EP4271741A1 - Rubber composition with longer lasting antiozonation - Google Patents
Rubber composition with longer lasting antiozonationInfo
- Publication number
- EP4271741A1 EP4271741A1 EP20968171.7A EP20968171A EP4271741A1 EP 4271741 A1 EP4271741 A1 EP 4271741A1 EP 20968171 A EP20968171 A EP 20968171A EP 4271741 A1 EP4271741 A1 EP 4271741A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- moiety
- rubber composition
- rubber
- combinations
- ozone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000005060 rubber Substances 0.000 title claims abstract description 89
- 230000002045 lasting effect Effects 0.000 title description 7
- 238000004073 vulcanization Methods 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 14
- 235000019241 carbon black Nutrition 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920003244 diene elastomer Polymers 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 239000012763 reinforcing filler Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 150000001408 amides Chemical group 0.000 claims description 7
- 150000002148 esters Chemical group 0.000 claims description 7
- 150000002576 ketones Chemical group 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 150000003573 thiols Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 claims description 4
- LHGMHYDJNXEEFG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminocyclohexa-2,5-dien-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C=CC(=O)C=C1 LHGMHYDJNXEEFG-UHFFFAOYSA-N 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 2
- 125000003172 aldehyde group Chemical group 0.000 claims 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims 2
- NZNWJKIJAJGFJV-UHFFFAOYSA-N CC(C)CC(C)NC(C=C1)=CC=C1N=C(C=C1)C=CC1=O Chemical compound CC(C)CC(C)NC(C=C1)=CC=C1N=C(C=C1)C=CC1=O NZNWJKIJAJGFJV-UHFFFAOYSA-N 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 229920003049 isoprene rubber Polymers 0.000 claims 1
- 239000011115 styrene butadiene Substances 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 12
- 238000013508 migration Methods 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 9
- 150000004060 quinone imines Chemical group 0.000 abstract description 6
- 238000006385 ozonation reaction Methods 0.000 abstract description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005923 long-lasting effect Effects 0.000 abstract description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 45
- 238000009472 formulation Methods 0.000 description 25
- 238000005336 cracking Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000000806 elastomer Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000523 sample Substances 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000010058 rubber compounding Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001299 aldehydes Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 5
- 102100028626 4-hydroxyphenylpyruvate dioxygenase Human genes 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 e.g. Polymers 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229920002469 poly(p-dioxane) polymer Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FKHKSWSHWLYDOI-UHFFFAOYSA-N 2-phenylbenzene-1,4-diamine Chemical class NC1=CC=C(N)C(C=2C=CC=CC=2)=C1 FKHKSWSHWLYDOI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- PUYVXGYHLVKSKH-UHFFFAOYSA-N 4-[4-(dimethylamino)anilino]phenol Chemical compound C1=CC(N(C)C)=CC=C1NC1=CC=C(O)C=C1 PUYVXGYHLVKSKH-UHFFFAOYSA-N 0.000 description 2
- GLUKPDKNLKRLHX-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;sulfuric acid Chemical compound OS(O)(=O)=O.CN(C)C1=CC=C(N)C=C1 GLUKPDKNLKRLHX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- 241000277338 Oncorhynchus kisutch Species 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 239000012936 vulcanization activator Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- FHILEYKYROYCLO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[4-(4-methylpentan-2-ylamino)anilino]phenol Chemical compound CC(C)CC(C)NC(C=C1)=CC=C1NC(C=C1C(C)(C)C)=CC(C(C)(C)C)=C1O FHILEYKYROYCLO-UHFFFAOYSA-N 0.000 description 1
- AXGXWNLRODIIQQ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[4-(4-methylpentan-2-ylamino)phenyl]iminocyclohexa-2,5-dien-1-one Chemical compound CC(C)CC(C)NC(C=C1)=CC=C1N=C(C=C1C(C)(C)C)C=C(C(C)(C)C)C1=O AXGXWNLRODIIQQ-UHFFFAOYSA-N 0.000 description 1
- NDACNGSDAFKTGE-UHFFFAOYSA-N 3-hydroxydiphenylamine Chemical compound OC1=CC=CC(NC=2C=CC=CC=2)=C1 NDACNGSDAFKTGE-UHFFFAOYSA-N 0.000 description 1
- CBNWZEYDJZUZIK-UHFFFAOYSA-N 4-[3-methyl-4-(4-methylpentan-2-ylamino)anilino]phenol Chemical compound CC(C)CC(C)NC(C=C1)=C(C)C=C1NC(C=C1)=CC=C1O CBNWZEYDJZUZIK-UHFFFAOYSA-N 0.000 description 1
- UWLOQQAQKSYLDP-UHFFFAOYSA-N 4-[4-(4-methylpentan-2-ylamino)anilino]phenol Chemical compound CC(C)CC(C)Nc1ccc(Nc2ccc(O)cc2)cc1 UWLOQQAQKSYLDP-UHFFFAOYSA-N 0.000 description 1
- WNMOHMVPTWKTKQ-UHFFFAOYSA-N 4-[4-[(3,5-dinitrothiophen-2-yl)amino]anilino]phenol Chemical compound [O-][N+](C1=C(NC(C=C2)=CC=C2NC(C=C2)=CC=C2O)SC([N+]([O-])=O)=C1)=O WNMOHMVPTWKTKQ-UHFFFAOYSA-N 0.000 description 1
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- NWCROCYXOFKJJG-UHFFFAOYSA-N 5-(4-hydroxyanilino)-2-(4-methylpentan-2-ylamino)phenol Chemical compound CC(C)CC(C)NC(C=CC(NC(C=C1)=CC=C1O)=C1)=C1O NWCROCYXOFKJJG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- QYRVLYSZLHKAAM-UHFFFAOYSA-N CC(C)CC(C)NC(C=C1)=CC=C1N=C(C=C1)C=CC1=S Chemical compound CC(C)CC(C)NC(C=C1)=CC=C1N=C(C=C1)C=CC1=S QYRVLYSZLHKAAM-UHFFFAOYSA-N 0.000 description 1
- CDCGROUZTLAMIL-UHFFFAOYSA-N CC(C)CC(C)NC(C=CC(N=C(C=C1)C=CC1=O)=C1)=C1O Chemical compound CC(C)CC(C)NC(C=CC(N=C(C=C1)C=CC1=O)=C1)=C1O CDCGROUZTLAMIL-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- ZKUVICJQDGCOBI-UHFFFAOYSA-N N-(2-aminophenyl)-N-phenylhydroxylamine Chemical compound ON(C1=C(C=CC=C1)N)C1=CC=CC=C1 ZKUVICJQDGCOBI-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical class ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008380 degradant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 239000002272 engine oil additive Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 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
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- FMMQDMHSGNXJSQ-UHFFFAOYSA-N n,n-diphenylhydroxylamine Chemical class C=1C=CC=CC=1N(O)C1=CC=CC=C1 FMMQDMHSGNXJSQ-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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical class C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000010966 qNMR Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08K5/16—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
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- Tires and other articles that are made of rubber are manufactured from rubber compositions that include rubber, e.g., natural rubber, synthetic rubber or combinations thereof, reinforcing fillers, vulcanizing agents, and other components that improve the physical mechanical characteristics of both the uncured and the cured rubber compositions.
- rubber e.g., natural rubber, synthetic rubber or combinations thereof, reinforcing fillers, vulcanizing agents, and other components that improve the physical mechanical characteristics of both the uncured and the cured rubber compositions.
- PPDs may include N-isopropyl-N-phenyl-p-phenylene (IPPD), N-l,3-dimethylbutyl-N’- phenyl-p-phenylendiamine (6PPD), N, N'-bis-(l,4-dimethylpentyl)-p-phenylenediamine (77PD), N-cyclohexyl-N'-phenyl-/?-phenylenediamine (CHPPD), and N.N’-diphenyl-p- phenylenediamine (DPPD).
- IPPD N-isopropyl-N-phenyl-p-phenylene
- 6PPD N-l,3-dimethylbutyl-N’- phenyl-p-phenylendiamine
- 77PD N, N'-bis-(l,4-dimethylpentyl)-p-phenylenediamine
- CHPPD N-cyclohexyl-N
- the antiozonant has to migrate to the surface in order to react with and provide protection against ozone in the environment, such as in the case of tire sidewalls and treads.
- the migration rate dictates the service life of the rubber articles; the faster the migration to tiie surface, the better the initial protection.
- too fast a migration to the surface will not only negatively impact the long-term protection due to surface leaching and/or volatilization, but also cause “staining” of the article due to excessive surface concentration. Therefore, some longer-lasting antiozonants of larger molecular sizes have been proposed and developed.
- US6,444,759 discloses a rubber composition having protective agent as a salt form of p-phenylenediamine and acid; said composition not comprising an elastomeric copolymer having glycidyl groups.
- US5, 047, 530 teaches the preparation and use of a larger molecule, substituted triazine for longer lasting and non-staining ozone protection.
- hindered phenols for example, 2,2'- methylenebis(4-methyl-6-tert-butylphenol)
- antioxidants are often used as an antioxidant in rubber compositions, even though they have no protection against ozone attack
- these hindered phenols are generally non-staining, they are often compounded in light colored articles where staining should be minimized, such as white sidewalls and colored treads in tires.
- the exact mechanisms are still not well known, it is generally accepted that it is the hydroxyl group that acts as a primary antioxidant by donating a hydrogen atom to a radical, scavenging the radical generated during oxidation or aging.
- US8,207,247 teaches a process to mix a rubber composition comprising natural rubber and an additive selected from aforementioned chemicals, preferably a quinonedimine.
- US10,723,969 discloses the use of alkylated hydroxy-phenyl-phenylamine, or sPPA-OH, reference the structure below, in automobile engine lubricating oil to provide antioxidation and deposit control performance.
- US 10,723,969 teaches the use of a single amine structure, and does not teach that this engine oil additive would be useful as a tire antidegradant.
- Such embodiments include a tire component; the tire component comprising a rubber composition that is based upon a crosslinkable elastomer composition; the cross-linkable elastomer composition comprising, per 100 parts by weight of rubber (phr), a highly unsaturated diene elastomer, a reinforcing filler, a vulcanization package, and an anti-degradant of a hydroxylated form of substituted phenyl-p- phenylenediamine (I), herein denoted as sPPD-OH, or a “quinoneimine” form of substituted (hydroxy)phenylamine (U), herein denoted as sPAQI having the following structures respectively:
- m is 1 or 2
- n is 0, 1, or 2
- p is 0, 1, 2, 3, or 4
- q is 0, 1, 2, 3, or 4
- the summation of m and p is less than 6
- the summation of n and q is less than 5.
- X is selected from oxygen, sulfur, and nitrogen.
- each of R’ and R can be the same or different, and is selected from an alkyl moiety, a cycloalkyl moiety, an aryl moiety, an amine moiety, an amide moiety, an alcohol moiety, an aldehyde moiety, a ketone moiety, a carboxylic acid moiety, an ether moiety, an ester moiety, and a thiol moiety, or combinations thereof.
- FIG. 1 provides schematic view of a “composite” ozone test specimen to determine the migration of the antiozonant.
- FIG. 1 provides schematic view of a “composite” ozone test specimen to determine the migration of the antiozonant.
- the present invention pertains to a rubber having a longer lasting antiozonant.
- embodiments and/or methods of the invention one or more examples of which are illustrated in or with the drawings.
- Each example is provided by way of explanation of the invention, not limitation of the invention.
- In feet it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention.
- features or steps illustrated or described as part of one embodiment can be used with another embodiment or steps to yield a still further embodiments or methods.
- the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
- Methods that are embodiments of the present invention include methods for manufacturing a tire component, such methods comprising mixing together components of a rubber composition into a non-productive mix, the components including a highly unsaturated diene elastomer, a reinforcing filler, and an antiozonant of a hydroxylated form of substituted phenyl-p-phenylenediamine sPPD-OH or a quinoneimine form of the substituted p- (hydroxy)phenylamine sPAQL
- Such methods may further include cooling the non-productive mix and mixing a vulcanizing package into the non-productive mix to convert the non-productive mix to a productive mix.
- the aforementioned antiozonant can be added at the same time as the vulcanizing package into the non-productive mix to form the productive mix.
- the method may further include forming the tire component from the productive mix.
- dPPD-OH denoted for 4-(4-(dimethylamino)phenylamino)phenol
- dPAQI denoted for 4-(4-(dimethylamino)phenylimino)cyclohexa-2,5-dienone
- a model molecule for sPADI provided not only comparable initial antiozonation performances, but also significantly improved longevity for antiozonation performances in a rubber formulation.
- a rubber composition comprising, a rubber, a reinforcing filler, a vulcanization system, and an antidegradant of (I) hydroxylated form of substituted phenyl-p- phenylenediamine, sPPD-OH, or (II) quinoneimine form of substituted p- (hydroxy)phenylamine, sPAQI, as shown below, (I)
- n is 0, 1, or 2; typically m is 1 and n is 0 or 1, and in many embodiments, m is 1 and n is 0.
- p is 0, 1, 2, 3, or 4; q is 0, 1, 2, 3, or 4; typically p is 0 or 1 and q is 0 or 1, and in many embodiments, both p and q are 0.
- the summation of m and p is less than 6; the summation of n and q is less than 5.
- X is selected from oxygen, sulfur, and nitrogen; typically X is an oxygen or a sulfur.
- each of R’ and R can be the same or different, and is selected from an alkyl moiety, a cycloalkyl moiety, an aryl moiety, an amine moiety, an amide moiety, an alcohol moiety, an aldehyde moiety, a ketone moiety, a carboxylic acid moiety, an ether moiety, an ester moiety, and a thiol moiety, or combinations thereof.
- each of R’ and each of R” is selected from an alkyl moiety, a cycloalkyl moiety, and an aryl moiety or combinations thereof.
- R1 and R2 can be the same or different, and is selected from hydrogen, an alkyl moiety, a cycloalkyl moiety, an aryl moiety, an amine moiety, an amide moiety, an alcohol moiety, an aldehyde moiety, a ketone moiety, a carboxylic acid moiety, an ether moiety, an ester moiety, and a thiol moiety, or combinations thereof.
- Ri and R2 are hydrogens, there will be no substitution.
- m is 1 or 2; in many embodiments m is 1.
- m is 1, there will be one hydroxyl group on the phenyl ring in (I) but not any hydroxyl group in (II) on the 6- membered ring in (II); and the hydroxyl group in (I) can be located at any position on the phenyl ring available for substitution, preferably on the para position relative to the -NH group.
- n is 0, 1 or 2; in many embodiments n is 0 or 1.
- n is 0, there will be not any hydroxyl group on the phenyl ring in (I) and (II).
- n is 1, there will be only one hydroxyl group on the phenyl ring, and it can be located at any position available for substitution.
- n is 2, there will be two hydroxyl groups on the phenyl ring, which can be located at any position available for substitution.
- p is 0, 1, 2, 3, or 4, as long as the summation of p and m is less than 6. In many embodiments, p is 0, 1 or 2. When p is 0, there will be no R’ substitution.
- q is 0, 1, 2, 3, or 4, as long as the summation of q and n is less than 5. In many embodiments, q is 0, 1 or 2. When q is 0, there will be no R” substitution.
- X is selected from oxygen, sulfur, and nitrogen; typically X is an oxygen or a sulfur.
- the location of X can be at any position on the 6-membered ring; preferably X is at the 4-position relative to the double bounded N.
- the location of each R' can be at any position on the 6-membered rings; preferably at least one R’ is adjacent to the hydroxyl group in (I) or adjacent to X in (II).
- the location of R” can be at any position on the phenyl ring in both (I) and (II).
- Each of the Ri, Ri, R’, and R” moieties may be characterized for particular embodiments per the following.
- the alkyl moiety may range, for example, between 1 and 24 carbons or alternatively between any range of the combination of such numbers including, for example, between 1 and 18 carbons, between 1 and 7 carbons, between 3 and 18 carbons, between 4 and 9 carbons, and the alkyl moiety may be straight or branched.
- the cycloalkyl moiety and the aryl moiety may be formed of between 3 and 7 members making up the ring or alternatively between 3 and 6 members or between 5 and 6 members.
- the members are typically carbon but in some embodiments, the cycloalkyl and aryl moieties may be heterocyclic so that one of more of the members making up tire ring may be oxygen, nitrogen, sulfur, or combinations thereof, the remaining members being carbon.
- Each of the other moieties including amine, amide, alcohol, aldehyde, ketone, carboxylic acid, ether, ester, and thiol, may be characterized by having numbers of carbons ranging between 1 and 24, straight or branched.
- Examples of useful antidegradants according to (I) and (II) include, but are not limited to: 4-((4-(dimethylamino)phenyl)amino)phenoI in (I-a); 4-((4-((4-methylpentan-2- yl)amino)phenyl)amino)phenol in (I-b); 4-((3-methyl-4-((4-methylpentan-2- yl)amino)phenyl)amino)phenol in (I-c); 2,6-di-tert-butyl-4-((4-((4-methylpentan-2- yl)amino)phenyl)amino)phenol in (I-d); 5-((4-hydroxyphenyl)amino)-2-((4-methylpentan-2- yl)amino)phenol in (I-e); 4-((4-((3,5-dinitrothiophen-2-yl)amino)
- the rubber elastomers suitable for use with particular embodiments of the present invention include highly unsaturated diene elastomers, for example, polybutadiene rubber (BR), polyisoprene rubber (IR), natural rubber (NR), styrene-butadiene rubber (SBR), isobutylene isoprene rubber (IIR) butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
- the polyisoprenes include synthetic cis- 1,4 polyisoprene, which may be characterized as possessing cis- 1,4 bonds at more than 90 mol.% or alternatively, at more than 98 mol.%.
- Particular embodiments of the disclosed rubber compositions include only natural rubber.
- rubber elastomers that are copolymers and include, for example, butadiene-styrene copolymers (SBR), butadiene-isoprene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene- butadiene-styrene copolymers (SBIR) and mixtures thereof.
- Carbon black which is an organic filler, is well known to those having ordinary skill in the rubber compounding field.
- the carbon black included in the rubber compositions produced by the methods disclosed herein may, in particular embodiments for example, be in an amount of between 30 phr and 150 phr or alternatively between 40 phr and 100 phr or between 40 phr and 80 phr.
- Suitable carbon blacks are any carbon blacks known in the art and suitable for the given purpose for example, any carbon black having a BET surface area or a specific CTAB surface area both of which are less than 400 m2/g or alternatively, between 20 and 200 m2/g may be suitable for particular embodiments based on the desired properties of tile cured rubber composition.
- the CTAB specific surface area is the external surface area determined in accordance with Standard AFNOR-NFT-45007 of November 1987.
- Suitable carbon blacks of the type HAF, ISAF and SAF, for example, are conventionally used in tire treads.
- Non-limitative examples of carbon blacks include, for example, the N115, N134, N234, N299, N326, N33O, N339, N343, N347, N375 and the 600 series of carbon blacks, including, but not limited to N630, N650 and N660 carbon blacks.
- silica may also be usefill as reinforcement filler.
- the silica may be any reinforcing silica known to one having ordinary skill in the art including, for example, any precipitated or pyrogenic silica having a BET surface area and a specific CTAB surface area both of which are less than 450 m2/g or alternatively, between 20 and 400 m2/g may be suitable for particular embodiments based on the desired properties of the cured rubber composition.
- Particular embodiments of rubber compositions disclosed herein may include a silica having a CTAB of between 80 and 200 m2/g, between 100 and 190 m2/g, between 120 and 190 m2/g or between 140 and 180 m2/g.
- a suitable coupling agent is one that is capable of establishing a sufficient chemical and/or physical bond between the inorganic filler and the diene elastomer, which is at least bifunctional, having, for example, the simplified general formula "Y-T-X", in which: Y represents a functional group ("Y" function) which is capable of bonding physically and/or chemically with the inorganic filler, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the surface hydroxyl (OH) groups of the inorganic filler (for example, surface silanols in the case of silica); X represents a functional group f'X" function) which is capable of bonding physically and/or chemically with the diene elastomer, for example by means of a sulfur atom; T represents a divalent organic group making it possible to link Y and X.
- fillers may also be included as reinforcing fillers to the elastomer system, for example, graphene, graphite, zeolite, and so forth.
- Plasticizers include oils, resins (from petroleum or other natural renewable resources, e.g., sunflower seeds, citrus orange peels). Processing oils are well known to one having ordinary skill in the art, are generally extracted from petroleum and are classified as being paraffinic, aromatic or naphthenic type processing oil, including MES and TDAE oils. Processing oils are also known to inente, inter alia, plant-based oils, such as sunflower oil, rapeseed oil and vegetable oil.
- Some of the rubber compositions disclosed herein may include an elastomer, such as a styrene-butadiene rubber, that has been extended with one or more such processing oils but such oil is limited in the rubber composition of particular embodiments as being no more than 40 phr of the total elastomer content of the rubber composition.
- an elastomer such as a styrene-butadiene rubber
- Vulcanization system is preferably, for particular embodiments, one based on sulfur and on an accelerator but other vulcanization agents known to one skilled in the art may be useful as well, for example, peroxide and ionic crosslinking agents.
- Vulcanization agents as used herein are those materials that cause the cross-linkage of the rubber and therefore may be added only to the productive mix so that premature curing does not occur, such agents including, for example, elemental sulfur, sulfur donating agents, and peroxides.
- Use may be made of any compound capable of acting as an accelerator of the vulcanization of elastomers in the presence of sulfur, in particular those chosen from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated to "MBTS”), N-cyclohexyl-2- benzothiazolesulphenamide (abbreviated to “CBS”), N,N-dicyclohexyl-2- benzothiazolesulphenamide (abbreviated to “DCBS”), N-tert-butyl-2- benzothiazolesulphenamide (abbreviated to “TBBS”), N-tert-butyl-2-benzothiazole- sulphenimide (abbreviated to "TBSI”) and the mixtures of these compounds.
- a primary accelerator of the sulfenamide type is used.
- the rubber composition may also include vulcanization retarders, a vulcanization system based, for example, on sulfur or on a peroxide, vulcanization accelerators, vulcanization activators, and so forth.
- the vulcanization system may further include various known secondary accelerators or vulcanization activators, such as zinc oxide, stearic acid and guanidine derivatives (in particular diphenylguanidine, or “DPG”).
- the rubber compositions disclosed herein may further include, in addition to the compounds already described, all or part of the components often used in diene rubber compositions intended for the manufacture of tires, such as additional protective agents of the type that include antioxidants and/or antiozonants, such as 6PPD, 77PD, TMQ, hindered phenol, and wax. There may also be added, if desired, one or more conventional non-reinforcing fillers such as clays, bentonite, talc, chalk kaolin, aluminosilicate, fiber, or coal.
- the rubber compositions that are embodiments of the present invention may be produced in suitable mixers in a manner known to those having ordinary skill in the art. Typically, the mixing may occur using two successive preparation phases, a first phase of thermomechanical working at high temperature followed by a second phase of mechanical working at a lower temperature.
- the first phase includes thoroughly mixing, typically by kneading, the various ingredients of the composition but excluding some of the vulcanization system such as the vulcanization agents, the accelerators, and the retarders.
- This first phase is carried out in a suitable kneading device, such as an internal mixer of the Banbury type, until under the action of the mechanical working and the high shearing imposed on the mixture, a maximum temperature of generally between 120°C and 190°C is reached, indicating that the components are well dispersed.
- NMR analysis Structural analyses as well as molar purity determination of the sPPD-OH and sPAQI are conducted with NMR analysis. Spectra are acquired on Avance 3, 400MHz, BRUKER spectrometer fitted with a “large band” BBFO-zgrad 5mm probe. Quantitative NMR experience uses a 30° simple impulse and a repeating period of 3 seconds between each 64 acquisitions. Samples are solubilized in deuterated dimethylsulfoxide (DMSO). This solvent is also used for the lock signal. Calibration is done on deuterated DMSO protons signal at 2.44 ppm with a TMS reference at 0 ppm. NMR experience is coupled with 2D HSQC and HMBC experiences in order to determine the structure of molecules given in the attribution tables. Molar quantification of purity is given from NMR ID *H spectrum.
- Rheometer the curing and cured characteristics of the rubber compositions are conducted by using MDR (moving die rheometer) according to ASTM D2084. The test is conducted at 150°C.
- Static ozone cracking test the static ozone surface cracking is evaluated using a test closely related to the ASTM 1149-99 Standard Test Method for rubber deterioration titled Surface Ozone Cracking in a Chamber.
- the testing utilized in the examples that follow differs in the construction of tire sample holder, which was a rod rather than a wooden block holder as required under the ASTM test method. Rectangular samples are made by sheeting the green rubber, molding into a specified mold, curing at a specified cure temp and time, cooling down, cutting with a die, then folding in half and stapling such that the curvature of the loop has a maximum local strain of 18%. These samples are hung on a rod for 2 days under ambient conditions before being placed in an ozone chamber.
- the ozone chamber conditions are set at 50 parts per hundred million ozone (pphm) and a temperature of 40°C for a specified duration.
- the samples are periodically evaluated for cracks.
- the surface cracks of tile samples are then evaluated using the Rubber Deterioration Test Grades that consists of three numbers. The first number indicates the number of cracks in the sample, the second rates foe width of foe cracks and foe third number is the depth of foe crack. The higher foe numbers, foe more severe foe ozone cracks. Zero indicates that no cracks are observed.
- the ozone cracking index is foe product of foe three numbers determined by foe Rubber Deterioration Test Grades. A normalized index is used by normalizing foe index of a “comparative formulation” to that of the “witness formulation”.
- Dynamic ozone cracking test the sample preparation and ozone cracking indexing are identical to those of static ozone cracking test described above, except that foe samples are subjected to a cyclic strain up to 25% at 30RPM for up to 2 days in the ozone chamber.
- Antiozonant migration and antiozonation longevity teste the migration of an antiozonant in a rubber to its surrounding rubbers is conducted in a “composite” ozone sample, and the longevity of the antiozonation is assessed by grading the surface ozone cracks on the “composite” ozone sample after exposure to ozone environment.
- the “composite” sample is then cured at specified conditions, and purposely left at ambient condition for 14 days.
- the sample is then stapled/looped on a rod, making sure that the “comparative formulation” is facing outside on foe loop.
- foe sample is exposed to ozone in foe ozone chamber for a specified duration.
- foe surface ozone cracks of the “comparative formulation” is graded, and a normalized cracking index is calculated exactly foe same way as described in foe “static ozone cracking test”.
- a faster migration of an antiozonant from a “comparative formulation” skim will result in a lower residual concentration of the antiozonant in this “comparative formulation”, and thus a severer ozone cracking after exposed to ozone environment Therefore, a smaller ozone cracking index indicates a slower migration and a longer lasting protection agent
- NMR l H purity of the crude product was 95%mol.
- the crude solid was crystallized from ethyl acetate (from 80°C to -18°C) to give dark blue crystals (12.98g, 0.057 mol) with a yield of 77%.
- the melting point is 153°C.
- the NMR ! H purity was 97%mol. Table 1. Characterization of dPAQI by NMR and 13 C in DMSO.
- This example shows the synthesis and characterization of 4-(4- (dimethylamino)phenylamino)phenol, denoted as dPPD-OH, with the synthesis route showing in the following equation, and NMR characterization showing in Table 2.
- the temperature is kept under 0°C during the addition. Stirring was continued under 0°C for 2 hours and the blue precipitate was filtrated, washed for several times by water (300 mL). A dark blue solid (5.5g) was obtained.
- the NMR purity is 59%mol of dPAQI and 12% mol of dPPD-OH.
- This example demonstrates the anti-ozone performances of the new chemicals in this invention at static and dynamic conditions.
- Table 3 showed the static and dynamic ozone cracking indices of formulations with 1.2 phr 6PPD, dPPD-OH, and dPAQI, respectively, in which the ozone rubber samples were cured for 15 minutes at 150°C before the cracking test. Notice that the higher the cracking index, the more sever the cracking, and the lower the anti-ozonation performance.
- the dPPD-OH in Fl-1 and dPAQI in Fl-2 indicated at least equivalent antiozonation performances at both static and dynamic conditions, as represented by their corresponding ozone cracking indices.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2020/067702 WO2022146442A1 (en) | 2020-12-31 | 2020-12-31 | Rubber composition with longer lasting antiozonation |
Publications (2)
Publication Number | Publication Date |
---|---|
EP4271741A1 true EP4271741A1 (en) | 2023-11-08 |
EP4271741A4 EP4271741A4 (en) | 2024-09-18 |
Family
ID=82259613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20968171.7A Pending EP4271741A4 (en) | 2020-12-31 | 2020-12-31 | Rubber composition with longer lasting antiozonation |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP4271741A4 (en) |
CN (1) | CN116964157A (en) |
WO (1) | WO2022146442A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024129797A1 (en) | 2022-12-13 | 2024-06-20 | Compagnie Generale Des Etablissements Michelin | Rubber composition with longer lasting antiozonation system |
WO2024129798A1 (en) | 2022-12-13 | 2024-06-20 | Compagnie Generale Des Etablissements Michelin | Rubber composition with longer lasting antiozonation system |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007042418A2 (en) * | 2005-10-11 | 2007-04-19 | Ciba Specialty Chemicals Holding Inc. | Non-staining antidegradants for vulcanized elastomers |
FR2931158B1 (en) * | 2008-05-15 | 2010-07-30 | Michelin Soc Tech | RUBBER COMPOSITION FOR PNEUMATIC INCORPORATING A NEW ANTI-OXIDANT SYSTEM |
EP2900749B1 (en) * | 2012-09-25 | 2019-06-26 | Compagnie Générale des Etablissements Michelin | Rubber composition with low resin crosslinking |
US10287418B2 (en) * | 2015-12-22 | 2019-05-14 | Eastman Chemical Company | Compounds with antidegradant and antifatigue efficacy and compositions including said compounds |
-
2020
- 2020-12-31 EP EP20968171.7A patent/EP4271741A4/en active Pending
- 2020-12-31 WO PCT/US2020/067702 patent/WO2022146442A1/en active Application Filing
- 2020-12-31 CN CN202080108267.6A patent/CN116964157A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2022146442A1 (en) | 2022-07-07 |
CN116964157A (en) | 2023-10-27 |
EP4271741A4 (en) | 2024-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101960988B1 (en) | Coupling agent for rubber/carbon black, and rubber composition containing same for use in tires | |
US10173973B2 (en) | Alkylidene aminoguanidine and salt thereof, modifying composition, modified rubber for tire, rubber composition for tire, and tire | |
US9650492B2 (en) | Rubber composition for tires comprising an acetylacetonate compound | |
EP2900746B1 (en) | Rubber composition and method for low resin crosslinking | |
JP6190383B2 (en) | Rubber composition containing blocked mercaptosilane coupling agent | |
JP2010509415A (en) | Rubber composition for tires containing a novel antioxidant system | |
US20130030097A1 (en) | Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt | |
US20240093000A1 (en) | Rubber composition with longer lasting antiozonation | |
WO2022146442A1 (en) | Rubber composition with longer lasting antiozonation | |
JP5650746B2 (en) | Rubber composition containing thiazole | |
US8754164B2 (en) | Rubber composition comprising a 1,2,4-triazine | |
US9034969B2 (en) | Rubber composition comprising a thiazoline | |
WO2024129798A1 (en) | Rubber composition with longer lasting antiozonation system | |
WO2024129797A1 (en) | Rubber composition with longer lasting antiozonation system | |
US9187620B2 (en) | Rubber composition comprising a thiadiazole | |
CN117693429A (en) | Compound, rubber mixture containing said compound, vehicle tyre having at least one component comprising said rubber mixture, method for producing said compound and use of said compound as an ageing-protecting agent and/or antiozonant and/or colorant | |
EP4267402A1 (en) | Rubber composition | |
CN118318001A (en) | Compound, rubber blend containing the compound, vehicle tyre comprising the rubber blend in at least one component, method for producing the compound and use of the compound as an ageing protection agent and/or antiozonant and/or dye | |
WO2022146410A1 (en) | Method for forming rubber composition | |
CN117693430A (en) | Compound, rubber blend comprising the compound, vehicle tyre comprising the rubber blend in at least one component, method for producing the compound and use of the compound as an ageing protectant and/or antiozonant and/or dye | |
CN117677657A (en) | Compound, rubber blend comprising the compound, vehicle tyre comprising the rubber blend in at least one component, method for producing the compound and use of the compound as an ageing protectant and/or antiozonant and/or dye | |
BR112020019114B1 (en) | RUBBER COMPOSITION COMPRISING A REINFORCEMENT LOAD WITH A SPECIFIC LOW SURFACE |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230727 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Free format text: PREVIOUS MAIN CLASS: C08K0005180000 Ipc: C08K0003040000 |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20240819 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B61C 1/00 20060101ALI20240812BHEP Ipc: C09C 1/56 20060101ALI20240812BHEP Ipc: C09C 1/44 20060101ALI20240812BHEP Ipc: C08K 5/47 20060101ALI20240812BHEP Ipc: C08K 5/18 20060101ALI20240812BHEP Ipc: C08K 3/06 20060101ALI20240812BHEP Ipc: C08K 3/04 20060101AFI20240812BHEP |