EP3727880A1 - Composition comprising a polysulfide compound - Google Patents
Composition comprising a polysulfide compoundInfo
- Publication number
- EP3727880A1 EP3727880A1 EP18836488.9A EP18836488A EP3727880A1 EP 3727880 A1 EP3727880 A1 EP 3727880A1 EP 18836488 A EP18836488 A EP 18836488A EP 3727880 A1 EP3727880 A1 EP 3727880A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- equal
- hydrogen atom
- general formula
- range
- 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- Withdrawn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 188
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 32
- 239000005077 polysulfide Substances 0.000 title claims abstract description 29
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 238000004132 cross linking Methods 0.000 claims abstract description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 229920001971 elastomer Polymers 0.000 claims description 38
- 239000012763 reinforcing filler Substances 0.000 claims description 38
- 229920003244 diene elastomer Polymers 0.000 claims description 32
- 239000006229 carbon black Substances 0.000 claims description 28
- 239000000806 elastomer Substances 0.000 claims description 28
- 238000004073 vulcanization Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- -1 aldehyde amines Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 3
- 150000002357 guanidines Chemical class 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000006235 reinforcing carbon black Substances 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000012991 xanthate Substances 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 235000019241 carbon black Nutrition 0.000 description 27
- 230000003014 reinforcing effect Effects 0.000 description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- 229910052725 zinc Inorganic materials 0.000 description 18
- 239000011256 inorganic filler Substances 0.000 description 16
- 229910003475 inorganic filler Inorganic materials 0.000 description 15
- 150000001993 dienes Chemical class 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 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 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 8
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 8
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 8
- 229960002447 thiram Drugs 0.000 description 8
- SZNCKQHFYDCMLZ-UHFFFAOYSA-L zinc;propan-2-yloxymethanedithioate Chemical compound [Zn+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S SZNCKQHFYDCMLZ-UHFFFAOYSA-L 0.000 description 8
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 7
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000012766 organic filler Substances 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 230000000295 complement effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 125000002897 diene group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NOEQBAWHYSNNCQ-UHFFFAOYSA-N tetrathiecane Chemical compound C1CCCSSSSCC1 NOEQBAWHYSNNCQ-UHFFFAOYSA-N 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 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
- 229920002521 macromolecule Polymers 0.000 description 3
- 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 3
- 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 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 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 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 238000000518 rheometry Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000012936 vulcanization activator Substances 0.000 description 2
- 239000004711 α-olefin Substances 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
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005160 1H NMR spectroscopy Methods 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
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical class COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-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
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920006978 SSBR Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 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
- 230000002411 adverse Effects 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001504 aryl thiols Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000007767 bonding agent Substances 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
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- PCERBVBQNKZCFS-UHFFFAOYSA-N dibenzylcarbamodithioic acid Chemical class C=1C=CC=CC=1CN(C(=S)S)CC1=CC=CC=C1 PCERBVBQNKZCFS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 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
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
Definitions
- the present invention relates to the field of crosslinking of unsaturated polymers, in particular elastomers, and more particularly diene elastomers.
- the present invention particularly relates to compositions comprising unsaturated polymers and polysulfide compounds which may be crosslinking agents.
- Unsaturated polymers are part of the constitution of many objects of everyday life, such as tires, shoe soles, seals, glues, foam articles, profiles for the automobile, etc. These are macromolecules having carbon-carbon double bonds, also called unsaturations, in their main chain and / or in their side chain (s).
- the principle of vulcanization also called sulfur crosslinking, lies in the creation of sulfur bridges between different chains of macromolecules by reaction on the double bonds of these chains of a vulcanizing agent.
- the vulcanizing agent also called sulfur donor, is a compound that is capable of releasing sulfur by heating to the vulcanization temperature.
- the most known and most commonly used vulcanizing agent is elemental sulfur.
- thermo aging a limited resistance vulcanisais obtained due to thermal aging of the latter.
- thermal stresses are the effect of overcuring, which when the temperature of the vulcanizate reaches a value close to the vulcanization temperature, causes a phenomenon of reversion.
- Reversion is a rupture of the network of crosslinking by destruction or shortening of the bridges of sulfur created during vulcanization; that is to say a reduction of the polysulphide bridges in favor of monosulphide or disulfide bridges. This rupture of the network adversely modifies the mechanical properties of the vulcanisai.
- compositions comprising unsaturated polymers capable of being crosslinked at high temperature, in order to save time, without their elongation breaking properties being reduced.
- the invention relates to a composition based on at least one unsaturated polymer and at least one polysulfurized compound of general formula (I).
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- a polysulfide compound of general formula (I) allows, surprisingly, to crosslink at high temperatures compositions based on at least one unsaturated polymer, in particular at least one elastomer and more particularly at least one diene elastomer while limiting the phenomenon of reversion and improving the elongation properties of these compositions and in particular their kinetics of crosslinking.
- the vulcanisais obtained from the compositions of the invention have the advantage of being more thermally stable, especially at high temperatures.
- the compositions of the invention also have the advantage of being produced more rapidly without a reduction in their mechanical properties, in particular without reducing their breaking elongation properties.
- the invention relates to an article comprising at least one composition as definie above.
- this article is a tire.
- the invention relates to a process for the manufacture of a composition
- a composition comprising at least one unsaturated polymer, at least one filler and at least one polysulfurized compound of general formula (I)
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- step (a) the filler is mixed with the unsaturated polymer in a mixer; b) the mixture of step (a) is mechanically kneaded one or more times until a maximum temperature of less than or equal to 200 ° C. is reached; ,
- step (b) cooling the mixture obtained at the end of step (b) to a temperature below 100 ° C;
- step (c) is incorporated in the mixture obtained at the end of step (c) said polysulfurized compound of general formula (I) and,
- step (d) kneading the mixture obtained at the end of step (d) to a temperature below 120 ° C.
- the invention relates to the use of at least one polysulfide compound of general formula (I) as a crosslinking agent for unsaturated polymers.
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- the invention relates to a process for crosslinking unsaturated polymers, said process comprising at least the following steps:
- a and B together represent a covalent bond or when A represents a hydrogen atom and B represents a group -S-Ri- (S) m - R 2 ⁇ SH or a hydrogen atom;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom; and heating the mixture obtained above to a temperature greater than or equal to 130.degree. C., preferably lying in the range 130.degree. C. to 200.degree.
- the invention relates to a crosslinking system comprising at least one vulcanization accelerator and at least one polysulfurized compound of general formula (I)
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a -S-R- (S) m -R 2 -SH group or a hydrogen atom;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- the measurements are carried out at 150 ° C. or at 190 ° C. with an oscillating chamber rheometer, according to the standard DIN53529 - part 3 (June 1983).
- the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition following the crosslinking reaction.
- the measurements are processed according to DIN53529 - Part 2 (March 1983): the minimum and maximum torques, measured in dN.m (deciNewton.meter) are respectively named C min and C max , the distance noted ACouple ( in dN.min) between C max and C min which makes it possible to assess the crosslinking efficiency.
- the conversion rate constant expressed in min 1 of order 1, calculated between 30% and 80% of conversion is also measured which makes it possible to assess the kinetics of crosslinking.
- the percentage of reversion is calculated from the vulcanization isotherm measured by the method DIN-53529.
- the value of C max corresponds to the maximum torque in dN.m reached during the ascending phase of vulcanization. When there is a phenomenon of reversion, then the measured torque decreases with time.
- the percentage of reversion that appears 5 minutes after reaching the C max torque has been calculated: it therefore corresponds to the rheometric torque measured according to the vulcanization isotherm, 5 minutes after the C max has been reached.
- the measured properties are the modules of the compositions, as determined in tensile tests. These tests make it possible to determine the elastic stress and the properties at break. They are carried out in accordance with the French standard NF T 46-002 of September 1988. The elongations at break (in%) are measured in second elongation (ie after an accommodation cycle). The measurements of elongation at break (denoted AR) are carried out under the normal conditions of temperature (23 ⁇ 2 ° C.) and hygrometry (50 ⁇ 5% relative humidity), according to the French standard NF T 40- 101 (December 1979), and also at 100 ° C.
- Nominal secant moduli or apparent stresses, in MPa, referred to strain, without unit
- 10%, 100% or 300% elongation denoted MA10, MA100 and MA300
- true stresses at break in MPa
- 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. a and b excluded) while any range of values referred to as “a to b” means the range of values from “a” to "b” (ie including strict bounds a and b).
- the term "phr” (usually “phr” in English) the part by weight of a constituent per hundred parts by weight of the elastomer or elastomers, that is to say the total weight of or elastomers.
- the carbon-containing 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.
- a first subject of the invention relates to a composition based on at least one unsaturated polymer and at least one polysulfurized compound of general formula (I)
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- composition based on is meant a composition comprising the mixture and / or the reaction product in situ of the various basic constituents used, some of these constituents being able to react and / or being intended for react with each other, at least partially, during the various phases of manufacture of the composition, or during the subsequent firing, modifying the composition as it was initially prepared.
- the compositions as implemented for the invention may be different in the uncrosslinked state and in the crosslinked state.
- the composition of the invention comprises at least one unsaturated polymer, that is to say a single unsaturated polymer or a mixture of unsaturated polymers.
- the unsaturated polymer is an elastomer.
- the unsaturated polymer is a diene elastomer.
- elastomer or "rubber”, the two terms being considered as synonymous
- the two terms being considered as synonymous
- elastomeric origin at least in part ( ie, a homopolymer or copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).
- the diene elastomers can be classified in two categories: "essentially unsaturated” or "essentially saturated”.
- essentially unsaturated is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). moles).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). moles).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). moles).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). moles).
- essentially saturated is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is less than 15% (% by weight). moles), such as butyl rubbers or copolymers of dienes and alpha-olefins EPDM type.
- iene elastomer can be understood more particularly to be used in the compositions according to the invention:
- the invention applies to any type of diene elastomer.
- the composition is intended for the preparation of pneumatic tires, those skilled in the art will understand that the present invention is preferably carried out with essentially unsaturated diene elastomers, in particular of the type (a) or (b) above.
- 1,3-butadiene or isoprene
- 2,3-di (C 1 -C 5) alkyl-1,3-butadienes such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl 1,3-butadiene, 2-methyl-3-ethyl-
- Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, 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 amounts of modifying agent. and / or randomizing 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.
- silanol or polysiloxane functional groups having a silanol end as described, for example, in FR 2,740,778, US 6,013,718 and WO 2008/141702
- 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).
- elastomers such as SBR, BR, NR or IR
- functionalized elastomers may be used in a blend with each other or with unfunctionalized elastomers.
- a functionalized silanol or polysiloxane elastomer having a silanol end, in admixture with a coupled and / or stanned tin elastomer may be used, the latter representing a rate of from 5 to 50 %, for example from 25 to 50%.
- styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) in trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40
- butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
- the diene elastomer of the composition of the invention is chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated to BR), synthetic polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these diene elastomers.
- BR polybutadienes
- IR synthetic polyisoprenes
- NR natural rubber
- 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.
- SBR butadiene-styrene copolymers
- BIR isoprene-butadiene copolymers
- SIR isoprene-styrene copolymers
- NBR butadiene-acrylonitrile copolymers
- NSBR butadiene-styrene-acrylonitrile copolymers
- an SBR elastomer In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, or a high styrene content, for example 35 to 35% by weight, is used in particular. 45%, a vinyl ring content of the butadiene part of between 15% and 70%, a content (mol%) of trans 1,4 bonds of between 15% and 75% and a Tg of between -10 ° C. and 55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of 1,4 cis bonds. More preferably still, the diene elastomer is natural rubber or a synthetic polyisoprene.
- the diene elastomers may be used in blending (mixing) with each other.
- the compositions in accordance with the invention may preferably contain a single diene elastomer, functionalized or not, or a mixture of several diene elastomers, functionalized or not, this or these diene elastomers may be used in combination with any type of elastomer synthetic other than diene, or with polymers other than elastomers, for example thermoplastic polymers.
- the level of diene elastomer in the composition is more than 50 phr (that is to say 50 to 100 phr), more preferably at least 60 phr (that is to say 60 to 100 phr), more preferably at least 70 phr (that is to say from 70 to 100 phr), more preferably still at least 80 phr (i.e. from 80 to 100 phr) and very preferably at least 90 phr (that is to say from 90 to 100 phr).
- the level of diene elastomer is very preferably 100 phr.
- composition of the invention comprises at least one polysulfurized compound of general formula (I)
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom.
- the polysulfide compound of general formula (I) has the function of crosslinking the unsaturated polymer chains, in particular the chains of the elastomers, in particular the chains of the diene elastomers.
- This polysulfurized compound of general formula (I) may be a crosslinking agent. It can advantageously replace the elemental sulfur usually used in a crosslinking.
- the composition of the invention does not comprise elemental sulfur or comprises elemental sulfur at a level of less than 1 phr, preferably less than or equal to 0.5 phr.
- a and B together form a covalent bond is meant that the sulfur atoms adjacent to A and B respectively are connected directly by a covalent bond.
- the polysulfurized compound of general formula (I) is cyclic.
- divalent hydrocarbon group means a group comprising carbon and hydrogen atoms. This group may optionally be interrupted by at least one heteroatom.
- the hydrocarbon group may be optionally branched, in particular substituted with C 1 -C 6 alkyl groups, with phenyl or with benzyl.
- the grouping hydrocarbon may also and preferably be linear, that is to say, it is not branched. It can also be cyclical. Whatever its linear, cyclic or branched form, it may optionally comprise one or more carbon-carbon double bonds.
- heteroatom is meant in the sense of the present invention, the sulfur atoms, the nitrogen atoms, the silicon atoms and the phosphorus atoms.
- R 1 and R 2 represent, independently of one another, alkylene radicals containing from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, more preferably still from 2 to 8 carbon atoms.
- Ri and R 2 are identical.
- R 1 and R 2 represent, independently of one another, identical or different groups, preferably identical, selected from the group formed by -CH 2 -CH 2 -; -CH 2 -CH 2 -CH 2 -; -CH 2 -CH 2 -CH 2 -CH 2 -; -CH 2- (CH 2 ) 3 -CH 2- ; -CH 2- (CH 2 ) 4 -CH 2- ; -CH 2- (CH 2 ) 5 -CH 2- ; -CH 2- (CH 2 ) 6 -CH 2-,
- m represents a number included in a range from 1 to 2, preferably m is equal to 1.
- n represents a number included in a range from 3 to 8, preferably from 3 to 6, more preferably is equal to 3 or 4.
- p represents a number in a range from 1 to 30, preferably from 1 to 15, more preferably from 1 to 3.
- a and B form a covalent bond.
- the polysulfide compound of general formula (I) is a cyclic compound.
- A represents a hydrogen atom and B represents a hydrogen atom or a group -S-Ri - (S) m -R 2 -SH; of preferably A represents a hydrogen atom and B represents a group -S-Ri - (S) m -R 2 -SH.
- the polysulfide compound of general formula (I) is a non-cyclic compound.
- polysulfide compounds of general formula (I), including their preferred variants, may be mixtures of polysulfide compounds of general formula (I) in which case the indices n, m and p are average values. These indices can therefore be integers like fractional numbers.
- the polysulfurized compound of general formula (I) can be in the form of a mixture of cyclic and non-cyclic form.
- A represents a hydrogen atom
- B represents a group -S-Ri - (S) m -R 2 - SH
- the level of the polysulfurized compound of general formula (I) in the composition is in a range from 0.5 to 10 phr, preferably ranging from 0.5 to 5 phr, preferably ranging from 0, 5 to 3 pce.
- the polysulfide compound of general formula (I) may be used alone in the composition of the invention or in combination with one or more co-crosslinking agents. These co-crosslinking agents are well known to those skilled in the art and may be incorporated during the first non-productive phase and / or during the productive phase of manufacture of the composition as described later.
- co-agents may be vulcanization activators, vulcanization accelerators, well known to those skilled in the art.
- stearic acid derivative As vulcanization activators, mention may be made of zinc oxide and stearic acid derivatives.
- stearic acid salt As an example of a stearic acid salt that may be used in the context of the present invention, there may be mentioned in particular zinc or magnesium stearate.
- vulcanization accelerators well known to those skilled in the art, one will preferably choose from the group consisting of thiazoles, sulfenamides, guanidines, amines, aldehyde-amines, dithiophosphates, xanthates thiurams, dithiocarbamates and mixtures thereof.
- benzothiazyl-2-cyclohexyl sulfenamide CBS
- benzothiazyldicyclohexy-1 sulfenamide DCBS
- benzothiazoyl-2-tert.-butyl sulfenamide TBBS
- 2- mercaptobenzothiazole MCT
- benzothiazole disulfide MBTS
- ZMBT benzothiazyl-2-sulfene morpholide
- MPS benzothiazyl-2-sulfene morpholide
- DPG guanidine diphenyl
- TPG triphenyl guanidine
- DPG diorthotolyl guanidine
- DOG diorthotolyl guanidine
- OTBG o-tolylbiguanide
- benzothiazole disulfide MBTS
- TMTD tetramethylthiuram dis
- the composition of the invention comprises at least one complementary vulcanization accelerator, different from the accelerator described above, selected from the group consisting of diphenyl guanidine (DPG), triphenyl guanidine (TPG), diorthotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC) ), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthat
- DPG diphen
- the complementary vulcanization accelerator is zinc dibenzyldithiocarbamate (ZBEC).
- ZBEC zinc dibenzyldithiocarbamate
- polysulfide compounds of general formula (I) useful for the invention may be prepared by any means known to those skilled in the art.
- a process generally comprising a step of reacting a sulfur compound with a compound of formula (II) according to the following reaction scheme can be used:
- R 1, R 2 and m have the same definitions (and same preferred variants) as those mentioned in the general formula (I).
- the polysulfide compounds of general formula (I) may in particular be obtained by an oxidative coupling reaction of the alkylthiol precursors, corresponding arylthiols.
- the reactions described in the following references make it possible to obtain polysulphide compounds by oxidative coupling.
- compositions according to the invention with only the ingredients described above are sufficient to respond to the technical problem, particularly that of obtaining compositions having improved kinetics of crosslinking while limiting or suppressing the phenomenon of reversion to high temperatures of 50.degree. vulcanization.
- compositions of the invention may further comprise additional ingredients.
- the composition of the invention further comprises at least one filler; that is to say a single charge or a mixture of several charges.
- reinforcing fillers As a filler, mention may be made of reinforcing fillers, semi-reinforcing fillers and inert fillers.
- compositions of the invention comprise a reinforcing filler or a mixture of several reinforcing fillers.
- the term "reinforcing filler” is intended to mean any type of filler known for its ability to reinforce a rubber composition that can be used in particular for the manufacture of a tire, for example an organic filler such as black carbon or even a reinforcing inorganic filler.
- the reinforcing filler is selected from carbon black, a reinforcing inorganic filler (preferably silica) and mixtures thereof.
- the reinforcing filler comprises carbon black.
- carbon blacks are suitable all carbon blacks, including the black type HAF, ISAF, SAF conventionally used in tires (so-called pneumatic grade black).
- the reinforcing carbon blacks of the 100, 200 or 300 series for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or even targeted applications, blacks of higher series (eg N660, N683, N772).
- the carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).
- carbon blacks are preferentially suitable reinforcing carbon blacks having a specific surface CTAB (determined according to the French standard NF T 45-007 November 1987, method B) greater than or equal to 90 m 2 / g. More preferably, carbon blacks having a CTAB upper surface area greater than or equal to 120 m 2 / g, more preferably a CTAB specific surface area in a range of from 120 m 2 / g to 180 m 2 / g, are more preferable.
- CTAB specific surface CTAB
- the reinforcing filler may comprise an organic filler other than carbon black.
- organic fillers other than carbon blacks mention may be made of the functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792, WO-A-2006/069793, WO-A-1 2008/003434 and WO-A-2008/003435.
- the reinforcing filler may comprise a reinforcing inorganic filler, preferably a silica.
- any inorganic or mineral filler (whatever its color and its origin (natural or synthetic), also called “white” charge, charge “Clear” or “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 for manufacturing tire, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) at its area.
- -OH hydroxyl groups
- reinforcing inorganic filler is present indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
- reinforcing inorganic filler also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
- reinforcing inorganic fillers are particularly suitable mineral fillers of the siliceous type, in particular of silica (SiO 2 ), or of the aluminous type, in particular of alumina (Al 2 O 3).
- the composition may contain a type of silica or a blend of several silicas.
- the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface and a CTAB specific surface area both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
- the BET surface area is determined by gas adsorption using the method of Brunauer-Emmett-Teller described in "The Journal of the American Chemical Society” (Vol 60, page 309, February 1938), and more specifically according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160 ° C - relative pressure range p / po: 0 , 05 to 0.2]
- HDS highly dispersible precipitated silicas
- a reinforcing inorganic filler is present in the composition, in particular a silica
- a coupling agent or bonding agent
- a coupling agent at least bifunctional intended to ensure a sufficient connection, of a chemical nature and or physical, between the inorganic filler (surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
- polysulfide silanes called “symmetrical” or “asymmetrical” according to their particular structure, are used, as described for example in the applications W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005 / 016650).
- the rubber compositions in accordance with the invention contain coupling agents, their level is preferably in a range from 4 to 12 phr, more preferably from 3 to 8 phr.
- compositions may optionally also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents that are capable in a known manner, by means of a improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents, well known to those skilled in the art , being, for example, hydrolysable silanes such as alkylalkoxy silanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
- these agents well known to those skilled in the art , being, for example, hydrolysable silanes such as alkylalkoxy silanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes
- polysulfide silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described, for example, in claims WO 03/002648 (or US 2005/016651) and WO 00/002649 (or US 2005/016650).
- the reinforcing filler (or a reinforcing filler mixture) comprises mainly by weight of carbon black.
- the carbon black used as a reinforcing filler is predominant in weight; that is to say, it represents the highest rate in phr among the reinforcing fillers of the composition.
- the carbon black represents more than 50% by weight (> 50% by weight) of the total weight of the reinforcing filler, preferably more than 60% by weight.
- Other types of reinforcing filler may be used in a minor minority relative to carbon black in the compositions according to the invention, in particular other reinforcing organic fillers or reinforcing inorganic fillers such as silica.
- a reinforcing inorganic filler is a minority when its weight does not represent the highest level in phr of the reinforcing fillers of the composition; that is to say, the reinforcing inorganic filler represents less than 50% by weight ( ⁇ 50% by weight) of the total weight of the reinforcing filler, preferably less than 40% by weight.
- the level of carbon black in the composition of the invention is then preferably in a range from 20 to 150 phr, preferably from 30 to 90 phr, more preferably from 35 to 80 phr. pce, the optimum being of course differ depending on the particular applications targeted.
- the silica content in the composition is preferably less than 10 phr.
- the reinforcing filler (or a reinforcing filler mixture) comprises predominantly by weight of the silica.
- the silica used as a reinforcing filler is predominant in weight; that is to say, it represents the highest rate in phr among the reinforcing fillers of the composition.
- the silica represents more than 50% by weight (> 50% by weight) of the total weight of the reinforcing filler, preferably more than 60% by weight.
- Other types of reinforcing filler may be used in a minor proportion to the silica in the compositions according to the invention, in particular other reinforcing organic fillers such as carbon black.
- Carbon black is a minority when its weight does not represent the highest level in phr of the reinforcing fillers of the composition; that is, carbon black is less than 50% by weight ( ⁇ 50% by weight) of the total weight of the reinforcing filler, preferably less than 40% by weight.
- the level of silica in the composition of the invention is then preferably in a range from 20 to 150 phr, preferably from 30 to 90 phr, more preferably from 35 to 80 phr, the optimum being of course differ according to the particular applications concerned.
- the content of carbon black in the composition is preferably less than 10 phr, and more preferably 5 phr.
- the composition of the invention may comprise at least one semi-reinforcing filler.
- the semi-reinforcing fillers are not capable of reinforcing by themselves a rubber composition intended for the manufacture of tires, in other words they are not able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade, however they allow an increase in tensile modulus of a rubber composition in which they are incorporated, that is why they are called "semi-reinforcing".
- As a semi-reinforcing filler mention may be made of graphite.
- the composition of the invention may comprise at least one inert filler.
- the inert fillers that may be used in the compositions of the invention may be chosen from chalk, clay, bentonite, talc, kaolin, glass microbeads, glass flakes and a mixture of these compounds.
- compositions of the invention may optionally additionally comprise all or part of the usual additives usually used in elastomer compositions, for example pigments, protective agents such as anti-ozone waxes, chemical ozonants, antioxidants, plasticizing agents such as plasticizing oils or hydrocarbon resins well known to those skilled in the art, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M).
- additives usually used in elastomer compositions for example pigments, protective agents such as anti-ozone waxes, chemical ozonants, antioxidants, plasticizing agents such as plasticizing oils or hydrocarbon resins well known to those skilled in the art, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M).
- compositions of the present invention can be used for the preparation of articles.
- Another object of the present invention relates to an article comprising at least one composition as defined above.
- the term "pneumatic object” means any object which takes its usable form when it is inflated with a gas (or gases) for inflation such as air for example.
- pneumatic objects examples include pneumatic boats, pneumatic tires, balls or balls used for play or sport.
- the article comprising at least one composition as described above is a pneumatic object a tire.
- This tire may be intended to equip including non-motorized vehicles such as bicycles, tourism-type motor vehicles, SUV (Sport Utility Vehicles), two wheels (including motorcycles), aircraft, industrial vehicles chosen among vans, heavy goods vehicles (ie metro, buses, road machinery (trucks and trailers)), off-road vehicles, such as agricultural or civil engineering machinery, others transport or handling vehicles.
- non-motorized vehicles such as bicycles, tourism-type motor vehicles, SUV (Sport Utility Vehicles), two wheels (including motorcycles), aircraft, industrial vehicles chosen among vans, heavy goods vehicles (ie metro, buses, road machinery (trucks and trailers)), off-road vehicles, such as agricultural or civil engineering machinery, others transport or handling vehicles.
- Another article may be a semi-finished product for a pneumatic tire. It can be any type of rubber, such as in particular treads, underlays, sidewalls, layers of beads, layers of protectors, sheets of underlays, sheets of rubber blocks .
- foam articles based on the above composition and of blowing agents having insulating, soundproofing, anti-vibration or reinforcement properties, used in the field of sports and leisure-like structure. of balloon, epaulette of protection.
- foam or “foam structure” is meant an object or article or material of lower density than that of the starting material.
- compositions are manufactured in appropriate mixers, using for example 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 "non-phase” phase). at high temperature, up to a maximum temperature of between 130.degree. C. and 200.degree. C., preferably between 145.degree. C. and 185.degree. C., followed by a second phase of mechanical work (sometimes referred to as a productive phase). ) At a lower temperature, typically below 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking agent or the crosslinking system.
- Another object of the present invention relates to a method of manufacturing a composition
- a composition comprising at least one unsaturated polymer, at least one filler, preferably at least one reinforcing filler as described above and at least one a polysulfide compound of general formula (I)
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m - FL - SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom;
- said method comprising at least the following steps:
- step (a) the filler is mixed with the unsaturated polymer in a mixer; b) the mixture of step (a) is mechanically kneaded one or more times until a maximum temperature of less than or equal to 200 ° C. is reached; ,
- step (b) cooling the mixture obtained at the end of step (b) to a temperature below 100 ° C; d) is incorporated in the mixture obtained at the end of step (c) said polysulfurized compound of general formula (I) and,
- step (d) kneading the mixture obtained at the end of step (d) to a temperature below 120 ° C.
- the method may further comprise a step (f) during which the composition obtained at the end of step e) is extruded or calendered.
- the method may further comprise a step (g) during which the mixture obtained is heated at the end of step (e) or the extruded or calendered composition obtained at the end of step (f) at a temperature greater than or equal to 130 ° C, preferably in the range of 130 ° C to 200 ° C.
- the first phase is conducted in a single thermomechanical step during which is introduced into a suitable mixer such as a conventional internal mixer, all the necessary constituents, the possible complementary coating or processing agents and other various additives, except for the polysulfide compound of the general formula (I), (including these preferred embodiments and its preferred variants) or the crosslinking system comprising the compound polysulfide of general formula (I), (including these preferred embodiments and its preferred variants) and the co-agent.
- a suitable mixer such as a conventional internal mixer
- the polysulfide compound of the general formula (I), (including these preferred embodiments and its preferred variants) or the crosslinking system comprising the compound polysulfide of general formula (I), (including these preferred embodiments and its preferred variants) and the co-agent After cooling the mixture thus obtained during the first non-productive phase, the polysulfurized compound of general formula (I) (including these preferred embodiments and its preferred variants) or the crosslinking system comprising the compound is then incorporated.
- polysulfide of general formula (I), (including these preferred embodiments and its preferred variants) and the co-agent at low temperature ie a temperature of less than or equal to 120 ° C., generally in an external mixer such as roll mixer, the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes
- the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or still extruded.
- the crosslinking (or baking) is conducted according to any procedure known to those skilled in the art, at a temperature, at a pressure and for a suitable duration depending on the nature and use of the composition.
- the crosslinking is carried out in a known manner at a temperature generally greater than or equal to 130.degree. C., in a range from 130.degree. C. to 200.degree. C., for a sufficient time which may vary for example between 5 and 90 minutes. . 2.4 Use of the Compound of General Formula (I) and Crosslinking Process
- Another object of the invention relates to the use of at least one polysulfurized compound of general formula (I) as crosslinking agent for unsaturated polymers.
- a and B together form a covalent bond or A represents a hydrogen atom and B represents a group -S-Ri - (S) m - R 2 -SH or a hydrogen atom;
- n is a number in a range from 1 to 3;
- n is a number greater than or equal to 3;
- p is a number greater than or equal to 1;
- R 1 and R 2 represent, independently of one another, identical or different divalent hydrocarbon groups containing from 1 to 18 carbon atoms, optionally interrupted by a heteroatom
- polysulfide compounds of general formula (I) also apply to this use as a crosslinking agent for unsaturated polymers.
- the polymers are elastomers, more preferably diene elastomers, as described above.
- Another object of the present invention relates to a process for crosslinking unsaturated polymers, said process comprising at least the following steps:
- Another object of the present invention relates to a crosslinking system comprising at least one vulcanization accelerator and at least one polysulfide compound of general formula (I) as described above, including its embodiments and its variants. previously described.
- Vulcanization accelerators are well known to those skilled in the art and have been described above.
- the vulcanization accelerator is selected from the group consisting of thiazoles, sulfenamides, guanidines, amines, aldehyde amines, dithiophosphates, xanthates, thiurams, dithiocarbamates and mixtures thereof.
- a vulcanization accelerator from benzothiazyl-2-cyclohexyl sulfenamide (CBS), benzothiazyldicyclohexy-1 sulfenamide (DCBS), benzothiazoyl-2-tert-butyl.
- TBBS sulfenamide
- MCT 2-mercaptobenzothiazole
- MBTS benzothiazole disulfide
- ZMBT 2-mercaptobenzothiazole zinc or sodium salt
- benzothiazyl-2-sulfene morpholide MS
- DPG diphenyl guanidine
- TPG triphenyl guanidine
- DDG diorthotolyl guanidine
- OTBG o-tolylbiguanide
- benzothiazole disulfide MBTS
- TMTD tetramethylthiuram disulfide
- TBzTD tetrabenzylthiuram disulfide
- ZBEC zinc dibenzyldithiocarbamate
- ZDMC zinc N, N'-dimethylcarbamodithioates
- ZDEC zinc N, N'-diethylcarbamodithioates
- ZDEC zinc N, N'-dibut
- the crosslinking system comprises a complementary vulcanization accelerator, different from the accelerator described above, selected from the group consisting of diphenyl guanidine (DPG), triphenyl guanidine (GPT). , diorthotolyl guanidine (DOTG), o-tolylbiguanide (OTBG), benzothiazole disulfide (MBTS), tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC), zinc N, N'-dimethylcarbamodithioates (ZDMC), zinc N, N'-diethylcarbamodithioates (ZDEC), zinc N, N'-dibutylcarbamodithioates (ZDBC), zinc N, N'-dibenzylcarbamodithioates (ZDBC), zinc isopropylxanthate
- DPG diphen
- the vulcanization accelerators are commercially available from many suppliers such as Nocil, Lanxess, Flexsys for example.
- the crosslinking system of the invention may further comprise a stearic acid derivative and zinc oxide.
- stearic acid derivative stearic acid or a salt of stearic acid, both of which are well known to those skilled in the art.
- stearic acid salt useful in the context of the present invention include zinc stearate or magnesium.
- compositions comprising an unsaturated polymer reinforced with carbon black, these compositions differing from each other by the following technical characteristic:
- composition Cl is a non-compliant composition comprising elemental sulfur as a crosslinking agent
- composition C2 is a non-conforming composition comprising a polysulfide compound of formula different from general formula (I): 1,2,3,4-tetrathiecane; and
- composition C3 is a composition in accordance with the invention comprising a polysulfurized compound of general formula (I): compound A.
- 1,2,3,4-Tetrathiecane is synthesized according to Reaction Scheme No. 1 and according to the following synthesis protocol:
- the molar purity is greater than 98 mol%. (1H NMR).
- the product is then taken up in chloroform (6 mL of the solvent to 1 g of product) and is heated at 50 ° C (bath temperature) for 3 hours. An insoluble fraction and a soluble fraction are obtained.
- Compound A is thus obtained in the form of a mixture of the cyclic form (insoluble fraction) and of the open form (soluble fraction).
- the proportion of the reactants is such that the value of the index n is centered on 3.
- the insoluble fraction (cyclic form) is filtered and washed on the filter with chloroform (50 mL) and dried at room temperature under atmospheric pressure. At the end of this treatment, a white polymer product (9.8 g) is obtained. This product being insoluble in the usual solvents, it has not been characterized.
- the soluble fraction (open form) is in turn concentrated and analyzed by NMR (see NMR characterization below). The product obtained contains oligomers in which the index p has a value in the range from 12 to 23.
- the NMR data are as follows:
- compositions C1 to C3 are presented in Table I. The amounts are expressed in parts per 100 parts of elastomers (phr). The compositions are formulated with iso-mole of sulfur.
- the mixture thus obtained is recovered and cooled on an external mixer at room temperature (23 ° C.).
- the polysulfurized compound of general formula (I) ((7) or (8) depending on the composition) and the crosslinking accelerator are incorporated into the mixture on the external mixer (homofilizer), then twelve passes in the portfolio are made to homogenize The mixture.
- compositions are then calendered in the form of rubber plates with a thickness of 2 to 3 mm for measuring the rheometric and mechanical properties.
- compositions indicated below are those measured after firing (or crosslinking) at t 90 (cf method DIN 53529) at 150 ° C. or at 190 ° C. 3.4 - Results
- composition C1 not according to the invention comprising elemental sulfur as crosslinking agent has a reversion phenomenon at high temperatures (firing temperature at 190 ° C).
- composition C3 according to the invention comprising a polysulfide compound of general formula (I) instead of elemental sulfur (composition C1 not in accordance with the invention) does not exhibit a reversion phenomenon at high temperatures. Cooking. Moreover, the composition C3 according to the invention has elongation properties greater than those of the composition Cl, regardless of the firing temperature.
- composition C3 according to the invention has a higher firing kinetics than the composition C2 not according to the invention comprising a polysulfide compound of formula different from that of the formula (I), whatever the cooking temperature.
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Abstract
Description
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FR2918064B1 (en) | 2007-06-28 | 2010-11-05 | Michelin Soc Tech | PROCESS FOR THE PREPARATION OF POLYETHER BLOCK DIENE COPOLYMER, REINFORCED RUBBER COMPOSITION AND PNEUMATIC WRAPPING. |
FR2951178B1 (en) | 2009-10-08 | 2012-08-17 | Michelin Soc Tech | FUNCTIONALIZED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME. |
-
2018
- 2018-12-18 EP EP18836488.9A patent/EP3727880A1/en not_active Withdrawn
- 2018-12-18 WO PCT/FR2018/053372 patent/WO2019122688A1/en unknown
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