US3114710A - Thickened hydrocarbon compositions - Google Patents
Thickened hydrocarbon compositions Download PDFInfo
- Publication number
- US3114710A US3114710A US7781A US778160A US3114710A US 3114710 A US3114710 A US 3114710A US 7781 A US7781 A US 7781A US 778160 A US778160 A US 778160A US 3114710 A US3114710 A US 3114710A
- Authority
- US
- United States
- Prior art keywords
- acid
- salt
- liquid hydrocarbon
- polyvalent metal
- hydrocarbon
- 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
- 229930195733 hydrocarbon Natural products 0.000 title claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 29
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 24
- 150000003839 salts Chemical class 0.000 claims description 32
- -1 MERCAPTOMETHYLPHOSPHONO COMPOUND Chemical class 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000004519 grease Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- MOFCYHDQWIZKMY-UHFFFAOYSA-N chloromethylphosphonic acid Chemical compound OP(O)(=O)CCl MOFCYHDQWIZKMY-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 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
- ARRDXFYXBCFIAI-UHFFFAOYSA-N decylsulfanylmethylphosphonic acid Chemical compound C(CCCCCCCCC)SCP(O)(O)=O ARRDXFYXBCFIAI-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 238000000034 method Methods 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
- 150000007513 acids Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 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
- 229910052748 manganese Inorganic materials 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
- 239000003208 petroleum Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 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
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000001183 hydrocarbyl group 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
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000243 solution Substances 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
- 230000008719 thickening Effects 0.000 description 2
- 150000003751 zinc Chemical class 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
- CHJJBUJCUJHDIJ-UHFFFAOYSA-N 1-chloropentylphosphonic acid Chemical class C(CCC)C(P(O)(=O)O)Cl CHJJBUJCUJHDIJ-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
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-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
- YFLPIZLPODNMOC-UHFFFAOYSA-N [chloromethyl(phenylmethoxy)phosphoryl]oxymethylbenzene Chemical compound C=1C=CC=CC=1COP(=O)(CCl)OCC1=CC=CC=C1 YFLPIZLPODNMOC-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
- 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 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
- 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
- NVNPBQGYMZQDIN-UHFFFAOYSA-N chloromethyl-phenoxy-phenylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound ClCP(OC1=CC=CC=C1)(=S)SC1=CC=CC=C1 NVNPBQGYMZQDIN-UHFFFAOYSA-N 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
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-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
- 239000010771 distillate fuel oil Substances 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
- 235000019441 ethanol Nutrition 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000001050 lubricating effect Effects 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
- 238000002156 mixing Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 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
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 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
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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
- C10M5/00—Solid or semi-solid compositions containing as the essential lubricating ingredient mineral lubricating oils or fatty oils and their use
-
- 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
-
- 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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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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
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- 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
- C10N2040/20—Metal working
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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
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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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
- C10N2040/20—Metal working
- C10N2040/241—Manufacturing joint-less pipes
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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
- C10N2040/20—Metal working
- C10N2040/242—Hot working
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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
- C10N2040/20—Metal working
- C10N2040/243—Cold working
-
- 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
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
-
- 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
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
-
- 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
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
-
- 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
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
-
- 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
- C10N2040/46—Textile oils
-
- 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 improved liquid hydrocarbon compositions and to additives therefor. More particularly, the invention relates to gelled or grease-like hydrocarbon compositions.
- liquid hydrocarbon compositions are improved with respect to wear-inhibiting and extreme pressure properties and may be transformed into stable gels or greases by incorporating therein a minor amount of an oil-soluble metal salt of a hydrocarbyl thiomethyl phosphonic acid or monoester thereof.
- the acid portion of the polyvalent metal salt has the general formula R1 X X131 XH (I) wherein R is an oil-soluble hydrocarbyl group, such as an alkyl, aryl, aralkyl, alkaryl or cycloalkyl radical having at least 6 carbon atoms and preferably is a C1048 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.
- R is an oil-soluble hydrocarbyl group, such as an alkyl, aryl, aralkyl, alkaryl or cycloalkyl radical having at least 6 carbon atoms and preferably is a C1048 alkyl radical
- the R s are the same or different groups which may be hydrogen or a C alkyl radical
- 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, 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.
- an alkaline earth metal e.g., Ca, Mg, Ba, Sr
- 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 H C 10-13 alkyl-S C Hi P where R is the same as defined in (l) 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 Patented Dec. 17, 1%63 ice 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., Na or K mercaptides.
- Suitable halomethylphosphono compounds include chloromethylphosphonic acid, mono or dihydrocarbyl chloromethylphosphonates, e.g., mono or dibutyl chloromethylphosphonate, mono or di-2-ethylhexyl chloromethylphosphonate, mono or diluaryl chloromethylphosphonate, mono or diphenyl chloromethylphosphonate, mono or dicyclohexyl chloromethylphosphonate, mono or dibenzyl chloromethylphosphonate, dibutyl chloromethyldithiophosphonate, diphenyl chloromethyldithiophosphonate, dibutyl chloromethyltrithiophosphonate, and alkali metal salts such as Na and K salts of chioromethylphosphonic acid, Na and K salts of monobutyl chloromethylphosphonic acid, N a and K salts of rnonodecyl chloromethylphosphonic acid and the like.
- alkali metal salts such as Na and K
- a preferred method of making the thiomethylphosnates 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.
- EXAMPIJE II phonate monobutyl dodecylmercaptomethyl acid thiophosphonate, monobutyl phenylmercaptomethyl acid phosphonate, monooctyl cyclohexylmercaptomethylthio acid thiophosphonate.
- the above thiomethylphosphonic 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 the sodium salt thus formed with an excess of an aqueous 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 extraction.
- suitable means such as by neutralizing the acid with an aqueous solution of sodium hydroxide or carbonate and mixing the sodium salt thus formed with an excess of an aqueous 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 extraction.
- the reaction is generally conducted at ambient temperature, but may vary from, say, C. to 120 C.
- EXAMPLE III Preparation of Basic Iron Salt of Monobutyl Decylthiomethylphosphonale
- the product of Example II was neutralized with an aqueous solution of sodium hydroxide to which was added an excess of an aqueous mixture of ferrous ammonium sulfate at ambient temperature while constantly stirring 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 and the product analyzed as follows:
- the following illustrate additional metal salts of this invention Cr, Mn, Fe, Co, Ni, Cu, Al and Zn salts of octylmercaptomethylphosphonic acid, dodecylmercaptomethylphosphonic acid, cyclohexylmercaptomethylphosphonic acid, benzylmercaptomethylphosphonic acid, phenylmercaptomethylphosphonic acid, butyl decylmercaptomethyl acid phosphonate, phenyl decylmercaptomethyl acid phosphonate, monotbiobutyl dodecylmercaptomethyl acid phosphonate, monobutyl phenylmercaptomethyl acid phosphonate, monothiooctyl cyclohexylmercaptomethyl acid thiophosphonate 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 oils, hydraulic oils, dielectric compositions and other industrial oils.
- 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 gelling agents for gasoline, fuel oils, and other light oil products.
- 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 hydrocarbon liquid composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufiicient to impart extreme pressure properties to the liquid hydrocarbon and gel it to a grease structure of an oil-soluble polyvalent metal salt of a hydrocarbyl mercaptomethylphosphono compound having the general formula wherein R is an oil-soluble C hydrocarbyl radical, the R s are selected independently from the group consisting of hydrogen and C alkyl radical, and X is a chalcogen having an atomic number from 8 to 16.
- a liquid hydrocarbon composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to impart extreme pressure properties to the hydrocarbon liquid and gel it to a grease structure, of a polyvalent metal salt of C alkylmercaptomethylphosphonic acid.
- a liquid hydrocarbon composition comprising a major amount of a liquid hydrocarbon and a minor amount, suificient to impart extreme pressure properties to the liquid hydrocarbon and gel it to a grease structure, of a polyvalent metal salt of a monoestcr of C1048 alkylmercaptomethylphosphonic acid.
- a liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to increase the viscosity of the fuel, of a polyvalent metal salt of C1048 alkylmercaptomethylphosphonic acid.
- a liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to thicken the fuel to a solid, of a basic polyvalent metal salt of decylmercaptomethylphosphonic acid, the metal portion of the salt being selected from the group consisting of Zn, Cd, Fe and Al.
- a liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to thicken the fuel to a solid, of a neutral polyvalent metal salt of decylmercaptomethylphosphonic acid, the metal portion of the salt being selected from the group consisting of Zn, Cd, Fe and A1.
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Description
3,114,710 THICKENED HYDROCAUN CGMPUSETIQNS George M. Calhoun, Berkeley, Calif., assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 1%, H60, fier. No. 7,7 81 lib Claims. (Cl. 252-325) This invention relates to improved liquid hydrocarbon compositions and to additives therefor. More particularly, the invention relates to gelled or grease-like hydrocarbon compositions.
In general, in order to prepare suitable greases from liquid hydrocarbons by thickening with soaps, such as stearates or hydroxy-stearates, certain petroleum fractions of particular viscosity ranges and chemical composition are required. With very light petroleum fractions, such as gasoline, kerosene, or distillate fuel oil, conventional thickeners such as soaps are either ineffective or require such large amounts or specific equipment and techniques for their manufacture so as to make their preparation impractical.
It is an object of the present invention to provide novel stable and improved gels or grease-like compositions. It is a further object to provide a gel or grease from liquid hydrocarbons of wide boiling range. It is a still further object of this invention to provide a gel or grease from a light liquid petroleum base. It is a further object to provide a novel class of compounds which impart beneficial antiwear and extreme pressure properties to liquid hydrocarbons. These and other objects of the invention will be apparent from the following detailed description thereof.
It has now been discovered that liquid hydrocarbon compositions are improved with respect to wear-inhibiting and extreme pressure properties and may be transformed into stable gels or greases by incorporating therein a minor amount of an oil-soluble metal salt of a hydrocarbyl thiomethyl phosphonic acid or monoester thereof. The acid portion of the polyvalent metal salt has the general formula R1 X X131 XH (I) wherein R is an oil-soluble hydrocarbyl group, such as an alkyl, aryl, aralkyl, alkaryl or cycloalkyl radical having at least 6 carbon atoms and preferably is a C1048 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, 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 H C 10-13 alkyl-S C Hi P where R is the same as defined in (l) 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 Patented Dec. 17, 1%63 ice 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., Na or K mercaptides. Suitable halomethylphosphono compounds include chloromethylphosphonic acid, mono or dihydrocarbyl chloromethylphosphonates, e.g., mono or dibutyl chloromethylphosphonate, mono or di-2-ethylhexyl chloromethylphosphonate, mono or diluaryl chloromethylphosphonate, mono or diphenyl chloromethylphosphonate, mono or dicyclohexyl chloromethylphosphonate, mono or dibenzyl chloromethylphosphonate, dibutyl chloromethyldithiophosphonate, diphenyl chloromethyldithiophosphonate, dibutyl chloromethyltrithiophosphonate, and alkali metal salts such as Na and K salts of chioromethylphosphonic acid, Na and K salts of monobutyl chloromethylphosphonic acid, N a and K salts of rnonodecyl chloromethylphosphonic acid and the like.
A preferred method of making the thiomethylphosnates 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 Stoichiometric amounts of the potassium salt of decyl mercaptan and monochloromethylphosphonic acid were dispersed in an aqueous solution of ethyl alcohol and the mixture was refluxed at 7 8 C. under a nitrogen atmosphere for about 1 day. The potassium declymercaptomethylphosphonate was then treated with strong hydrochloric acid to spring free the phosphonic acid which was recovered by extraction with ether. The final product, decylmercaptomethylphosphonic acid, analyzed as follows:
Equivalent Weight First Both Hydro- Hydrogen gens Found 49.1 9.4 12.0 11.2 261 132 Expected 40.2 9.4 11.94 11. 54 268.3 134.1
EXAMPIJE II phonate, monobutyl dodecylmercaptomethyl acid thiophosphonate, monobutyl phenylmercaptomethyl acid phosphonate, monooctyl cyclohexylmercaptomethylthio acid thiophosphonate.
The above thiomethylphosphonic 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 the sodium salt thus formed with an excess of an aqueous 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 extraction. The reaction is generally conducted at ambient temperature, but may vary from, say, C. to 120 C.
The following examples illustrate the preparation of the polyvalent metal salts of the invention.
EXAMPLE III Preparation of Basic Iron Salt of Monobutyl Decylthiomethylphosphonale The product of Example II was neutralized with an aqueous solution of sodium hydroxide to which was added an excess of an aqueous mixture of ferrous ammonium sulfate at ambient temperature while constantly stirring 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 and the product analyzed as follows:
Percent Percent Fe S Percent P Found 7.1 Expected 7. 9
EXAMPLE IV Preparation of the Neutral Iron Salt of the Monoester of Example II The neutral salt of the monobutyl decylthiomethyl phosphonate was similarly prepared by following the general procedure of Example III in neutralizing the product The cadmium salt of mono-butyl decylthiomethylphosphonate was prepared by the procedure of Example I, 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... 14. 7 8. 8.00 Ex pcctccL- 14. 83 8. 46 8. 18
EXAMPLE v1 Preparation of Zinc Salt of ZlJOnObutyl Decylthz'omethylphosphonate The zinc salt of monobutyl decylthiomethylphosphonate was prepared following the procedure of Example V using zinc chloride as the neutralizing agent and the product analyzed as follows:
The following illustrate additional metal salts of this invention: Cr, Mn, Fe, Co, Ni, Cu, Al and Zn salts of octylmercaptomethylphosphonic acid, dodecylmercaptomethylphosphonic acid, cyclohexylmercaptomethylphosphonic acid, benzylmercaptomethylphosphonic acid, phenylmercaptomethylphosphonic acid, butyl decylmercaptomethyl acid phosphonate, phenyl decylmercaptomethyl acid phosphonate, monotbiobutyl dodecylmercaptomethyl acid phosphonate, monobutyl phenylmercaptomethyl acid phosphonate, monothiooctyl cyclohexylmercaptomethyl acid thiophosphonate 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 oils, hydraulic oils, dielectric compositions and other industrial oils. vThey 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 gelling agents for gasoline, fuel oils, and other light oil products.
The addition of 2% of the additive of Example III to kerosene at ambient temperature formed a solid fuel composition capableof 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%.
The addition of 1% of additive of Example IV to JP-4 jet fuel yields a heavy oil of SAE viscosity and the addition 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 A1 salt of decylthiomethylphosphonic 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, salts of dodecylthiomercaptophosphonic acid, benzylthiomethylphosphonic acid, butyl dodecylthiomethyl acid phosphonate, cyclohexyl decylthiomethyl acid phosphonate, butyl decylthiomethyl acid thiophosphonate.
I claim as my invention:
1. A hydrocarbon liquid composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufiicient to impart extreme pressure properties to the liquid hydrocarbon and gel it to a grease structure of an oil-soluble polyvalent metal salt of a hydrocarbyl mercaptomethylphosphono compound having the general formula wherein R is an oil-soluble C hydrocarbyl radical, the R s are selected independently from the group consisting of hydrogen and C 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 C alkyl radical, X is oxygen.
3. The composition of claim 1 wherein R is a C alkyl radical, each R is hydrogen and X is oxygen.
4. The composition of claim 1 wherein R is a C1048 alkyl radical, and X is sulfur.
5. A liquid hydrocarbon composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to impart extreme pressure properties to the hydrocarbon liquid and gel it to a grease structure, of a polyvalent metal salt of C alkylmercaptomethylphosphonic acid.
6. A liquid hydrocarbon composition comprising a major amount of a liquid hydrocarbon and a minor amount, suificient to impart extreme pressure properties to the liquid hydrocarbon and gel it to a grease structure, of a polyvalent metal salt of a monoestcr of C1048 alkylmercaptomethylphosphonic acid.
7. A liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to increase the viscosity of the fuel, of a polyvalent metal salt of C1048 alkylmercaptomethylphosphonic acid.
8. A liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to thicken the fuel to a solid, of a basic polyvalent metal salt of decylmercaptomethylphosphonic acid, the metal portion of the salt being selected from the group consisting of Zn, Cd, Fe and Al.
9. A liquid hydrocarbon fuel composition comprising a major amount of a liquid hydrocarbon and a minor amount, sufficient to thicken the fuel to a solid, of a neutral polyvalent metal salt of decylmercaptomethylphosphonic acid, the metal portion of the salt being selected from the group consisting of Zn, Cd, Fe and A1.
10. A gasoline containing a minor amount, suficient to thicken the gasoline to a solid, of iron salt of decylmercaptornethylphosphonic acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,795,492 Aylesworth et al June 11, 1957 2,838,555 Goldsmith June 10, 1958 2,838,557 Verley June 10, 1953 2,854,468 Max Sept. 30, 1958 2,881,201 Schrader Apr. 7, 1959 2,911,292 Baldeschwieler Nov. 3, 1959 2,947,693 Boyle et al Aug. 2, 1960 2,971,019 Ladd et al Feb. 7, 1961 2,991,244 Pattenden et a1. July 4, 1961 FOREIGN PATENTS 751,755 Great Britain July 4, 1956
Claims (1)
1. A HYDROCARBON LIQUID COMPOSITION COMPRISING A MAJOR AMOUNT OF A LIQUID HYDROCARBON AND A MINOR AMOUNT, SUFFICIENT TO IMPART EXTREME PRESSURE PROPERTIES TO THE LIQUID HYDROCARBON AND GEL IT TO A GREASE STRUCTURE OF AN OIL-SOLUBLE POLYVALENT METAL SALT OF A HYDROCARBYL MERCAPTOMETHYLPHOSPHONO COMPOUND HAVING THE GENERAL FORMULA
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| US7781A US3114710A (en) | 1960-02-10 | 1960-02-10 | Thickened hydrocarbon compositions |
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| US7781A US3114710A (en) | 1960-02-10 | 1960-02-10 | Thickened hydrocarbon compositions |
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| US2991244A (en) * | 1957-12-31 | 1961-07-04 | Exxon Research Engineering Co | Lubricating compositions containing phosphonic acid salts |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3226322A (en) * | 1961-12-28 | 1965-12-28 | Shell Oil Co | Liquid hydrocarbon composition and additives therefor |
| US4396436A (en) * | 1981-07-20 | 1983-08-02 | Aluminum Company Of America | Method and flushing for removing hydraulic fluid from hydraulic systems |
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