US3630897A - Color stabilization of lubricating compositions - Google Patents
Color stabilization of lubricating compositions Download PDFInfo
- Publication number
- US3630897A US3630897A US864210A US3630897DA US3630897A US 3630897 A US3630897 A US 3630897A US 864210 A US864210 A US 864210A US 3630897D A US3630897D A US 3630897DA US 3630897 A US3630897 A US 3630897A
- Authority
- US
- United States
- Prior art keywords
- lubricating
- poly
- lubricating compositions
- phenylene sulfide
- color
- 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
- 230000001050 lubricating effect Effects 0.000 title abstract description 26
- 239000000203 mixture Substances 0.000 title description 53
- 230000006641 stabilisation Effects 0.000 title description 2
- 238000011105 stabilization Methods 0.000 title description 2
- -1 POLY(PHENYLENE SULFIDE) Polymers 0.000 abstract description 40
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003921 oil Substances 0.000 abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 4
- 239000004519 grease Substances 0.000 description 16
- 239000000654 additive Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000010687 lubricating oil Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000012990 dithiocarbamate Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 150000004659 dithiocarbamates Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001462 antimony Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- KFOVCSCTVBPFHX-UHFFFAOYSA-N 1,4-dichloro-2-cyclohexylsulfanylbenzene Chemical compound ClC1=CC=C(Cl)C(SC2CCCCC2)=C1 KFOVCSCTVBPFHX-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- AZAMPMUEKXNYFW-UHFFFAOYSA-N 1-[2-(2-oxopyrrolidin-1-yl)ethyl]pyrrolidin-2-one Chemical compound O=C1CCCN1CCN1C(=O)CCC1 AZAMPMUEKXNYFW-UHFFFAOYSA-N 0.000 description 1
- WRTAZRGRFBCKBU-UHFFFAOYSA-N 2,5-dibromoaniline Chemical compound NC1=CC(Br)=CC=C1Br WRTAZRGRFBCKBU-UHFFFAOYSA-N 0.000 description 1
- NMHJIYQWKWHDSX-UHFFFAOYSA-N 2,5-dichlorobenzamide Chemical compound NC(=O)C1=CC(Cl)=CC=C1Cl NMHJIYQWKWHDSX-UHFFFAOYSA-N 0.000 description 1
- LFXZSGVZSSMCMB-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1Cl LFXZSGVZSSMCMB-UHFFFAOYSA-N 0.000 description 1
- LSEAAPGIZCDEEH-UHFFFAOYSA-N 2,6-dichloropyrazine Chemical compound ClC1=CN=CC(Cl)=N1 LSEAAPGIZCDEEH-UHFFFAOYSA-N 0.000 description 1
- MYCIGSPXIAEGLA-UHFFFAOYSA-N 3,4-dichlorofuran Chemical compound ClC1=COC=C1Cl MYCIGSPXIAEGLA-UHFFFAOYSA-N 0.000 description 1
- BMJOPWQYDZAFDZ-UHFFFAOYSA-N 3,4-difluoro-1h-pyrrole Chemical compound FC1=CNC=C1F BMJOPWQYDZAFDZ-UHFFFAOYSA-N 0.000 description 1
- XTXSYIDBXZXGCG-UHFFFAOYSA-N 4,8-diiodoquinoline Chemical compound C1=CC=C2C(I)=CC=NC2=C1I XTXSYIDBXZXGCG-UHFFFAOYSA-N 0.000 description 1
- ADNGVMQRBXRIJC-UHFFFAOYSA-N 4-bromo-1-(4-bromo-2-methylphenyl)sulfinyl-2-methylbenzene Chemical compound CC1=CC(Br)=CC=C1S(=O)C1=CC=C(Br)C=C1C ADNGVMQRBXRIJC-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDQZPXCKTHKGQM-UHFFFAOYSA-L bis(dipentylcarbamothioylsulfanyl)lead Chemical compound [Pb+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC KDQZPXCKTHKGQM-UHFFFAOYSA-L 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- 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
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
-
- 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/02—Macromolecular compounds obtained by reactions of monomers 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
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- 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
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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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
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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
- C10N2040/02—Bearings
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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
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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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
- NCSH Metal salts of substituted dithiocarbamic acids are useful in providing improved resistance to coking under severe engine operating conditions, as stabilizers to prevent oxidative thickening of oils and lubricants under extreme pressure conditions, and to provide other improved properties in lubricants. More specifically, these additives are polyvalent metal salts of N-aliphatic hydrocarbon substituted dithiocarbamic acids containing sufficient aliphatic carbon atoms to impart oil solubility to the molecule. These polyvalent metal dithiocarbamates are usually employed in amounts from 0.1 to 5 to percent by weight of a lubricating composition.
- the shelf-life is extended, good color stability is obtained over an indefinite time, and the composition maintains a uniform clean fresh new appearance.
- metal dithiocarbamate additives can be employed in a wide variety of lubricating compositions or formulations.
- Such lubricating compositions range, for example, from motor oils, gear oils, cutting oils, to greases and to specialty lubricants.
- Most lubricating compositions utilize a mineral oil base such as a conventionally refined crude oil lubricating stock having a viscosity in the range of 50 to 1500 SUS at F.
- various synthetic base oils can be used.
- the synthetics include polymerized olefins, copolymers ,of alkylene glycols and oxides, organic esters of polybase organic and inorganic acids, silicone polymers.
- Various metallic soaps are used in the formulations, particularly the grease formulations.
- Additives can include finely divided silica or other ingredients for a variety of purposes.
- the dithiocarbamate salts used as additives can be represented by the formula:
- R groups represent hydrogen or organic groupings, and can be the same or dissimilar.
- Each R group when other than hydrogen should have a minimum of 4 carbon atoms in the group.
- the R groups can be selected from alkyl, aryl, alkylaryl, cycloalkyl, and combinations thereof. Heterocyclic groupings can be utilized, including sulfur, oxygen, phosphorous, and nitrogen, where particular functions are desired. Normally, aliphatic hydrocarbon groups are employed so that each R group is an alkyl group of from 4 to about 20 carbon atoms.
- salts of substituted dithiocarbamic acid mentioned in the literature as additives for lubricating compositions are those of aluminum, antimony, bismuth, cadmium, chromium, cobalt, copper, iron, lead, magnesium, manganese, mercury, nickel, tin, zinc, and others.
- the poly(phenylene sulfide) polymers to color-stabilize and improve the shelf-life of lubricating compositions are employed in a range of from about 0.1 to about 3 weight percent based on the weight of the total lubricating composition. We have found a range of between 0.5 and 1.5 weight percent to be quite effective, and prefer not to use over 1 percent since we find no particular increase in efffectiveness, only a slight increased cost for the final composition.
- Lubricating grease compositions were prepared.
- the grease compositions were of the same formulation with only the additives varied in accordance with the present invention.
- Group 1 samples were a lubricating grease composition containing a lead diamyldithiocarbamate additive as the metal dithiocarbamate in the proportion of 2.5 percent by weight of the composition.
- Group 2 samples were identical to the first group except further containing 1 weight percent of poly(phenylene sulfide) as additional additive.
- Group 3 samples were identical to Group 1 except that 2.5 weight percent antimony dialkyldithiocarbamate was used as the metal dithiocarbamate.
- Group 4 samples were identical to Group 3 except further containing 1 weight percent of poly(phenylene sulfide) as color stabilizer.
- the lubricating composition used in the groups of samples was a mineral oil-based formation incorporating a lithium soap and a polyolefin.
- the mineral oil component had a viscosity of 7085 SUS at 210 F., pour point maximum 5 F., flash point minimum 430 F., fire point minimum of 480 F.
- the soap incorporated was a lithium l2-hydroxy stearate. Soap content was between 6 and 12 weight percent. Polyolefin content was between 5 and 6 weight percent. Nil water content. Original color a light creamy tan. Texture of the grease composition was buttery to medium fiber. The grease corresponded to the Ford body grease specification ESBM1C93A.
- the method includes reacting at least one polyhalo-substituted cyclic compound containing unsat uration between adjacent ring atoms and wherein the halogen atoms are attached to the ring carbon atoms, with an alkali metal sulfide, in a polar organic compound, at an elevated temperature.
- the polar compound selected will substantially disperse both the alkali metal sulfide and the polyhalo-substituted aromatic compound.
- the polyhalo-substituted compounds which can be employed as primary reactants are represented by formulas given in detail in the Edmonds et al. patent.
- the preferred compounds are those which contain not more than 3 halogen atoms, and particularly preferred are the dihalo-substituted compounds.
- polyhalo-substituted compounds are useful including 1,4-dichlorobenzene, 1,4-diiodobenzene, 1,4-difiuorobenzene, 2,5-dibromoaniline, 1,2,4 S-tetrabromobenzene, methyl 2-5-dichlorobenzoate, 2,5-dichlorobenzamide, 2,5-dibromothiophene, ethyl 2,4,5-trichloroacetanilide, 1-cyclohexylthio-2,5-dichlorobenzene 4,4- dibromodiphenyl, 3,4-dichlorofuran, 3,4-difluoropyrrole, 2,5-dichloropyridene, 4,8-diiodoquinoline, p,p'-dichlorodiphenyl ether, 3,3'-dichlorodiphenyl dimethylsilane, di(2-methyl-4-bromoph
- Alkali metal sulfides useful in the process include the monosulfides of sodium, potassium, lithium, rubidium and cesium.
- a particularly preferred reactant is sodium sulfide. Either anhydrous or hydrated forms of the sulfides are useful.
- Polar organic compounds useful as solvents and dispersants include amides, lactams, sulfones, and the like- Examples include hexamethylphosphoramide, tetramethyl urea, N,N'-ethylenedipyrrolidone N-metl1yl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactm, sulfolane, dimethylacetamide, low molecular weight polyamides, and the like.
- Preparation of the poly(phenylene sulfide) polymers by this process is carried out by contacting reactants in a polar solvent at a temperature of from about 125 to 550 C., preferably from about 300 to 500 C.
- the mole ratio of polyhalo-substituted aromatic or heterocyclic compound to alkali metal sulfide should be at least 0.121 and will generally not exceed 2.0: 1.
- the amount of polar organic solvent or dispersant present in the reaction zone can vary widely from about to 2500 milliliters of alkali metal sulfide.
- lubricants and lubricating compositions stabilized according to our invention can be prepared by methods known to the art for formulating oils, greases, and the like.
- base oils and other ingredients including our stabilizing additive poly(phenylene sulfide) are brought together in a mixing or blending vessel.
- the solid ingredients should be in a state of finely divided subdivision.
- the mixture is heated with constant agitation and blended at temperatures ranging from about ambient to 500 F. for a sufficient time to obtain maximum homogeneity.
- the blended formulation then is cooled to room temperature. If desired, the blended compositions can be packaged while in a more fluid condition due to the elevated blending temperatures and then cooled to room temperature.
- poly(phenylene sulfide) additive can be added by blending or stirring into an already compounded formulation, heated, if necessary, to a suitably convenient blending temperature depending on the formulation consistency.
- Poly(phenylene sulfide) is quite heatstable to well above 500 F., so is readily blended within the suggested range without decomposition.
- An improved color stabilized lubricating oil or grease composition containing from 0.1 to 10 weight percent of an antimony salt of a dithiocarbamic acid having the formula:
- each R is hydrogen or alkyl, aryl, alkylaryl, cycloalkyl, or combination thereof, and where other than hydrogen contains from 4 to 20 carbon atoms, said antimony salt tending to severely discolor said lubricating oil or grease composition, and from 0.01 to 3 weight percent of poly(phenylene sulfide) substantially stabilizing the original color of said lubricating oil or grease composition.
- said polyhalogenated compound is a dihalo-substituted ring compound wherein the halogen atoms thereof are selected from at least one of fluorine chlorine, bromine, and iodine, and are attached to ring carbon atoms; the said alkali metal sulfide is selected from sulfides of lithium, sodium, potassium, and rubidium; the said polar organic compound is a compound that will substantially disperse both the said polyhalogenated compound and the said alkali metal sulfide and is selected from amides, lactams, sulfones, and mixtures thereof.
- dihalo-substituted ring compound is selected from p-dichlorobenzene, 4,4'-dibromodipheny1, 2,5-dibromothiophene, 4,4'-bis'p-bromophenyl ether, and 2,5-dich1orobenzene sulfonic acid;
- the said polar organic compound is selected from at least one of hexamethylphosphoramide, tetramethylurea N,N'-ethylenedipyrrolidorie, N-methyl-Z- pyrrolidone, pyrrolidone, caprolactam, N-ethyl caprolactam, sulfolane, dimethylacetamide, and mixtures thereof.
- the improved color stabilized lubricating oil or grease composition according to claim 5 containing from 0.5 to 1.5 weight percent of said poly(phenylene sulfide).
- composition is a mineral oil based formulation incorporating a lithium soap and a polyolefin, wherein the,
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Abstract
THE DARKENING AND DISCOLORATION OF LUBRICATING GREASES AND OILS INDUCED BY THE USE OF METAL SALTS OF SUBSTITUTED DITHIOCARBAMIC ACID ARE EFFECTIVELY PREVENTED BY THE INCLUSION OF SMALL AMOUNTS OF POLY(PHENYLENE SULFIDE) IN THE LUBRICATING COMPOSITON.
Description
United States Patent 3,630,897 COLQR STABILIZATION 0F LUBRICATING COMPOSITIONS Raymond Rohde and Andrew E. Skeen, Bartlesville, Okla, assignors to Phillips Petroleum Company No Drawing. Filed Oct. 6, 1969, Ser. No. 864,210 Int. Cl. 010m 1/32, 1/38 U.S. Cl. 25233.6 7 Claims ABSTRACT OF THE DISCLOSURE The darkening and discoloration of lubricating greases and oils induced by the use of metal salts of substituted dithiocarbamic acid are effectively prevented by the inclusion of small amounts of poly(phenylene sulfide) in the lubricating composition.
3 H NCSH Metal salts of substituted dithiocarbamic acids are useful in providing improved resistance to coking under severe engine operating conditions, as stabilizers to prevent oxidative thickening of oils and lubricants under extreme pressure conditions, and to provide other improved properties in lubricants. More specifically, these additives are polyvalent metal salts of N-aliphatic hydrocarbon substituted dithiocarbamic acids containing sufficient aliphatic carbon atoms to impart oil solubility to the molecule. These polyvalent metal dithiocarbamates are usually employed in amounts from 0.1 to 5 to percent by weight of a lubricating composition.
Unfortunately, 'with the good effects have come side effects. Most freshly formulated lubricating compositions have a light clean-looking color, a creamy appearance, which greatly improves appearance and saleability of the formulations. Lubricating compositions containing these salts, however, have shown a tendency to darken severely and quickly.
Darkening of these formulations in many instances is erroneously attributed by the consumer to old or aged materials, or, in some instances, to use of recovered or reclaimed ingredients. Further, variations between the color-appearance of separate packages is observed, even though similarly compounded and of equal quality. These factors reduce commercial acceptance of the formulations.
We have discovered that this discoloration of lubricating compositions containing metal salts of substituted dithiocarbamic acid can be effectively avoided by including minor amounts of poly(phenylene sulfide) in the formulation.
More specifically, by including small amounts of poly- (phenylene sulfide) in the lubricating composition, the shelf-life is extended, good color stability is obtained over an indefinite time, and the composition maintains a uniform clean fresh new appearance.
Therefore, it is an object of our invention to improve the shelf-life and color stability of lubricating compositions.
3,630,897 Patented Dec. 28, 1971 'ice It is a further object of our invention to prevent the agedarkening of lubricating compositions due to metal dithiocarbarnate additives in the composition.
These metal dithiocarbamate additives, and hence our color stabilizer poly(phenylene sulfide), can be employed in a wide variety of lubricating compositions or formulations. Such lubricating compositions range, for example, from motor oils, gear oils, cutting oils, to greases and to specialty lubricants. Most lubricating compositions utilize a mineral oil base such as a conventionally refined crude oil lubricating stock having a viscosity in the range of 50 to 1500 SUS at F. In addition to such natural base oils, various synthetic base oils can be used. The synthetics include polymerized olefins, copolymers ,of alkylene glycols and oxides, organic esters of polybase organic and inorganic acids, silicone polymers. Various metallic soaps are used in the formulations, particularly the grease formulations. Additives can include finely divided silica or other ingredients for a variety of purposes.
The dithiocarbamate salts used as additives can be represented by the formula:
in which the R groups represent hydrogen or organic groupings, and can be the same or dissimilar. Each R group, when other than hydrogen should have a minimum of 4 carbon atoms in the group. The R groups can be selected from alkyl, aryl, alkylaryl, cycloalkyl, and combinations thereof. Heterocyclic groupings can be utilized, including sulfur, oxygen, phosphorous, and nitrogen, where particular functions are desired. Normally, aliphatic hydrocarbon groups are employed so that each R group is an alkyl group of from 4 to about 20 carbon atoms.
Among the salts of substituted dithiocarbamic acid mentioned in the literature as additives for lubricating compositions are those of aluminum, antimony, bismuth, cadmium, chromium, cobalt, copper, iron, lead, magnesium, manganese, mercury, nickel, tin, zinc, and others.
The poly(phenylene sulfide) polymers to color-stabilize and improve the shelf-life of lubricating compositions are employed in a range of from about 0.1 to about 3 weight percent based on the weight of the total lubricating composition. We have found a range of between 0.5 and 1.5 weight percent to be quite effective, and prefer not to use over 1 percent since we find no particular increase in efffectiveness, only a slight increased cost for the final composition.
The following examples demonstrate the effectiveness of our invention, and should be considered as illustrative and not as delimiting.
EXAMPLE I Lubricating grease compositions were prepared. The grease compositions were of the same formulation with only the additives varied in accordance with the present invention.
Group 1 samples were a lubricating grease composition containing a lead diamyldithiocarbamate additive as the metal dithiocarbamate in the proportion of 2.5 percent by weight of the composition.
Group 2 samples were identical to the first group except further containing 1 weight percent of poly(phenylene sulfide) as additional additive.
Group 3 samples were identical to Group 1 except that 2.5 weight percent antimony dialkyldithiocarbamate was used as the metal dithiocarbamate.
Group 4 samples were identical to Group 3 except further containing 1 weight percent of poly(phenylene sulfide) as color stabilizer.
Both groups of samples not containing our additive, i.e., Groups 1 and 3, darkened in less than a month. Group 1 samples turned black or near-black in less than a thirty day interval. Group 3 samples turned a dark unpleasant red.
In distinction, Groups 2 and 4 containing our color stabilizer, poly(phenylene sulfide) as per our invention, all stayed clear and fresh with a bright new creamy appearance for two years and two months without color deterioration. The test was ended at that time as there was no observable deterioration of color over a very long and conclusive interval.
The lubricating composition used in the groups of samples was a mineral oil-based formation incorporating a lithium soap and a polyolefin. The mineral oil component had a viscosity of 7085 SUS at 210 F., pour point maximum 5 F., flash point minimum 430 F., fire point minimum of 480 F. The soap incorporated was a lithium l2-hydroxy stearate. Soap content was between 6 and 12 weight percent. Polyolefin content was between 5 and 6 weight percent. Nil water content. Original color a light creamy tan. Texture of the grease composition was buttery to medium fiber. The grease corresponded to the Ford body grease specification ESBM1C93A.
While other methods of producing poly(phenylene sulfide) may be used the method described in the hereinbefore referenced U.S. Letters Pat. 3,354,129 is particularly useful. The method includes reacting at least one polyhalo-substituted cyclic compound containing unsat uration between adjacent ring atoms and wherein the halogen atoms are attached to the ring carbon atoms, with an alkali metal sulfide, in a polar organic compound, at an elevated temperature. The polar compound selected will substantially disperse both the alkali metal sulfide and the polyhalo-substituted aromatic compound.
The polyhalo-substituted compounds which can be employed as primary reactants are represented by formulas given in detail in the Edmonds et al. patent. The preferred compounds are those which contain not more than 3 halogen atoms, and particularly preferred are the dihalo-substituted compounds.
A wide variety of polyhalo-substituted compounds are useful including 1,4-dichlorobenzene, 1,4-diiodobenzene, 1,4-difiuorobenzene, 2,5-dibromoaniline, 1,2,4 S-tetrabromobenzene, methyl 2-5-dichlorobenzoate, 2,5-dichlorobenzamide, 2,5-dibromothiophene, ethyl 2,4,5-trichloroacetanilide, 1-cyclohexylthio-2,5-dichlorobenzene 4,4- dibromodiphenyl, 3,4-dichlorofuran, 3,4-difluoropyrrole, 2,5-dichloropyridene, 4,8-diiodoquinoline, p,p'-dichlorodiphenyl ether, 3,3'-dichlorodiphenyl dimethylsilane, di(2-methyl-4-bromophenyl) sulfoxide, methyl di(3-ethyl- 4-chlorophenyl) phosphite 4-bromophenyl 3-n-butyl 4-chlorophenyl sulfone, 2,5-dichlorobenzene sulfonic acid, 2,6-dichloropyrazine, 4,4-bis-p-bromophenyl ether, and others as shown in the aforementioned Edmonds patent.
Alkali metal sulfides useful in the process include the monosulfides of sodium, potassium, lithium, rubidium and cesium. A particularly preferred reactant is sodium sulfide. Either anhydrous or hydrated forms of the sulfides are useful.
Polar organic compounds useful as solvents and dispersants include amides, lactams, sulfones, and the like- Examples include hexamethylphosphoramide, tetramethyl urea, N,N'-ethylenedipyrrolidone N-metl1yl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactm, sulfolane, dimethylacetamide, low molecular weight polyamides, and the like.
Preparation of the poly(phenylene sulfide) polymers by this process is carried out by contacting reactants in a polar solvent at a temperature of from about 125 to 550 C., preferably from about 300 to 500 C. The mole ratio of polyhalo-substituted aromatic or heterocyclic compound to alkali metal sulfide should be at least 0.121 and will generally not exceed 2.0: 1. The amount of polar organic solvent or dispersant present in the reaction zone can vary widely from about to 2500 milliliters of alkali metal sulfide.
The lubricants and lubricating compositions stabilized according to our invention can be prepared by methods known to the art for formulating oils, greases, and the like.
For example, base oils and other ingredients, including our stabilizing additive poly(phenylene sulfide) are brought together in a mixing or blending vessel. For maximum mixing convenience and subsequent lubricating properties, the solid ingredients should be in a state of finely divided subdivision. The mixture is heated with constant agitation and blended at temperatures ranging from about ambient to 500 F. for a sufficient time to obtain maximum homogeneity. The blended formulation then is cooled to room temperature. If desired, the blended compositions can be packaged while in a more fluid condition due to the elevated blending temperatures and then cooled to room temperature.
Alternatively the poly(phenylene sulfide) additive can be added by blending or stirring into an already compounded formulation, heated, if necessary, to a suitably convenient blending temperature depending on the formulation consistency. Poly(phenylene sulfide) is quite heatstable to well above 500 F., so is readily blended within the suggested range without decomposition.
Our examples and discussions have pointed out a serious problem involved in the use of substituted metal dithiocarbamates in lubricating compositions, and have clearly disclosed that our invention is the solution. The use of poly(phenylene sulfide) polymers eliminates the discoloration problem.
Reasonable variations and modifications of our invention are possible within the scope of our disclosure without departing from the scope and spirit thereof as disclosed in the specification and claims.
We claim:
1. An improved color stabilized lubricating oil or grease composition containing from 0.1 to 10 weight percent of an antimony salt of a dithiocarbamic acid having the formula:
wherein each R is hydrogen or alkyl, aryl, alkylaryl, cycloalkyl, or combination thereof, and where other than hydrogen contains from 4 to 20 carbon atoms, said antimony salt tending to severely discolor said lubricating oil or grease composition, and from 0.01 to 3 weight percent of poly(phenylene sulfide) substantially stabilizing the original color of said lubricating oil or grease composition.
2.. The improved color stabilized lubricating oil or grease composition according to claim 1 wherein said poly(phenylene sulfide) has been prepared by reacting under polymerization conditions at least one polyhalosubstituted cyclic compound containing unsaturation between adjacent ring atoms and wherein the halogen atoms thereof are attached to ring carbon atoms with an alkali metal sulfide in the presence of a polar organic compound capable of substantially dispersing both said polyhalosubstituted aromatic compound and said alkali metal sulfide, at an elevated temperature.
3. The improved color stabilized lubricating oil or grease composition according to claim 2 wherein said polymerization conditions include a reaction time of from 200 to 1600 minutes, a temperature of from to 550 F., a mole ratio of said polyhalogenated ring compound to said alkali metal sulfide of from 0.1:1 to 2:1, and from 100 to 2500 ml. of said polar organic compound per mole of said alkali metal sulfide.
4. The improved color stabilized lubricating oil or grease composition according to claim 3 wherein said polyhalogenated compound is a dihalo-substituted ring compound wherein the halogen atoms thereof are selected from at least one of fluorine chlorine, bromine, and iodine, and are attached to ring carbon atoms; the said alkali metal sulfide is selected from sulfides of lithium, sodium, potassium, and rubidium; the said polar organic compound is a compound that will substantially disperse both the said polyhalogenated compound and the said alkali metal sulfide and is selected from amides, lactams, sulfones, and mixtures thereof.
5. The improved color stabilized lubricating oil or grease composition according to claim 4 wherein said dihalo-substituted ring compound is selected from p-dichlorobenzene, 4,4'-dibromodipheny1, 2,5-dibromothiophene, 4,4'-bis'p-bromophenyl ether, and 2,5-dich1orobenzene sulfonic acid; the said polar organic compound is selected from at least one of hexamethylphosphoramide, tetramethylurea N,N'-ethylenedipyrrolidorie, N-methyl-Z- pyrrolidone, pyrrolidone, caprolactam, N-ethyl caprolactam, sulfolane, dimethylacetamide, and mixtures thereof.
6. The improved color stabilized lubricating oil or grease composition according to claim 5 containing from 0.5 to 1.5 weight percent of said poly(phenylene sulfide).
7. The improved color stabilized lubricating oil or grease composition according to claim 6 wherein said composition is a mineral oil based formulation incorporating a lithium soap and a polyolefin, wherein the,
References Cited UNITED STATES PATENTS 2,825,695 3/1958 Mahoney et a1. 25233.6 3,248,325 4/1966 Graham 252---33.6 3 354,129 11/1967 Edmonds et al. 252-63] X DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US86421069A | 1969-10-06 | 1969-10-06 |
Publications (1)
Publication Number | Publication Date |
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US3630897A true US3630897A (en) | 1971-12-28 |
Family
ID=25342752
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US864210A Expired - Lifetime US3630897A (en) | 1969-10-06 | 1969-10-06 | Color stabilization of lubricating compositions |
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US (1) | US3630897A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3772197A (en) * | 1970-12-04 | 1973-11-13 | Cities Service Oil Co | Lubricating oil composition |
US4226733A (en) * | 1978-11-17 | 1980-10-07 | Mobil Oil Corporation | Lubricant compositions stabilized against ultra-violet degradation |
US4479883A (en) * | 1982-01-06 | 1984-10-30 | Exxon Research & Engineering Co. | Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates |
FR2601686A1 (en) * | 1986-07-17 | 1988-01-22 | Mitsui Toatsu Chemicals | LUBRICANT |
WO1994024100A1 (en) * | 1993-04-20 | 1994-10-27 | Imperial Chemical Industries Plc | Bismuth dithiocarbamates and their use as additive for lubricants |
US5385683A (en) * | 1993-10-05 | 1995-01-31 | Ransom; Louis J. | Anti-friction composition |
US5576273A (en) * | 1995-11-20 | 1996-11-19 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing bismuth compounds |
-
1969
- 1969-10-06 US US864210A patent/US3630897A/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3772197A (en) * | 1970-12-04 | 1973-11-13 | Cities Service Oil Co | Lubricating oil composition |
US4226733A (en) * | 1978-11-17 | 1980-10-07 | Mobil Oil Corporation | Lubricant compositions stabilized against ultra-violet degradation |
US4479883A (en) * | 1982-01-06 | 1984-10-30 | Exxon Research & Engineering Co. | Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates |
FR2601686A1 (en) * | 1986-07-17 | 1988-01-22 | Mitsui Toatsu Chemicals | LUBRICANT |
WO1994024100A1 (en) * | 1993-04-20 | 1994-10-27 | Imperial Chemical Industries Plc | Bismuth dithiocarbamates and their use as additive for lubricants |
US5385683A (en) * | 1993-10-05 | 1995-01-31 | Ransom; Louis J. | Anti-friction composition |
US5576273A (en) * | 1995-11-20 | 1996-11-19 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing bismuth compounds |
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