US3177233A - Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid - Google Patents
Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid Download PDFInfo
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- US3177233A US3177233A US305810A US30581063A US3177233A US 3177233 A US3177233 A US 3177233A US 305810 A US305810 A US 305810A US 30581063 A US30581063 A US 30581063A US 3177233 A US3177233 A US 3177233A
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- Prior art keywords
- acid
- oil
- polyvalent metal
- salt
- metal salts
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- 150000003839 salts Chemical class 0.000 title claims description 25
- 229910052751 metal Inorganic materials 0.000 title claims description 13
- 239000002184 metal Substances 0.000 title claims description 13
- -1 alkyl mercaptomethyl phosphonic acid Chemical class 0.000 title description 32
- 239000002253 acid Substances 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003502 gasoline Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- MOFCYHDQWIZKMY-UHFFFAOYSA-N chloromethylphosphonic acid Chemical compound OP(O)(=O)CCl MOFCYHDQWIZKMY-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- AZGWMCAPHYSHNE-UHFFFAOYSA-N 1-sulfanylundecylphosphonic acid Chemical compound CCCCCCCCCCC(S)P(O)(O)=O AZGWMCAPHYSHNE-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- LAYURVHZIIBYAP-UHFFFAOYSA-N benzylsulfanylmethylphosphonic acid Chemical compound OP(O)(=O)CSCC1=CC=CC=C1 LAYURVHZIIBYAP-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- XAKRTGZVYPZHCO-UHFFFAOYSA-O hydroxy-methoxy-oxophosphanium Chemical compound CO[P+](O)=O XAKRTGZVYPZHCO-UHFFFAOYSA-O 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LSGPZYLAHPLSBS-UHFFFAOYSA-N 1-[butoxy(chloromethyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCl)OCCCC LSGPZYLAHPLSBS-UHFFFAOYSA-N 0.000 description 1
- CWTHQOPTQAZCJV-UHFFFAOYSA-N 10-phenyldecane-1-thiol Chemical compound SCCCCCCCCCCC1=CC=CC=C1 CWTHQOPTQAZCJV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical class COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- MVWGPENDPGDDOO-UHFFFAOYSA-N C(CCCCCCCCCCC)SCP(O)(O)=O Chemical compound C(CCCCCCCCCCC)SCP(O)(O)=O MVWGPENDPGDDOO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KBSLZAADCLMYMJ-UHFFFAOYSA-L P([O-])([O-])=S.[Fe+2] Chemical compound P([O-])([O-])=S.[Fe+2] KBSLZAADCLMYMJ-UHFFFAOYSA-L 0.000 description 1
- VYIGFALZSKQAPJ-UHFFFAOYSA-L [Fe+2].[O-]P([O-])=O Chemical compound [Fe+2].[O-]P([O-])=O VYIGFALZSKQAPJ-UHFFFAOYSA-L 0.000 description 1
- FLPSWUXKDMMXBJ-UHFFFAOYSA-N [chloromethyl(cyclohexyloxy)phosphoryl]oxycyclohexane Chemical compound ClCP(OC1CCCCC1)(OC1CCCCC1)=O FLPSWUXKDMMXBJ-UHFFFAOYSA-N 0.000 description 1
- WGCJUPJNMGWDAU-UHFFFAOYSA-N [chloromethyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(CCl)OC1=CC=CC=C1 WGCJUPJNMGWDAU-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- ORUGPWKFNPKJGA-UHFFFAOYSA-N benzylsulfanylphosphonic acid Chemical compound OP(O)(=O)SCC1=CC=CC=C1 ORUGPWKFNPKJGA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 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
- 150000001661 cadmium Chemical class 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- ISIPUCJUDOMIDU-UHFFFAOYSA-N decoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCOP(O)(O)=S ISIPUCJUDOMIDU-UHFFFAOYSA-N 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
- ARRDXFYXBCFIAI-UHFFFAOYSA-N decylsulfanylmethylphosphonic acid Chemical compound C(CCCCCCCCC)SCP(O)(O)=O ARRDXFYXBCFIAI-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical class CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JPIROWHTPUZLPV-UHFFFAOYSA-N phenylsulfanylmethylphosphonic acid Chemical compound OP(O)(=O)CSC1=CC=CC=C1 JPIROWHTPUZLPV-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Definitions
- Mg Be, Ba, Sr, or another polyvalent metal such as Cr,
- the anionic portions of these polyvalent metal salts which are preferred are anions of acids which have the formula 0 OH Gin-1a 2.1 y1SCH1] 0R1 11 where R is the same as defined in (I) and preferably a C alkyl radical.
- the acidic compounds represented by the above formulas are prepared by reacting a mercaptan or mercaptide having at least 6 carbon atoms with a halomethylphosphono compound such as chloromethylphosphonic acid or chloromethylphosphonate or their thio derivatives, in a suitable solvent, such as an aqueous alcoholic solution, at reflux temperature and under inert conditions until the reaction is completed, which may require from 1 to about 5 days.
- the mercaptans include: aliphatic mercaptans, such as hexyl, octyl, decyl, dodecyl and octadecyl mercaptans; cycloalkyl mercaptans, such as cyclohexyl mercaptan and dicyclohexyl mercaptan; and aralkyl mercaptans, such as phenyldecyl ,mercaptan and benzyl mercaptan.
- the corresponding mercaptides can be used such as the alkali metal, e.g., Naor K mercap'tides.
- Suitable halomethylphosphono compounds include chloromethylphosphonic acid, mono or dihydrocarbyl chloromethylphosphonates, e.g., mono or dibutyl chloromethylphosphonate, mono or di-2-ethylhexy1 chloromethylphosphonate, mono ordilauryl chloromethylphosphonate, mono or diphenyl chloromethylphosphonate, mono or dicyclohexyl chloromethylphosphonate, mono or 'dibenzyl chloromethylphosphonate, dibutyl chloromethyldithiophosphonate,
- diphenyllchloromethyldithiophosphonate dibutyl chlorornethyltrithiophosphonate, and alkali metal salts such as Na and Kflsalts of chloromethylphosphonic acid, Na
- a preferred method of making the thiarnethylphosphonates is to react a suitable mercapto compound, such as an alkali metal, e.g., Na or K, C1048 alkyl mercaptide with an alkali metal, e.g., Na or K, salt of chloromethylphosphonic acid in an alcoholic solution under reflux conditions and under an inert atmosphere to form the alkali metal salt of an alkyl mercaptomethylphosphonic acid.
- the salt is then treated with a strong acid such as hydrochloric acid to spring free the alkylmercaptomethylphosphonic acid, which can be converted into the desired polyvalent metal salts.
- EXAMPLE II The monobutyl ester of decylmercaptomethylphosphonic acid was prepared by fully esterifying the acid of Example I and thereafter partially hydrolyzing the dies'ter with alcoholic KOH under reflux conditions for about 24 hours.
- the above thiamethylpliosphonic acids are converted to the neutral or basic polyvalent metal salts by suitable means such as by neutralizing the acid with an aqueous solution of sodium hydroxide or carbonate and mixing solution of the desired polyvalent metal compounds such as a sulfate, nitrate, chloride, acetate or the like and removing -the precipitated organic polyvalent metal salt 'by suitable means, such as filtration, decantation, or ext
- suitable means such as by neutralizing the acid with an aqueous solution of sodium hydroxide or carbonate and mixing solution of the desired polyvalent metal compounds such as a sulfate, nitrate, chloride, acetate or the like and removing -the precipitated organic polyvalent metal salt 'by suitable means, such as filtration, decantation, or ext
- suitable means such as by neutralizing the acid with an aqueous solution of sodium hydroxide or carbonate and mixing solution of the desired polyvalent metal compounds such as a sulfate, nit
- the following illustrate additional metal salts of this invention Cr, Mn, Fe, Co, Ni, Cu, Al and Zn salts of octylmercaptomethylphosphonic acid, dodecylmercaptomethylphosphonic acid, cyclohexylmercaptomethyl phosphonic acid, benzylmercaptomethylphosphonic acid, phenylmercaptomethylphosphonic acid, butyl decylmercaptomethyl acid phosphonate, phenyl decylmercaptomethyl acid phosphonate, monothiobutyl dodecylmercaptomethyl acid phosphona-te, monobutyl phenylmercaptomethyl acid phosphonate, monothiooctyl cyclohexy1mercapto methyl acid thiop-hosphonate and the like.
- the additives of this invention are believed to be novel compounds. They are soluble in various hydrocarbons and mixtures thereof of wide boiling range. These are useful therein for varied purposes and generally in amounts of from about 0.0001% to about 10%, preferably from 0.001% to about 5.0% by weight.
- the polyvalent metal salts of mercaptomethylphosphono compounds of this invention are outstanding additives for improving, or gelling or thickening various liquid hydrocarbon products, such as natural and synthetic hydrocarbon lubricating oils, fuels (gasoline, kerosene, gas oil, burner fuel oil), slushing oils and various industrial oils, e.g., metal working and drawing oils, quenching oils, textile oil-s, hydraulic oils, dielectric compositions and other industrial oils. They are particularly outstanding when added in small amounts to hydrocarbon fuels such as gasoline or kerosene or lubricating oils and lubricating compositions in imparting extreme pressure and anti-wear properties to such materials. These additives are particularly useful as antioxidants and as gel-ling agents for gasoline, fuel oils, and other light oil products.
- Liquid 30% increase in viscosity of the gaso- Liquid 40% increase in (8) 0.2% aluminum decylmercaptoethyl phosphonate.
- Example VI The addition of only 1% of the additive of Example VI to an SAE 30 refined mineral oil produced a grease.
- Greases are also formed by addition to mineral oil (at ambient temperature) of from 1% to 5% of any of the following salts alone or in mixtures thereof:
- a polyvalent metal salt selected from the group consisting of Fe, Cd, Zn and A1 of an acid having the formula wherein R is an oil-soluble alkyl radical having at least 6 carbon atoms, R is selected from the group consisting of hydrogen, and an alkyl radical, and X is a chalcogen having an atomic number from 8 to 16.
- a polyvalent metal salt selected from the group consisting of Fe, Cd, Zn, and A1 of C1048 alkylmercaptomethylphosphonic acid.
- a polyvalent metal salt selected from the group consisting of Fe, Cd, Zn, and Al of a monoester of C1048 alkylmercaptomethylphosphonic acid.
- Cadmium salt of monobutyl ester of decyl mercaptomethylphosphonic acid 8.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Description
United States Patent 3,177,233 OIL-SOLUBLE POLYVALENT NETAL SALTS F ALKYL MERCAPTOMETHYL PHQSPHON- 1C AEZID George M. (Ialhonn, Cleveland, Ohio, assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Aug. 30, 1963, Ser. No. 305,810
1 11 Claims. (Cl. 260-4293) lain-V wherein Ris an oil-soluble hydrocarbyl group, such as an alkyl, aralkyl, alkaryl or cycloalkyl radical having at least 6 carbon atoms and preferably is a C alkyl radical, the R s are the same or different groups which may be hydrogen or a C alkyl radical and the Xs are oxygen or sulfur, preferably oxygen. The cationic portion of the salt is a polyvalent metal of variable or non-variable valence such as an alkaline earth metal, e.g., Ca,
. Mg, Be, Ba, Sr, or another polyvalent metal such as Cr,
Mn, Fe, Co, Ni, Cu, Zn,Cd, Al, or Sn, of which preferred ones are Fe, Ni, Cu, Zn, Cd, and Al.
The anionic portions of these polyvalent metal salts which are preferred are anions of acids which have the formula 0 OH Gin-1a 2.1 y1SCH1] 0R1 11 where R is the same as defined in (I) and preferably a C alkyl radical. The acidic compounds represented by the above formulas are prepared by reacting a mercaptan or mercaptide having at least 6 carbon atoms with a halomethylphosphono compound such as chloromethylphosphonic acid or chloromethylphosphonate or their thio derivatives, in a suitable solvent, such as an aqueous alcoholic solution, at reflux temperature and under inert conditions until the reaction is completed, which may require from 1 to about 5 days. The mercaptans include: aliphatic mercaptans, such as hexyl, octyl, decyl, dodecyl and octadecyl mercaptans; cycloalkyl mercaptans, such as cyclohexyl mercaptan and dicyclohexyl mercaptan; and aralkyl mercaptans, such as phenyldecyl ,mercaptan and benzyl mercaptan. Instead of the mercaptans, the corresponding mercaptides can be used such as the alkali metal, e.g., Naor K mercap'tides. Suitable halomethylphosphono compounds include chloromethylphosphonic acid, mono or dihydrocarbyl chloromethylphosphonates, e.g., mono or dibutyl chloromethylphosphonate, mono or di-2-ethylhexy1 chloromethylphosphonate, mono ordilauryl chloromethylphosphonate, mono or diphenyl chloromethylphosphonate, mono or dicyclohexyl chloromethylphosphonate, mono or 'dibenzyl chloromethylphosphonate, dibutyl chloromethyldithiophosphonate,
, diphenyllchloromethyldithiophosphonate, dibutyl chlorornethyltrithiophosphonate, and alkali metal salts such as Na and Kflsalts of chloromethylphosphonic acid, Na
acid and the-like.
3,177,233 Patented Apr. 6, 1965 A preferred method of making the thiarnethylphosphonates is to react a suitable mercapto compound, such as an alkali metal, e.g., Na or K, C1048 alkyl mercaptide with an alkali metal, e.g., Na or K, salt of chloromethylphosphonic acid in an alcoholic solution under reflux conditions and under an inert atmosphere to form the alkali metal salt of an alkyl mercaptomethylphosphonic acid. The salt is then treated with a strong acid such as hydrochloric acid to spring free the alkylmercaptomethylphosphonic acid, which can be converted into the desired polyvalent metal salts.
The following examples illustrate the preparation of the acid portion of the salt for use, in accordance with the present invention.
EXAMPLE I Equivalent Weight First Both Hydro- Hydrogen gBHS Found 49.1 9.4 12.0 11.2 261 132' Expected 49.2 9.4 11.94 11.54 268.3 134.1
EXAMPLE II The monobutyl ester of decylmercaptomethylphosphonic acid was prepared by fully esterifying the acid of Example I and thereafter partially hydrolyzing the dies'ter with alcoholic KOH under reflux conditions for about 24 hours.
The following additional representative compounds were prepared by the above method: octyhnercaptomethylphosphonic acid, phonic acid, cyclohexylmercaptomethylphosphonic acid,
benzylmercaptomethylphosphonic acid, butyl decylmerthe sodium salt thus formed with an excess of an aqueous captomethyl acid phosphonate, phenyl decylmercaptomethyl acid phosphonate, monobutyl dodecylmercaptomethyl acid thiophosphonate, monooctyl cyclohexylmer captomethylthio acid. thioplio sphonate. i
The above thiamethylpliosphonic acids are converted to the neutral or basic polyvalent metal salts by suitable means such as by neutralizing the acid with an aqueous solution of sodium hydroxide or carbonate and mixing solution of the desired polyvalent metal compounds such as a sulfate, nitrate, chloride, acetate or the like and removing -the precipitated organic polyvalent metal salt 'by suitable means, such as filtration, decantation, or ext The product of Example II was neutralized with, an
aqueous solution of sodium hydroxide to which was added an excess of an aqueous'rnixture of ferrous ammonium, sulfate at ambient temperature while constantly stirring dodecylmercaptomethylphosa the mixture. The iron thiophosphonate precipitated and the aqueous phase was removed by decantation. The salt was purified by dissolving it in benzene, separating the benzene from insoluble material, water-washing, and stripping the benzene from the purified product. The end product was a basic iron phosphonate, which may be represented by the formula T Fe- O--PCHzSC1oH2! (OH) O C 4H 2 and the product analyzed as follows:
Percent Percent Percent Fe P Found- 7. 14 9. 23 8. 32 Expected 7. 95 9. 12 8. 82
EXAMPLE IV Preparation of the neutral iron salt of the monoester of Example 11 The neutral salt of the rnonobutyl decylthiamethyl phosphonate was similarly prepared by following the general procedure of Example H1 in neutralizing the product of Example II with an excess of ferric nitrate. The neutral salt may be represented by the formula:
using cadmium nitrate as the neutralizing agent. The salt was dissolved in benzene and water-washed repeatedly and the solvents were then stripped off and the product analyzed as follows:
Percent Percent Percent Cd S P Found l4. 7 8. 85 8. 00 Expected 14. 83 8. 46 8. l8
EXAMPLE VI Preparation of zinc salt of monobatyl decylthiamethylphosphonate The zinc salt of monobutyl decylthiamethylphosphonate was prepared following the procedure of Example V using zinc chloride as the neutralizing agent and the product analyzed as follows:
Percent Percent Percent Zn P 6. 64 9. 08 8. 31 Expected. 9. 20 9.01 8. 72
The following illustrate additional metal salts of this invention: Cr, Mn, Fe, Co, Ni, Cu, Al and Zn salts of octylmercaptomethylphosphonic acid, dodecylmercaptomethylphosphonic acid, cyclohexylmercaptomethyl phosphonic acid, benzylmercaptomethylphosphonic acid, phenylmercaptomethylphosphonic acid, butyl decylmercaptomethyl acid phosphonate, phenyl decylmercaptomethyl acid phosphonate, monothiobutyl dodecylmercaptomethyl acid phosphona-te, monobutyl phenylmercaptomethyl acid phosphonate, monothiooctyl cyclohexy1mercapto methyl acid thiop-hosphonate and the like.
The additives of this invention are believed to be novel compounds. They are soluble in various hydrocarbons and mixtures thereof of wide boiling range. These are useful therein for varied purposes and generally in amounts of from about 0.0001% to about 10%, preferably from 0.001% to about 5.0% by weight.
The polyvalent metal salts of mercaptomethylphosphono compounds of this invention are outstanding additives for improving, or gelling or thickening various liquid hydrocarbon products, such as natural and synthetic hydrocarbon lubricating oils, fuels (gasoline, kerosene, gas oil, burner fuel oil), slushing oils and various industrial oils, e.g., metal working and drawing oils, quenching oils, textile oil-s, hydraulic oils, dielectric compositions and other industrial oils. They are particularly outstanding when added in small amounts to hydrocarbon fuels such as gasoline or kerosene or lubricating oils and lubricating compositions in imparting extreme pressure and anti-wear properties to such materials. These additives are particularly useful as antioxidants and as gel-ling agents for gasoline, fuel oils, and other light oil products.
In order to show the unexpected gelling properties which salts of the present invention possess, from 0.2% to 1% of the salts shown in Table I below were added to gasoline and the gelling effects noted.
TABLE I [B ase=gasoline1 Liquid, no change in physical state of the gasoline.
Liquid with about 10% increase in viscosity of the gasoline.
Liquid 30% increase in viscosity of the gaso- Liquid 40% increase in (8) 0.2% aluminum decylmercaptoethyl phosphonate.
(9) 1% aluminum decylmercaptoethyl phos phonate. 7
(l0) 1% iron monobutyl deeylphosphonate- (ll) 1% aluminum monobutyldecyl phosphona e.
vliscoslty of the gas- (12) 1% sodium monobutyldecylmercapto None (insoluble in methyl phosphonate. gasoline).
1 Gel=def1ned as a non-pourable mass, the viscosity of base gasoline increased by over 70-90%.
The addition of 2% of the additive of Example III to kerosene at ambient temperature formed a solid fuel composition capable of withstanding high temperatures, above 350 F., without essential change in structure or stability.
The addition of 400 parts per million of the additive of Example III to gasoline increased the viscosity of the gasoline 70%. i
The addition of 1% of additive of Example IV to JP-4 jet fuel yields a heavy oil of SAE viscosity and the ad:
Er k
dition of 1% additive of Example III to JP-4 fuel yields a sticky gel which can be burned without collapsing.
The addition of only 1% of the additive of Example VI to an SAE 30 refined mineral oil produced a grease.
The addition of 2% of neutral Al salt of decylthiamethylphosphonic acid to an SAE 30 refined mineral oil formed a grease.
Greases are also formed by addition to mineral oil (at ambient temperature) of from 1% to 5% of any of the following salts alone or in mixtures thereof:
Cd, Zn, Al, Fe, Sn, Mn, Mg, Ca, Ba, Be salts of dodecylthiamercaptophosphonic acid, benzylthiamethylphosphonic acid, butyl dodecylthiamethyl acid phosphonate, cyclohexyl decylthiamethyl acid phosphonate, butyl decylthiamethyl acid thiophosphonate.
I claim as my invention:
1. A polyvalent metal salt selected from the group consisting of Fe, Cd, Zn and A1 of an acid having the formula wherein R is an oil-soluble alkyl radical having at least 6 carbon atoms, R is selected from the group consisting of hydrogen, and an alkyl radical, and X is a chalcogen having an atomic number from 8 to 16.
2. The composition of claim 1 wherein R is a C1048 alkyl radical, R is a C alkyl radical, and X is oxygen,
3. The composition of claim 1 wherein R is a C1048 alkyl radical, R is hydrogen, and X is oxygen.
4. The composition of claim 1 wherein R is a C1048 alkyl radical, R is a C alkyl radical, and X is sulfur 5. A polyvalent metal salt selected from the group consisting of Fe, Cd, Zn, and A1 of C1048 alkylmercaptomethylphosphonic acid.
6. A polyvalent metal salt selected from the group consisting of Fe, Cd, Zn, and Al of a monoester of C1048 alkylmercaptomethylphosphonic acid.
7. Iron salt of C1048 alkylmercaptomethylphosphonic acid.
8. Iron salt of monobutyl ester of decyl mercaptomethylphosphonic acid.
9. Cadmium salt of monobutyl ester of decyl mercaptomethylphosphonic acid.
10. Zinc salt of monobutyl ester of decyl mercaptomethylphosphonic acid. a
11. Aluminum salt of monobutyl ester of decyl mercaptomethylphosphonic acid.
References Cited by the Examiner UNITED STATES PATENTS 2,346,155 4/44 Denison et a1 260-429 2,795,492 6/57 Aylesworth et al. 44-7 2,838,555 6/58 Goldsmith 2 260-461 2,838,557 6/58 Verley 260429.9 2,854,468 9/58 Max 260-461 2,881,201 4/59 Schrader 260-429 2,911,292 11/59 Baldeschwieler 44-68 2,947,693 8/60 Boyle et al. 260-429.9 2,971,019 2/61 Ladd et al 260-461 2,991,244 7/61 Pattenden et al. 252-327 FOREIGN PATENTS 751,755 7/56 Great Britain.
TOBIAS E. LEVOW, Primary Examiner.
Claims (1)
1. A POLYVALENT METAL SALT SELECTED FROM THE GROUP CONSISTING OF FE, CD, ZN AND AL OF AN ACID HAVING THE FORMULA
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US305810A US3177233A (en) | 1963-08-30 | 1963-08-30 | Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US305810A US3177233A (en) | 1963-08-30 | 1963-08-30 | Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid |
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| US3177233A true US3177233A (en) | 1965-04-06 |
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Cited By (6)
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|---|---|---|---|---|
| US3288627A (en) * | 1965-08-05 | 1966-11-29 | Addressograph Multigraph | Heat-sensitive diazotype material coated sheet |
| US3293208A (en) * | 1963-07-03 | 1966-12-20 | American Cyanamid Co | Stabilization of polyolefins with certain metal dithiophosphinate salts |
| US3412118A (en) * | 1962-08-31 | 1968-11-19 | Hooker Chemical Corp | Salts of 2, 6-and 2, 4, 6-substituted primary aryl phosphites |
| US4235991A (en) * | 1978-12-04 | 1980-11-25 | Occidental Research Corporation | Layered sulfonate end terminated organophosphorus inorganic polymers |
| EP1157994A1 (en) * | 2000-05-25 | 2001-11-28 | Institut Francais Du Petrole | Materials having organic groups containing sulfur and phosphorus bond through oxygen atoms to a mineral oxide |
| JP2002160908A (en) * | 2000-08-17 | 2002-06-04 | Inst Fr Petrole | Material having organic phosphorus-containing group which bonds to mineral oxide by oxygen atom |
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| US2346155A (en) * | 1942-02-23 | 1944-04-11 | Standard Oil Co | Compounded oil |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3412118A (en) * | 1962-08-31 | 1968-11-19 | Hooker Chemical Corp | Salts of 2, 6-and 2, 4, 6-substituted primary aryl phosphites |
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| US3288627A (en) * | 1965-08-05 | 1966-11-29 | Addressograph Multigraph | Heat-sensitive diazotype material coated sheet |
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| EP1157994A1 (en) * | 2000-05-25 | 2001-11-28 | Institut Francais Du Petrole | Materials having organic groups containing sulfur and phosphorus bond through oxygen atoms to a mineral oxide |
| FR2809400A1 (en) * | 2000-05-25 | 2001-11-30 | Inst Francais Du Petrole | MATERIALS COMPRISING ORGANIC GROUPS CONTAINING SULFUR AND PHOSPHORUS LINKED THROUGH OXYGEN ATOMS TO A MINERAL OXIDE |
| JP2002030090A (en) * | 2000-05-25 | 2002-01-29 | Inst Fr Petrole | Substance containing organic group containing sulfur and phosphorus and bonded with inorganic oxide through oxygen atom |
| US20060014635A1 (en) * | 2000-05-25 | 2006-01-19 | Alain Forestiere | Materials comprising organic groups containing sulphur and phosphorous bonded to a mineral oxide via oxygen atoms |
| US7160836B2 (en) * | 2000-05-25 | 2007-01-09 | Institut Francois Du Petrole | Materials comprising organic groups containing sulphur and phosphorous bonded to a mineral oxide via oxygen atoms |
| JP2002160908A (en) * | 2000-08-17 | 2002-06-04 | Inst Fr Petrole | Material having organic phosphorus-containing group which bonds to mineral oxide by oxygen atom |
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