITION BASED ON A ZINC ACRYLATE DERIVATIVE INCORPORATED FROM A MASTER MIXTURE |
PCT/FR2018/051035 WO2018202979A1 (en) | 2017-05-04 | 2018-04-25 | Rubber composition comprising a polyfunctional acrylate incorporated from a masterbatch |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3619050A1 true EP3619050A1 (en) | 2020-03-11 |
Family
ID=59699789
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18725287.9A Withdrawn EP3619050A1 (en) | 2017-05-04 | 2018-04-25 | Rubber composition comprising a polyfunctional acrylate incorporated from a masterbatch |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3619050A1 (en) |
FR (1) | FR3065959A1 (en) |
WO (1) | WO2018202979A1 (en) |
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FR2740778A1 (en) | 1995-11-07 | 1997-05-09 | Michelin & Cie | SILICA-BASED RUBBER COMPOSITION AND FUNCTIONALIZED DIENE POLYMER HAVING TERMINAL SILANOL FUNCTION |
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FR2765882B1 (en) | 1997-07-11 | 1999-09-03 | Michelin & Cie | CARBON BLACK-BASED RUBBER COMPOSITION HAVING SILICA ATTACHED TO ITS SURFACE AND ALCOXYSILANE FUNCTIONALIZED DIENE POLYMER |
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KR100632720B1 (en) | 1997-11-28 | 2006-10-16 | 꽁빠니 제네랄 드 에따블리세망 미쉘린-미쉘린 에 씨 | Reinforcing aluminous filler, a process for manufacturing said filler, a rubber composition comprising said filler, and a tyre and a tread for a tyre, reinforced with said filler |
EP1115785B1 (en) | 1998-07-22 | 2002-10-09 | Société de Technologie Michelin | Coupling system (white filler/diene elastomer) based on polysulphide alkoxysilane, enamine and guanidine derivative |
BR9912343A (en) | 1998-07-22 | 2001-04-17 | Michelin Soc Tech | Rubber composition, process for preparing a rubber composition, using a rubber composition, coupling system and in combination with a zinc dithiophosphate and a guanidic, pneumatic derivative, semi-finished rubber product for pneumatics , tread and coupling system. |
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FR3030544B1 (en) * | 2014-12-22 | 2017-01-13 | Michelin & Cie | PNEUMATIC COMPRISING A COMPOSITION COMPRISING A POLYFUNCTIONAL ACRYLATE DERIVATIVE AND A PEROXIDE |
FR3033329A1 (en) * | 2015-03-05 | 2016-09-09 | Michelin & Cie | PNEUMATIC COMPRISING A COMPOSITION COMPRISING A ZINC DIACRYLATE DERIVATIVE AND A PEROXIDE |
FR3037591A1 (en) | 2015-06-18 | 2016-12-23 | Michelin & Cie | TIRE WITH A TREAD COMPRISING A DIENE ELASTOMER, A THERMOPLASTIC ELASTOMER AND A THERMOPLASTIC RESIN COMPRISING POLYPHENYLENE ETHER PATTERNS |
-
2017
- 2017-05-04 FR FR1753927A patent/FR3065959A1/en not_active Withdrawn
-
2018
- 2018-04-25 WO PCT/FR2018/051035 patent/WO2018202979A1/en unknown
- 2018-04-25 EP EP18725287.9A patent/EP3619050A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
FR3065959A1 (en) | 2018-11-09 |
WO2018202979A1 (en) | 2018-11-08 |
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