US2736707A - Lubricant containing phosphate partial ester - aldehyde - amine condensation product - Google Patents
Lubricant containing phosphate partial ester - aldehyde - amine condensation product Download PDFInfo
- Publication number
- US2736707A US2736707A US295344A US29534452A US2736707A US 2736707 A US2736707 A US 2736707A US 295344 A US295344 A US 295344A US 29534452 A US29534452 A US 29534452A US 2736707 A US2736707 A US 2736707A
- Authority
- US
- United States
- Prior art keywords
- esters
- groups
- phosphorus
- aldehyde
- compounds
- 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
- 239000000314 lubricant Substances 0.000 title claims description 16
- 150000002148 esters Chemical class 0.000 title description 12
- 229910019142 PO4 Inorganic materials 0.000 title description 8
- 239000010452 phosphate Substances 0.000 title description 8
- 239000007859 condensation product Substances 0.000 title description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 239000010688 mineral lubricating oil Substances 0.000 claims description 6
- -1 ESTER ALDEHYDE Chemical class 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 235000014786 phosphorus Nutrition 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003879 lubricant additive Substances 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- NONNTIQBZWNPAA-UHFFFAOYSA-N 6-phenoxydodecan-6-ol Chemical compound CCCCCCC(O)(CCCCC)OC1=CC=CC=C1 NONNTIQBZWNPAA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- OBSCFZZYDILIJH-UHFFFAOYSA-N phosphorotrithious acid Chemical class SP(S)S OBSCFZZYDILIJH-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- PTMRDOLOEDPHLB-UHFFFAOYSA-N 2,3-dipentylphenol Chemical compound CCCCCC1=CC=CC(O)=C1CCCCC PTMRDOLOEDPHLB-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
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 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
- 239000010730 cutting oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- XQNIYBBHBZAQEC-UHFFFAOYSA-N diphosphorus trisulphide Chemical compound S=PSP=S XQNIYBBHBZAQEC-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical compound OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940116411 terpineol Drugs 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
- 150000007970 thio esters Chemical class 0.000 description 1
- 229940029273 trichloroacetaldehyde Drugs 0.000 description 1
- ITRFOBBKTCNNFN-UHFFFAOYSA-N tris(sulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound SP(S)(S)=S ITRFOBBKTCNNFN-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C07F9/1652—Polyol derivatives esterified at least twice by thiophosphoric acid groups
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- 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
- C07F9/201—Esters of thiophosphorus acids
- C07F9/2015—Esters of thiophosphorus acids with hydroxyalkyl compounds with further substituents on alkyl
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
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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
- 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
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- 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
- C10M2223/042—Metal salts thereof
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- 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
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- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- This invention relates to compositions containing a new class of organic phosphorus compounds. More particu vlarly it relates to lubricating compositions containing condensat'ion products obtained by reacting phosphate partial esters with both aldehydes and amines.
- phosphate esters as addition agents in lubricating compositions to improve various characteristics of the lubricating compositions such as their resistance to oxidation, corrosiveness, detergency, oiliness, viscosity index and so forth. More recently, it has been found that phosphate esters containing sulfur in direct linkage with the phosphorus are particularly valuable modifying agents for lubricants, and a large number of such compounds have been used, chiefly as multifunctional additives for extreme pressure lubricants. For example, it is disclosed in U. S.
- a further object of this invention is to provide improved lubricants containing these compounds.
- Another object of the invention is to provide a novel class of multifunctional lubricant additives.
- Another object of the invention is to provide a class of compounds having the property of imparting improved lubricating characteristics to a lubricant composition without having undesirable or deleterious effects upon other properties of the lubricant composition.
- novel compounds of my invention are the condensation products obtained by reacting partial esters and thio esters of phosphorus acids and thio acids of the types shown in the foregoing patent with aldehydes and primary amines. These compounds are preferably monomeric condensation products which are believed to have the following structure:
- X is oxygen or sulfur
- Y is either oxygen Or sulfur or is absent
- R5 is an organic radical
- R, R1, R2, R3 and R4 represent hydrogen or organic radicals which may be the same or different, at least one organic radical being attached to each phosphorus atom through an oxygen or a sulfur atom.
- the organic radicals may be aliphatic groups, including open chain and cyclic, saturated and unsaturated aliphatic groups, aromatic groups, or substituted aliphatic or aromatic groups. Sufficient alkyl carbon atoms are contained in these organic groups to impart oilsolubility to the molecule.
- These organic groups may also contain any of the inorganic substituents commonly employed in lubricant additives, such as halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, amino groups, mercaptan groups and so forth.
- My preferred compounds for use as lubricant additives may be represented by the following formula ticularly suitable for use as lubricant additives are the following:
- Addition agents of the above type have important advantages over the known types of phosphate ester additives, particularly in that they possess increased chemical stability and decreased acidity and corrosiveness and do not add to the non-volatile ash content of the lubricant. They are anti-oxidant and corrosion-inhibiting both when used alone and with other more corrosive additives.
- the amount of these phosphorus compounds which may be added to lubricating oils may be varied depending upon the effect desired and upon the characteristics of the base oil. In general, small proportions, for example from 0.1% to 10%, and preferably from about 0.5% to about 2%, are employed. However either greater or less amounts may be used if desired.
- the compounds of my invention are preferably the monomeric condensation products as shown in the formula, a certain amount of more or less polymeric product is also formed in the condensation reaction, and such compounds are also included within the purview of this invention, since it is conceived that useful resins and high molecular Weight products having pour pointreducing and other valuable properties may be obtained by this reaction.
- the esters used in preparing the condensation products of my invention may be one or more of the following types: mono-esters of phosphorous and phosphoric acid, di-esters of phosphorous and phosphoric acids, mono-thio esters of phosphorous and phosphoric acids, di-thio esters of phosphorous and phosphoric acids, monoand di-esters of tri-thio phosphorous acids, monoand di-thio esters of tri-thio phosphorous acids, monoand di-esters of tetra-thio phosphoric acid, and monoand di-thio esters of tetra-thio phosphoric acids.
- Esters of the above types may be obtained by any of the familiar esterification reactions between an aliphatic or aromatic alcohol or mercaptan and an oxygen and/or sulfur-containing phosphorus acid, such as phosphorous acid, phosphoric acid, thio phosphorous acid, thio phosphoric acid, phosphorus pentoxide, or a phosphorus sulfide such as phosphorus pentasulfide, phosphorus trisulfide or phosphorus heptasulfide, or by other ester-forming reactions such as the reaction between a halogenated hydrocarbon and a phosphorus acid salt such as disodium hydrogen phosphate.
- an oxygen and/or sulfur-containing phosphorus acid such as phosphorous acid, phosphoric acid, thio phosphorous acid, thio phosphoric acid, phosphorus pentoxide, or a phosphorus sulfide such as phosphorus pentasulfide, phosphorus trisulfide or phosphorus
- Esters suitable for preparing the preferred compounds of our invention may be readily obtained by reacting an alcohol or a mercaptan with phosphorus pentasulfide.
- the reaction of an alcohol with phosphorus pentasulfide and the condensation of the ester obtained with an aldehyde and a primary amine take place according to the following equations:
- R and R are organic groups and R is an organic group or hydrogen.
- the alcohols employed in the above reaction may be aliphatic alcohols, including straight or branched chain or cyclic alcohols, preferably those containing from about 4 to about 20 carbon atoms in the molecule, aromatic alcohols, preferably alkylated aromatic alcohols, or heterocyclic alcohols and such alcohols containing substituent groups in so far as these do not interfere to any appreciable extent with the esterification or condensation reaction.
- Suitable alcohols which may be mentioned in clude amyl alcohol, octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, benzyl alcohol, phenyl ethyl alcohol, diamyl phenoxy ethanol, cyclohexanol, methyl cyclohexanol, terpineol, cardanol, phenol, naphthol, cresol, xylenol, chlorophenol, octyl phenol, diamyl phenol and hydroquinone.
- the corresponding mercaptans and thio phenols may be used in place of these alcohols.
- mixtures of two or more difierent alcohols or mercaptans or mixtures of both alcohols and mercaptans may be employed in the esterification reaction in order to obtain mixed esters.
- the aldehydcs and amines employed in the condensation reaction may likewise be aliphatic, aromatic or heterocyclic in character and may contain substituent groups such as those mentioned above in so far as these do not interfere with the condensation reaction.
- Suitable aldehydes which may be mentioned include formaldehyde, acetaldehyde, trichloroacetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde and furfural.
- suitable amines are monoamyl amine, monobutylamine, monocyclohexyl amine, monocetyl amine and monolauryl amine.
- the amines may be employed as such or in the form of their salts, such as an amine hydrochloride.
- the condensation reaction is carried out by reacting a phosphate partial ester of the type described above with an aldehyde and a primary amine, preferably in an alcohol solution which is slightly acid with hydrochloric acid.
- the molar ratio of phosphate esterzaminezaldehyde employed in the reaction may range from about 2:1:2 to about 2:3:4. It is preferably about 2:112.
- a diamyl phenoxy ethanol-P285 reaction product was prepared by adding 222 g. of P285 to a solution of 1112 g. of diamyl phenoxy ethanol in 2 l. of toluene with stirring, and refluxing the reaction mixture for minutes. The solution was then filtered through asbestos and the solvent distilled from the filtrate. 1200 .g. of reaction product was obtained, analyzing 8.69% sulfur and 4.20% phosphorus, as compared with theoretical values of 9.78% and 4.74%, respectively. 440 g. of this product was added to a solution of g. of monolauryl amine in the form of hydrochloride in 500 cc. of absolute alcohol which had been made slightly acid with hydrochloric acid.
- a Mid-Continent paraflinic base lubricating oil was used in the example, the use of my compounds as lubricant additives is not limited to any particular base conditions existing in an internal combustion engine.
- a lubricating oil at an elevated temperature is oral lubricating oil bases of a wide variety obtained from continuously circulated and recirculated over a bearing 20
- Varimls yp of Crlldfis of Synthetic Oils y any of the specimen in the presence of air and of catalytic metal conventional refining methods and also in other oleaginous surfaces, and the corrosiveness of the oil determined by materials such as animal or vegetable oils.
- the test apparatus comprises cant composition such as pour point depressors, oiliness a stainless steel motor-driven spinner enclosing a copperagents, corrosion inhibitors, antioxidants, extreme preslead bearing specimen and a stationary stainless steel shaft sure agents, viscosity index improving agents and thickconnected to a base plate assembly.
- Copper baflies are ening agents such as soaps either in minor amounts or also attached to the base plate assembly for the purpose in grease-forming proportions. of imparting turbulence to the oil and to act as oxida- Obviously many modifications and Variations of the tion catalysts.
- the bearing specimen is connected to the invention as hereinbefore set forth, may be made withspinner by means of a special non-wearing bushing, so that the entire weight loss of the bearing is attributable to the corrosive action of the oil.
- the spinner enclosing the bearing'specimen is immersed in the test oil maintained at 350 F. in a glass vessel and is rotated at a speed of 3000 revolutions per minute about the stainless steel stationary shaft.
- the oil is forced through the out departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
- a lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 per cent by weight of a compound having the formula:
- a lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 per cent by weight of a compound having the formula:
- a lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 descnbed' per cent by weight of a compound having the formula:
- a lubricant composition comprising a major amount of a. mineral lubricating oil and about 0.1 to about 10 to 16 carbon atoms, and Riepresents one or more alkyl per cent by weight of a compound having the formula: groups.
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Description
Unit
fice LUBRICANT CGNTAIN *G PHOSPHATE PARTEAL ESTER ALDEHYDE AMENE QQNDENSATEGN PRODUCT This invention relates to compositions containing a new class of organic phosphorus compounds. More particu vlarly it relates to lubricating compositions containing condensat'ion products obtained by reacting phosphate partial esters with both aldehydes and amines.
This is a division of my copending application Serial No. 180,902, filed August 22, 1950.
It is old in the art to employ phosphate esters as addition agents in lubricating compositions to improve various characteristics of the lubricating compositions such as their resistance to oxidation, corrosiveness, detergency, oiliness, viscosity index and so forth. More recently, it has been found that phosphate esters containing sulfur in direct linkage with the phosphorus are particularly valuable modifying agents for lubricants, and a large number of such compounds have been used, chiefly as multifunctional additives for extreme pressure lubricants. For example, it is disclosed in U. S. 2,242,260, to Prutton, that extreme pressure agents are produced by reacting phosphorus pentasulfide with various organic compounds including stearic acid, lauryl alcohol, benzyl alcohol, naphthenic acid, butyl stearate, phenol and chlorophenol. Extreme pressure agents are also prepared by the method of U. S. 2,396,719. to Musselman et aL, whereby phosphorus pentasulfide is reacted with an alcohol. The reaction product is preferably further reacted with a base such as ammonia, an amine or a metal oxide or hydroxide. U. S. 2,252,985, to Rutherford et 211., discloses that the oxidation resistance of a lubricant is increased by the addition of alkaline earth metal salts of esters obtained by reacting aliphatic or arematic alcohols or mercaptans' with sulfur-containing acids of phosphorus. U. S. 2,470,405, to Leland, discloses that the load bearing quality of cutting Oils is improved by the addition of esters having the formulas P(XR)a and XP(XR)3, wherein X is either oxygen or sulfur, at least one R is hydrogen and the remaining Rs are aliphatic or aromatic hydrocarbon radicals. U. S. 2,368,000, to Cook, discloses anti-foaming agents prepared by reacting phos phorus pentasulfide with branched chain alcohols and neu tralizing the product with heavy metal salts. U. S. 2,343,831, to Osborne, discloses dialkyl and diaryl dithio phosphate polysulfides as extreme pressure agents.
While compounds of the above type are very effective in improving a number of lubricant properties, they also possess certain disadvantages which are more or less serious depending upon the purpose for which the lubricant is to be employed. The esters themselves are highly acidic and corrosive, so that they must usually be em- Cs Hu ployed in the form of their salts or other compounds. However, many of these compounds heretofore proposed hydrolyze or otherwise decompose at high temperatures, and the use of metal salts is undesirable in many cases, as for example where there are rigid restrictions upon the permissible amount of non-volatile ash remaining after combustion.
It is an object of the present invention to provide improved organic phosphorus compounds. A further object of this invention is to provide improved lubricants containing these compounds. Another object of the invention is to provide a novel class of multifunctional lubricant additives. Another object of the invention is to provide a class of compounds having the property of imparting improved lubricating characteristics to a lubricant composition without having undesirable or deleterious effects upon other properties of the lubricant composition.
The novel compounds of my invention are the condensation products obtained by reacting partial esters and thio esters of phosphorus acids and thio acids of the types shown in the foregoing patent with aldehydes and primary amines. These compounds are preferably monomeric condensation products which are believed to have the following structure:
wherein X is oxygen or sulfur, Y is either oxygen Or sulfur or is absent, R5 is an organic radical and R, R1, R2, R3 and R4 represent hydrogen or organic radicals which may be the same or different, at least one organic radical being attached to each phosphorus atom through an oxygen or a sulfur atom. The organic radicals may be aliphatic groups, including open chain and cyclic, saturated and unsaturated aliphatic groups, aromatic groups, or substituted aliphatic or aromatic groups. Sufficient alkyl carbon atoms are contained in these organic groups to impart oilsolubility to the molecule. These organic groups may also contain any of the inorganic substituents commonly employed in lubricant additives, such as halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, amino groups, mercaptan groups and so forth.
My preferred compounds for use as lubricant additives may be represented by the following formula ticularly suitable for use as lubricant additives are the following:
Addition agents of the above type have important advantages over the known types of phosphate ester additives, particularly in that they possess increased chemical stability and decreased acidity and corrosiveness and do not add to the non-volatile ash content of the lubricant. They are anti-oxidant and corrosion-inhibiting both when used alone and with other more corrosive additives.
The amount of these phosphorus compounds which may be added to lubricating oils may be varied depending upon the effect desired and upon the characteristics of the base oil. In general, small proportions, for example from 0.1% to 10%, and preferably from about 0.5% to about 2%, are employed. However either greater or less amounts may be used if desired.
While the compounds of my invention are preferably the monomeric condensation products as shown in the formula, a certain amount of more or less polymeric product is also formed in the condensation reaction, and such compounds are also included within the purview of this invention, since it is conceived that useful resins and high molecular Weight products having pour pointreducing and other valuable properties may be obtained by this reaction.
The esters used in preparing the condensation products of my invention may be one or more of the following types: mono-esters of phosphorous and phosphoric acid, di-esters of phosphorous and phosphoric acids, mono-thio esters of phosphorous and phosphoric acids, di-thio esters of phosphorous and phosphoric acids, monoand di-esters of tri-thio phosphorous acids, monoand di-thio esters of tri-thio phosphorous acids, monoand di-esters of tetra-thio phosphoric acid, and monoand di-thio esters of tetra-thio phosphoric acids. Esters of the above types may be obtained by any of the familiar esterification reactions between an aliphatic or aromatic alcohol or mercaptan and an oxygen and/or sulfur-containing phosphorus acid, such as phosphorous acid, phosphoric acid, thio phosphorous acid, thio phosphoric acid, phosphorus pentoxide, or a phosphorus sulfide such as phosphorus pentasulfide, phosphorus trisulfide or phosphorus heptasulfide, or by other ester-forming reactions such as the reaction between a halogenated hydrocarbon and a phosphorus acid salt such as disodium hydrogen phosphate. Esters suitable for preparing the preferred compounds of our invention may be readily obtained by reacting an alcohol or a mercaptan with phosphorus pentasulfide. The reaction of an alcohol with phosphorus pentasulfide and the condensation of the ester obtained with an aldehyde and a primary amine take place according to the following equations:
wherein R and R are organic groups and R is an organic group or hydrogen.
The alcohols employed in the above reaction may be aliphatic alcohols, including straight or branched chain or cyclic alcohols, preferably those containing from about 4 to about 20 carbon atoms in the molecule, aromatic alcohols, preferably alkylated aromatic alcohols, or heterocyclic alcohols and such alcohols containing substituent groups in so far as these do not interfere to any appreciable extent with the esterification or condensation reaction. Suitable alcohols which may be mentioned in clude amyl alcohol, octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, benzyl alcohol, phenyl ethyl alcohol, diamyl phenoxy ethanol, cyclohexanol, methyl cyclohexanol, terpineol, cardanol, phenol, naphthol, cresol, xylenol, chlorophenol, octyl phenol, diamyl phenol and hydroquinone. The corresponding mercaptans and thio phenols may be used in place of these alcohols. Instead of a single alcohol or mercaptan, mixtures of two or more difierent alcohols or mercaptans or mixtures of both alcohols and mercaptans may be employed in the esterification reaction in order to obtain mixed esters.
The aldehydcs and amines employed in the condensation reaction may likewise be aliphatic, aromatic or heterocyclic in character and may contain substituent groups such as those mentioned above in so far as these do not interfere with the condensation reaction. Suitable aldehydes which may be mentioned include formaldehyde, acetaldehyde, trichloroacetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde and furfural. Examples of suitable amines are monoamyl amine, monobutylamine, monocyclohexyl amine, monocetyl amine and monolauryl amine. The amines may be employed as such or in the form of their salts, such as an amine hydrochloride.
The condensation reaction is carried out by reacting a phosphate partial ester of the type described above with an aldehyde and a primary amine, preferably in an alcohol solution which is slightly acid with hydrochloric acid. The molar ratio of phosphate esterzaminezaldehyde employed in the reaction may range from about 2:1:2 to about 2:3:4. It is preferably about 2:112.
The following detailed procedure illustrates a method which may be used for preparing the compounds of my invention.
EXAMPLE Preparation of a condensation product of diamylphenoxy ethanol-P285 reaction product with formaldehyde and monolauryl amine, having the probable formula:
A diamyl phenoxy ethanol-P285 reaction product was prepared by adding 222 g. of P285 to a solution of 1112 g. of diamyl phenoxy ethanol in 2 l. of toluene with stirring, and refluxing the reaction mixture for minutes. The solution was then filtered through asbestos and the solvent distilled from the filtrate. 1200 .g. of reaction product was obtained, analyzing 8.69% sulfur and 4.20% phosphorus, as compared with theoretical values of 9.78% and 4.74%, respectively. 440 g. of this product was added to a solution of g. of monolauryl amine in the form of hydrochloride in 500 cc. of absolute alcohol which had been made slightly acid with hydrochloric acid. 55 grams of an aqueous solution containing 37% of formaldehyde by weight was next added and the reaction mixture heated with stirring for 2 hours and then 5 poured into a separatory funnel. The lower layer separating out in the separatory funnel was dissolved in ether, washed 3 times with water, and dried over CaClz. The ether solution was finally filtered and the ether removed by stripping. 372.5 g. of product was obtained which analyzed 3.91% phosphorus, 8.16% sulfur and 0.829% nitrogen, as compared with theoretical values of 4.08%, 8.43%. and 0.927%, respectively.
The value of this compound as a lubricant additive has been demonstrated by means of a special test which is designed to show the corrosiveness and oxidation stability of a lubricating oil under the bearing lubrication The above table shows the, substantial improvementin the corrosiveness o'fa mineral lubricating oil obtained by the addition of a small amount of a phosphorus compound of my invention.
In the standard Almen test for measuring the extreme pressure properties of lubricating compositions, a blend of 1.0% of this condensation product with the same base oil as described above, had an Almen value of 18 pounds, as compared with 9 pounds for the base oil alone.
According to the particular compound of this class selected, improvements in anticorrosiveness and extreme pressure properties as well as other properties such as detergency and so forth which are exhibited by the phosphate esters generally, may be obtained in varying degrees.
Although a Mid-Continent paraflinic base lubricating oil was used in the example, the use of my compounds as lubricant additives is not limited to any particular base conditions existing in an internal combustion engine. In stock, since these compounds may be employed in minthis test a lubricating oil at an elevated temperature is oral lubricating oil bases of a wide variety obtained from continuously circulated and recirculated over a bearing 20 Varimls yp of Crlldfis of Synthetic Oils y any of the specimen in the presence of air and of catalytic metal conventional refining methods and also in other oleaginous surfaces, and the corrosiveness of the oil determined by materials such as animal or vegetable oils. Other commeasuring the loss in Weight of the bearing at two hour pounding ingredients may also be present in the lubriintervals up to ten hours. The test apparatus comprises cant composition such as pour point depressors, oiliness a stainless steel motor-driven spinner enclosing a copperagents, corrosion inhibitors, antioxidants, extreme preslead bearing specimen and a stationary stainless steel shaft sure agents, viscosity index improving agents and thickconnected to a base plate assembly. Copper baflies are ening agents such as soaps either in minor amounts or also attached to the base plate assembly for the purpose in grease-forming proportions. of imparting turbulence to the oil and to act as oxida- Obviously many modifications and Variations of the tion catalysts. The bearing specimen is connected to the invention as hereinbefore set forth, may be made withspinner by means of a special non-wearing bushing, so that the entire weight loss of the bearing is attributable to the corrosive action of the oil. The spinner enclosing the bearing'specimen is immersed in the test oil maintained at 350 F. in a glass vessel and is rotated at a speed of 3000 revolutions per minute about the stainless steel stationary shaft. The oil is forced through the out departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
I claim:
1. A lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 per cent by weight of a compound having the formula:
2. A lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 per cent by weight of a compound having the formula:
bearing clearance by capillary attraction and centrifugal force and is sprayed into the air through holes near the periphery of the rotating spinner.
The above test was also carried out with the addition of lead peroxide to the test oil, in order to simulate the R ,0 s H H s 0R4 conditions prevailing in the crank-case of an engine when \H (g gasoline containing high concentrations of tetraethyl lead I is used. According to this modification of the test, one R10 R 35 gram of powdered lead peroxide (PbOz) is thoroughly mixed into a 125 cc. sample of the test oil before the beginning of the test and an additional gram of lead peroxide in a 5 cc. portion of the test oil is added at each' two hour interval during the test.
The following table shows results obtained in the above described tests with a solvent-refined, dewaxed, Mid-Continent lubricating oil of S. A. E. 30 grade containing 1.0% of the phosphate ester-aldehyde-amine condensation prodwherein R is selected from the group consisting of hydrogen and aliphatic hydrocarbon groups, R1, R2, R3 and R4 are selected from the group consisting of C4C20 aliphatic hydrocarbon groups, alkylated phenyl groups and alkoxyaralkyl groups, and R5 is an aliphatic hydrocarbon group.
3. A lubricant composition comprising a major amount of a mineral lubricating oil and about 0.1 to about 10 descnbed' per cent by weight of a compound having the formula:
Corrosion test results Weight loss in mg. R20 f: H H i/O R PS N -s- Hours of test Base 011+ Base 011+ i I! I B350 Oil 1.0% addi- 1.0% addi- R10 R 5 R OR:
tive tive-l-PbOa H3 H wherein R is selected from the group consisting of hydroggig 8:2 gen and aliphatic hydrocarbon groups, R1, R2, R3 and 82.84 2H0 H R4 are alkoxyaralkyl groups and R5 is an aliphatic hydro- 96-102 5232 2. 1 carbon group 4. A lubricant composition comprising a major amount of a. mineral lubricating oil and about 0.1 to about 10 to 16 carbon atoms, and Riepresents one or more alkyl per cent by weight of a compound having the formula: groups.
R! Re @O-Rr-O 1 15 III \OR;OQ Ra Ra wherein R1, R2, R3 and R4 are low molecular weight 10 References Cited inthe file of this patent alkylene groups, R5 is an alkyl group containing about 5 UNITED STATES PATENTS 2,586,656 Hook et a1. Feb. 19, 1952
Claims (1)
- 2. A LUBRICANT COMPOSITION COMPRISING A MAJOR AMOUNT OF A MINERAL LUBRICATING OIL AND ABOUT 0.1 TO ABOUT 10 PER CENT BY WEIGHT OF A COMPOUND HAVING THE FORMULA:
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US180901A US2736737A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde condensation product and lubricant containing the same |
US180902A US2736738A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde-amine condensation product and lubricant containing the same |
US295344A US2736707A (en) | 1950-08-22 | 1952-06-24 | Lubricant containing phosphate partial ester - aldehyde - amine condensation product |
US300757A US2736706A (en) | 1950-08-22 | 1952-07-24 | Lubricant containing a phosphorus acid ester-aldehyde condensation product |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US180901A US2736737A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde condensation product and lubricant containing the same |
US180902A US2736738A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde-amine condensation product and lubricant containing the same |
US295344A US2736707A (en) | 1950-08-22 | 1952-06-24 | Lubricant containing phosphate partial ester - aldehyde - amine condensation product |
US300757A US2736706A (en) | 1950-08-22 | 1952-07-24 | Lubricant containing a phosphorus acid ester-aldehyde condensation product |
Publications (1)
Publication Number | Publication Date |
---|---|
US2736707A true US2736707A (en) | 1956-02-28 |
Family
ID=32303692
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US180901A Expired - Lifetime US2736737A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde condensation product and lubricant containing the same |
US180902A Expired - Lifetime US2736738A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde-amine condensation product and lubricant containing the same |
US295344A Expired - Lifetime US2736707A (en) | 1950-08-22 | 1952-06-24 | Lubricant containing phosphate partial ester - aldehyde - amine condensation product |
US300757A Expired - Lifetime US2736706A (en) | 1950-08-22 | 1952-07-24 | Lubricant containing a phosphorus acid ester-aldehyde condensation product |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US180901A Expired - Lifetime US2736737A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde condensation product and lubricant containing the same |
US180902A Expired - Lifetime US2736738A (en) | 1950-08-22 | 1950-08-22 | Phosphate partial ester-aldehyde-amine condensation product and lubricant containing the same |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US300757A Expired - Lifetime US2736706A (en) | 1950-08-22 | 1952-07-24 | Lubricant containing a phosphorus acid ester-aldehyde condensation product |
Country Status (1)
Country | Link |
---|---|
US (4) | US2736737A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3105819A (en) * | 1959-12-21 | 1963-10-01 | Shell Oil Co | Lubricating compositions |
US3859219A (en) * | 1972-11-17 | 1975-01-07 | Chevron Res | Bisphosphoramide-sulfur compound containing lubricant |
US3865740A (en) * | 1972-05-22 | 1975-02-11 | Chevron Res | Multifunctional lubricating oil additive |
US3909430A (en) * | 1972-08-07 | 1975-09-30 | Chevron Res | Lubricating composition |
US4032461A (en) * | 1974-09-06 | 1977-06-28 | The Lubrizol Corporation | Phosphorus and sulfur containing amides and thioamides as lubricating oil additives and lubricating oil compositions containing same |
US4208357A (en) * | 1974-09-06 | 1980-06-17 | The Lubrizol Corporation | Process for preparing phosphorus and sulfur containing amides and thioamides |
WO2017185819A1 (en) * | 2016-04-27 | 2017-11-02 | 中国石油化工股份有限公司 | Benzotriazole derivative, manufacturing method therefor and use thereof |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2841520A (en) * | 1956-07-16 | 1958-07-01 | Fmc Corp | Pesticidal phosphorus esters |
US2882198A (en) * | 1956-07-16 | 1959-04-14 | Fmc Corp | Pesticidal phosphorus esters |
US2928862A (en) * | 1956-07-16 | 1960-03-15 | Fmc Corp | Pesticidal phosphorus esters |
US2873228A (en) * | 1956-07-16 | 1959-02-10 | Fmc Corp | Pesticidal phosphorus esters |
US2959546A (en) * | 1956-08-28 | 1960-11-08 | Exxon Research Engineering Co | Silver corrosion inhibited lubricating composition |
US3017422A (en) * | 1958-01-08 | 1962-01-16 | Universal Oil Prod Co | Composition of matter |
US3238131A (en) * | 1960-12-23 | 1966-03-01 | Shell Oil Co | Lubricating compositions containing bis(phosphono-methyl) disulfides |
US3240704A (en) * | 1961-01-30 | 1966-03-15 | Sinclair Research Inc | Lubricating compositions having oilsoluble phosphorus-containing condensation products |
BE619347A (en) * | 1961-06-26 | |||
US3256190A (en) * | 1962-10-18 | 1966-06-14 | Texaco Inc | Thiophosphonoxyalkanes |
US3263000A (en) * | 1962-11-19 | 1966-07-26 | Universal Oil Prod Co | Diisopropyl-dithiophosphatyl thioketals |
US3243371A (en) * | 1962-12-10 | 1966-03-29 | Shell Oil Co | Lubricating composition |
US3354195A (en) * | 1964-01-29 | 1967-11-21 | Stauffer Chemical Co | Phosphoro (mono or di) thioate thiocarbonates |
US3396213A (en) * | 1964-02-24 | 1968-08-06 | Shell Oil Co | Preparation of (monocyclic aryl) methyl, alpha, alpha-dithiol-bis |
DE1670711C3 (en) * | 1966-06-25 | 1974-03-21 | Bayer Ag, 5090 Leverkusen | Process for the production of Thionothiolphosphor - (- phosphonic, phosphinic) acide star |
US4000101A (en) * | 1970-07-14 | 1976-12-28 | Weston Chemical Corporation | Thiophosphites and ultraviolet light stabilizer for olefin polymers |
GB1424513A (en) * | 1972-06-13 | 1976-02-11 | Ciba Geigy Ag | Organic phosphates |
US3919095A (en) * | 1973-07-30 | 1975-11-11 | Mobil Oil Corp | Organic compositions containing antioxidant and antiwear additives |
US4010144A (en) * | 1974-03-13 | 1977-03-01 | Hooker Chemicals & Plastics Corporation | Flame retardant phosphate ester derivatives of ortho novolaks |
US4056480A (en) * | 1975-06-10 | 1977-11-01 | Monsanto Company | Hydraulic fluids |
US4220611A (en) * | 1978-06-29 | 1980-09-02 | Sandoz, Inc. | Polyoxyalkylene bridged phosphate esters |
DE3025277A1 (en) * | 1979-07-06 | 1981-01-08 | Ciba Geigy Ag | LUBRICANT ADDITIVES |
EP0090506B1 (en) * | 1982-03-26 | 1988-10-26 | Mobil Oil Corporation | Lubricant compositions containing a dithiophosphoric acid ester-aldehyde reaction product |
US4800030A (en) * | 1985-12-28 | 1989-01-24 | Idemitsu Kosan Company Limited | Refrigerator oil composition |
US5547614A (en) * | 1989-11-14 | 1996-08-20 | Akzo Nobel N.V. | Flame retardant mixture of polybrominated diphenyl oxide and organic diphosphate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2586656A (en) * | 1949-08-18 | 1952-02-19 | American Cyanamid Co | S-aminoalkylidene dithiophosphoric acid triesters |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2328570A (en) * | 1938-08-16 | 1943-09-07 | Eastman Kodak Co | Azo compounds and material colored therewith |
US2266514A (en) * | 1938-09-09 | 1941-12-16 | American Cyanamid Co | Esters of dithiophosphoric acids |
US2343831A (en) * | 1941-06-26 | 1944-03-07 | American Cyanamid Co | Lubricating composition |
US2389718A (en) * | 1943-01-07 | 1945-11-27 | American Cyanamid Co | Disubstituted dithiophosphates |
US2382622A (en) * | 1944-01-03 | 1945-08-14 | Victor Chemical Works | Glycol esters of phenylphosphonic acid |
US2443264A (en) * | 1944-02-19 | 1948-06-15 | Standard Oil Dev Co | Compounded lubricating oil |
US2436141A (en) * | 1946-03-07 | 1948-02-17 | Du Pont | Dialkyl esters of long-chain alkylphosphonates |
US2586655A (en) * | 1948-03-26 | 1952-02-19 | American Cyanamid Co | S-alkoxymethyl-o, o'-dialkyldithiophosphates |
US2565920A (en) * | 1948-03-26 | 1951-08-28 | American Cyanamid Co | Triesters of dithiophosphoric acid |
US2531129A (en) * | 1948-03-26 | 1950-11-21 | American Cyanamid Co | Mineral lubricating oil compositions containing dialkyldithio-phosphoric acid-formaldehyde condensation products |
US2589675A (en) * | 1949-11-29 | 1952-03-18 | American Cyanamid Co | Production of s-hydroxybenzyl o, odithiophosphoric acid triesters |
US2566288A (en) * | 1950-06-03 | 1951-08-28 | American Cyanamid Co | Dialkyldithiophosphatomethylureas |
-
1950
- 1950-08-22 US US180901A patent/US2736737A/en not_active Expired - Lifetime
- 1950-08-22 US US180902A patent/US2736738A/en not_active Expired - Lifetime
-
1952
- 1952-06-24 US US295344A patent/US2736707A/en not_active Expired - Lifetime
- 1952-07-24 US US300757A patent/US2736706A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2586656A (en) * | 1949-08-18 | 1952-02-19 | American Cyanamid Co | S-aminoalkylidene dithiophosphoric acid triesters |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3105819A (en) * | 1959-12-21 | 1963-10-01 | Shell Oil Co | Lubricating compositions |
US3865740A (en) * | 1972-05-22 | 1975-02-11 | Chevron Res | Multifunctional lubricating oil additive |
US3909430A (en) * | 1972-08-07 | 1975-09-30 | Chevron Res | Lubricating composition |
US3859219A (en) * | 1972-11-17 | 1975-01-07 | Chevron Res | Bisphosphoramide-sulfur compound containing lubricant |
US4032461A (en) * | 1974-09-06 | 1977-06-28 | The Lubrizol Corporation | Phosphorus and sulfur containing amides and thioamides as lubricating oil additives and lubricating oil compositions containing same |
US4208357A (en) * | 1974-09-06 | 1980-06-17 | The Lubrizol Corporation | Process for preparing phosphorus and sulfur containing amides and thioamides |
WO2017185819A1 (en) * | 2016-04-27 | 2017-11-02 | 中国石油化工股份有限公司 | Benzotriazole derivative, manufacturing method therefor and use thereof |
CN107312036A (en) * | 2016-04-27 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of benzotriazole derivatives, its manufacture method and its application |
US10822359B2 (en) | 2016-04-27 | 2020-11-03 | China Petroleum & Chemical Corporation | Benzotriazole derivative, preparation process and the use thereof |
RU2737740C2 (en) * | 2016-04-27 | 2020-12-02 | Чайна Петролеум Энд Кемикал Корпорейшн | Benzotriazole derivative, a method for production and use thereof |
Also Published As
Publication number | Publication date |
---|---|
US2736737A (en) | 1956-02-28 |
US2736706A (en) | 1956-02-28 |
US2736738A (en) | 1956-02-28 |
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