US3350348A - Lubricating oil additives - Google Patents
Lubricating oil additives Download PDFInfo
- Publication number
- US3350348A US3350348A US445697A US44569765A US3350348A US 3350348 A US3350348 A US 3350348A US 445697 A US445697 A US 445697A US 44569765 A US44569765 A US 44569765A US 3350348 A US3350348 A US 3350348A
- Authority
- US
- United States
- Prior art keywords
- lubricating oil
- grams
- reaction
- temperature
- acid
- 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.)
- Expired - Lifetime
Links
- 239000010687 lubricating oil Substances 0.000 title claims description 39
- 239000000654 additive Substances 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims description 41
- 239000003921 oil Substances 0.000 claims description 23
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010688 mineral lubricating oil Substances 0.000 claims description 3
- 239000010689 synthetic lubricating oil Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000002253 acid Substances 0.000 description 24
- -1 alkenylaryl radical Chemical class 0.000 description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004440 Isodecyl alcohol Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical class [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- CGKKDGMMKSOGLM-UHFFFAOYSA-N 1-chloroethyl acetate Chemical compound CC(Cl)OC(C)=O CGKKDGMMKSOGLM-UHFFFAOYSA-N 0.000 description 1
- ATXWGWHZGZFBHI-UHFFFAOYSA-N 1-chloroethyl benzoate Chemical compound CC(Cl)OC(=O)C1=CC=CC=C1 ATXWGWHZGZFBHI-UHFFFAOYSA-N 0.000 description 1
- IXMVJDKNCLOWPR-UHFFFAOYSA-N 1-chloroethyl propanoate Chemical compound CCC(=O)OC(C)Cl IXMVJDKNCLOWPR-UHFFFAOYSA-N 0.000 description 1
- VBEFTAAXOJJJKG-UHFFFAOYSA-N 1-chloropropyl acetate Chemical compound CCC(Cl)OC(C)=O VBEFTAAXOJJJKG-UHFFFAOYSA-N 0.000 description 1
- CWPPDTVYIJETDF-UHFFFAOYSA-N 2,2,4-trimethylpentan-1-ol Chemical compound CC(C)CC(C)(C)CO CWPPDTVYIJETDF-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 235000010523 Cicer arietinum Nutrition 0.000 description 1
- 244000045195 Cicer arietinum Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000014647 Lens culinaris subsp culinaris Nutrition 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ORZGJQJXBLFGRP-WAYWQWQTSA-N bis(ethenyl) (z)-but-2-enedioate Chemical compound C=COC(=O)\C=C/C(=O)OC=C ORZGJQJXBLFGRP-WAYWQWQTSA-N 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- IHXBXGHGYCSRAP-UHFFFAOYSA-N bis(ethenyl) benzene-1,4-dicarboxylate Chemical compound C=COC(=O)C1=CC=C(C(=O)OC=C)C=C1 IHXBXGHGYCSRAP-UHFFFAOYSA-N 0.000 description 1
- AJCHRUXIDGEWDK-UHFFFAOYSA-N bis(ethenyl) butanedioate Chemical compound C=COC(=O)CCC(=O)OC=C AJCHRUXIDGEWDK-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical class OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- BGVWGPMAGMJLBU-UHFFFAOYSA-N ethenyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC=C)=CC=CC2=C1 BGVWGPMAGMJLBU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical class O* 0.000 description 1
- VKLBOGVYSJFJPY-UHFFFAOYSA-N hydroxy-(2-nonylphenoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)(S)=S VKLBOGVYSJFJPY-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000005027 hydroxyaryl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1653—Esters of thiophosphoric acids with arylalkanols
-
- 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
- C10M2223/047—Thioderivatives not containing metallic elements
-
- 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
- C10N2040/02—Bearings
Definitions
- This invention relates to a novel class of compositions useful in lubricating oils and to the method of preparing same. More specifically, it relates to novel oil-soluble compositions and lubricating oil compositions having improved antioxidant activity, bearing corrosion protection and extreme pressure properties, containing the same.
- lubricating oils are generally formulated with antioxidants which are designed to inhibit the formation of oxidation products and thus lengthen the life of the lubricating oil.
- antioxidants which are designed to inhibit the formation of oxidation products and thus lengthen the life of the lubricating oil.
- organophosphorus sulfur compounds are a useful type of inhibitor.
- novel compounds of this invention have the structure:
- n is an integer of 1 to 2;
- R is an alkyl, including both primary and secondary alkyl, or cycloalkyl or al- 3,35%,348 Patented Oct. 31, 1967 ice kenyl radical containing from 1 to 12 carbon atoms, or an aryl, alkylaryl or alkenylaryl radical having from 1 to 5 alkyl substituents attached to the aromatic nucleus, the alkyl substituents containing from 1 to 12 carbon atoms and having a total of up to 18 carbon atoms, or a hydroxy or halogen derivative of the above-defined alkyl or aryl radical;
- R is hydrogen or an alkyl or cycloalkyl or alkenyl radical or (when n is 2) an alkylene, alkenylene or arylene radical having from 1 to 11 carbon atoms; or an aryl radical, such as phenyl or naphthyl, or aralkyl or alkaryl or an alkenylaryl radical, the
- n 1 and R may be the bracketed group itself; or when n is 2 and R is alkylene, alkenylene or arylene, the carboxylates are dibasic as indicated by the formula Suitable dicarboxylates include oxalates, succinates, maleates, fumarates, phthalates, or cyclohexane dicarboxylates.
- a phosphorodithioic acid reactant is mixed gradually and with agitation, with an alkyl carboxylate reactant reactive at the alpha carbon at a temperature in the range of about 40 to about C.
- R, R and R have the aforementioned definitions (R"' being substantially the same as R" except that it is the alkylidene or aralkylidene thereof by virtue of the double bond as shown), M is an alkali metal, and X is either a halogen group such as chloro, iodo or bromo, or a tosyl group.
- the ratio of the alkyl carboxylate to the phosphorodithioic reactant is at least stoichiometric and usually in the range of about 0.75 to 4.0, and preferably 1.0 to 1.5, moles of carboxylic ester per mole of phosphorodithioic acid compound.
- the temperature is held at the temperature of the reaction until the reaction is deemed complete.
- the total reaction time takes about 30 minutes to five hours, preferably 1 to 2 hours.
- the reaction is preferably carried out in a liquid phase. If sufficient phosphorodithioic acid reactant is used no additional solvent is necessary. If desired, an organic solvent which is not reactive to the reaction mixture may be added. Such solvents include benzene, n-heptane, cyclohexane, or any of the known solvent-refined processing oils.
- the temperature for the reaction is maintained at a moderate level, in the range of about 40 C. to about 150 C., and preferably from about 45 C. to 90 C. Once the product has been formed in the reaction mixture the temperature can be increased without danger of thermal decomposition of the product.
- Suitable esters ⁇ or use as the carboxylate reactants in this invention include the vinyl and substituted vinyl esters of carboxylates described hereinabove and specifically vinyl acetate, vinyl propionate, vinyl butyrate, butenyl propionate and other aliphatic acid esters containing up to 12 carbon atoms, including branched aliphatic acid esters, such as vinyl isobutyrate.
- Aromatic esters include vinyl benzoate and vinyl naphthoate.
- esters which may also be used include dicarboxylic acid esters, such as divinyl succinate; aryl dicarboxylic acid esters, such as divinyl phthalate and divinyl terephthalate: and the unsaturated carboxylic esters, such as divinyl maleate and di- 'vinyl fumarate.
- Halogenated esters include alpha-chloroethyl acetate, alpha-chloroethyl propionate, alpha-chloroethyl benzoate, alpha-chloropropyl acetate, di-alpha- :chloroethyl succinate.
- the tosylated methyl esters and alpha-tosyl alkyl esters are readily obtained.
- the phosphorodithioic acid ester reactants are normally prepared by the reaction of 4 moles of an alcohol or phenol with one mole of phosphorus pentasulfide as follows:
- Suitable alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, oleyl alcohol, isohexyl alcohol, isodecyl alcohol, trimethylpentyl alcohol, crotyl alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol, dimethylbutyl alcohol, and cyclic alcohols, such as cyclohexanol.
- Suitable aromatic alcohols include phenol and alkylphenols which have up to 5 alkyl groups on the ring, including cresol and nonylphenol.
- Halogenated alcohols may also be used, such as chlorophenol and ethylene or propylene chlorohydrin.
- the resulting product is hereafter referred to as 0,0-dialkylor 0,0-diarylphosphorodithioic acid.
- Mixed esters may also be utilized, and hence any combinations of the above alkyl and aryl compounds are satisfactory in employing the present invention.
- the alkali metal salts are prepared by simply reacting the esters with metal hydroxides or alkoxides in a conventional neutralization reaction.
- the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate products of this invention have excellent solubility in the typical lubricating oils in which they are intended to be used. Generally their solubility exceeds the amount required to obtain the desired antioxidant and anticorrosion characteristics furnished by these products.
- Example 1 Preparati0n 0 0,0-diisobutylphosphorodithioic acid Into a four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer are added 296 grams (4.0 moles) of isobutyl alcohol and the contents are heated to 75 C. At that temperature 222 grams (1.0 mole) of phosphorus pentasulfide are added portionwise over an hour period with agitation. After all of the sulfide reactant is introduced, the temperature is raised to 90 C. and held for three hours. The evolution of hydrogen sulfide gas indicates a substantially complete reaction. The reaction product is cooled and filtered.
- Example 2 Preparati0n of 1-(0,0-diisobutylphosphorodithiato) ethyl acetate
- the temperature during this addition is maintained at 78 C.
- the reaction mixture is heated for one hour at a temperature ranging from C. to C.
- the reaction mixture is then passed into a rotary film evaporator heated by a boiling water bath and the unreacted vinyl acetate removed under reduced pressure.
- the yield of product is 650.9 grams of an amber-colored oil indicating a yield of about 99%.
- This product was also produced by the alternative procedure as follows:
- Example 3 Preparation of 1-(0,O-di0leylph0sphor0dithiato) ethyl acetate 0,0-dioleylphosphorodithioic acid prepared through the reaction of 400 grams (1.6 moles) of oleyl alcohol and 100 grams (0.45 mole) of phosphorus pentasulfide is charged into a reaction flask equipped with a stirrer and thermometer and heated to 45 C. Vinyl acetate (103 grams, 1.2 moles) is then added over a half-hour period with agitation. During this addition, the temperature rises to 85 C. The reaction product is then maintained at 85- 90 C. with stirring for an additional hour and topped to a vapor temperature of 100 C. at 0.2 mm. to give 453 grams of a dark, amber colored adduct.
- Example 4 Pre paration of 1- 0,0-di-2,2,4-trimethylpentylphosphorodithiato) ethyl acetate
- the phosphorodithioic acid obtained in the example is prepared by a reaction between 122 grams (0.55 mole) of phosphorus pentasulfide and 260 grams (2.0 moles) of 2,2,4-trimethylpentan-l-ol, according to the procedure of Example 1.
- To this acid are added 69 grams (0.8 mole) of vinyl acetate over a 10-minute period at a temperature of 60 C. When the addition is complete, the temperature of the reaction mixture is raised to the reflux temperature, in the range of about 90 to 95 C. Refluxing is continued for four and one-quarter hours.
- the reaction product is washed with a aqueous sodium hydroxide solution to remove excess acid and dried over sodium sulfate.
- the treated product is distilled under a nitrogen atmosphere at 3.5 mm. Hg pressure to a pot temperature of 120 C.
- the liquid product obtained from this procedure is slightly hazy. Further treatment by sodium sulfate followed by filtration through Hi-Flo (diatomaceous earth filter aid) produces a clear yellow liquid substance.
- the reaction yields 337 grams (96%) of product.
- Example 5 Preparation of 1-(0,0-diphenylph0sphor0- dithiat0)ethyl acetate
- the acid in this example is obtained by reacting phenol with phosphorus pentasulfide using the procedure of Example 1.
- a solution of 43 grams (0.50 mole) of vinyl acetate in 250 ml. of benzene is added Into a reaction flask equipped with a stirrer and thermometer is added a solution of 43 grams (0.50 mole) of vinyl acetate in 250 ml. of benzene. This solution is heated as a second solution, consisting of 70.6 grams (0.25 mole) of 0,0-diphenylphosphorodithioic acid in 200 ml. of benzene, is added over a half-hour period with agitation. The temperature is raised to 70 C.
- Example 6 Preparation of 1- [0,0-di(n0nylphenyl)phosph0rodithiat01ethyl acetate
- the acid is prepared in this example by using nonylphenol in the reaction with phosphorus pentasnlfide.
- a solution containing 116 grams (0.20 mole) of 0,0-di (nonylphenyl)phosphorodithioic acid in 150 ml. of henzene is added to a reaction flask equipped with a stirrer and thermometer.
- To this solution are added 34.4 grams (0.40 mole) of vinyl acetate over an 18-minute period with agitation. The temperature during this addition is maintained at about C. and the agitation is continued at this temperature for an additional hour.
- 131 grams (96% yield) of a clear yellow liquid adduct remains.
- Example 7 Preparati0n of 1-(0,0-dimethylphosphor0- dithiat0)ethyl acetate Using similar procedures as in the previous examples to produce the acid, 215 grams (2.5 moles) of vinyl acetate are added to 2.0 moles of 0,0-dimethylphosphorodithioic acid prepared from the reaction between methanol and phosphorus pentasulfide, as described in Example 1. The reaction mixture requires frequent ice bath applications to keep the temperature at about 40 C. to C. After the vinyl acetate addition the reaction mixture is heated at C. for an additional hour. The product obtained from this reaction is 400.7 grams (82% yield) of a straw-colored clear liquid product.
- Example 8 Preparation of 1-(0,0-cliis0pentylphosphorodithiato) ethyl acetate
- the acid is obtained by a reaction between isopentyl alcohol and phosphorus pentasulfide using the procedure of Example 1.
- Into a reaction flask equipped with a stirrer and thermometer are added 100 grams (0.37 mole) of 0,0-diisopentylphosphorodithioic acid.
- 50 grams (0.58 mole) of vinyl acetate over a half-hour period with agitation. During this addition the temperature is raised to C., afterward the reaction mixture is maintained at 90 C. with agitation for an additional hour.
- Unreacted vinyl acetate is removed under reduced pressure in a rotary film evaporator heated by a boiling water bath.
- the adduct consists of 125 grams yield) of an amber-colored oil.
- Example 9 Preparati0n of 1-(0,0-diisobutylphosphorodithiat0)ethyl benzoate Using similar procedures as in the previous examples, 50 grams (0.336 mole) of vinyl benzoate are added to 81.5 grams (0.336 mole) of 0,0-diisobutylphosphorodithioic acid in benzene. The addition takes half an hour during which time the temperature is held at about 85 C. The reaction mixture is held for an additional hour at 85 C. A yield of pale yellow liquid adduct is obtained.
- Example 10 Preparation 0f 1-(0,0-a'i-(1,3-dimethylbatyl)ph0sph0rodithiato)ethyl acetate
- the acid used in this example is obtained by a reaction between 4 moles of 1,3-dimethylbutan-1-ol with 1.1 moles of phosphorus pentasulfide as described in Example 1.
- To the crude product of this reaction are added 170 grams (2 moles) of vinyl acetate over a 15 minute period. During the addition the temperature is in the range of 60 C. to 70 C. Benzene ml.) is added.
- the reaction mixture is agitated and heated at a temperature of from 90 C. to 95 C. for a total of 6 hours.
- the reaction product is washed with 10% aqueous sodium hydroxide solution, dried over sodium sulfate and distilled under nitrogen at 3.5 mm. Hg pressure to a pot temperature of 120 C.
- the remaining liquid has the following analysis:
- Example 11 Preparati0n of 1-(0,0-di-isobutylph0sphorodithiato) ethyl butyrate
- the acid used for this example is the same as that prepared in Example 1.
- 100 grams (0.88 mole) of vinyl butyrate is added to grams (0.70 mole) 0,0-di-isobutylphosphorodithioic acid with agitation.
- the addition takes half an hour in which time the temperature is increased from 45 C. to 85 C.
- the reaction mixture is held for an additional hour at 85 C.
- the unreacted vinyl butyrate is removed leaving a liquid product having the following analysis:
- Example ]4 Preparati0n of di[1-(0,0-diis0butylph0sph0r0dithiat0)]ethyl succinate
- di-l-chloroethyl succinate prepared by the reaction of 26.7 grams (0.173 mole) of succinyl chloride with grams (0.46 mole) of acetaldehyde in 100 m1.
- benzene containing 0.2 gram of dry zinc chloride there is added dropwise over a 15 minute period a solution of 97 grams (0.35 mole) of potassium 0,0-diisobutylphosphorodithioate in 150 ml. of N,N-dimethylformamide while stirring.
- the temperature is maintained at 50 C. during the addition and is then raised to 80 and stirring is continued at this temperature for one additional hour.
- di-l-(0,0-diisobutylphosphorodithiato)ethyl succinate for which the infrared spectrum is very similar to that of 1-(0,0-diisobutylphosphorodithiato)ethyl acetate.
- Example 15 Preparati0n of 1 (0,0-diis0decylph0sphorodithiato) ethyl acetate
- the acid is obtained by a reaction between isodecyl alcohol and phosphorus pentasulfide using the procedure of Example 1.
- Into a reaction flask equipped with a stirrer and thermometer are added 790 grams (1.9 moles) of 0,0-diisodecylphosphorodithioic acid.
- To the contents of the flask are added 250 grams (3.0 moles) of vinyl acetate.
- the reaction mixture is held for 2 hours at a temperature of 80 to 90 C. Unreacted vinyl acetate is thereafter removed.
- the yield of the liquid adduct is 100%; it has the following analysis:
- compositions of this invention prevent the oxidation of lubricating oils, even in the presence of metal catalysts.
- bearing corrosion test it will be noted by comparison that the same lubricating oil containing no additives at all permits an extremely high weight loss.
- EXTREME PRESSURE PROPERTIES The extreme pressure properties of two products prepared in the above examples were tested using SAE solvent-refined mineral base oil.
- the oil was blended with (1) 6.2% of the product of Example 4 and (2) 5.2% of the product of Example 10.
- the two oil blends were tested on an SAE load machine. In this test, two cylinders, driven at different speeds, are rotated against one another, and these roll and slide in line contact under controlled loads. The faster cylinder was operated at 500 rpm. The load is increased until failure, i.e. scutfing or seizure occurs; the loading rate is about 78 lbs. per second. At this point the total load is reported. Each sample oil was tested twice.
- Oil composition Seizure load, lbs. (1) Composition 4 270,275 (2) Composition 10 270,290
- L-l CATERPILLAR ENGINE TEST The products of Examples 2 and 6 were tested in a lubricating oil in the L-l Caterpillar Engine Test using a non-metallic detergent.
- the Caterpillar engine test determines the ability of the oil to prevent deposits around important parts of the engine including the piston and crankcase areas.
- a l-cylinder, 4-cycle Caterpillar engine is run under the following operating conditions:
- the duration of the test was 480 hours
- the diesel fuel of the engine contained 1% sulfur.
- a typical refined lubricating oil each containing 1% by weight of the products of Examples 2 and 6 and 3% of a commercial detergent.
- the engine was examined for deposits at various times during the run. The test results are reported below.
- the engine rating expresses the over-all conditions of the engine at the end of the test run; a scale of to 100 is used, a 100 rating indicating a perfectly clean engine.
- the lacquer demerits indicate the amount of deposits coating the rings, the grooves and lands and the skirts of the piston; demerits are given for quantity of coating and degree of lacquering as evidence by color standards, and the sticking tendencies of the piston ring; the scale is from 0 to 100, a rating of 0 indicating completely clean surfaces and no demerits of any kind.
- the top groove packing rating indicates in percent of volume the amount of the carbon deposited in the top groove of the piston; the scale is from 0 to 100%, a rating of 0 indicating a completely clean groove.
- THERMAL GRAVIMETRIC TEST This test investigates the stability of the novel com-- pounds of this invention at high temperatures by subjecting the compounds to increasing heat while the rate of weight loss is observed.
- the temperature at which weight loss rate is markedly increased is designated as the inflection temperature; hence, a high inflection temperature indicates satisfactory stability.
- the products which were tested have been prepared according to the procedures used in the above examples, including products not specifically described hereinbefore.
- a lubricating oil composition comprising a major amount of a lubricating oil selected from the group consisting of a mineral lubricating oil and a synthetic lubricating oil, said oil being of lubricating viscosity suitable for lubricating high frictional surfaces of engines, and a minor amount of a 1-(0,0-diorganophosphorodithiato) alkyl carboxylate the said alkyl group having at least two carbon atoms.
- R is selected from the group consisting of alkyl, hydroxyalkyl, and haloalkyl having from 1 to 12 carbon atoms and aryl, hydroxyaryl, haloaryl, and alkaryl having up to 5 alkyl substituents on the aromatic nucleus with from 1 to 12 carbon atoms per alkyl substituent and a total of up to 18 carbon atoms.
- R is selected from the group consisting of methyl, butyl, isobutyl, pentyl, dimethylbutyl, trimethylpentyl, and decyl.
- R is selected from the group consisting of phenyl, methylphenyl, butylphenyl and nonylphenyl.
- the lubricating oil composition of claim 3 wherein the carboxylate group is selected from the group consisting of acetate, propionate, butyrate, succinate and benzoate.
- l-(0,0-diorganophosphorodithiato)alkyl carboxylate is l-(0,0-diisobutylphosphorodithiato)ethyl benzoate.
- reaction sequence (a) should appear as shown below instead of as in the patent:
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Description
United States Patent Ofi 3,350,348 LUBRICATING OIL ADDITIVES Milton Braid, Harrington, and Herbert Myers, Cherry Hill, N.J., assignors to Mobil Oil Corporation, a corporation of New York No Drawing. Filed Apr. 5, 1965, Ser. No. 445,697 18 Claims. (Cl. 252--46.6)
This invention relates to a novel class of compositions useful in lubricating oils and to the method of preparing same. More specifically, it relates to novel oil-soluble compositions and lubricating oil compositions having improved antioxidant activity, bearing corrosion protection and extreme pressure properties, containing the same.
The temperatures and pressure conditions existing in present-day automotive, aircraft and marine engines are known to accelerate the deterioration of lubricating oils. This deterioration, which is usually attributed to the oxidation of the oil, produces acids and sludge, it increases the fluid viscosity and, as a consequence, it reduces the lubricating ability of the oil. Certain parts of the engine, particularly copper-lead type bearings, become corroded by the acids. The accumulation of sludge produced from this oxidation, from impurities in the suction air, or from ignition products becomes deposited around the various parts of the engine. The pressure exerted within the engine and the gears at the elevated temperatures also tends to aggravate these effects, resulting in physical abrasion of the moving parts.
To overcome this oxidation, lubricating oils are generally formulated with antioxidants which are designed to inhibit the formation of oxidation products and thus lengthen the life of the lubricating oil. For example, organophosphorus sulfur compounds are a useful type of inhibitor.
It is a major object of this invention, therefore, to provide novel organic phosphorus-sulfur compounds and a method for their preparation. Another object of this invention is to provide lubricating oil compositions containing these novel oil-soluble, non-metallic organic phosphorus-sulfur compounds. Another object of this invention is to provide lubricating oil compositions having improved stability against oxidation and extreme pressure and temperature conditions found in present-day automotive, aircraft and marine engines. A further object of this invention is to provide lubricating oil compositions having improved inhibition to engine bearing corrosion.
The aforementioned and other objects we achieve by adding to a lubricating oil an amount sufficient to reduce oxidation decomposition thereof of a 1-(0,0di0rganophosphorodithioato)alkyl carboxylate. These novel compounds are highly soluble in lubricating oil and are effective in preventing oxidation of the oil even under high temperature conditions.
The novel compounds of this invention have the structure:
wherein n is an integer of 1 to 2; R is an alkyl, including both primary and secondary alkyl, or cycloalkyl or al- 3,35%,348 Patented Oct. 31, 1967 ice kenyl radical containing from 1 to 12 carbon atoms, or an aryl, alkylaryl or alkenylaryl radical having from 1 to 5 alkyl substituents attached to the aromatic nucleus, the alkyl substituents containing from 1 to 12 carbon atoms and having a total of up to 18 carbon atoms, or a hydroxy or halogen derivative of the above-defined alkyl or aryl radical; R is hydrogen or an alkyl or cycloalkyl or alkenyl radical or (when n is 2) an alkylene, alkenylene or arylene radical having from 1 to 11 carbon atoms; or an aryl radical, such as phenyl or naphthyl, or aralkyl or alkaryl or an alkenylaryl radical, the aromatic nucleus being substituted with up to 5 alkyl groups each having from 1 to 12 carbon atoms, with a total number of up to 18 carbon atoms, or the halo derivatives thereof; and R" is alkyl, aralkyl, aryl, haloalkyl and haloaryl having similar substituent groups as R above. When n is 1 and R may be the bracketed group itself; or when n is 2 and R is alkylene, alkenylene or arylene, the carboxylates are dibasic as indicated by the formula Suitable dicarboxylates include oxalates, succinates, maleates, fumarates, phthalates, or cyclohexane dicarboxylates.
In the typical procedure for preparing the compositions of this invention, a phosphorodithioic acid reactant is mixed gradually and with agitation, with an alkyl carboxylate reactant reactive at the alpha carbon at a temperature in the range of about 40 to about C.
The preferred reaction sequences are alternativel as wherein R, R and R have the aforementioned definitions (R"' being substantially the same as R" except that it is the alkylidene or aralkylidene thereof by virtue of the double bond as shown), M is an alkali metal, and X is either a halogen group such as chloro, iodo or bromo, or a tosyl group.
The ratio of the alkyl carboxylate to the phosphorodithioic reactant is at least stoichiometric and usually in the range of about 0.75 to 4.0, and preferably 1.0 to 1.5, moles of carboxylic ester per mole of phosphorodithioic acid compound. When both of the reactants have been combined, the temperature is held at the temperature of the reaction until the reaction is deemed complete. Generally, the total reaction time takes about 30 minutes to five hours, preferably 1 to 2 hours.
The reaction is preferably carried out in a liquid phase. If sufficient phosphorodithioic acid reactant is used no additional solvent is necessary. If desired, an organic solvent which is not reactive to the reaction mixture may be added. Such solvents include benzene, n-heptane, cyclohexane, or any of the known solvent-refined processing oils.
At the end of the reaction, excess carboxylate is removed by vacuum distillation. If an organic solvent has been added, this too is removed by distillation. Other reaction products, reactants or solvents may be removed by washing. The residual product is in the form of an oilsoluble liquid. If a process oil is used as the reaction solvent, the oil may be allowed to remain in the product for subsequent addition to the final lubricating composition.
As discussed earlier, the temperature for the reaction is maintained at a moderate level, in the range of about 40 C. to about 150 C., and preferably from about 45 C. to 90 C. Once the product has been formed in the reaction mixture the temperature can be increased without danger of thermal decomposition of the product.
Suitable esters {or use as the carboxylate reactants in this invention include the vinyl and substituted vinyl esters of carboxylates described hereinabove and specifically vinyl acetate, vinyl propionate, vinyl butyrate, butenyl propionate and other aliphatic acid esters containing up to 12 carbon atoms, including branched aliphatic acid esters, such as vinyl isobutyrate. Aromatic esters include vinyl benzoate and vinyl naphthoate. Other esters which may also be used include dicarboxylic acid esters, such as divinyl succinate; aryl dicarboxylic acid esters, such as divinyl phthalate and divinyl terephthalate: and the unsaturated carboxylic esters, such as divinyl maleate and di- 'vinyl fumarate. Halogenated esters include alpha-chloroethyl acetate, alpha-chloroethyl propionate, alpha-chloroethyl benzoate, alpha-chloropropyl acetate, di-alpha- :chloroethyl succinate. Similarly the tosylated methyl esters and alpha-tosyl alkyl esters are readily obtained.
The phosphorodithioic acid ester reactants are normally prepared by the reaction of 4 moles of an alcohol or phenol with one mole of phosphorus pentasulfide as follows:
Suitable alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, oleyl alcohol, isohexyl alcohol, isodecyl alcohol, trimethylpentyl alcohol, crotyl alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol, dimethylbutyl alcohol, and cyclic alcohols, such as cyclohexanol. Suitable aromatic alcohols include phenol and alkylphenols which have up to 5 alkyl groups on the ring, including cresol and nonylphenol. Halogenated alcohols may also be used, such as chlorophenol and ethylene or propylene chlorohydrin. The resulting product is hereafter referred to as 0,0-dialkylor 0,0-diarylphosphorodithioic acid. Mixed esters may also be utilized, and hence any combinations of the above alkyl and aryl compounds are satisfactory in employing the present invention. The alkali metal salts are prepared by simply reacting the esters with metal hydroxides or alkoxides in a conventional neutralization reaction.
The 1-(0,0-diorganophosphorodithiato)alkyl carboxylate products of this invention have excellent solubility in the typical lubricating oils in which they are intended to be used. Generally their solubility exceeds the amount required to obtain the desired antioxidant and anticorrosion characteristics furnished by these products.
The following examples and test results illustrate the typical manner of carrying out and utilizing the invention thereby. Any mention of parts and percentage in these examples unless otherwise specified will be deemed to be on a weight basis.
4 Example 1.-Preparati0n 0 0,0-diisobutylphosphorodithioic acid Into a four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer are added 296 grams (4.0 moles) of isobutyl alcohol and the contents are heated to 75 C. At that temperature 222 grams (1.0 mole) of phosphorus pentasulfide are added portionwise over an hour period with agitation. After all of the sulfide reactant is introduced, the temperature is raised to 90 C. and held for three hours. The evolution of hydrogen sulfide gas indicates a substantially complete reaction. The reaction product is cooled and filtered.
Example 2.Preparati0n of 1-(0,0-diisobutylphosphorodithiato) ethyl acetate Into a flask equipped with a stirrer, condenser, dropping funnel and thermometer are added 484.6 grams (2 moles) of the 0,0-diisobutylphosphorodithioic acid prepared in Example 1 and thereafter with stirring 258.3 grams (3.0 moles) of vinyl acetate are added dropwise to the acid over a half-hour period. The temperature during this addition is maintained at 78 C. At the end of the addition period, the reaction mixture is heated for one hour at a temperature ranging from C. to C. The reaction mixture is then passed into a rotary film evaporator heated by a boiling water bath and the unreacted vinyl acetate removed under reduced pressure. The yield of product is 650.9 grams of an amber-colored oil indicating a yield of about 99%.
Analysis.Calcd for C H O PS P, 9.44; S, 19.5. Found: P, 9.45; S, 18.5.
This product was also produced by the alternative procedure as follows:
To 121.4 grams (0.991 mole) of l-chloroethyl acetate in 100 ml. of N,N-dimethylformamide there is added drop by drop a solution of 210.7 grams (0.75 mole) of potassium 0,0-diisobutylphosphorodithioate (prepared from the acid of Example 1 and potassium hydroxide) in ml. of N,N-dimethylformamide while stirring. The addition requires 20 minutes and the temperature is maintained at 3035 C. The temperature is then increased to 62 C. and heating and stirring are continued for one additional hour. The reaction product is washed with water extracted with benzene and rewashed. Benzene is removed by distillation and the residue is distilled in a molecular still at less than 0.01 mm. pressure. There is obtained grams of 1-(0,0-diisobutylphosphorodithiato)ethyl acetate.
Analysis.Calcd for C H O PS P, 9.44; S, 19.5. Found: P, 9.56; S, 19.0.
Example 3.Preparation of 1-(0,O-di0leylph0sphor0dithiato) ethyl acetate 0,0-dioleylphosphorodithioic acid prepared through the reaction of 400 grams (1.6 moles) of oleyl alcohol and 100 grams (0.45 mole) of phosphorus pentasulfide is charged into a reaction flask equipped with a stirrer and thermometer and heated to 45 C. Vinyl acetate (103 grams, 1.2 moles) is then added over a half-hour period with agitation. During this addition, the temperature rises to 85 C. The reaction product is then maintained at 85- 90 C. with stirring for an additional hour and topped to a vapor temperature of 100 C. at 0.2 mm. to give 453 grams of a dark, amber colored adduct.
Analysis.-Calcd for C H O PS P, 4.3; S, 8.9. Found: P, 4.9, S, 8.6.
Example 4 .Pre paration of 1- 0,0-di-2,2,4-trimethylpentylphosphorodithiato) ethyl acetate The phosphorodithioic acid obtained in the example is prepared by a reaction between 122 grams (0.55 mole) of phosphorus pentasulfide and 260 grams (2.0 moles) of 2,2,4-trimethylpentan-l-ol, according to the procedure of Example 1. To this acid are added 69 grams (0.8 mole) of vinyl acetate over a 10-minute period at a temperature of 60 C. When the addition is complete, the temperature of the reaction mixture is raised to the reflux temperature, in the range of about 90 to 95 C. Refluxing is continued for four and one-quarter hours. The reaction product is washed with a aqueous sodium hydroxide solution to remove excess acid and dried over sodium sulfate. The treated product is distilled under a nitrogen atmosphere at 3.5 mm. Hg pressure to a pot temperature of 120 C. The liquid product obtained from this procedure is slightly hazy. Further treatment by sodium sulfate followed by filtration through Hi-Flo (diatomaceous earth filter aid) produces a clear yellow liquid substance. The reaction yields 337 grams (96%) of product.
Analysis.Calcd for C H O PS P, 7.0; S, 14.5. Found: P, 6.9; S, 14.2.
Example 5 .Preparation of 1-(0,0-diphenylph0sphor0- dithiat0)ethyl acetate The acid in this example is obtained by reacting phenol with phosphorus pentasulfide using the procedure of Example 1. Into a reaction flask equipped with a stirrer and thermometer is added a solution of 43 grams (0.50 mole) of vinyl acetate in 250 ml. of benzene. This solution is heated as a second solution, consisting of 70.6 grams (0.25 mole) of 0,0-diphenylphosphorodithioic acid in 200 ml. of benzene, is added over a half-hour period with agitation. The temperature is raised to 70 C. and the mixture is agitated for an additional 18 minutes. At the end of this time, the benzene and unreacted vinyl acetate are removed under reduced pressure. The remaining 86.5 grams of crude product is cooled whereupon 21.0 grams of a white solid separates out of said product, leaving 65.5 grams of the liquid adduct. The adduct is separated from the precipitate by filtration.
Analysis.Calcd for CHI-117041382: P, S, Found: P, 9.14; S, 16.9.
Example 6.Preparation of 1- [0,0-di(n0nylphenyl)phosph0rodithiat01ethyl acetate The acid is prepared in this example by using nonylphenol in the reaction with phosphorus pentasnlfide. A solution containing 116 grams (0.20 mole) of 0,0-di (nonylphenyl)phosphorodithioic acid in 150 ml. of henzene is added to a reaction flask equipped with a stirrer and thermometer. To this solution are added 34.4 grams (0.40 mole) of vinyl acetate over an 18-minute period with agitation. The temperature during this addition is maintained at about C. and the agitation is continued at this temperature for an additional hour. Upon removal of the benzene and unreacted vinyl acetate, 131 grams (96% yield) of a clear yellow liquid adduct remains.
Analysis.-Calcd for C H O PS P, 5.0; S, 10.3. Found: P, 4.7; S, 10.4.
Example 7.Preparati0n of 1-(0,0-dimethylphosphor0- dithiat0)ethyl acetate Using similar procedures as in the previous examples to produce the acid, 215 grams (2.5 moles) of vinyl acetate are added to 2.0 moles of 0,0-dimethylphosphorodithioic acid prepared from the reaction between methanol and phosphorus pentasulfide, as described in Example 1. The reaction mixture requires frequent ice bath applications to keep the temperature at about 40 C. to C. After the vinyl acetate addition the reaction mixture is heated at C. for an additional hour. The product obtained from this reaction is 400.7 grams (82% yield) of a straw-colored clear liquid product.
Analysis.-Calcd for C H O PS P, 12.7; S, 26.2. Found: P, 12.5; S, 23.2.
Example 8.Preparation of 1-(0,0-cliis0pentylphosphorodithiato) ethyl acetate The acid is obtained by a reaction between isopentyl alcohol and phosphorus pentasulfide using the procedure of Example 1. Into a reaction flask equipped with a stirrer and thermometer are added 100 grams (0.37 mole) of 0,0-diisopentylphosphorodithioic acid. To the contents of the flask are added 50 grams (0.58 mole) of vinyl acetate over a half-hour period with agitation. During this addition the temperature is raised to C., afterward the reaction mixture is maintained at 90 C. with agitation for an additional hour. Unreacted vinyl acetate is removed under reduced pressure in a rotary film evaporator heated by a boiling water bath. The adduct consists of 125 grams yield) of an amber-colored oil.
Analysis.-Calcd for C H O PS P, 8.7; S, 18.0. Found: P, 9.0; S, 17.0.
Example 9.Preparati0n of 1-(0,0-diisobutylphosphorodithiat0)ethyl benzoate Using similar procedures as in the previous examples, 50 grams (0.336 mole) of vinyl benzoate are added to 81.5 grams (0.336 mole) of 0,0-diisobutylphosphorodithioic acid in benzene. The addition takes half an hour during which time the temperature is held at about 85 C. The reaction mixture is held for an additional hour at 85 C. A yield of pale yellow liquid adduct is obtained.
Analysis.Calcd for C H O PS P, 7.91; S, 16.4. Found: P, 7.86; S, 15.3.
Example 10.Preparation 0f 1-(0,0-a'i-(1,3-dimethylbatyl)ph0sph0rodithiato)ethyl acetate The acid used in this example is obtained by a reaction between 4 moles of 1,3-dimethylbutan-1-ol with 1.1 moles of phosphorus pentasulfide as described in Example 1. To the crude product of this reaction are added 170 grams (2 moles) of vinyl acetate over a 15 minute period. During the addition the temperature is in the range of 60 C. to 70 C. Benzene ml.) is added. The reaction mixture is agitated and heated at a temperature of from 90 C. to 95 C. for a total of 6 hours. The reaction product is washed with 10% aqueous sodium hydroxide solution, dried over sodium sulfate and distilled under nitrogen at 3.5 mm. Hg pressure to a pot temperature of 120 C. The remaining liquid has the following analysis:
Analysis.Calcd for C H O PS P, 8.1; S, 16.7. Found: P, 8.3; S, 16.5.
Example 11.Preparati0n of 1-(0,0-di-isobutylph0sphorodithiato) ethyl butyrate The acid used for this example is the same as that prepared in Example 1. Using similar procedures as in the previous examples, 100 grams (0.88 mole) of vinyl butyrate is added to grams (0.70 mole) 0,0-di-isobutylphosphorodithioic acid with agitation. The addition takes half an hour in which time the temperature is increased from 45 C. to 85 C. The reaction mixture is held for an additional hour at 85 C. The unreacted vinyl butyrate is removed leaving a liquid product having the following analysis:
Analysis.Calcd for C H O PS P, 8.7; S, 18.0. Found: P, 9.2; S, 18.5.
Example 12.-Preparati0n of 1 [0,0-di(batylphenyl) phosphorodithiatokthyl propionate 7 Example 13.Preparatin of 1-(0,0-di-mixed organoph0sph0r0dithiat0)ethyl acetate Using the procedure as in Example 1, a mixture of nonylphenol and cresol isomers (meta and para), in a 1:1 mole ratio, are reacted with phosphorus pentasulfide using 6.48 moles of the mixed phenols and 1.62 moles of sulfide. To the crude product of this reaction are added 425 grams (4.94 moles) of vinyl acetate over a 1 hour period, with the temperature in the range of about 45 to 80 C. The mixture is agitated and the temperature is maintained at 80 C. for about 1.25 hours. Excess vinyl acetate is stripped as in the above examples leaving 1660 grams of a straw-colored product.
Example ]4.Preparati0n of di[1-(0,0-diis0butylph0sph0r0dithiat0)]ethyl succinate To the di-l-chloroethyl succinate prepared by the reaction of 26.7 grams (0.173 mole) of succinyl chloride with grams (0.46 mole) of acetaldehyde in 100 m1. of benzene containing 0.2 gram of dry zinc chloride there is added dropwise over a 15 minute period a solution of 97 grams (0.35 mole) of potassium 0,0-diisobutylphosphorodithioate in 150 ml. of N,N-dimethylformamide while stirring. The temperature is maintained at 50 C. during the addition and is then raised to 80 and stirring is continued at this temperature for one additional hour.
After washing and distilling to remove solvent, there is obtained di-l-(0,0-diisobutylphosphorodithiato)ethyl succinate for which the infrared spectrum is very similar to that of 1-(0,0-diisobutylphosphorodithiato)ethyl acetate.
Example 15.Preparati0n of 1 (0,0-diis0decylph0sphorodithiato) ethyl acetate The acid is obtained by a reaction between isodecyl alcohol and phosphorus pentasulfide using the procedure of Example 1. Into a reaction flask equipped with a stirrer and thermometer are added 790 grams (1.9 moles) of 0,0-diisodecylphosphorodithioic acid. To the contents of the flask are added 250 grams (3.0 moles) of vinyl acetate. The reaction mixture is held for 2 hours at a temperature of 80 to 90 C. Unreacted vinyl acetate is thereafter removed. The yield of the liquid adduct is 100%; it has the following analysis:
Analysis.-Calcd for C24H47'O4PS2: P, 6.25; S, 12.9. Found: P, 6.03; S, 12.6.
tion. The temperature is maintained in the range of 85 to 88 C. for 1 hour. Thereafter the excess vinyl acetate and the benzene are removed by vacuum distillation. The analysis of the remaining liquid product obtained is:
Analysis.Calcd for: I, 6.56; S, 13.6. Found: P, 7.03; S, 14.2.
EVALUATION OF THE PRODUCTS The products of the above examples were evaluated typical engineering tests, namely the oxidation stability test and the bearing corrosion test.
(a) The oxidation stability test.In this test the product is added to a solvent-refined, mineral lubricating oil. This oil composition is heated to 325 F. and dry air at the rate of 10 liters per hour is passed through it in the presence of iron, copper, aluminum and lead. After hours the neutralization number for each composition is obtained using the ASTM D 974-1 method or procedure. The additives are rated in terms of the minimum weight percent of phosphorus required to limit the rise in the neutralization number to 2.0. The additives which are 8 efiective at approximately 0.125% or less by Weight of phosphorus are deemed to be satisfactory additives.
(b) Bearing corrosion test-The minimum amount of the additive to be tested is added to a solvent-refined mineral base oil in the presence or absence of a detergent and the oil composition is used to lubricate a copperlead bearing in a CRC L-38 test engine run for 40 hours. At the end of the run the test bearing is removed and weighed. If there is a loss of weight of the bearing of over 50 mg, the lubricating oil is deemed to have failed.
The data obtained in testing the composition of this invention using the above test methods are compiled in the table below.
Percent Phos- Bearing Weight Example No. phorus, in oxida- Loss, mg.
tion stability test 0.09 15. 0.059 1 25 16 0. 044 1 33 No additive 3, 669
1 Detergent present.
The above results show that the compositions of this invention prevent the oxidation of lubricating oils, even in the presence of metal catalysts. In the bearing corrosion test, it will be noted by comparison that the same lubricating oil containing no additives at all permits an extremely high weight loss.
EXTREME PRESSURE PROPERTIES The extreme pressure properties of two products prepared in the above examples were tested using SAE solvent-refined mineral base oil. The oil was blended with (1) 6.2% of the product of Example 4 and (2) 5.2% of the product of Example 10. The two oil blends were tested on an SAE load machine. In this test, two cylinders, driven at different speeds, are rotated against one another, and these roll and slide in line contact under controlled loads. The faster cylinder was operated at 500 rpm. The load is increased until failure, i.e. scutfing or seizure occurs; the loading rate is about 78 lbs. per second. At this point the total load is reported. Each sample oil was tested twice.
Oil composition: Seizure load, lbs. (1) Composition 4 270,275 (2) Composition 10 270,290
L-l CATERPILLAR ENGINE TEST The products of Examples 2 and 6 were tested in a lubricating oil in the L-l Caterpillar Engine Test using a non-metallic detergent.
The Caterpillar engine test determines the ability of the oil to prevent deposits around important parts of the engine including the piston and crankcase areas. A l-cylinder, 4-cycle Caterpillar engine is run under the following operating conditions:
Oil temperature F Jacket temperature F. 180 Speed r.p.m. 1000 Brake load, H.P 19.8
The duration of the test was 480 hours The diesel fuel of the engine contained 1% sulfur. A typical refined lubricating oil each containing 1% by weight of the products of Examples 2 and 6 and 3% of a commercial detergent. The engine was examined for deposits at various times during the run. The test results are reported below.
PRODUCT OF EXAMPLE 2 The engine rating expresses the over-all conditions of the engine at the end of the test run; a scale of to 100 is used, a 100 rating indicating a perfectly clean engine. The lacquer demerits indicate the amount of deposits coating the rings, the grooves and lands and the skirts of the piston; demerits are given for quantity of coating and degree of lacquering as evidence by color standards, and the sticking tendencies of the piston ring; the scale is from 0 to 100, a rating of 0 indicating completely clean surfaces and no demerits of any kind. The top groove packing rating indicates in percent of volume the amount of the carbon deposited in the top groove of the piston; the scale is from 0 to 100%, a rating of 0 indicating a completely clean groove.
THERMAL GRAVIMETRIC TEST This test investigates the stability of the novel com-- pounds of this invention at high temperatures by subjecting the compounds to increasing heat while the rate of weight loss is observed. The temperature at which weight loss rate is markedly increased is designated as the inflection temperature; hence, a high inflection temperature indicates satisfactory stability. The products which were tested have been prepared according to the procedures used in the above examples, including products not specifically described hereinbefore.
The above test results indicate that the products of this invention are not only highly useful high-temperature antioxidant and corrosion inhibitors, but they also possess extreme pressure characteristics for use in the lubrication of present-day engines. It has been found that the presence of from about 0.05% to about by weight of these additives in oil formulation provides satisfactory performance of lubricating composition and aids in extending the life of the oil. Furthermore, these additives are compatible with other typical oil additives such as pour point depressors, viscosity index improvers, antirust agents, as well as other detergents. Moreover, they are found to have unexpectedly higher solubility in lubricating oils than other dithiophosphoric compounds.
The above disclosure is hereby given as an illustration of the present invention and should not be deemed a limitation thereof except where expressly stated therein and as limited by the following claims.
We claim:
1. A lubricating oil composition comprising a major amount of a lubricating oil selected from the group consisting of a mineral lubricating oil and a synthetic lubricating oil, said oil being of lubricating viscosity suitable for lubricating high frictional surfaces of engines, and a minor amount of a 1-(0,0-diorganophosphorodithiato) alkyl carboxylate the said alkyl group having at least two carbon atoms.
2. The lubricating oil composition of claim 1, wherein the carboxylate group contains from 1 to 12 carbon atoms.
3. The lubricating oil composition of claim 1, wherein the carboxylate group has the formula F il and R is selected from the group consisting of alkyl, hydroxyalkyl, and haloalkyl having from 1 to 12 carbon atoms and aryl, hydroxyaryl, haloaryl, and alkaryl having up to 5 alkyl substituents on the aromatic nucleus with from 1 to 12 carbon atoms per alkyl substituent and a total of up to 18 carbon atoms.
5. The lubricating oil composition of claim 1, wherein the alkyl carboxylate is ethyl carboxylate.
6. The lubricating oil composition of claim 1, wherein the said 1 (0,0 diorganophosphorodit-hiato)alkyl carboxylate is present in the said oil in an amount ranging from about 0.05% to about 15% by weight of composition.
7. The lubricating oil composition of claim 4 wherein R is alkyl.
8. The lubricating oil composition of claim 7 wherein R is selected from the group consisting of methyl, butyl, isobutyl, pentyl, dimethylbutyl, trimethylpentyl, and decyl.
9. The lubricating oil composition of claim 4 wherein R is aryl.
10. The lubricating oil composition of claim 9 wherein R is selected from the group consisting of phenyl, methylphenyl, butylphenyl and nonylphenyl.
11. The lubricating oil composition of claim 3 wherein the carboxylate group is selected from the group consisting of acetate, propionate, butyrate, succinate and benzoate.
12. The lubricating oil composition of claim 1 wherein the alkyl carboxylate is ethyl acetate.
13. The lubricating oil composition of claim 1 wherein the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate is 1(0,0-dibutylphosphorodithiato)ethyl acetate.
14. The lubricating oil composition of claim 1 wherein the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate is l-(0,0-diphenylphosphorodithiato)ethyl acetate.
15. The lubricating oil composition of claim 1 wherein the l-(0,0-diorganophosphorodithiato)alkyl carboxylate is l-(0,0-diisobutylphosphorodithiato)ethyl benzoate.
16. The lubricating oil composition of claim 1 wherein the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate is 1-(0,0-dioleylphosphorodithiato)ethyl acetate.
17. The lubricating oil composition of claim 1 wherein the 1-(0,0-diorganophosphorodithiato)alkyl carboxylate is l-(0,0-dinonylphenylphosphorodithiato)ethyl acetate.
18. The lubricating oil composition of claim 1 wherein the l-(0,0-diorganophosphorodithiato)alkyl carboxylate 1 1' is di[1 (0,0 diisobutylphosphorodithiato) ]ethy1 succinate.
References Cited UNITED STATES PATENTS 2,865,804 12/1958 Bavley et a1 260-930 2,875,228 2/1959 Birum 252-466 2,883,319 4/1959 Bavley et a1 260-928 12 McConnell et a1 260-952 Peale et a1 260-952 Vegter 260-928 Chupp 260-952 0 DANIEL E. WYMAN Primary Examiner.
L. G. XIARHOS, W. H. CANNON, Assistant Examiners.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,350,348 October 31, 1967 Milton Braid et a1.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, lines 39 to 42, reaction sequence (a) should appear as shown below instead of as in the patent:
S O S O T 1 Ir (R0) -P-s-M+x-cH-0-c-R Ro) -p-s-cu-o-c-R +MX same column 2, lines 47 to 49, the product of reaction sequence (b) should appear as shown below instead of as in the patent:
S O 1 u (R0) -P-S-CH-O- -R column 7, line 54, for "grames" read grams Signed and sealed this 12th day of November 1968.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. Attesting Officer EDWARD J. BRENNER Commissioner of Patents UNITED STATES PATENT OFFICE Certificate Patent No. 3,350,348 Patented October 31, 1967 Milton Braid and Herbert Myers Application having been made by Milt0n Braid and Herbert Myers, the inventors named 1n the patent above identified, and Mob l Oil Co ration, a. corporation of New York, the assignee, for the issuance of a certificate un er the provisions of Title 35, Section 256, of the Umted States Code, deleting the name of Milton Braid as a joint inventor and a showing and p1:oof of facts satis the requirements of the said section having been subnntted it is this 2nd day of member 1971, certified that the name of the said Milton Braid is hereby deleted from the said patent as a joint inventor with the said Herbert Myers.
FRED W. SHERLING Associate Solicitor.
Claims (1)
1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF A LUBRICATING OIL SELECTED FROM THE GROUP CONSISTING OF A MINERAL LUBRICATING OIL AND A SYNTHETIC LUBRICATING OIL, SAID OIL BEING OF LUBRICATING VISCOSITY SUITABLE FOR LUBRICATING HIGH FRICTIONAL SURFACES OF ENGINES, AND A MINOR AMOUNT OF A 1-(O,O-DIORGANOPHOSPHORODITHIATO)ALKYL CARBOXYLATE THE SAID ALKYL GROUP HAVING AT LEAST TWO CARBON ATOMS.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US445697A US3350348A (en) | 1965-04-05 | 1965-04-05 | Lubricating oil additives |
NL6603247A NL6603247A (en) | 1965-04-05 | 1966-03-11 | |
FR53262A FR1482059A (en) | 1965-04-05 | 1966-03-14 | New additives for lubricating oils |
DE1966M0069025 DE1593002B2 (en) | 1965-04-05 | 1966-04-02 | USE OF 1- (O, O-DIORGANODITHIOPHOSPHORIC ACID) -ALKYLCARBONIC ACID ESTERS AS AN ADDITIVE TO LUBRICATING OILS |
GB14825/66A GB1094284A (en) | 1965-04-05 | 1966-04-04 | New phosphorodithioate esters and lubricating oils containing them |
BE679063D BE679063A (en) | 1965-04-05 | 1966-04-05 | |
US666464A US3646172A (en) | 1965-04-05 | 1967-09-08 | 1 - (o o - diorganophosphorodithiato) alkyl carboxylates and process for making same |
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US445697A US3350348A (en) | 1965-04-05 | 1965-04-05 | Lubricating oil additives |
US66646467A | 1967-09-08 | 1967-09-08 |
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US3350348A true US3350348A (en) | 1967-10-31 |
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US445697A Expired - Lifetime US3350348A (en) | 1965-04-05 | 1965-04-05 | Lubricating oil additives |
US666464A Expired - Lifetime US3646172A (en) | 1965-04-05 | 1967-09-08 | 1 - (o o - diorganophosphorodithiato) alkyl carboxylates and process for making same |
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US666464A Expired - Lifetime US3646172A (en) | 1965-04-05 | 1967-09-08 | 1 - (o o - diorganophosphorodithiato) alkyl carboxylates and process for making same |
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US (2) | US3350348A (en) |
BE (1) | BE679063A (en) |
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NL (1) | NL6603247A (en) |
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US4322303A (en) * | 1979-09-18 | 1982-03-30 | Ciba-Geigy Corporation | Dithiophosphate stabilizers |
US5057235A (en) * | 1988-06-23 | 1991-10-15 | Mobil Oil Corporation | Sulfur-phosphorus adducts of chromium catalyzed polyalphaolefins |
US5071577A (en) * | 1988-12-30 | 1991-12-10 | Mobil Oil Corporation | Phosphite derived propylene based multifunctional lubricants and multifunctional lubricant additives |
US5116523A (en) * | 1988-06-23 | 1992-05-26 | Mobil Oil Corporation | Sulfide adducts of high viscosity index polyalphaolefins |
US5334319A (en) * | 1990-06-18 | 1994-08-02 | Tonen Corporation | Composition for hydraulic lubrication and coupling |
US5334320A (en) * | 1990-06-29 | 1994-08-02 | Tonen Corporation | Compositions for hydraulic, lubricating and coupling |
US5362419A (en) * | 1992-06-02 | 1994-11-08 | Ciba-Geigy Corporation | Dithiophosphoric acid derivatives as lubricant additives |
US5512189A (en) * | 1993-03-02 | 1996-04-30 | Mobil Oil Corporation | Antiwear and antioxidant additives |
US6380139B1 (en) * | 1992-06-02 | 2002-04-30 | Ciba Specialty Chemicals Corporation | Bisdithiophosphoric acid derivatives as lubricant additives |
US6468946B2 (en) | 1998-07-06 | 2002-10-22 | The Lubrizol Corporation | Mixed phosphorus compounds and lubricants containing the same |
US6486102B1 (en) * | 1999-01-28 | 2002-11-26 | Unisor | Oil-in-water emulsion comprising at least one lubricating additive |
US20090093384A1 (en) * | 2007-10-03 | 2009-04-09 | The Lubrizol Corporation | Lubricants That Decrease Micropitting for Industrial Gears |
CN101818094A (en) * | 2010-05-15 | 2010-09-01 | 兰州惠锋生物科技有限公司 | Clean energy efficient sulphohydrocarbon ester ash-free antiwear agent and preparation method thereof |
US9481841B2 (en) | 2004-12-09 | 2016-11-01 | The Lubrizol Corporation | Process of preparation of an additive and its use |
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JPS5226506A (en) * | 1975-08-27 | 1977-02-28 | Nippon Oil Co Ltd | Lubricating oil composition for compressor |
US4175043A (en) * | 1978-09-21 | 1979-11-20 | Mobil Oil Corporation | Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same |
US4199460A (en) * | 1978-09-26 | 1980-04-22 | The United States Of America As Represented By The Secretary Of Agriculture | Fatty acid-derived lubricants and additives |
US4435338A (en) * | 1980-09-29 | 1984-03-06 | Ciba-Geigy Corporation | Dithiophosphates |
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US3166581A (en) * | 1958-07-18 | 1965-01-19 | Shell Oil Co | S-acyloxyalkyl and s-acyloxyalkenyl esters of o, o-diorgano-phosphorothiolic acids |
US3168436A (en) * | 1960-04-07 | 1965-02-02 | Monsanto Co | S-[alpha-(4-nitrobenzoyloxy)benzyl] o, o-diethyl phosphorodithioate |
-
1965
- 1965-04-05 US US445697A patent/US3350348A/en not_active Expired - Lifetime
-
1966
- 1966-03-11 NL NL6603247A patent/NL6603247A/xx unknown
- 1966-04-02 DE DE1966M0069025 patent/DE1593002B2/en active Granted
- 1966-04-04 GB GB14825/66A patent/GB1094284A/en not_active Expired
- 1966-04-05 BE BE679063D patent/BE679063A/xx unknown
-
1967
- 1967-09-08 US US666464A patent/US3646172A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2875228A (en) * | 1955-12-30 | 1959-02-24 | Monsanto Chemicals | Esters of thiolcarboxylic acids |
US2865804A (en) * | 1957-07-02 | 1958-12-23 | Pfizer & Co C | Pesticides |
US2883319A (en) * | 1957-07-02 | 1959-04-21 | Pfizer & Co C | Pesticides |
US2945053A (en) * | 1957-12-16 | 1960-07-12 | Eastman Kodak Co | Phosphorothiolothionates derived from esters of halogen-containing acids |
US3166581A (en) * | 1958-07-18 | 1965-01-19 | Shell Oil Co | S-acyloxyalkyl and s-acyloxyalkenyl esters of o, o-diorgano-phosphorothiolic acids |
US2997442A (en) * | 1960-03-30 | 1961-08-22 | Louise F Peale | Lubricating oil composition |
US3168436A (en) * | 1960-04-07 | 1965-02-02 | Monsanto Co | S-[alpha-(4-nitrobenzoyloxy)benzyl] o, o-diethyl phosphorodithioate |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4322303A (en) * | 1979-09-18 | 1982-03-30 | Ciba-Geigy Corporation | Dithiophosphate stabilizers |
US5057235A (en) * | 1988-06-23 | 1991-10-15 | Mobil Oil Corporation | Sulfur-phosphorus adducts of chromium catalyzed polyalphaolefins |
US5116523A (en) * | 1988-06-23 | 1992-05-26 | Mobil Oil Corporation | Sulfide adducts of high viscosity index polyalphaolefins |
US5071577A (en) * | 1988-12-30 | 1991-12-10 | Mobil Oil Corporation | Phosphite derived propylene based multifunctional lubricants and multifunctional lubricant additives |
US5334319A (en) * | 1990-06-18 | 1994-08-02 | Tonen Corporation | Composition for hydraulic lubrication and coupling |
US5334320A (en) * | 1990-06-29 | 1994-08-02 | Tonen Corporation | Compositions for hydraulic, lubricating and coupling |
US5362419A (en) * | 1992-06-02 | 1994-11-08 | Ciba-Geigy Corporation | Dithiophosphoric acid derivatives as lubricant additives |
US6380139B1 (en) * | 1992-06-02 | 2002-04-30 | Ciba Specialty Chemicals Corporation | Bisdithiophosphoric acid derivatives as lubricant additives |
US5512189A (en) * | 1993-03-02 | 1996-04-30 | Mobil Oil Corporation | Antiwear and antioxidant additives |
US6468946B2 (en) | 1998-07-06 | 2002-10-22 | The Lubrizol Corporation | Mixed phosphorus compounds and lubricants containing the same |
US6486102B1 (en) * | 1999-01-28 | 2002-11-26 | Unisor | Oil-in-water emulsion comprising at least one lubricating additive |
US9481841B2 (en) | 2004-12-09 | 2016-11-01 | The Lubrizol Corporation | Process of preparation of an additive and its use |
US20090093384A1 (en) * | 2007-10-03 | 2009-04-09 | The Lubrizol Corporation | Lubricants That Decrease Micropitting for Industrial Gears |
CN101818094A (en) * | 2010-05-15 | 2010-09-01 | 兰州惠锋生物科技有限公司 | Clean energy efficient sulphohydrocarbon ester ash-free antiwear agent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
GB1094284A (en) | 1967-12-06 |
BE679063A (en) | 1966-10-05 |
US3646172A (en) | 1972-02-29 |
DE1593002A1 (en) | 1970-05-14 |
NL6603247A (en) | 1966-10-06 |
DE1593002B2 (en) | 1976-11-11 |
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