CA3083929A1 - Alkylphenol detergents - Google Patents
Alkylphenol detergents Download PDFInfo
- Publication number
- CA3083929A1 CA3083929A1 CA3083929A CA3083929A CA3083929A1 CA 3083929 A1 CA3083929 A1 CA 3083929A1 CA 3083929 A CA3083929 A CA 3083929A CA 3083929 A CA3083929 A CA 3083929A CA 3083929 A1 CA3083929 A1 CA 3083929A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent
- composition
- alkylphenol
- previous
- lubricating
- 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
- 239000003599 detergent Substances 0.000 title claims abstract description 146
- -1 polyene compounds Chemical class 0.000 claims abstract description 56
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 51
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 145
- 230000001050 lubricating effect Effects 0.000 claims description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 45
- 239000002270 dispersing agent Substances 0.000 claims description 33
- 150000001336 alkenes Chemical class 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 27
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 229960002317 succinimide Drugs 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 9
- 150000004291 polyenes Chemical class 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 235000007586 terpenes Nutrition 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 150000003505 terpenes Chemical class 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 5
- 229960001860 salicylate Drugs 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims 2
- 125000002298 terpene group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 238000005516 engineering process Methods 0.000 abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003879 lubricant additive Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 44
- 235000019198 oils Nutrition 0.000 description 44
- 125000000217 alkyl group Chemical group 0.000 description 25
- 239000000314 lubricant Substances 0.000 description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 11
- 239000003607 modifier Substances 0.000 description 11
- 229940095050 propylene Drugs 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 239000000344 soap Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 150000003902 salicylic acid esters Chemical class 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000002199 base oil Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 125000002947 alkylene group Polymers 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 7
- 239000004034 viscosity adjusting agent Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000005266 diarylamine group Chemical group 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229920013639 polyalphaolefin Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000008236 biological pathway Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229940035422 diphenylamine Drugs 0.000 description 4
- 230000002124 endocrine Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 150000003900 succinic acid esters Chemical class 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 3
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical group 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 3
- OPGSZKAUCDYOSY-GZARNWDXSA-N (3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-tetraene Chemical compound CC(=C)\C=C\C\C(=C\CC\C(=C\C)\C)\C OPGSZKAUCDYOSY-GZARNWDXSA-N 0.000 description 2
- BFTWKGJWVHTNGW-GZARNWDXSA-N (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene Chemical compound CC(=C)\C=C\CC\C(=C\C\C(=C\C)\C)\C BFTWKGJWVHTNGW-GZARNWDXSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 2
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 2
- PZSOILRADXWRKA-UHFFFAOYSA-N 2,6,10-trimethyldodec-2-ene Chemical compound CCC(C)CCCC(C)CCC=C(C)C PZSOILRADXWRKA-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Chemical group 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GLOYGJPNNKTDIG-UHFFFAOYSA-N SC=1N=NSC=1S Chemical class SC=1N=NSC=1S GLOYGJPNNKTDIG-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 239000013020 final formulation Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002314 glycerols Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 description 1
- NBZUAAUGEKOJBT-RVDMUPIBSA-N (E)-2,6,10-trimethyldodec-5-ene Chemical compound CCC(C)CCC\C(C)=C\CCC(C)C NBZUAAUGEKOJBT-RVDMUPIBSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XSNVIEBXRWMGQZ-NTCAYCPXSA-N (e)-2,6,10-trimethyldodec-6-ene Chemical compound CCC(C)CC\C=C(/C)CCCC(C)C XSNVIEBXRWMGQZ-NTCAYCPXSA-N 0.000 description 1
- MENOVFBLDHZHLF-MKMNVTDBSA-N (e)-3,7,11-trimethyldodec-2-ene Chemical compound C\C=C(/C)CCCC(C)CCCC(C)C MENOVFBLDHZHLF-MKMNVTDBSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- 150000000180 1,2-diols Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003899 tartaric acid esters Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical group CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- USEBTXRETYRZKO-UHFFFAOYSA-L zinc;n,n-dioctylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCN(C([S-])=S)CCCCCCCC.CCCCCCCCN(C([S-])=S)CCCCCCCC USEBTXRETYRZKO-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
- C10M2207/0285—Overbased salts thereof used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The disclosed technology relates to hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts, where the hydrocarbyl group includes moieties equivalent to 5 to 10 carbon branched polyene compounds. Such compounds and their salts are useful as lubricant additives.
Description
TITLE
Alkylphenol Detergents BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts having oligomers of branched olefins, including branched polyenes, such as terpenes. Such compounds and their salts are useful as lubricant additives.
Alkylphenol Detergents BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts having oligomers of branched olefins, including branched polyenes, such as terpenes. Such compounds and their salts are useful as lubricant additives.
[0002] Phenol-based detergents are known. Among these are phenates based on phenolic monomers, linked with sulfur bridges or alkylene bridges such as meth-ylene linkages derived from formaldehyde. The phenolic monomers themselves are typically substituted with an aliphatic hydrocarbyl group to provide a measure of oil solubility. The hydrocarbyl groups may be alkyl groups, and, historically, do-decylphenol (or propylene tetramer-substituted phenol) has been widely used.
An early reference to basic sulfurized polyvalent metal phenates is U.S. Patent 2,680,96, Walker et al., June 1, 1954; see also U.S. Patent 3,372, 1 16, Meinhardt, March 6, 1968.
An early reference to basic sulfurized polyvalent metal phenates is U.S. Patent 2,680,96, Walker et al., June 1, 1954; see also U.S. Patent 3,372, 1 16, Meinhardt, March 6, 1968.
[0003] Recently, however, certain alkylphenols and products prepared from them have come under increased scrutiny due to their association as potential endo-crine disruptive materials. In particular, alkylphenol detergents which are based on phenols alkylated with oligomers of propylene, specifically propylene tetramer (or tetrapropenyl), may contain residual alkyl phenol species. There is interest, therefore, in developing alkyl-substituted phenol detergents, for uses in lubricants, fuels, and as industrial additives, which contain a reduced or eliminated amount of dodecylphe-nol component and other substituted phenols having propylene oligomer substituents of 10 to 15 carbon atoms. Nevertheless, it is desirable that the products should have similar oil-solubility parameters as phenates prepared from C10-15 propylene oligo-mers.
[0004] There have been several efforts to prepare phenate detergents that do not contain C. alkyl phenols derived from oligomers of propylene. U.S. Patent 7,435,709, Stonebraker et al., October 14, 2008, discloses a linear alkylphenol de-rived detergent substantially free of endocrine disruptive chemicals. It comprises a salt of a reaction product of (1) an olefin having at least 10 carbon atoms, where greater than 90 mole % of the olefin is a linear C20-C30 n-alpha olefin, and wherein less than 10 mole % of the olefin is a linear olefin of less than 20 carbon atoms, and less than 5 mole %of the olefin a branched chain olefin of 18 carbons or less, and (2) a hydroxyaromatic compound
[0005] U.S. Application 2011/0190185, Sinquin et al, August 4, 2011, dis-closes an overbased salt of an oligomerized alkylhydroxyaromatic compound. The alkyl group is derived form an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 C and a final boiling point of greater than 325 C. The propylene oligomers may contain a distribution of carbon atoms that comprise at least about 50 weight percent of C 14 to C20 carbon atoms.
[0006] U.S. Application 201 1/0124539, Sinquin et al, May 26, 2011, dis-closes an overbased, sulfurized salt of an alkylated hydroxyaromatic compound.
The alkyl substituent is a residue of at least one isomerized a-olefin having from 15 to about 99 wt. % branching. The hydroxyaromatic compound may be phenol, cresols, xylenols, or mixtures thereof.
The alkyl substituent is a residue of at least one isomerized a-olefin having from 15 to about 99 wt. % branching. The hydroxyaromatic compound may be phenol, cresols, xylenols, or mixtures thereof.
[0007] U.S. Application 2011/0118160, Campbell et al., May 19, 2011, dis-closes an alkylated hydroxyaromatic compound substantially free of endocrine dis-ruptive chemicals. An alkylated hydroxyaromatic compound is prepared by reacting a hydroxyaromatic compound with at least one branched olefinic propylene oligomer having from about 20 to about 80 carbon atoms. Suitable hydroxyaromatic com-pounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
[0008] U.S. Application 2010/0029529, Campbell et al., February 4, 2010, discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound.
The alkyl group is derived from an olefin mixture comprising propylene oligomers having an initial boing point of at least about 195 C and a final boiling point of no more than about 325 C. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
The alkyl group is derived from an olefin mixture comprising propylene oligomers having an initial boing point of at least about 195 C and a final boiling point of no more than about 325 C. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
[0009] U.S. Application 2008/0269351, Campbell et al., October 30, 2008, discloses an alkylated hydroxyaromatic compound substantially free of endocrine disruptive chemicals, prepared by reacting a hydroxyaromatic compound with a branched olefinic oligomer having from about 20 to about 80 carbon atoms.
[0010] U.S. Application 2017/0211008, Walker et al., July 27, 2017, discloses metal salts and overbased metal salts of an oligomerized alkylphenol compound.
The alkyl group is derived from oligomers of an olefin compound containing 3 to 8 carbon atoms, and wherein the polyolefin-derived alkyl group comprises at least 30 mol per-cent of an olefin with 4 or more carbon atoms, especially n-butene.
The alkyl group is derived from oligomers of an olefin compound containing 3 to 8 carbon atoms, and wherein the polyolefin-derived alkyl group comprises at least 30 mol per-cent of an olefin with 4 or more carbon atoms, especially n-butene.
[0011] WO/PCT application 2013/059173, Cook et al., discloses discloses an overbased salt of an oligomerized alkylhydroxyaromatic compound. The alkyl group is a combination of very short hydrocarbyl group (i.e. 1 to 8 carbon atoms) and a long hydrocarbyl group (at least about 25 carbon atoms). Suitable compounds incude those made from a mixture of para-cresol and polyisobutylene-substituted phenol.
[0012] Other general technology includes that of U.S. Patent 6,310,009, Car-rick et al., October 30, 2001 , which discloses salts of the general structure om Om X Y
X
p where R1 may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18 carbon atoms.
It is understood that R1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon at-oms in the R1 groups (number average).
SUMMARY OF THE INVENTION
X
p where R1 may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18 carbon atoms.
It is understood that R1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon at-oms in the R1 groups (number average).
SUMMARY OF THE INVENTION
[0013] The disclosed technology, may solve at least one problem of providing a phenolic material with appropriate oil solubility, providing anti-wear performance, frictional performance, providing oxidation performance, viscosity performance, and detergency (characteristic of moderate chain length alkyl groups). In one embodi-ment the disclosed technology may also solve the problem of containing C12 alkyl phenol moieties i.e., the disclosed technology may be free from or substantially free from C12 alkyl phenol moieties typically formed from oligomerisation or polymeri-sation of propylene.
[0014]
One aspect of the disclosed technology relates to an alkylphenol deter-gent composition comprising at least one phenol moiety having a hydrocarbyl group attached thereto. The hydrocarbyl group can include at least one oligomer having monomers equivalent, in some embodiments, to 5 to 10 carbon atom branched olefins, and in some embodiments, more particularly to 5 to 10 carbon atom branched poly-enes. In embodiments, the monomers making up the oligomers can be equivalent to isoprene. The oligomer itself can be equivalent to a terpene, and more particularly can be equivalent to any of (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tet-raene; (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene; (E)-2,9-dim ethy1-(prop-l-ene-2 -yl)deca-1,3,8-triene;
(3E,6E, 10E)-2,6, 10-trim ethyldodeca-1,3,6, 10-tetraene; (E)-7,11 -di methyl-3 -methyl enedodeca-1,6,10-tri ene; (6E,10E)-7,11,15-tri-methy1-3 -methylenehexadeca-1,6, 10,14 -tetraene;
(3E,6E, 10E)-3,7, 11,15-tetra-methyl hexadeca-1,3 ,6,10, 1-pentaene; (6E,10E,14E)-7, 11,14-trim ethy1-3-methyl ene-hexadeca-1,6, 10,14 -tetraene; (3E,9E,13E)-2, 10,13 -trimethy1-6-(prop-1-en-2-yl)pen-tadeca- 1,3,9,13 -tetraene.
One aspect of the disclosed technology relates to an alkylphenol deter-gent composition comprising at least one phenol moiety having a hydrocarbyl group attached thereto. The hydrocarbyl group can include at least one oligomer having monomers equivalent, in some embodiments, to 5 to 10 carbon atom branched olefins, and in some embodiments, more particularly to 5 to 10 carbon atom branched poly-enes. In embodiments, the monomers making up the oligomers can be equivalent to isoprene. The oligomer itself can be equivalent to a terpene, and more particularly can be equivalent to any of (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tet-raene; (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene; (E)-2,9-dim ethy1-(prop-l-ene-2 -yl)deca-1,3,8-triene;
(3E,6E, 10E)-2,6, 10-trim ethyldodeca-1,3,6, 10-tetraene; (E)-7,11 -di methyl-3 -methyl enedodeca-1,6,10-tri ene; (6E,10E)-7,11,15-tri-methy1-3 -methylenehexadeca-1,6, 10,14 -tetraene;
(3E,6E, 10E)-3,7, 11,15-tetra-methyl hexadeca-1,3 ,6,10, 1-pentaene; (6E,10E,14E)-7, 11,14-trim ethy1-3-methyl ene-hexadeca-1,6, 10,14 -tetraene; (3E,9E,13E)-2, 10,13 -trimethy1-6-(prop-1-en-2-yl)pen-tadeca- 1,3,9,13 -tetraene.
[0015]
The oligomer can also be equivalent to a hydrogenated (partial or com-plete) form of a terpene, such as, for example, any of 3,7,11-trimethyldodec-1-ene;
2,6, 10-trim ethyl dodec-2-ene; (E)-3,7, 11 -trimethyl dodec-2 -ene; 2,6-dim ethyl-10-methyl enedodecane; (E)-2,6,10-trimethyldodec-6-ene; (E)-3,7,11-trimethyldodec-ene; (E)-2,6,10-trimethyldodec-5-ene; 3,7, 11 -trimethyl dodeca-1, 10-diene
The oligomer can also be equivalent to a hydrogenated (partial or com-plete) form of a terpene, such as, for example, any of 3,7,11-trimethyldodec-1-ene;
2,6, 10-trim ethyl dodec-2-ene; (E)-3,7, 11 -trimethyl dodec-2 -ene; 2,6-dim ethyl-10-methyl enedodecane; (E)-2,6,10-trimethyldodec-6-ene; (E)-3,7,11-trimethyldodec-ene; (E)-2,6,10-trimethyldodec-5-ene; 3,7, 11 -trimethyl dodeca-1, 10-diene
[0016]
In embodiments, the hydrocarbyl unit of the alkylphenol detergent can contain from 15 to 60 carbon atoms.
In embodiments, the hydrocarbyl unit of the alkylphenol detergent can contain from 15 to 60 carbon atoms.
[0017] The alkylphenol detergent can include alkylphenol moiety equivalent to any of 4-(3,7, 11 -trimethyldodecan-2 -yl)phenol ; 4 -(2,6,10-trimethyl dodecan-2 -yl)phenol ; 4-(3,7, 11 -trimethyl dodec-10-en-2-yl)phenol ; 4-(2,6,10-trimethyldodec-11 -en-2-yl)phenol .
[0018]
The alkylphenol detergent can be a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate detergent, a salicylate detergent, or mixtures thereof. The alkylphenol detergent can include one or more alkali metals, one or more alkaline earth metals, or mixtures thereof. The alkylphenol detergent compo-sition can be overbased, and in embodiments, have a metal ratio of at least 1.5, at least 5, or at least 7.
The alkylphenol detergent can be a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate detergent, a salicylate detergent, or mixtures thereof. The alkylphenol detergent can include one or more alkali metals, one or more alkaline earth metals, or mixtures thereof. The alkylphenol detergent compo-sition can be overbased, and in embodiments, have a metal ratio of at least 1.5, at least 5, or at least 7.
[0019] In an embodiment, the alklylphenol detergent can be an overbased sul-5 fur-coupled phenate detergent with a metal ratio of at least 1.5.
[0020] In an embodiment, the alkylphenol detergent composition can be a sul-fur-bridged phenate represented by the structure OH OH OH
Sy Sy wherein each R is an aliphatic hydrocarbyl group equivalent to an oligomer of iso-prene, higher branched olefins, or mixtures thereof, that contains 15 to 60 carbon atoms; each y can be 1 to 4; and n = 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.
Sy Sy wherein each R is an aliphatic hydrocarbyl group equivalent to an oligomer of iso-prene, higher branched olefins, or mixtures thereof, that contains 15 to 60 carbon atoms; each y can be 1 to 4; and n = 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.
[0021] In an embodiment, the alkylphenol detergent can be a neutral or over-based salt of alkylsalicylic acid.
[0022] In an embodiment, the alkylphenol detergent can be an alkylsalicylate represented by the structure where R is an aliphatic hydrocarbyl group equivalent to an oligomer of isoprene, higher branched olefins, or mixtures thereof, and wherein the hydrocarbyl group con-tains 15 to 60 carbon atoms.
[0023] Another aspect of the technology relates to a lubricating composition having (a) an oil of lubricating viscosity and (b) the alkylphenol detergent composi-tion as described herein. In embodiments, lubricating composition can be substan-tially free to free of an alkylphenol-containing detergent wherein the alkylphenol is derived from oligomers of propene. The lubricating composition can also include other additives, such as, for example, other detergents besides the instant alkylphenol detergent, zinc dialkyldithiophosphate, dispersants, antiwear agents, extreme pres-sure agents, corrosion inhibitors, etc.
[0024] A further aspect of the technology relates to methods of lubricating a mechanical device, for example, by supplying to the device the lubricating composi-tion described herein containing the alkylphenol detergent. The mechanical device can be, for example, an internal combustion engine, an automotive driveline device, such as a transmission or an axle, or an off-highway vehicle. The technology could also be employed in industrial applications, such as industrial hydraulics.
DETAILED DESCRIPTION OF THE INVENTION
DETAILED DESCRIPTION OF THE INVENTION
[0025] Various preferred features and embodiments will be described below by way of non-limiting illustration.
[0026] The disclosed technology includes an alkylphenol detergent composi-tion (or just alkylphenol for short), a lubricating composition containing the alkylphe-nol, a method for lubricating a mechanical device with a lubricating composition containing the alkylphenol, and a use of the alkylphenol, all of which will be more particularly described herein.
[0027] One aspect of the disclosed technology is an alkylphenol detergent composition. The alkylphenol detergent will include at least one phenol moiety with .. at least one hydrocarbyl group attached thereto. Those of ordinary skill in the art can observe a chemical composition and readily imagine the moieties to which the com-position may be derived from. As used herein, reference to the phenol moiety means that moiety of the alkylphenol detergent composition one of ordinary skill in the art could imagine would be derived from a phenol, i.e., of Formula I.
Formula I
OH
Formula I
OH
[0028] The alkylphenol will also include a hydrocarbyl group. As used herein, the term "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon char-acter. Examples of hydrocarbyl groups include, for example: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon sub-stituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent;
and hetero substituents, that is, substituents which similarly have a predominantly hy-drocarbon character but contain other than carbon in a ring or chain.
and hetero substituents, that is, substituents which similarly have a predominantly hy-drocarbon character but contain other than carbon in a ring or chain.
[0029] While the hydrocarbyl group can include elements of non-hydrocarbyl character (i.e., nitrogen, halogens, etc.), in many embodiments the hydrocarbyl group can be of substantially, or even completely, hydrocarbon character. In some embodi-ments, the hydrocarbyl group can be of substantially or completely aliphatic character.
[0030] The hydrocarbyl group can comprise, consist essentially of, or consist of at least one oligomer, and the at least one oligomer itself can comprise, consist essentially of, or consist of monomers equivalent to 5 to 10 carbon atom branched olefins. By employing the terminology "equivalent to," it is recognized that the ref-erenced compound, in this case the monomers of the oligomer, are slightly altered in their final state from their original state; for example, an oligomerized monomer ver-sus the lone monomer. In other words, the hydrocarbyl group, when looked at in discreet units, contains identifiable oligomer units, and the identifiable oligomer units can be further broken down into identifiable alkyl units that, as a monomer would be considered a 5 to 10 carbon atom branched olefin.
[0031] A branched olefin, as used herein, refers to an alkyl chain having at least one double bond and at least one tertiary carbon atom. Without limiting the branched olefin, examples of such branched olefins can be represented by the follow-ing example branched olefin formulas.
Ra Rb Ra Rb Ra Rb CRc '`ICH2)11 41Rc CRc H2 n H n Ra Rb Ra Rb Rc CRc H n where Ra, Rb, and Rc can be H or a lower Ci to C5 alkyl group; n and m can be, independently, integers of 0 to 6, with the proviso that n+m is from 1 to 6;
and the olefin has from 5 to 10 carbon atoms. An oligomer of such a branched olefin could be, for example, oligomers of the following formula.
Ra Rb CT(111'11R) H2 n where Ra, Rb, Rc, m and n are as above, and y is an integer of 2 to 18, or 2 to 15, or 2 to 12.
Ra Rb Ra Rb Ra Rb CRc '`ICH2)11 41Rc CRc H2 n H n Ra Rb Ra Rb Rc CRc H n where Ra, Rb, and Rc can be H or a lower Ci to C5 alkyl group; n and m can be, independently, integers of 0 to 6, with the proviso that n+m is from 1 to 6;
and the olefin has from 5 to 10 carbon atoms. An oligomer of such a branched olefin could be, for example, oligomers of the following formula.
Ra Rb CT(111'11R) H2 n where Ra, Rb, Rc, m and n are as above, and y is an integer of 2 to 18, or 2 to 15, or 2 to 12.
[0032] The branched olefin can also be polyenes. That is, the hydrocarbyl group can comprise, consist essentially of, or consist of at least one oligomer, and the at least one oligomer itself can comprise, consist essentially of, or consist of mon-omers equivalent to 5 to 10 carbon atom branched polyene compounds. As used herein a polyene is a poly-unsaturated alkylene compound having at least 2 double bonds (also known as a diene), and in some cases 3, 4, or 5 double bonds.
[0033] Branched polyene compounds can be described as alkyl chains having at least two double bonds in the chain, and at least one tertiary carbon atom.
Although the polyene compound may include more than 2 double bonds, an example branched polyene compound may be a branched conjugated diene represented by the following formula, )T p 2 ..4 where R1, R2, R3, and R4 are independently H, or lower Ci to C5 alkyl groups;
with the proviso that at least one of R1, R2, R3, and R4 is an alkyl group and that taken together the conjugated diene has a total of from 5 to 10 carbon atoms.
Although the polyene compound may include more than 2 double bonds, an example branched polyene compound may be a branched conjugated diene represented by the following formula, )T p 2 ..4 where R1, R2, R3, and R4 are independently H, or lower Ci to C5 alkyl groups;
with the proviso that at least one of R1, R2, R3, and R4 is an alkyl group and that taken together the conjugated diene has a total of from 5 to 10 carbon atoms.
[0034] The at least one oligomer in the hydrocarbyl group can be oligomerized from 5 to 10 carbon atom branched olefin/polyenes, or the oligomer may be prepared in some other manner. For example, the oligomer may be formed by 1,2-monomer addition or 1,4-monomer addition. In one embodiment, oligomers of 5 to 10 carbon atom branched polyenes may formed by 1,4-addition of the monomers, followed by partial hydrogenation of the resulting material to form a mono-olefinic alkylating agent, which could then react with phenol to form the oligomeric alkyl phenol.
The hydrocarbyl group may also be derived from an alkylating agent containing a het-eroatom, such as phytol or farnesol, which may be prepared from reacting monomers of a mono or polyene containing a heteroatom. For instance, Tetrahedron Vol 43. No.
19. pp. 4481 to 4486, 1987 describes the synthesis of phytol from two C10 units derived from geraniol.
In another example, the oligomer may also be produced via biological activity, such as through the fermentation of a cell culture system that is capable of producing the desired branched olefin/polyene or a composition having the appearance of an oli-gomer containing monomers equivalent to 5 to 10 carbon atom branched olefin/pol-5 yene compounds. For instance, WO 2011/160081 provides a biological pathway for the production of isoprene, and the use of the so-produced isoprene to produce oli-gomers (also called terpenes, i.e., having a formula of (C5H8), where n is 2, 3,4, 5 or higher). The hydrocarbyl group may also be derived from an alkylating agent produced from a biological pathway, including, for instance, a biological pathway 10 for the production of natural phytol from the crude extraction of silkworm excre-ment, Moms alba leaf, bamboo leaf, pine needle and Ginkgo biloba leaf, for exam-ple as taught in CN 102807471 A Dec 05, 2012. Other biological pathways are known to produce the oligomers (e.g., terpenes) themselves.
The hydrocarbyl group may also be derived from an alkylating agent containing a het-eroatom, such as phytol or farnesol, which may be prepared from reacting monomers of a mono or polyene containing a heteroatom. For instance, Tetrahedron Vol 43. No.
19. pp. 4481 to 4486, 1987 describes the synthesis of phytol from two C10 units derived from geraniol.
In another example, the oligomer may also be produced via biological activity, such as through the fermentation of a cell culture system that is capable of producing the desired branched olefin/polyene or a composition having the appearance of an oli-gomer containing monomers equivalent to 5 to 10 carbon atom branched olefin/pol-5 yene compounds. For instance, WO 2011/160081 provides a biological pathway for the production of isoprene, and the use of the so-produced isoprene to produce oli-gomers (also called terpenes, i.e., having a formula of (C5H8), where n is 2, 3,4, 5 or higher). The hydrocarbyl group may also be derived from an alkylating agent produced from a biological pathway, including, for instance, a biological pathway 10 for the production of natural phytol from the crude extraction of silkworm excre-ment, Moms alba leaf, bamboo leaf, pine needle and Ginkgo biloba leaf, for exam-ple as taught in CN 102807471 A Dec 05, 2012. Other biological pathways are known to produce the oligomers (e.g., terpenes) themselves.
[0035] An oligomer containing monomers equivalent to 5 to 10 carbon atom branched olefins could be, for example, oligomers of the following formula R4)7 where R1, R2, R3, and R4 and y are the same as defined above.
[0036] The branched polyene compound containing 5 to 10 carbon atoms may include isoprene monomers of Formula IV.
Formula IV
In addition to isoprene, suitable branched olefins 2-methyl-l-butene, 3-methyl-l-bu-tene, 4-methyl-l-pentene, 2-m ethyl-l-pentene, 3 -methyl-l-pentene, 2-methyl-l-hex-ene, 3 -methyl -1-hexene, 5 -methyl -1-hexene, 4-methyl -1-hexene, 2-methyl -1-hep-tene, 2.3 -dim ethyl -1,3 -butadiene, 2,4-dimethyl -1,3 -pentadi ene, 3 -methyl -1,3-penta-diene, and mixtures thereof.
Formula IV
In addition to isoprene, suitable branched olefins 2-methyl-l-butene, 3-methyl-l-bu-tene, 4-methyl-l-pentene, 2-m ethyl-l-pentene, 3 -methyl-l-pentene, 2-methyl-l-hex-ene, 3 -methyl -1-hexene, 5 -methyl -1-hexene, 4-methyl -1-hexene, 2-methyl -1-hep-tene, 2.3 -dim ethyl -1,3 -butadiene, 2,4-dimethyl -1,3 -pentadi ene, 3 -methyl -1,3-penta-diene, and mixtures thereof.
[0037] In an embodiment, the oligomer contains units equivalent to isoprene.
An isoprene oligomer containing 15 to 60 carbon atoms would contain 3 to 12 iso-prene monomer units. An isoprene polymer or oligomer containing 15 to 30 carbon atoms would contain 3 or 6 isoprene monomer units.
An isoprene oligomer containing 15 to 60 carbon atoms would contain 3 to 12 iso-prene monomer units. An isoprene polymer or oligomer containing 15 to 30 carbon atoms would contain 3 or 6 isoprene monomer units.
[0038] In an embodiment, the oligomer can be a trimer of isoprene, which can be envisioned in the following forms (2E,5E,7E,1oE)-3,6,10-trimethyldodeca-2,5,7,10-tetraene (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene (E)-2,9-dimethy1-5-(prop-1-en-2-y1)deca4,3,84riene (3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-tetraene (E)-7,11-dimethy1-3-methylenedodeca-1,6,10-triene
[0039] Tetramers of isoprene may also be employed in the oligomer, and can be envisioned in the following forms (6E,10E)-7,11,15-trimethy1-3-methylenehexadeca-1,6,10,14-tetraene (3E,6E,10E)-3,7,11,15-tetramethylhexadeca-1,3,6,10,14-pentaene (6E,10E,14E)-7,11,14-trimethy1-3-methylenehexadeca-1,6,10,14-tetraene (3E,9E,13E)-2,10,13-trimethy1-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetraene
[0040] In one embodiment, the hydrocarbyl group of the alkylphenol detergent can comprise, consist essentially of, or consist of oligomer compounds comprising, consisting essentially of, or consisting of at least 50 mol% monomers equivalent to isoprene, at least 75 mol% monomers equivalent to isoprene, or at least 90 mol%
monomers equivalent to isoprene. In one embodiment, the hydrocarbyl group in the alkylphenol detergent consists of oligomers of isoprene.
monomers equivalent to isoprene. In one embodiment, the hydrocarbyl group in the alkylphenol detergent consists of oligomers of isoprene.
[0041] In some embodiments, the oligomer can be hydrogenated forms, either partial or complete, of what the oligomer of the alkylene units would otherwise ap-.. pear as. Hydrogenation may be performed, for example, by any hydrogenating agent known to a skilled artisan. For example, a saturated oligomer of polyene compounds can be prepared by hydrogenating at least a portion of the double bonds in the oligo-mer in the presence of a hydrogenation reagent, such as hydrogen in the presence of a catalyst, or by treatment with hydrazine in the presence of a catalyst.
[0042] In some embodiments, at least a portion of the C=C bonds of the oli-gomer is reduced to the corresponding C¨C bonds by hydrogenation. In some em-bodiments, all of the C=C bonds of the oligomer are reduced to the corresponding C-C bonds by hydrogenation. In an embodiment, the oligomer can include a hydrogen-ated form of oligomer in the form of any of the following structures:
[0043] Whether prepared from the oligomerization of discreet units or other-wise, one of ordinary skill in the art will recognize the presence of the oligomers and monomers therein equivalent to 5 to 10 carbon atom branched polyenes within the hydrocarbyl group.
[0044] The hydrocarbyl group can contain from 10 to 200 carbon atoms, or in some examples 12 to 100 carbon atoms, or even 15 to 80 carbon atoms. In some em-bodiments, the hydrocarbyl group can have 15 to 60 carbon atoms, or in some cases 15 to 30 or 45 carbon atoms, or 20 to 30 carbon atoms.
[0045] The alkylphenol detergent, including the phenol moiety and the hydro-carbyl group, may include the structure represented by the following formula.
OH
where R represents the hydrocarbyl group described above. For example, the al-kylphenol can include the structure shown in the following formulas.
OH OH
OH OH
OH
where R represents the hydrocarbyl group described above. For example, the al-kylphenol can include the structure shown in the following formulas.
OH OH
OH OH
[0046] In certain embodiments, the alkylphenol-containing detergent may be a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate detergent, or mixtures thereof. Detergents of this type are ionic (usually metal) salts of bridged phenolic compounds. The bridged phenolic compound material may be represented 5 by the structure:
OH OH OH
Sy Sy or more generally OH OH OH
Xy, Xy or isomers thereof, wherein each R represents the hydrocarbyl group described above 10 having substantially or completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and mixtures thereof, each y can be 1 to 4.
OH OH OH
Sy Sy or more generally OH OH OH
Xy, Xy or isomers thereof, wherein each R represents the hydrocarbyl group described above 10 having substantially or completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and mixtures thereof, each y can be 1 to 4.
[0047] The average number of carbon atoms in all the R groups, combined, may be 15 to 100 (or 20 to 50, or 24 to 36 or 14 to 20 or 18 to 36). Where the bridging 15 group may be listed as "X", each X may independently a carbon-containing bridge, or an alkylene group, or a methylene group, or a bridge of 1 or more sulfur atoms represented by Sy, where y may be 1 to 4, especially 1 or 2. In these structures, n may, in certain embodiments, be 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4. That is, the bridged material may, in these embodiments, contain 2 to 10 bridged phenolic groups, or 3 to 7, or 3 to 5, or 4 such groups. Since n may be zero, it may be evident that throughout this specification, the expression "oligomeric" may be interpreted to in-clude dimeric species. Accordingly, sometimes the expression "dimeric or oligo-meric" may be used to express this concept, which may include, as above, as an ex-ample, 0 to 8 interior units bracketed by [ ]. or 2 to 10 units overall.
[0048] In one embodiment, the sulfur-bridged alkylphenol-containing deter-gent may be an oligomer of p-(isoprene)phenol. A sulfur-bridged oligomer of ol-igo(isoprene)phenol may be represented by the structure OH OH OH
=Sy Sy where n = 0 to 4, and m = 1 to 4 and each y can be 1 to 4.
=Sy Sy where n = 0 to 4, and m = 1 to 4 and each y can be 1 to 4.
[0049] In certain embodiments, the alkylene-bridged phenate detergent may be a saligenin detergent. A saligenin detergent contains a bridged-alkyl phenol com-.. pound that may be an alkylene coupled alkylphenol represented by the structure OH OH
X
II
where each R represents the hydrocarbyl group described above having 15 to 60, or in some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and mixtures thereof; where the each bridging group (X) may be independently a carbon-containing bridge, or a hydro-carbylether linkage (such as ¨CH2-0-CH2-), or an alkylene group, or a methylene group; each Y may be independently -CHO or -CH2OH; wherein the -CHO groups comprise at least about 10 mole percent of the X and Y groups; and n may be an integer from 1 to 10.
X
II
where each R represents the hydrocarbyl group described above having 15 to 60, or in some cases 15 to 30 carbon atoms; aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms; methyl groups; and mixtures thereof; where the each bridging group (X) may be independently a carbon-containing bridge, or a hydro-carbylether linkage (such as ¨CH2-0-CH2-), or an alkylene group, or a methylene group; each Y may be independently -CHO or -CH2OH; wherein the -CHO groups comprise at least about 10 mole percent of the X and Y groups; and n may be an integer from 1 to 10.
[0050] In certain embodiments, the alkylene-bridged phenate detergent may be a salixarate detergent. A salixarate detergent contains a bridged-alkyl phenol com-pound that may be an alkylene coupled alkylphenol that may be further bridged or coupled to salicylic acid. The bridged phenol of a salixarate may be represented by the structure (V) X
OH OH
(V) where R represents the hydrocarbyl group described above having substantially or completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl groups; and mixtures thereof; where the each bridging group (X) may be inde-pendently a carbon-containing bridge, or an alkylene group, or a methylene group;
and n may be an integer from 1 to 10.
OH OH
(V) where R represents the hydrocarbyl group described above having substantially or completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl groups; and mixtures thereof; where the each bridging group (X) may be inde-pendently a carbon-containing bridge, or an alkylene group, or a methylene group;
and n may be an integer from 1 to 10.
[0051] The bridged alkylphenol detergents may be neutral or overbased or su-perbased. Such overbased detergents are generally single phase, homogeneous New-tonian systems characterized by a metal and/or ammonium content in excess of that which would be present for neutralization according to the stoichiometry of the metal or ammonium and the particular acidic organic compound reacted with the metal or ammonium compound. The overbased materials are typically prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid such as carbon dioxide) with a mixture of bridged alkylphenol compounds (referred to as a sub-strate), a stoichiometric excess of a metal base, typically in a reaction medium of an one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic substrate. Typically also a small amount of promoter such as a phenol or .. alcohol is present, and in some cases a small amount of water. The acidic organic substrate will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
[0052] In certain embodiments, the overbased bridged-phenol detergent may be a metal-containing detergent, an amine or ammonium containing detergent, or mixtures thereof. In one embodiment, the overbased metal-containing detergent may be zinc, sodium, calcium or magnesium salts of a phenate, sulfur containing phenate, salixarate or saligenin. In one embodiment, the overbased detergent comprises a salt of an alkylamine or quaternary ammonium compound. Overbased salixarates, phen-ates and saligenins typically have a total base number (TBN) (by ASTM D3896) of 120 to 600 mg KOH/g.
[0053] In certain embodiments, the alkylphenol detergent composition may be an alkylsalicylate or salicylate detergent. A salicylate detergent may be a neutral or overbased metal salt of alkylsalicylic acid. Alkylsalicylic acid may be represented by the formula (VI) (VI) where R represents the hydrocarbyl group described above having substantially or completely aliphatic character and 15 to 60, or in some cases 15 to 30 carbon atoms;
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl groups; and mixtures thereof.
aliphatic hydrocarbyl groups containing 30 to 200 or 35 to 80 carbon atoms;
methyl groups; and mixtures thereof.
[0054] The alkylsalicylate may be a neutral or nearly neutral salt of alkylsali-cylic acid; by nearly neutral, it is meant that there is an excess of base of no more than 15 mol percent, i.e. if the salt is metal-containing, the metal ratio is 1.15 or less.
In one embodiment, the neutral salt of the alkylsalicylic acid may be an amine or ammonium salt, a metal salt, or mixtures thereof.
In one embodiment, the neutral salt of the alkylsalicylic acid may be an amine or ammonium salt, a metal salt, or mixtures thereof.
[0055] Amines suitable for use in the preparation of the neutral amine salted alkylsalicylate are not overly limited and may include any alkyl amine, di- or tri-alkyl amine, though generally are fatty acid amines derived from fatty carboxylic acids.
The alkyl group present in the amine may contain from 10 to 30 carbon atoms, or from 12 to 18 carbon atoms, and may be linear or branched. In some embodiments, the alkyl group may be linear and unsaturated. Typical amines include 2-ethylexhyl-amine, pentadecylamine, octadecylamine, cetyl amine, oleylamine, decylamine, do-decylamine, dimethyldodecylamine, tridecyl amine, heptadecylamine, octadecyla-mine, stearylamine, and any combination thereof. In some embodiments, the fatty acid derived amine salt of an alkylsalicylic acid may be a salt of oleylamine.
In certain embodiments, the amine may be a gamma-aminoester compound; aminoesters of this type may be derived from Michael addition of a primary amine to an alkyl diester of itaconic acid represented by the formula Rio where Rio and Rii are hydrocarbyl groups containing 2 to 30 carbon atoms, and Ri2 is a hydrocarbyl group containing 4 to 50 carbon atoms. In some embodiments, of the aminoester compound is an alkyl group that has at least one hydrocarbyl group 5 substituted at the 1-, or 2-position of the alkyl group. In one embodiment, the ami-noester is dibutyl 2-(((2-ethylhexyl)-amino)methyl)succinate.
The alkyl group present in the amine may contain from 10 to 30 carbon atoms, or from 12 to 18 carbon atoms, and may be linear or branched. In some embodiments, the alkyl group may be linear and unsaturated. Typical amines include 2-ethylexhyl-amine, pentadecylamine, octadecylamine, cetyl amine, oleylamine, decylamine, do-decylamine, dimethyldodecylamine, tridecyl amine, heptadecylamine, octadecyla-mine, stearylamine, and any combination thereof. In some embodiments, the fatty acid derived amine salt of an alkylsalicylic acid may be a salt of oleylamine.
In certain embodiments, the amine may be a gamma-aminoester compound; aminoesters of this type may be derived from Michael addition of a primary amine to an alkyl diester of itaconic acid represented by the formula Rio where Rio and Rii are hydrocarbyl groups containing 2 to 30 carbon atoms, and Ri2 is a hydrocarbyl group containing 4 to 50 carbon atoms. In some embodiments, of the aminoester compound is an alkyl group that has at least one hydrocarbyl group 5 substituted at the 1-, or 2-position of the alkyl group. In one embodiment, the ami-noester is dibutyl 2-(((2-ethylhexyl)-amino)methyl)succinate.
[0056] In certain embodiments, the neutral salt of the alkylsalicylic acid may be a quaternary ammonium salt, also referred to as a quaternary nitrogen compound.
Quaternary nitrogen compounds are characterized in that the nitrogen atom is four-10 coordinate; this results in a cationic species that is not protic, i.e.
an acidic proton is not released under basic conditions. Quaternary nitrogen compounds may be charac-terized as falling into two large groups, four coordinate tetrahydrocarbylammonium compounds, for example tetrabutylammonium, and three coordinate aromatic com-pounds, for example N-hydrocarbylpyridinium.
15 [0057] The alkylphenol-containing detergents, be they phenates, saligenins, salixrates, or salicylates, may be metal-containing detergents. Metal-containing de-tergents may be neutral, or very nearly neutral, or overbased. An overbased detergent contains a stoichiometric excess of a metal base for the acidic organic substrate. This is also referred to as metal ratio. The term "metal ratio" is the ratio of the total equiv-20 alents of the metal to the equivalents of the acidic organic compound. A
neutral metal salt has a metal ratio of one. A salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio is also explained in standard textbook entitled "Chemistry and Technol-ogy of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Cop-yright 2010, page 219, sub-heading 7.25.
[0058] In one embodiment the overbased metal-containing alkylphenol deter-gent may be calcium or magnesium overbased detergent. In one embodiment, the overbased detergent may comprise a calcium alkylphenol detergent with a metal ratio of at least 1.5, at least 3, at least 5, or at least 7. In certain embodiments, the overbased calcium alkylphenol detergent may have a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to 16.
[0059] Alternatively, the alkylphenol detergent may be described as having TBN. Overbased phenates and salicylates typically have a total base number of to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg KOH/g. The amount of the alkylphenol-containing detergent present in a lubricant composition may be defined as the amount necessary to deliver an amount, or range of amounts, of TBN
to the lubricant composition. In certain embodiments, the alkylphenol-containing de-tergent may be present in a lubricant composition in amount to deliver 0.5 to to the composition, or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.
[0060] Overbased detergents may also be defined as the ratio of the neutral detergent salt, also referred to as detergent soap, and the detergent ash. The overbased detergent may have a weight ratio of ash to soap of 3:1 to 1:8, or 1.5:1 to 1 to 4.1, or 1.3:1 to 1:3.4.
[0061] The product of the disclosed technology may beneficially be used as an additive in a lubricant. The amount of the alkylphenol detergent in a lubricant may be 0.1 to 8 percent by weight, on an oil-free basis, but including the calcium carbonate and other salts present in an overbased composition. When present as an overbased detergent, the amount may typically be in the range of 0.1 to 25 weight percent, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15 percent. The higher amounts are typical of marine diesel cylinder lubricants, e.g., 1 or 3 or 5 percent up to 25, 20, or 15 percent. Amounts used in gasoline or heavy-duty diesel engines (not marine) will typically be in lower ranges, such as 0.1 to 10 percent or 0.5 to 5 or 1 to 3 percent by weight.
When used as a substantially neutral or non-overbased salt, its amount may typically be correspond-ingly less for each of the engine types, e.g., 0.1 to 10 percent or 0.2 to 8 or 0.3 to 6 percent.
[0062] In certain embodiments, the amount of the alkylphenol detergent in a lubricant may be measured as the amount of alkylphenol-containing soap that is pro-vided to the lubricant composition, irrespective of any overbasing. In one embodi-ment, the lubricant composition may contain 0.05 weight percent to 1.5 weight per-cent alkylphenol-containing soap, or 0.1 weight percent to 0.9 weight percent al-kylphenol-containing soap. In one embodiment, the alkylphenol-containing soap pro-vides 20 percent by weight to 100 percent by weight of the total detergent soap in the lubricating composition. In one embodiment the alkylphenol-containing soap pro-vides 30 percent by weight to 80 percent by weight of the total detergent soap, or 40 percent by weight to 75 percent by weight of the total detergent soap of the lubricat-ing composition.
[0063] A lubricant composition may contain alkylphenol-containing deter-gents different from that of the disclosed technology. In one embodiment, the lubri-cant composition of the disclosed technology comprises the alkylphenol detergent of the disclosed technology in an amount 0.1 to 25 weight percent, or 0.2 to 23, or 0.3 to 20, or 0.5 to 15 weight percent, and is free of or substantially free of an alkylphenol-containing detergent derived from alkylphenol which is derived from oligomers of pro-pylene, especially tetrapropenyl. "Substantially free of' in this case means no more than 0.01 weight percent or an amount considered to arise through contamination or other unintentional means. In some embodiments, the lubricant composition can in-clude the alkylphenol detergent at from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the lubricating composition.
Oil of Lubricating Viscosity [0064] Another aspect of the technology is a lubricant containing the alkylphe-nol detergent composition. The lubricating composition includes an oil of lubricating viscosity. Such oils include natural and synthetic oils, oil derived from hydrocrack-ing, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mix-tures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication W02008/147704, paragraphs [0054] to [0056]
(a similar disclosure is provided in US Patent Application 2010/197536, see [0072]
to [0073]). A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of W02008/147704 (a similar disclosure is provided in US Patent Application 2010/197536, see [0075] to [0076]).
Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
[0065] Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011).
The five base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or <90 wt % saturates, viscosity index 80 to less than 120); Group II (sulfur content <0.03 wt %, and >90 wt % saturates, viscosity index 80 to less than 120); Group III
(sulfur content <0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV
(all polyalphaolefins (PA0s)); and Group V (all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity may also be a Group II+ base oil, which is an unofficial API category that refers to a Group II base oil having a viscosity index greater than or equal to 110 and less than 120, as described in SAE
publication "Design Practice: Passenger Car Automatic Transmissions," fourth Edition, AE-29, 2012, page 12-9, as well as in US 8,216,448, column 1 line 57. The oil of lubricating viscosity may also be a Group III+ base oil, which, again, is an unofficial API category that refers to a Group III base oil having a viscosity index of greater than 130, for example 130 to 133 or even greater than 135, such as 135-145. Gas to liquid ("GTL") oils are sometimes considered Group III+ base oils.
[0066] The oil of lubricating viscosity may be an API Group IV oil, or mixtures thereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared by metallocene catalyzed processes or from a non-metallocene process. The oil of lubricating viscosity may also comprise an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group II+, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubri-cating viscosity is often an API Group II, Group II+, Group III or Group IV
oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group II+, Group III oil or mixtures thereof.
[0067] The oil of lubricating viscosity, or base oil, will overall have a kinematic viscosity at 100 C of 2 to 10 cSt or, in some embodiments 2.25 to 9 or 2.5 to 6 or 7 or 8 cSt, as measured by ASTM D445. Kinematic viscosities for the base oil at 100 C
of from about 3.5 to 6 or from 6 to 8 cSt are also suitable.
[0068] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the per-formance additives in the composition. Illustrative amounts may include 50 to 99 per-cent by weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent.
[0069] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
[0070] A lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the pres-ence of other performance additives (as described herein below).
[0071] The other performance additives can include at least one of metal de-activators, viscosity modifiers (other than the soot dispersing additive of the present invention), detergents, friction modifiers, antiwear agents, corrosion inhibitors, dis-persants (other than those of the present invention), extreme pressure agents, antiox-idants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives.
[0072] In one embodiment the invention provides a lubricating composition further comprising an overbased metal-containing detergent in addition to the al-kylphenol-containing detergent of the present invention. The metal of the metal-con-taining detergent may be zinc, sodium, calcium, barium, or magnesium.
Typically the metal of the metal-containing detergent may be sodium, calcium, or magnesium.
[0073] The overbased metal-containing detergent may be chosen from sul-fonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, sa-licylates, and mixtures thereof, or borated equivalents thereof. The overbased deter-gent may be borated with a borating agent such as boric acid.
[0074] The overbased metal-containing detergent may also include "hybrid"
detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sul-fonates/phenates/salicylates, as described; for example, in US Patents 6,429,178;
6,429,179; 6,153,565; and 6,281,179. Where, for example, a "hybrid" sul-fonate/phenate detergent is employed, the "hybrid" detergent would be considered 5 equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
[0075] Typically, an overbased metal-containing detergent may be a zinc, so-dium, calcium or magnesium salt of a sulfonate, a phenate, sulfur containing phenate, salixarate or salicylate. Overbased sulfonates, salixarates, phenates and salicylates 10 typically have a total base number of 120 to 700 TBN.
[0076] Typically, the overbased metal-containing detergent may be a calcium or magnesium overbased detergent.
[0077] In another embodiment the lubricating composition further comprises a calcium sulfonate overbased detergent having a TBN of 120 to 700. The overbased 15 sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
[0078] Overbased sulfonates typically have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis). Overbased detergents are known in the art. In one embodiment the sulfonate detergent may be a predominantly linear 20 alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919). Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof.
The pre-dominantly linear alkylbenzene sulfonate detergent may be particularly useful for 25 assisting in improving fuel economy. In one embodiment the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds as dis-closed in paragraphs [0046] to [0053] of US Patent Application 2008/0119378.
[0079] In one embodiment the lubricating composition further comprises 0.01 wt % to 2 wt %, or 0.1 to 1 wt % of a detergent different from the alkylphenol detergent of the disclosed technology, wherein the further detergent is chosen from sulfonates, non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
[0080] In one embodiment the lubricating composition further comprises a "hybrid"detergent formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicy-lates, or sulfonates/phenates/salicylates.
[0081] The lubricating composition in a further embodiment comprises an an-tioxidant, wherein the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof. The antioxidants include diarylamines, alkylated diarylamines, hin-dered phenols, or mixtures thereof. When present the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.
[0082] The diarylamine or alkylated diarylamine may be a phenyl-a-naphthyl-amine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof. The alkylated diphenylamine may include di-nonylated diphenyla-mine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one em-bodiment the diphenylamine may include nonyl diphenylamine, dinonyl diphenyla-mine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In another embodiment the alkylated diphenylamine may include nonyl diphenylamine, or di-nonyl diphenylamine. The alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
[0083] The hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methy1-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-butyl¨phenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-butyl¨phenol. In one em-bodiment the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
[0084] The lubricating composition may in a further embodiment include a dispersant, or mixtures thereof. The dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, am-ide, or ester-amide, or mixtures thereof. In one embodiment the dispersant may be present as a single dispersant. In one embodiment the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succin-imide dispersant.
[0085] The succinimide dispersant may be derived from an aliphatic polyam-ine, or mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
In one embodiment the aliphatic polyamine may be chosen from ethylenediamine, di-ethyl enetri amine, triethylenetetramine, tetra¨ethylene¨pentamine, pentaethyl ene-hexamine, polyamine still bottoms, and mixtures thereof.
[0086] In one embodiment the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide. For instance, a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A
poly-olefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and a polyamine as described above.
[0087] The dispersant may be an N-substituted long chain alkenyl succin-imide. An example of an N substituted long chain alkenyl succinimide is polyisobu-tylene succinimide. Typically the polyisobutylene from which polyisobutylene suc-cinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are dis-closed, for instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP
Patent Application 0 355 895 A.
[0088] The dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment the post-treated dispersant is borated. In one embodiment the post-treated dispersant is reacted with dimercaptothiadiazoles. In one embodiment the post-treated dispersant is reacted with phosphoric or phosphorous acid. In one em-bodiment the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Patent Application US2009/0054278.
[0089] When present, the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3 wt %
of the lubricating composition.
[0090] The succinimide dispersant may comprise a polyisobutylene succin-imide, wherein the polyisobutylene from which polyisobutylene succinimide is de-rived has a number average molecular weight of 350 to 5000, or 750 to 2500.
[0091] In one embodiment the friction modifier may be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides. The friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
[0092] As used herein the term "fatty alkyl" or "fatty" in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
[0093] Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as con-densation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tar-tramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols;
condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiou-rea and salts thereof.
[0094] Friction modifiers may also encompass materials such as sulfurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum di-thiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
[0095] In another embodiment the friction modifier may be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
[0096] The lubricating composition optionally further includes at least one an-tiwear agent. Examples of suitable antiwear agents include titanium compounds, tar-trates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized ole-fins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
[0097] The antiwear agent may in one embodiment include a tartrate, or tar-trimide as disclosed in International Publication W02006/044411 or Canadian Patent CA 1183125. The tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8. The antiwear agent may in one embodiment include a citrate as is disclosed in US Patent Application 2005/0198894.
[0098] Another class of additives includes oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651. The oil-soluble titanium com-pounds may function as antiwear agents, friction modifiers, antioxidants, deposit con-trol additives, or more than one of these functions. In one embodiment the oil soluble titanium compound is a titanium (IV) alkoxide. The titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof. The monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide is titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide is tita-nium (IV) 2 ethylhexoxide. In one embodiment, the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
[0099] In one embodiment, the oil soluble titanium compound is a titanium carboxylate. In a further embodiment the titanium (IV) carboxylate is titanium ne-odecanoate.
[0100] The lubricating composition may in one embodiment further include a 5 phosphorus-containing antiwear agent. Typically the phosphorus-containing anti-wear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition. In some 10 .. embodiments, the antiwear agent may be present in an amount sufficient to provide from 0 to 0.12 wt% phosphorus to the lubricating composition, or from 0.01 to 0.08 wt%, or 0.03 to 0.08 wt%, or even 0.025 to 0.06 wt% phosphorus.
[0101] Extreme Pressure (EP) agents that are soluble in the oil include sulfur-and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of 15 dispersants (typically succinimide dispersants), derivative of chlorinated hydrocar-bon EP agents and phosphorus EP agents. Examples of such EP agents include chlo-rinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-sub-stituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis¨(chlorobenzyl) disulfide, dibutyl tetrasul-20 .. fide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipen-tene, sulfurized terpene, and sulfurized Diels-Alder adducts;
phosphosulfurized hy-drocarbons such as the reaction product of phosphorus sulfide with turpentine or me-thyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phos-phites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pen-25 tylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phos-phite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids or derivatives including, for example, the amine salt of a reaction product of a dialkyldithiophosphoric acid with propylene oxide and subse-30 quently followed by a further reaction with P205; and mixtures thereof (as described in US 3,197,405).
[0102] Foam inhibitors that may be useful in the lubricant compositions of the disclosed technology include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, poly-propylene oxides and (ethylene oxide-propylene oxide) polymers.
[0103] Other viscosity modifiers may include a block copolymer comprising (i) a vinyl aromatic monomer block and (ii) a conjugated diene olefin monomer block (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-iso-prene copolymer), a polymethacrylate, or mixtures thereof.
[0104] Pour point depressants that may be useful in the lubricant compositions of the disclosed technology include polyalphaolefins, esters of maleic anhydride-sty-rene copolymers, poly(meth)acrylates, polyacrylates or polyacrylami des.
[0105] Demulsifiers include trialkyl phosphates, and various polymers and co-polymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.
[0106] Metal deactivators include derivatives of benzotriazoles (typically tol-yltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyl-dithiobenzothiazoles. The metal deactivators may also be described as corrosion in-hibitors.
[0107] Seal swell agents include sulfolene derivatives Exxon Necton37TM
(FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
[0108] In an embodiment, the lubricating composition can be employed to lu-bricate a mechanical device. The mechanical device can be associated with an auto-motive vehicle. For example, the mechanical device may be a driveline device.
[0109] Driveline devices include automatic transmissions, manual transmis-sion, dual clutch transmissions, or an axle or differential. A driveline device lubricating composition in different embodiments may have a composition as disclosed in the follow-ing table:
Additive Embodiments (wt %) A
Alkylphenol Detergent 0.01 to 2 0.01 to 2 0.01 to 2 0.01 to 2 Dispersant 1 to 4 0.1 to 10, 2 to 0 to 5 1 to 6 Extreme Pressure Agent 3 to 6 0 to 6 0 to 3 0 to 6 Overbased Detergent 0 to 1 0.01 to 3, 0.5 to 6 0.01 to 0.025 to 2 Antioxidant 0 to 5 0.01 to 10 or 0 to 3 0 to 2 Friction Modifier 0 to 5 0.01 to 5 0.1 to 1.5 0 to 5 Viscosity Modifier 0.1 to 70 0.1 to 15 1 to 60 0.1 to Any Other Performance Additive 0 to 10 0 to 8 or 10 0 to 6 0 to 10 Oil of Lubricating Viscosity Balance to 100 %
Footnote:
The viscosity modifier in the table above may also be considered as an alternative to an oil of lubricating viscosity.
Column A may be representative of an automotive or axle gear lubricant.
Column B may be representative of an automatic transmission lubricant.
Column C may be representative of an off-highway lubricant.
Column D may be representative of a manual transmission lubricant.
[0110] The mechanical device can be an internal combustion engine, such as, for example, a spark ignited internal combustion engine or a compression ignition internal combustion engine. An engine lubricant composition in different embodi-ments may have a composition as disclosed in the following table:
Additive Embodiments (wt %) A
Alkylphenol Detergent 0.05 to 10 0.2 to 5 0.5 to 2 Corrosion Inhibitor 0.05 to 2 0.1 to 1 0.2 to 0.5 Other Overbased Detergent 0 to 9 0.5 to 8 1 to 5 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2 Dispersant 0 to 12 0 to 8 0.5 to 6 Antioxidant 0.1 to 13 0.1 to 10 0.5 to 5 Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5 Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to 8 0 to 6 Oil of Lubricating Viscosity Balance to 100 %
[0111] The mechanical device may also be in a hydraulic system. A
hydraulic lubricant may also comprise a formulation defined in the following table:
Hydraulic Lubricant compositions Additive Embodiments (wt %) A
Alkylphenol detergent as de- 0.01 to 2.0 0.01 to 1.5 0.01 to 1.0 scribed herein Antioxidant 0 to 4.0 0.02 to 3.0 0.03 to 1.5 Dispersant 0 to 2.0 0.005 to 1.5 0.01 to 1.0 Other Detergent - beside al- 0 to 5.0 0.001 to 1.5 0.005 to 1.0 kylphenol detergent as de-scribed herein Anti-wear Agent 0 to 5.0 0.001 to 2 0.1 to 1.0 Friction Modifier 0 to 3.0 0.02 to 2 0.05 to 1.0 Viscosity Modifier 0 to 10.0 0.5 to 8.0 1.0 to 6.0 Any Other Performance Addi- 0 to 1.3 0.00075 to 0.5 0.001 to 0.4 tive (antifoam / demulsi-fier/pour point depressant) Metal Deactivator 0 to 0.1 0.01 to 0.04 0.015 to 0.03 Rust Inhibitor 0 to 0.2 0.03 to 0.15 0.04 to 0.12 Extreme Pressure Agent 0 to 3.0 0.005 to 2 0.01 to 1.0 Oil of Lubricating Viscosity Balance to Balance to 100 Balance to 100% 100%
[0112] The disclosed technology further provides a method of lubricating a circulating oil system.
[0113] The disclosed technology further provides a method of lubricating a turbine system.
[0114] The alkylphenol can be employed to lubricate any of the foregoing me-chanical devices by supplying to the mechanical device the aforementioned lubricat-ing compositions.
[0115] The amount of each chemical component described is presented exclu-sive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
[0116] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are included within the scope of the pre-sent invention; the present invention encompasses the composition prepared by admix-ing the components described above.
[0117] As used herein, the term "about" means that a value of a given quantity is within 20% of the stated value. In other embodiments, the value is within 15%
of the stated value. In other embodiments, the value is within 10% of the stated value. In other embodiments, the value is within 5% of the stated value. In other embodiments, the value is within 2.5% of the stated value. In other embodiments, the value is within 1% of the stated value.
[0118] Additionally, as used herein, the term "substantially" means that a value of a given quantity is within 10% of the stated value. In other embodiments, the value is within 5% of the stated value. In other embodiments, the value is within 2.5% of the stated value. In other embodiments, the value is within 1% of the 5 stated value.
[0119] Each of the documents referred to above is incorporated herein by ref-erence, including any prior applications, whether or not specifically listed above, from which priority is claimed. The mention of any document is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled per-10 .. son in any jurisdiction. Except in the Examples, or where otherwise explicitly indi-cated, all numerical quantities in this description specifying amounts of materials, re-action conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined.
15 Similarly, the ranges and amounts for each element of the invention can be used to-gether with ranges or amounts for any of the other elements.
[0120] As used herein, the transitional term "comprising," which is synony-mous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
How-20 ever, in each recitation of "comprising" herein, it is intended that the term also encom-pass, as alternative embodiments, the phrases "consisting essentially of" and "consist-ing of," where "consisting of' excludes any element or step not specified and "con-sisting essentially of' permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the com-25 .. position or method under consideration.
[0121] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without de-parting from the scope of the subject invention. In this regard, the scope of the in-30 vention is to be limited only by the following claims.
Quaternary nitrogen compounds are characterized in that the nitrogen atom is four-10 coordinate; this results in a cationic species that is not protic, i.e.
an acidic proton is not released under basic conditions. Quaternary nitrogen compounds may be charac-terized as falling into two large groups, four coordinate tetrahydrocarbylammonium compounds, for example tetrabutylammonium, and three coordinate aromatic com-pounds, for example N-hydrocarbylpyridinium.
15 [0057] The alkylphenol-containing detergents, be they phenates, saligenins, salixrates, or salicylates, may be metal-containing detergents. Metal-containing de-tergents may be neutral, or very nearly neutral, or overbased. An overbased detergent contains a stoichiometric excess of a metal base for the acidic organic substrate. This is also referred to as metal ratio. The term "metal ratio" is the ratio of the total equiv-20 alents of the metal to the equivalents of the acidic organic compound. A
neutral metal salt has a metal ratio of one. A salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio is also explained in standard textbook entitled "Chemistry and Technol-ogy of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Cop-yright 2010, page 219, sub-heading 7.25.
[0058] In one embodiment the overbased metal-containing alkylphenol deter-gent may be calcium or magnesium overbased detergent. In one embodiment, the overbased detergent may comprise a calcium alkylphenol detergent with a metal ratio of at least 1.5, at least 3, at least 5, or at least 7. In certain embodiments, the overbased calcium alkylphenol detergent may have a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to 16.
[0059] Alternatively, the alkylphenol detergent may be described as having TBN. Overbased phenates and salicylates typically have a total base number of to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg KOH/g. The amount of the alkylphenol-containing detergent present in a lubricant composition may be defined as the amount necessary to deliver an amount, or range of amounts, of TBN
to the lubricant composition. In certain embodiments, the alkylphenol-containing de-tergent may be present in a lubricant composition in amount to deliver 0.5 to to the composition, or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.
[0060] Overbased detergents may also be defined as the ratio of the neutral detergent salt, also referred to as detergent soap, and the detergent ash. The overbased detergent may have a weight ratio of ash to soap of 3:1 to 1:8, or 1.5:1 to 1 to 4.1, or 1.3:1 to 1:3.4.
[0061] The product of the disclosed technology may beneficially be used as an additive in a lubricant. The amount of the alkylphenol detergent in a lubricant may be 0.1 to 8 percent by weight, on an oil-free basis, but including the calcium carbonate and other salts present in an overbased composition. When present as an overbased detergent, the amount may typically be in the range of 0.1 to 25 weight percent, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15 percent. The higher amounts are typical of marine diesel cylinder lubricants, e.g., 1 or 3 or 5 percent up to 25, 20, or 15 percent. Amounts used in gasoline or heavy-duty diesel engines (not marine) will typically be in lower ranges, such as 0.1 to 10 percent or 0.5 to 5 or 1 to 3 percent by weight.
When used as a substantially neutral or non-overbased salt, its amount may typically be correspond-ingly less for each of the engine types, e.g., 0.1 to 10 percent or 0.2 to 8 or 0.3 to 6 percent.
[0062] In certain embodiments, the amount of the alkylphenol detergent in a lubricant may be measured as the amount of alkylphenol-containing soap that is pro-vided to the lubricant composition, irrespective of any overbasing. In one embodi-ment, the lubricant composition may contain 0.05 weight percent to 1.5 weight per-cent alkylphenol-containing soap, or 0.1 weight percent to 0.9 weight percent al-kylphenol-containing soap. In one embodiment, the alkylphenol-containing soap pro-vides 20 percent by weight to 100 percent by weight of the total detergent soap in the lubricating composition. In one embodiment the alkylphenol-containing soap pro-vides 30 percent by weight to 80 percent by weight of the total detergent soap, or 40 percent by weight to 75 percent by weight of the total detergent soap of the lubricat-ing composition.
[0063] A lubricant composition may contain alkylphenol-containing deter-gents different from that of the disclosed technology. In one embodiment, the lubri-cant composition of the disclosed technology comprises the alkylphenol detergent of the disclosed technology in an amount 0.1 to 25 weight percent, or 0.2 to 23, or 0.3 to 20, or 0.5 to 15 weight percent, and is free of or substantially free of an alkylphenol-containing detergent derived from alkylphenol which is derived from oligomers of pro-pylene, especially tetrapropenyl. "Substantially free of' in this case means no more than 0.01 weight percent or an amount considered to arise through contamination or other unintentional means. In some embodiments, the lubricant composition can in-clude the alkylphenol detergent at from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the lubricating composition.
Oil of Lubricating Viscosity [0064] Another aspect of the technology is a lubricant containing the alkylphe-nol detergent composition. The lubricating composition includes an oil of lubricating viscosity. Such oils include natural and synthetic oils, oil derived from hydrocrack-ing, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mix-tures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication W02008/147704, paragraphs [0054] to [0056]
(a similar disclosure is provided in US Patent Application 2010/197536, see [0072]
to [0073]). A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of W02008/147704 (a similar disclosure is provided in US Patent Application 2010/197536, see [0075] to [0076]).
Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
[0065] Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011).
The five base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or <90 wt % saturates, viscosity index 80 to less than 120); Group II (sulfur content <0.03 wt %, and >90 wt % saturates, viscosity index 80 to less than 120); Group III
(sulfur content <0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV
(all polyalphaolefins (PA0s)); and Group V (all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity may also be a Group II+ base oil, which is an unofficial API category that refers to a Group II base oil having a viscosity index greater than or equal to 110 and less than 120, as described in SAE
publication "Design Practice: Passenger Car Automatic Transmissions," fourth Edition, AE-29, 2012, page 12-9, as well as in US 8,216,448, column 1 line 57. The oil of lubricating viscosity may also be a Group III+ base oil, which, again, is an unofficial API category that refers to a Group III base oil having a viscosity index of greater than 130, for example 130 to 133 or even greater than 135, such as 135-145. Gas to liquid ("GTL") oils are sometimes considered Group III+ base oils.
[0066] The oil of lubricating viscosity may be an API Group IV oil, or mixtures thereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared by metallocene catalyzed processes or from a non-metallocene process. The oil of lubricating viscosity may also comprise an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group II+, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubri-cating viscosity is often an API Group II, Group II+, Group III or Group IV
oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group II+, Group III oil or mixtures thereof.
[0067] The oil of lubricating viscosity, or base oil, will overall have a kinematic viscosity at 100 C of 2 to 10 cSt or, in some embodiments 2.25 to 9 or 2.5 to 6 or 7 or 8 cSt, as measured by ASTM D445. Kinematic viscosities for the base oil at 100 C
of from about 3.5 to 6 or from 6 to 8 cSt are also suitable.
[0068] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the per-formance additives in the composition. Illustrative amounts may include 50 to 99 per-cent by weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent.
[0069] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
[0070] A lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the pres-ence of other performance additives (as described herein below).
[0071] The other performance additives can include at least one of metal de-activators, viscosity modifiers (other than the soot dispersing additive of the present invention), detergents, friction modifiers, antiwear agents, corrosion inhibitors, dis-persants (other than those of the present invention), extreme pressure agents, antiox-idants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives.
[0072] In one embodiment the invention provides a lubricating composition further comprising an overbased metal-containing detergent in addition to the al-kylphenol-containing detergent of the present invention. The metal of the metal-con-taining detergent may be zinc, sodium, calcium, barium, or magnesium.
Typically the metal of the metal-containing detergent may be sodium, calcium, or magnesium.
[0073] The overbased metal-containing detergent may be chosen from sul-fonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, sa-licylates, and mixtures thereof, or borated equivalents thereof. The overbased deter-gent may be borated with a borating agent such as boric acid.
[0074] The overbased metal-containing detergent may also include "hybrid"
detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sul-fonates/phenates/salicylates, as described; for example, in US Patents 6,429,178;
6,429,179; 6,153,565; and 6,281,179. Where, for example, a "hybrid" sul-fonate/phenate detergent is employed, the "hybrid" detergent would be considered 5 equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
[0075] Typically, an overbased metal-containing detergent may be a zinc, so-dium, calcium or magnesium salt of a sulfonate, a phenate, sulfur containing phenate, salixarate or salicylate. Overbased sulfonates, salixarates, phenates and salicylates 10 typically have a total base number of 120 to 700 TBN.
[0076] Typically, the overbased metal-containing detergent may be a calcium or magnesium overbased detergent.
[0077] In another embodiment the lubricating composition further comprises a calcium sulfonate overbased detergent having a TBN of 120 to 700. The overbased 15 sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
[0078] Overbased sulfonates typically have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis). Overbased detergents are known in the art. In one embodiment the sulfonate detergent may be a predominantly linear 20 alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919). Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof.
The pre-dominantly linear alkylbenzene sulfonate detergent may be particularly useful for 25 assisting in improving fuel economy. In one embodiment the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds as dis-closed in paragraphs [0046] to [0053] of US Patent Application 2008/0119378.
[0079] In one embodiment the lubricating composition further comprises 0.01 wt % to 2 wt %, or 0.1 to 1 wt % of a detergent different from the alkylphenol detergent of the disclosed technology, wherein the further detergent is chosen from sulfonates, non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
[0080] In one embodiment the lubricating composition further comprises a "hybrid"detergent formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicy-lates, or sulfonates/phenates/salicylates.
[0081] The lubricating composition in a further embodiment comprises an an-tioxidant, wherein the antioxidant comprises a phenolic or an aminic antioxidant or mixtures thereof. The antioxidants include diarylamines, alkylated diarylamines, hin-dered phenols, or mixtures thereof. When present the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt % of the lubricating composition.
[0082] The diarylamine or alkylated diarylamine may be a phenyl-a-naphthyl-amine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof. The alkylated diphenylamine may include di-nonylated diphenyla-mine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one em-bodiment the diphenylamine may include nonyl diphenylamine, dinonyl diphenyla-mine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In another embodiment the alkylated diphenylamine may include nonyl diphenylamine, or di-nonyl diphenylamine. The alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
[0083] The hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methy1-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-butyl¨phenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecy1-2,6-di-tert-butyl¨phenol. In one em-bodiment the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
[0084] The lubricating composition may in a further embodiment include a dispersant, or mixtures thereof. The dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, am-ide, or ester-amide, or mixtures thereof. In one embodiment the dispersant may be present as a single dispersant. In one embodiment the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succin-imide dispersant.
[0085] The succinimide dispersant may be derived from an aliphatic polyam-ine, or mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
In one embodiment the aliphatic polyamine may be chosen from ethylenediamine, di-ethyl enetri amine, triethylenetetramine, tetra¨ethylene¨pentamine, pentaethyl ene-hexamine, polyamine still bottoms, and mixtures thereof.
[0086] In one embodiment the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide. For instance, a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A
poly-olefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and a polyamine as described above.
[0087] The dispersant may be an N-substituted long chain alkenyl succin-imide. An example of an N substituted long chain alkenyl succinimide is polyisobu-tylene succinimide. Typically the polyisobutylene from which polyisobutylene suc-cinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are dis-closed, for instance in US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP
Patent Application 0 355 895 A.
[0088] The dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment the post-treated dispersant is borated. In one embodiment the post-treated dispersant is reacted with dimercaptothiadiazoles. In one embodiment the post-treated dispersant is reacted with phosphoric or phosphorous acid. In one em-bodiment the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Patent Application US2009/0054278.
[0089] When present, the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3 wt %
of the lubricating composition.
[0090] The succinimide dispersant may comprise a polyisobutylene succin-imide, wherein the polyisobutylene from which polyisobutylene succinimide is de-rived has a number average molecular weight of 350 to 5000, or 750 to 2500.
[0091] In one embodiment the friction modifier may be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides. The friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
[0092] As used herein the term "fatty alkyl" or "fatty" in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
[0093] Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as con-densation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tar-tramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols;
condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiou-rea and salts thereof.
[0094] Friction modifiers may also encompass materials such as sulfurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum di-thiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
[0095] In another embodiment the friction modifier may be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
[0096] The lubricating composition optionally further includes at least one an-tiwear agent. Examples of suitable antiwear agents include titanium compounds, tar-trates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized ole-fins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
[0097] The antiwear agent may in one embodiment include a tartrate, or tar-trimide as disclosed in International Publication W02006/044411 or Canadian Patent CA 1183125. The tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8. The antiwear agent may in one embodiment include a citrate as is disclosed in US Patent Application 2005/0198894.
[0098] Another class of additives includes oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651. The oil-soluble titanium com-pounds may function as antiwear agents, friction modifiers, antioxidants, deposit con-trol additives, or more than one of these functions. In one embodiment the oil soluble titanium compound is a titanium (IV) alkoxide. The titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof. The monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide is titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide is tita-nium (IV) 2 ethylhexoxide. In one embodiment, the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
[0099] In one embodiment, the oil soluble titanium compound is a titanium carboxylate. In a further embodiment the titanium (IV) carboxylate is titanium ne-odecanoate.
[0100] The lubricating composition may in one embodiment further include a 5 phosphorus-containing antiwear agent. Typically the phosphorus-containing anti-wear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition. In some 10 .. embodiments, the antiwear agent may be present in an amount sufficient to provide from 0 to 0.12 wt% phosphorus to the lubricating composition, or from 0.01 to 0.08 wt%, or 0.03 to 0.08 wt%, or even 0.025 to 0.06 wt% phosphorus.
[0101] Extreme Pressure (EP) agents that are soluble in the oil include sulfur-and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of 15 dispersants (typically succinimide dispersants), derivative of chlorinated hydrocar-bon EP agents and phosphorus EP agents. Examples of such EP agents include chlo-rinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-sub-stituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, organic sulfides and polysulfides such as dibenzyldisulfide, bis¨(chlorobenzyl) disulfide, dibutyl tetrasul-20 .. fide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipen-tene, sulfurized terpene, and sulfurized Diels-Alder adducts;
phosphosulfurized hy-drocarbons such as the reaction product of phosphorus sulfide with turpentine or me-thyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phos-phites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pen-25 tylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phos-phite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids or derivatives including, for example, the amine salt of a reaction product of a dialkyldithiophosphoric acid with propylene oxide and subse-30 quently followed by a further reaction with P205; and mixtures thereof (as described in US 3,197,405).
[0102] Foam inhibitors that may be useful in the lubricant compositions of the disclosed technology include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, poly-propylene oxides and (ethylene oxide-propylene oxide) polymers.
[0103] Other viscosity modifiers may include a block copolymer comprising (i) a vinyl aromatic monomer block and (ii) a conjugated diene olefin monomer block (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-iso-prene copolymer), a polymethacrylate, or mixtures thereof.
[0104] Pour point depressants that may be useful in the lubricant compositions of the disclosed technology include polyalphaolefins, esters of maleic anhydride-sty-rene copolymers, poly(meth)acrylates, polyacrylates or polyacrylami des.
[0105] Demulsifiers include trialkyl phosphates, and various polymers and co-polymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.
[0106] Metal deactivators include derivatives of benzotriazoles (typically tol-yltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyl-dithiobenzothiazoles. The metal deactivators may also be described as corrosion in-hibitors.
[0107] Seal swell agents include sulfolene derivatives Exxon Necton37TM
(FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
[0108] In an embodiment, the lubricating composition can be employed to lu-bricate a mechanical device. The mechanical device can be associated with an auto-motive vehicle. For example, the mechanical device may be a driveline device.
[0109] Driveline devices include automatic transmissions, manual transmis-sion, dual clutch transmissions, or an axle or differential. A driveline device lubricating composition in different embodiments may have a composition as disclosed in the follow-ing table:
Additive Embodiments (wt %) A
Alkylphenol Detergent 0.01 to 2 0.01 to 2 0.01 to 2 0.01 to 2 Dispersant 1 to 4 0.1 to 10, 2 to 0 to 5 1 to 6 Extreme Pressure Agent 3 to 6 0 to 6 0 to 3 0 to 6 Overbased Detergent 0 to 1 0.01 to 3, 0.5 to 6 0.01 to 0.025 to 2 Antioxidant 0 to 5 0.01 to 10 or 0 to 3 0 to 2 Friction Modifier 0 to 5 0.01 to 5 0.1 to 1.5 0 to 5 Viscosity Modifier 0.1 to 70 0.1 to 15 1 to 60 0.1 to Any Other Performance Additive 0 to 10 0 to 8 or 10 0 to 6 0 to 10 Oil of Lubricating Viscosity Balance to 100 %
Footnote:
The viscosity modifier in the table above may also be considered as an alternative to an oil of lubricating viscosity.
Column A may be representative of an automotive or axle gear lubricant.
Column B may be representative of an automatic transmission lubricant.
Column C may be representative of an off-highway lubricant.
Column D may be representative of a manual transmission lubricant.
[0110] The mechanical device can be an internal combustion engine, such as, for example, a spark ignited internal combustion engine or a compression ignition internal combustion engine. An engine lubricant composition in different embodi-ments may have a composition as disclosed in the following table:
Additive Embodiments (wt %) A
Alkylphenol Detergent 0.05 to 10 0.2 to 5 0.5 to 2 Corrosion Inhibitor 0.05 to 2 0.1 to 1 0.2 to 0.5 Other Overbased Detergent 0 to 9 0.5 to 8 1 to 5 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2 Dispersant 0 to 12 0 to 8 0.5 to 6 Antioxidant 0.1 to 13 0.1 to 10 0.5 to 5 Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5 Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to 8 0 to 6 Oil of Lubricating Viscosity Balance to 100 %
[0111] The mechanical device may also be in a hydraulic system. A
hydraulic lubricant may also comprise a formulation defined in the following table:
Hydraulic Lubricant compositions Additive Embodiments (wt %) A
Alkylphenol detergent as de- 0.01 to 2.0 0.01 to 1.5 0.01 to 1.0 scribed herein Antioxidant 0 to 4.0 0.02 to 3.0 0.03 to 1.5 Dispersant 0 to 2.0 0.005 to 1.5 0.01 to 1.0 Other Detergent - beside al- 0 to 5.0 0.001 to 1.5 0.005 to 1.0 kylphenol detergent as de-scribed herein Anti-wear Agent 0 to 5.0 0.001 to 2 0.1 to 1.0 Friction Modifier 0 to 3.0 0.02 to 2 0.05 to 1.0 Viscosity Modifier 0 to 10.0 0.5 to 8.0 1.0 to 6.0 Any Other Performance Addi- 0 to 1.3 0.00075 to 0.5 0.001 to 0.4 tive (antifoam / demulsi-fier/pour point depressant) Metal Deactivator 0 to 0.1 0.01 to 0.04 0.015 to 0.03 Rust Inhibitor 0 to 0.2 0.03 to 0.15 0.04 to 0.12 Extreme Pressure Agent 0 to 3.0 0.005 to 2 0.01 to 1.0 Oil of Lubricating Viscosity Balance to Balance to 100 Balance to 100% 100%
[0112] The disclosed technology further provides a method of lubricating a circulating oil system.
[0113] The disclosed technology further provides a method of lubricating a turbine system.
[0114] The alkylphenol can be employed to lubricate any of the foregoing me-chanical devices by supplying to the mechanical device the aforementioned lubricat-ing compositions.
[0115] The amount of each chemical component described is presented exclu-sive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
[0116] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are included within the scope of the pre-sent invention; the present invention encompasses the composition prepared by admix-ing the components described above.
[0117] As used herein, the term "about" means that a value of a given quantity is within 20% of the stated value. In other embodiments, the value is within 15%
of the stated value. In other embodiments, the value is within 10% of the stated value. In other embodiments, the value is within 5% of the stated value. In other embodiments, the value is within 2.5% of the stated value. In other embodiments, the value is within 1% of the stated value.
[0118] Additionally, as used herein, the term "substantially" means that a value of a given quantity is within 10% of the stated value. In other embodiments, the value is within 5% of the stated value. In other embodiments, the value is within 2.5% of the stated value. In other embodiments, the value is within 1% of the 5 stated value.
[0119] Each of the documents referred to above is incorporated herein by ref-erence, including any prior applications, whether or not specifically listed above, from which priority is claimed. The mention of any document is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled per-10 .. son in any jurisdiction. Except in the Examples, or where otherwise explicitly indi-cated, all numerical quantities in this description specifying amounts of materials, re-action conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined.
15 Similarly, the ranges and amounts for each element of the invention can be used to-gether with ranges or amounts for any of the other elements.
[0120] As used herein, the transitional term "comprising," which is synony-mous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
How-20 ever, in each recitation of "comprising" herein, it is intended that the term also encom-pass, as alternative embodiments, the phrases "consisting essentially of" and "consist-ing of," where "consisting of' excludes any element or step not specified and "con-sisting essentially of' permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the com-25 .. position or method under consideration.
[0121] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without de-parting from the scope of the subject invention. In this regard, the scope of the in-30 vention is to be limited only by the following claims.
Claims (34)
1. An alkylphenol detergent composition comprising at least one phenol moiety having a hydrocarbyl group attached thereto, the hydrocarbyl group compris-ing at least one oligomer comprising monomers equivalent to 5 to 10 carbon atom branched olefins.
2. The alkylphenol detergent composition of claim 1, where the monomers are equivalent to 5 to 10 carbon atom branched polyenes.
3. The alkylphenol detergent composition of claim 2, where the monomers are equivalent to isoprene.
4. The alkylphenol detergent composition of any previous claim, where the oli-gomer is a terpene.
5. The alkylphenol detergent composition of any previous claim, where the oli-gomer is equivalent to at least one of formula
6. The detergent composition of any previous claim, wherein the oligomer is equivalent to a partially or completely hydrogenated form of a terpene.
7. The detergent composition of claim 5, wherein the oligomer is equivalent to any of formula:
8. The detergent composition of any previous claim, where the hydrocarbyl unit comprises 15 to 60 carbon atoms.
9. The detergent composition of any previous claim, where the detergent com-prises an alkylphenol moiety of any of formula:
10. The detergent composition of any previous claim, wherein the detergent is a sulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenate de-tergent, a salicylate detergent, or mixtures thereof.
11. The detergent composition of any previous claim, where the detergent com-prises one or more alkali metals, one or more alkaline earth metals, or mixtures thereof.
12. The detergent composition of any previous claim, where the detergent is over-based.
13. The detergent composition of claim 12, where the overbased detergent has a metal ratio of at least 1.5, at least 5, or at least 7.
14. The detergent composition of any previous claim, wherein the detergent is an overbased sulfur-coupled phenate detergent with a metal ratio of at least 1.5.
15. The detergent composition of any previous claim, wherein the composition is a sulfur-bridged phenate represented by the structure wherein each R is an aliphatic hydrocarbyl group equivalent to an oligomer of isoprene, higher branched olefins, or mixtures thereof, that contains 15 to 60 carbon atoms; and n = 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.
16. The detergent composition of any previous claim, wherein the detergent is a neutral or overbased salt of alkylsalicylic acid.
17. The detergent composition of any previous claim, wherein the composition is an alkylsalicylate represented by the structure where R is an aliphatic hydrocarbyl group equivalent to an oligomer of iso-prene, higher branched olefins, or mixtures thereof, and wherein the hydro-carbyl group contains 15 to 60 carbon atoms
18. A lubricating composition comprising (a) an oil of lubricating viscosity and (b) the alkylphenol detergent composition of any previous claim.
19. The lubricating composition of claim 18, wherein the alkylphenol detergent is present from about 0.01 to about 2 wt%, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5 wt% of the lubricating composition.
20. The lubricating composition of claim 18 or 19, wherein the composition is substantially free of an alkylphenol-containing detergent wherein the al-kylphenol is derived from oligomers of propene.
21. The lubricating composition of any of claims 18 to 20, further comprising a zinc dialkyldithiophosphate.
22. The lubricating composition of any of claims 18 to 21, further comprising a dispersant.
23. The lubricating composition of claim 22, wherein the dispersant is a polyiso-butylene succinimide dispersant.
24. The lubricating composition of any of claims 22 to 23, wherein the dispersant is present at 0.1 to 5 wt %, or 0.3 to 4 wt %, or 0.5 to 3 wt %, or 1 to 2.5 or 3 wt %, or 1.5 to 4 wt %, or 1.5 to 3 wt %, or even 0.1 to 3 wt %, or 0.1 to 2.5 wt %, or 0.2 to 2 wt %.
25. The lubricating composition of any of claims 18 to 24, further comprising a phosphorus-containing antiwear agent chosen from (i) a non-ionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound.
26. The lubricating composition of any of claims 18 to 25, further comprising a thiadiazole.
27. The lubricating composition of claim 26, wherein the thiadiazole is present at 0.1 to 0.5 wt %,or 0.2 to 0.4 wt %, or 0.25 to 0.35 wt %., or even from 0.05 to 1 wt %, or 0.07 to 0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %.
28. A method of lubricating a mechanical device comprising supplying to the de-vice the lubricating composition of any of claims 18 to 27.
29. The method of claim 28, wherein the mechanical device is an internal com-bustion engine.
30. The method of claim 29, wherein the internal combustion engine is a heavy duty diesel compression ignited internal combustion engine or a spark assisted compression ignited internal combustion engine.
31. The method of claim 28, wherein the mechanical device is an automatic trans-mission.
32. The method of claim 28, wherein the mechanical device is a manual transmis-sion.
33. The method of claim 28, wherein the mechanical device is an automotive axle.
34. The method of claim 28, wherein the mechanical device is an off-highway vehicle.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US201762594251P | 2017-12-04 | 2017-12-04 | |
US62/594,251 | 2017-12-04 | ||
PCT/US2018/058850 WO2019112720A1 (en) | 2017-12-04 | 2018-11-02 | Alkylphenol detergents |
Publications (1)
Publication Number | Publication Date |
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CA3083929A1 true CA3083929A1 (en) | 2019-06-13 |
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ID=64362721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA3083929A Pending CA3083929A1 (en) | 2017-12-04 | 2018-11-02 | Alkylphenol detergents |
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US (1) | US20210230498A1 (en) |
EP (1) | EP3720935A1 (en) |
CN (1) | CN111433331A (en) |
CA (1) | CA3083929A1 (en) |
SG (1) | SG11202004886WA (en) |
WO (1) | WO2019112720A1 (en) |
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- 2018-11-02 CN CN201880077965.7A patent/CN111433331A/en active Pending
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WO2019112720A1 (en) | 2019-06-13 |
CN111433331A (en) | 2020-07-17 |
US20210230498A1 (en) | 2021-07-29 |
EP3720935A1 (en) | 2020-10-14 |
SG11202004886WA (en) | 2020-06-29 |
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