US3125526A - Lubricating greases containing borate - Google Patents
Lubricating greases containing borate Download PDFInfo
- Publication number
- US3125526A US3125526A US3125526DA US3125526A US 3125526 A US3125526 A US 3125526A US 3125526D A US3125526D A US 3125526DA US 3125526 A US3125526 A US 3125526A
- Authority
- US
- United States
- Prior art keywords
- borate
- grease
- lubricating
- fatty acid
- amine
- 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 Effects 0.000 title claims description 34
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title description 12
- -1 HYDROXY FATTY ACID Chemical class 0.000 claims description 80
- 239000004519 grease Substances 0.000 claims description 50
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 48
- 239000000194 fatty acid Substances 0.000 claims description 48
- 239000000344 soap Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 30
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 28
- 239000010687 lubricating oil Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 description 30
- 150000002430 hydrocarbons Chemical group 0.000 description 28
- 150000001412 amines Chemical class 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 230000000269 nucleophilic Effects 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 16
- 150000004665 fatty acids Chemical class 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 10
- 125000004432 carbon atoms Chemical group C* 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000002480 mineral oil Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- OSWPMRLSEDHDFF-UHFFFAOYSA-N Methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000004429 atoms Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 229940116351 sebacate Drugs 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Chemical group 0.000 description 4
- 239000011593 sulfur Chemical group 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical group NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 2
- 229940067597 Azelate Drugs 0.000 description 2
- HQRYXWLNTDHSLN-UHFFFAOYSA-N B(OC1=C(C(=C(C=C1)C1=C(C(=CC=C1)CCCCCCCCC)CCCCCCCCC)C1=C(C(=CC=C1)CCCCCCCCC)CCCCCCCCC)C(=O)OC)([O-])[O-] Chemical compound B(OC1=C(C(=C(C=C1)C1=C(C(=CC=C1)CCCCCCCCC)CCCCCCCCC)C1=C(C(=CC=C1)CCCCCCCCC)CCCCCCCCC)C(=O)OC)([O-])[O-] HQRYXWLNTDHSLN-UHFFFAOYSA-N 0.000 description 2
- BAMZBMSQKPLAKN-UHFFFAOYSA-N B(OC1=C(C(=C(C=C1)C1=CC=C(C=C1)CCCCCCCCC)C1=CC=C(C=C1)CCCCCCCCC)C(C)=O)([O-])[O-] Chemical compound B(OC1=C(C(=C(C=C1)C1=CC=C(C=C1)CCCCCCCCC)C1=CC=C(C=C1)CCCCCCCCC)C(C)=O)([O-])[O-] BAMZBMSQKPLAKN-UHFFFAOYSA-N 0.000 description 2
- BAGFULRGLVUWPL-UHFFFAOYSA-N B(OC1=C(C(=C(C=C1)CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC)[N+](=O)[O-])([O-])[O-] Chemical compound B(OC1=C(C(=C(C=C1)CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC)[N+](=O)[O-])([O-])[O-] BAGFULRGLVUWPL-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N Dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N Dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- FPLIHVCWSXLMPX-UHFFFAOYSA-M Lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 2
- SFDJOSRHYKHMOK-UHFFFAOYSA-N Nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 2
- UOKZUTXLHRTLFH-UHFFFAOYSA-N O-phenylhydroxylamine Chemical compound NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N Ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 2
- WBHHMMIMDMUBKC-GKUQOKNUSA-N Ricinoleic acid Natural products CCCCCC[C@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-GKUQOKNUSA-N 0.000 description 2
- 125000004416 alkarylalkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000111 anti-oxidant Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-L azelaate(2-) Chemical compound [O-]C(=O)CCCCCCCC([O-])=O BDJRBEYXGGNYIS-UHFFFAOYSA-L 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012612 commercial material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAKYREKCWXBHCW-UHFFFAOYSA-N dipentan-2-yl decanedioate Chemical compound CCCC(C)OC(=O)CCCCCCCCC(=O)OC(C)CCC UAKYREKCWXBHCW-UHFFFAOYSA-N 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecan-1-amine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010685 fatty oil Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N hexadecan-1-amine Chemical group CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- 239000008079 hexane Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000000640 hydroxylating Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229960001047 methyl salicylate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N tetradecan-1-amine Chemical group CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- 238000004450 types of analysis Methods 0.000 description 2
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
-
- 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
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic 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
- C10M2209/11—Complex polyesters
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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
- 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
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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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
- C10M2229/02—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
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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
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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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
- C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
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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
- C10M2229/044—Siloxanes with specific structure containing silicon-to-hydrogen bonds
-
- 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
-
- 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
-
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- This invention relates to lubricating greases and to a novel class of additives therefor. More particularly, it relates to lubricating greases containing intramolecular coordinated borate esters and amine complexes of such esters.
- the intramolecular coordinated borate esters which are employed as grease additives in accordance with this invention are compounds containing 1-3 OR or SR groups attached to a boron atom, where R is an aryl group containing a nucleophilic group in a position ortho to the ester linkage.
- nucleophilic group is meant a group containing an electron donating atom which is capable of undergoing chelation with a metal atom.
- Intramolecular coordination takes place in these compounds with the formation of a five or six membered ring including the boron atom, as shown below for an ester containing an ortho-nitrophenyl group:
- nucleophilic groups include, for example, ester, amide, keto, aldehyde and amino groups.
- hydroxy fatty acid soap thickened greases by employing therein minor amounts of compounds of the above class.
- the amine adducts of the intramolecular coordinated borate esters also impart improved water absorption properties to hydroxy fatty acid soap thickened greases of the types which normally absorb large amounts of water and undergo objectionably high penetration changes as a result of water absorption, such as lithium hydroxy fatty acid soap thickened greases containing sulfurized fatty oils as extreme pressure agents.
- Suitable borate esters for the purpose of this invention are compounds represented by the following formulas:
- R is a hydrocarbon or substituted hydrocarbon group
- R is hydrogen, a hydrocarbon group or substituted hydrocarbon group, at least one group represented by R being an aryl group containing an ortho positioned nucleophilic group as described above
- X is oxygen or sulfur
- n is a whole number from 0 to 2, inclusive
- m is a whole number from 1 to 3, inclusive
- the sum of n and m being 3
- n is a whole number from 0 to 3, inclusive
- m is a Whole number from 1 to 4, inclusive
- the sum of n and m is 4.
- Hydrocarbon groups represented by R and R include alkyl, aryl, alkaryl and aralkyl groups, and substituted derivatives thereof containing substituents such as hydroxy, alkoxy, phenoxy, amine, nitro groups, etc. and halogens.
- the preferred compounds are those wherein n and n equal zero, In being 3 and m being 4, and wherein all of the groups represented by R are hydrocarbon or substituted hydrocarbon groups, preferably containing at least 3 carbon atoms.
- the intramolecular coordinated borate esters are obtained by the conventional methods of preparing borate esters, such as by esterifying boric acid with alcohols, at least one of which is a hydroxy aryl compound having an ortho positioned nucleophilic substituent group.
- the compounds are conveniently obtained by reacting a boric acid diester with a hydroxy aryl compound of this character.
- suitable intramolecular coordinated borate esters include the following: di-isopropyl-monoomitrophenyl borate; di-stearyl-mono-o-nitrophenyl borate; dip-tert.-butylphenyl-monoo-carbomethoxy-phenyl borate; di-thiobutyl-monoo-nitro-thiophenyl borate; di-p-chloro phenyl-monoo-formylphenyl borate; di-(p-nonylphenyl)- mono-o-acetylphenyl borate; di- (2,4-dichlorophenyD- mono-o-carbomethoxyphenyl borate; di-p-cresyl-monooaminophenyl borate; di-sec.-butyl mono (2,4 dinitrophenyl) borate; tri-o-nitrophenyl borate; tri-o-nitro-thiophenyl borate; and mono
- the amine complexes of the above borate esters which are also employed in accordance with this invention are reaction products of the borate esters with aliphatic amines, including primary, secondary and tertiary monoamines containing at least six carbon atoms per molecule and diamines.
- suitable amines include dodecyl amine, tertiary tetradecyl amine, tertiary undecyl 3 amine, secondary dibutyl amine, hexadecylamine, ethylene diamine, hexane diamine, etc.
- the preferred compounds are monoamines containing from about 8 to about 26 aliphatic carbon atoms per molecule, particularly preferred compounds being primary amines wherein the alkyl group is a tertiary alkyl group.
- the complex may be prepared by merely mixing together the borate ester and amine at room temperature or at moderately increased temperatures in the presence or absence of a solvent. It may also be carried out by reacting together boric acid and alcohols, including a hydroxy aryl compound containing an ortho positioned nucleophilic group, together with the amine in an organic solvent such as benzene, toluene, etc. The borate ester and amine are usually reacted in a 1:1 mol ratio. However, complexes containing reduced amounts of amine, such as borate ester-amine mol ratios of 2:1 to 1021 may be employed in some cases, particularly where there are severe copper anti-corrosiveness requirements.
- the lubricating greases to which this invention relate are those containing metal soaps of high molecular weight hydroxy fatty acids in sufiicient proportions to provide at least a substantial thickening effect.
- the metal component may be any metal which is suitable for forming soaps employed as thickening agents in lubricating greases generally, including sodium, potassium, lithium, calcium, barium, strontium, aluminum, manganese, zinc, etc.
- the alkali metals and alkaline earth metals comprise a preferred class of metals for this purpose.
- the hydroxy fatty acid soap will usually be present in the composition in amounts from about 3 to about 15 percent by weight, although somewhat smaller or larger amounts are also suitable, such as amounts as low as about 2 percent by weight and as high as about 30 percent by weight of the composition.
- borate ester compounds are ordinarily employed in these lubricating greases in amounts in about the range 01-10 percent by weight, although somewhat larger or smaller amounts may be employed if desired. They are most suitably employed in amounts in about the range 0.55 percent by weight of the grease composition.
- Suitable soap forming acid materials which may be employed in the production of these greases include hydroxy fatty acids containing from about 12 to about 24 carbon atoms per molecule and one or more hydroxy groups separated from the carboxylic group by at least one carbon atom, and the glycerides and other esters of such acids.
- the preferred acids are substantially saturated acids containing from about 16 to about 22 carbon atoms and one or two hydroxy groups per molecule.
- Such materials may be obtained from naturally occurring glycerides, by hydroxylation of fatty acids, by hydrogenation of ricinoleic acid or castor oil, or otherwise by processes such as the catalytic oxidation of hydrocarbon oils and waxes which have been extracted and fractionated to the desired molecular range. Mixtures of lrydroxy acids together with unsubstituted fatty acids may be very suitably employed, wherein the hydroxy fatty acid comprises at least about one third of the fatty acid mixture.
- Lubricating oils employed in the greases include conventional mineral oils and synthetic coils, such as high molecular weight ethers, esters, silicones, etc.
- Suitable mineral oils include both parafiinic and naphthenic oils and blends thereof, having viseosities in the range from about 80 seconds Saybolt Universal at 100 F. to about 225 seconds Saybolt Universal at 210 F.
- a particularly suitable class of synthetic lubricating oils comprises synthetic dicarboxylic acid esters, such as di-2-ethylhexyl sebacate, (di-secondary amyl) sebacate, di-Z-ethylhcxyl azelate, etc.
- silicone polymers including dia kyl silicone polymers such as dimethyl silicone polymer, diethyl silicone polymer, and mixed aryl-alkyl silicone polymers such as phenyl methyl silicone polymer, having viscosities in the lubricating oil viscosity range.
- the grease preparation may be carried out in any suitable manner.
- the borate ester compound may be added either during the greater preparation or it may be incorporated into the preformed grease by heating a mixture of the grease and borate ester compound at about 150 F. with stirring, preferably followed by milling. It is conveniently added during the grease preparation when the mixture has cooled to about 200 F.
- the lubricating greases of this invention may also contain other additives of various types such as are commonly employed in lubricating greases, such as extreme pressure agents, anti-corrosives, anti-oxidants, etc., as Well as other thickening agents, such as conventional fatty acid soaps and finely divided solids having grease forming properties.
- lubricating greases comprising a preferred embodiment of this invention
- various intramolecular coordinated borate esters were added to a lithium hydroxy fatty acid soap thickened grease in amounts suflicient to give 1-10 precent by weight of the borate ester in the finished grease.
- the base grease consisted of a lubricating oil comprising 2-ethy1hexyl sebacats and a highly refined paratiinic distillate oil, having a Saybolt Universal viscosity of about seconds at 100 F, in a 3:1 ratio by weight, respectively, thickened to a grease consistency with 6.0 percent of lithium 12-hydroxystearate.
- the method comprised essentially heating the saponification mixture to 190 F. during about 35 minutes to allow for completion of the saponification, and thereafter heating the mixture to 400 F. while adding the major portion of the Z-ethylhexyl sebacate and circulating the mixture through a shear valve at 75 pounds pressure drop while the mixture was maintained at 400 F. The mixture was then cooled to 200 F. during about 2 /2 hours while additional amounts of mineral oil and Z-ethylhexyl sebacate were added. The grease was finally drawn and finished by milling in a Premier colloid mill. The borate ester compounds were incorporated into the base grease thus obtained by heating a mixture of the grease and borate ester compounds in suitable proportions at F. for 30 minutes with stirring.
- the borate ester compounds employed in these compositions were prepared by the method comprising treating a boric acid diester with a phenol containing an ortho positioned nucleophilic group. Following is a detailed description of the preparation of di-(dinonylphenyl)- mono-o-carbomethoxyphenyl borate: 61.8 grams of boric acid (1.0 mol), 694.0 grams of dinonylphenol (2.0 mols) and 250 ml. of xylene were charged to a 2 liter 3 necked flask equipped with a stirrer, condenser and distilling receiver, and the solution refluxed for 2.9 hours until 43 ml. of Water had been collected.
- Amine adducts or association complexes of these borate esters were prepared by adding an amine slowly to the ester in an inert solvent, employing equimolar proportions of the amine and borate ester.
- the amine employed for forming these complexes was a commercial material sold by Rohm & Haas under the trade name of Primene 81-R consisting of tertiary alkayl primary amines in the range from C H NH to C H NH
- Table I below shows representative results obtained by employing various intramolecular coordinated borate esters in a 3 percent concentration upon the dropping point and oxidation resistance of the lithium hydroxy fatty acid soap thickened grease.
- a lubricating grease consisting essentially of a lubrieating oil thickened to a grease consistency by a metal hydroxy fatty acid soap and containing about 0.1-10 percent by weight of a compound selected from the class consisting of intramolecular coordinated borate esters represented by the formulas:
- R is selected from the class consisting of hydrocarbon groups and substituted hydrocarbon groups
- R is selected from the class consisting of hydrogen, hydrocarbon groups and substituted hydrocarbon groups, at least one group represented by R being an aryl group containing an ortho positioned nucleophilic group
- X is selected from the class consisting of oxygen and sulfur
- n is a whole number from 0 to 2, inclusive
- m is a whole number from 1 to 3, inclusive
- the sum of n and m being 3
- n is a whole number from 0 to 3, inclusive
- m is a whole number from 1 to 4, inclusive
- the sum of n and m is 4.
- a lubricating grease according to claim 1 wherein the said nucleophilic group is chosen from the class consisting of nitro, amine, ketone, aldehyde and amide groups.
Description
United States Patent LUBRICATIN G GREASES CONTAINING BORATE ESTER COMPOUNDS William R. Siegart, Wappingers Falls, and Clemence J. Henry, Newburgh, N.Y., assignors to Texaco Inc., New
York, N.Y., a corporation of Delaware No Drawing. Filed Jan. 17, 1961, Ser. No. 83,186
, 7 Claims. (Cl. 252-403) This invention relates to lubricating greases and to a novel class of additives therefor. More particularly, it relates to lubricating greases containing intramolecular coordinated borate esters and amine complexes of such esters.
The intramolecular coordinated borate esters which are employed as grease additives in accordance with this invention are compounds containing 1-3 OR or SR groups attached to a boron atom, where R is an aryl group containing a nucleophilic group in a position ortho to the ester linkage. By nucleophilic group is meant a group containing an electron donating atom which is capable of undergoing chelation with a metal atom. Intramolecular coordination takes place in these compounds with the formation of a five or six membered ring including the boron atom, as shown below for an ester containing an ortho-nitrophenyl group:
Other such nucleophilic groups include, for example, ester, amide, keto, aldehyde and amino groups.
We have found, in accordance with the present invention, that increased dropping points and other advantages, including improved oxidation resistance, are obtained in hydroxy fatty acid soap thickened greases by employing therein minor amounts of compounds of the above class. In addition to these advantages, the amine adducts of the intramolecular coordinated borate esters also impart improved water absorption properties to hydroxy fatty acid soap thickened greases of the types which normally absorb large amounts of water and undergo objectionably high penetration changes as a result of water absorption, such as lithium hydroxy fatty acid soap thickened greases containing sulfurized fatty oils as extreme pressure agents.
It is not intended to imply that all of the compounds of this class improve the properties of hydroxy fatty acid soap thickened greases in exactly the same manner or to the same extent, since their properties in hydroxy fatty Patented Mar. 17, 1964 hydroxy fatty acid soap thickened greases were entirely unexpected on the basis of the experience with these compounds employed in conventional fatty acid soap thickened greases, wherein no advantages were obtained. While we do not intend to be limited by any particular theory, it appears on the basis of infrared analyses and other evidence that a stable coordinated compound is formed by electron sharing between the boron atom of the borate ester compound and the hydroxy group of the hydroxy fatty acid soap, which accounts for the diiference in the effect of the borate ester compounds in hydroxy fatty acid soap thickened greases and in conventional fatty acid soap thickened greases.
Suitable borate esters for the purpose of this invention are compounds represented by the following formulas:
where R is a hydrocarbon or substituted hydrocarbon group, R is hydrogen, a hydrocarbon group or substituted hydrocarbon group, at least one group represented by R being an aryl group containing an ortho positioned nucleophilic group as described above, X is oxygen or sulfur, n is a whole number from 0 to 2, inclusive, m is a whole number from 1 to 3, inclusive, the sum of n and m being 3, n is a whole number from 0 to 3, inclusive, m is a Whole number from 1 to 4, inclusive, and the sum of n and m is 4. Hydrocarbon groups represented by R and R include alkyl, aryl, alkaryl and aralkyl groups, and substituted derivatives thereof containing substituents such as hydroxy, alkoxy, phenoxy, amine, nitro groups, etc. and halogens. The preferred compounds are those wherein n and n equal zero, In being 3 and m being 4, and wherein all of the groups represented by R are hydrocarbon or substituted hydrocarbon groups, preferably containing at least 3 carbon atoms.
The intramolecular coordinated borate esters are obtained by the conventional methods of preparing borate esters, such as by esterifying boric acid with alcohols, at least one of which is a hydroxy aryl compound having an ortho positioned nucleophilic substituent group. The compounds are conveniently obtained by reacting a boric acid diester with a hydroxy aryl compound of this character.
Examples of suitable intramolecular coordinated borate esters include the following: di-isopropyl-monoomitrophenyl borate; di-stearyl-mono-o-nitrophenyl borate; dip-tert.-butylphenyl-monoo-carbomethoxy-phenyl borate; di-thiobutyl-monoo-nitro-thiophenyl borate; di-p-chloro phenyl-monoo-formylphenyl borate; di-(p-nonylphenyl)- mono-o-acetylphenyl borate; di- (2,4-dichlorophenyD- mono-o-carbomethoxyphenyl borate; di-p-cresyl-monooaminophenyl borate; di-sec.-butyl mono (2,4 dinitrophenyl) borate; tri-o-nitrophenyl borate; tri-o-nitro-thiophenyl borate; and mono-phenyl-di-o-carbomethoxyphenyl borate.
The amine complexes of the above borate esters which are also employed in accordance with this invention are reaction products of the borate esters with aliphatic amines, including primary, secondary and tertiary monoamines containing at least six carbon atoms per molecule and diamines. Examples of suitable amines include dodecyl amine, tertiary tetradecyl amine, tertiary undecyl 3 amine, secondary dibutyl amine, hexadecylamine, ethylene diamine, hexane diamine, etc. The preferred compounds are monoamines containing from about 8 to about 26 aliphatic carbon atoms per molecule, particularly preferred compounds being primary amines wherein the alkyl group is a tertiary alkyl group.
Formation of the borate ester-amine complexes takes place readily over a wide range of conditions. The complex may be prepared by merely mixing together the borate ester and amine at room temperature or at moderately increased temperatures in the presence or absence of a solvent. It may also be carried out by reacting together boric acid and alcohols, including a hydroxy aryl compound containing an ortho positioned nucleophilic group, together with the amine in an organic solvent such as benzene, toluene, etc. The borate ester and amine are usually reacted in a 1:1 mol ratio. However, complexes containing reduced amounts of amine, such as borate ester-amine mol ratios of 2:1 to 1021 may be employed in some cases, particularly where there are severe copper anti-corrosiveness requirements.
The lubricating greases to which this invention relate are those containing metal soaps of high molecular weight hydroxy fatty acids in sufiicient proportions to provide at least a substantial thickening effect. The metal component may be any metal which is suitable for forming soaps employed as thickening agents in lubricating greases generally, including sodium, potassium, lithium, calcium, barium, strontium, aluminum, manganese, zinc, etc. The alkali metals and alkaline earth metals comprise a preferred class of metals for this purpose. The hydroxy fatty acid soap will usually be present in the composition in amounts from about 3 to about 15 percent by weight, although somewhat smaller or larger amounts are also suitable, such as amounts as low as about 2 percent by weight and as high as about 30 percent by weight of the composition.
The borate ester compounds are ordinarily employed in these lubricating greases in amounts in about the range 01-10 percent by weight, although somewhat larger or smaller amounts may be employed if desired. They are most suitably employed in amounts in about the range 0.55 percent by weight of the grease composition.
Suitable soap forming acid materials which may be employed in the production of these greases include hydroxy fatty acids containing from about 12 to about 24 carbon atoms per molecule and one or more hydroxy groups separated from the carboxylic group by at least one carbon atom, and the glycerides and other esters of such acids. The preferred acids are substantially saturated acids containing from about 16 to about 22 carbon atoms and one or two hydroxy groups per molecule. Such materials may be obtained from naturally occurring glycerides, by hydroxylation of fatty acids, by hydrogenation of ricinoleic acid or castor oil, or otherwise by processes such as the catalytic oxidation of hydrocarbon oils and waxes which have been extracted and fractionated to the desired molecular range. Mixtures of lrydroxy acids together with unsubstituted fatty acids may be very suitably employed, wherein the hydroxy fatty acid comprises at least about one third of the fatty acid mixture.
Lubricating oils employed in the greases include conventional mineral oils and synthetic coils, such as high molecular weight ethers, esters, silicones, etc. Suitable mineral oils include both parafiinic and naphthenic oils and blends thereof, having viseosities in the range from about 80 seconds Saybolt Universal at 100 F. to about 225 seconds Saybolt Universal at 210 F. A particularly suitable class of synthetic lubricating oils comprises synthetic dicarboxylic acid esters, such as di-2-ethylhexyl sebacate, (di-secondary amyl) sebacate, di-Z-ethylhcxyl azelate, etc. and polymers obtained by condensing dicarboxylic acids with glycols as disclosed in U.S. 2,628,974, as well as the sulfur analogs of such esters. Other synthetic oils which may be employed in accordance with this invention include the silicone polymers, including dia kyl silicone polymers such as dimethyl silicone polymer, diethyl silicone polymer, and mixed aryl-alkyl silicone polymers such as phenyl methyl silicone polymer, having viscosities in the lubricating oil viscosity range.
The grease preparation may be carried out in any suitable manner. The borate ester compound may be added either during the greater preparation or it may be incorporated into the preformed grease by heating a mixture of the grease and borate ester compound at about 150 F. with stirring, preferably followed by milling. It is conveniently added during the grease preparation when the mixture has cooled to about 200 F.
The lubricating greases of this invention may also contain other additives of various types such as are commonly employed in lubricating greases, such as extreme pressure agents, anti-corrosives, anti-oxidants, etc., as Well as other thickening agents, such as conventional fatty acid soaps and finely divided solids having grease forming properties.
As an example of the lubricating greases comprising a preferred embodiment of this invention, various intramolecular coordinated borate esters were added to a lithium hydroxy fatty acid soap thickened grease in amounts suflicient to give 1-10 precent by weight of the borate ester in the finished grease. The base grease consisted of a lubricating oil comprising 2-ethy1hexyl sebacats and a highly refined paratiinic distillate oil, having a Saybolt Universal viscosity of about seconds at 100 F, in a 3:1 ratio by weight, respectively, thickened to a grease consistency with 6.0 percent of lithium 12-hydroxystearate. It was prepared by saponifying I-Iydrofol acids .200 with a slight excess of lithium hydroxide in the presence of a major proportion of the mineral oil contained in the grease. The method comprised essentially heating the saponification mixture to 190 F. during about 35 minutes to allow for completion of the saponification, and thereafter heating the mixture to 400 F. while adding the major portion of the Z-ethylhexyl sebacate and circulating the mixture through a shear valve at 75 pounds pressure drop while the mixture was maintained at 400 F. The mixture was then cooled to 200 F. during about 2 /2 hours while additional amounts of mineral oil and Z-ethylhexyl sebacate were added. The grease was finally drawn and finished by milling in a Premier colloid mill. The borate ester compounds were incorporated into the base grease thus obtained by heating a mixture of the grease and borate ester compounds in suitable proportions at F. for 30 minutes with stirring.
The borate ester compounds employed in these compositions were prepared by the method comprising treating a boric acid diester with a phenol containing an ortho positioned nucleophilic group. Following is a detailed description of the preparation of di-(dinonylphenyl)- mono-o-carbomethoxyphenyl borate: 61.8 grams of boric acid (1.0 mol), 694.0 grams of dinonylphenol (2.0 mols) and 250 ml. of xylene were charged to a 2 liter 3 necked flask equipped with a stirrer, condenser and distilling recevier, and the solution refluxed for 2.9 hours until 43 ml. of Water had been collected. 152.0 grams of methyl salicylate (1.0 mol) were added and the reflux carried out for 7 hours until 18 ml. of water had been collected. The flask was then cooled to room temperature and the solid removed by filtration and dried. The compound analyzed 0.94 percent boron, as compared with 1.26 percent, theory.
Amine adducts or association complexes of these borate esters were prepared by adding an amine slowly to the ester in an inert solvent, employing equimolar proportions of the amine and borate ester. The amine employed for forming these complexes was a commercial material sold by Rohm & Haas under the trade name of Primene 81-R consisting of tertiary alkayl primary amines in the range from C H NH to C H NH Table I below shows representative results obtained by employing various intramolecular coordinated borate esters in a 3 percent concentration upon the dropping point and oxidation resistance of the lithium hydroxy fatty acid soap thickened grease.
In contrast to the above results, no improvement was obtained by adding the intramolecular coordinated borate ester compounds to conventional fatty acid soap thickened greases.
Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and only such limitations should be improsed as are indicated in the appended claims.
We claim:
1. A lubricating grease consisting essentially of a lubrieating oil thickened to a grease consistency by a metal hydroxy fatty acid soap and containing about 0.1-10 percent by weight of a compound selected from the class consisting of intramolecular coordinated borate esters represented by the formulas:
Where R is selected from the class consisting of hydrocarbon groups and substituted hydrocarbon groups, R is selected from the class consisting of hydrogen, hydrocarbon groups and substituted hydrocarbon groups, at least one group represented by R being an aryl group containing an ortho positioned nucleophilic group, X is selected from the class consisting of oxygen and sulfur, n, is a whole number from 0 to 2, inclusive, m is a whole number from 1 to 3, inclusive, the sum of n and m being 3, n is a whole number from 0 to 3, inclusive, m is a whole number from 1 to 4, inclusive, and the sum of n and m is 4.
2. A lubricating grease according to claim 1 wherein the said nucleophilic group is chosen from the class consisting of nitro, amine, ketone, aldehyde and amide groups.
3. A lubricating greases according to claim 1 wherein the said borate ester is a compound represented by the said formulas wherein n and n equal 0 and the groups represented by R are chosen from the class consisting of hydrocarbon groups and substituted hydrocarbon groups.
4. A lubricating grease according to claim 1 wherein the metal component of the said metal hydroxy fatty acid soap is chosen from the group consisting of alkali metals and alkaline earth metals.
5. A lubricating grease according to claim 1 wherein the metal component of the said hydroxy fatty acid soap is lithium.
6. A lubricating grease according to claim 1 wherein the said lubricating oil is a mineral oil.
7. A lubricating grease according to claim 1 wherein the said lubricating oil is a dicarboxylic acid ester.
References (Iited in the file of this patent UNITED STATES PATENTS 2,154,098 Loane et a1. Apr. 11, 1939 2,160,917 Shoemaker et a1. June 6, 1939 2,846,394 Brunstrum et a1. Aug. 5, 1958 2,961,443 Ashby et a1 Nov. 22, 1960 3,007,873 Reynolds et a1 Nov. 7, 1961 3,014,061 Irish et al Dec. 19, 1961 3,020,307 Luvisi Feb. 6, 1962
Claims (1)
1. A LUBRICATING GREASE CONSISTING ESSENTIALLY OF A LUBRICATING OIL THICKENED TO A GREASE CONSISTENCY BY A METAL HYDROXY FATTY ACID SOAP AND CONTAINING ABOUT 0.1-10 PERCENT BY WEIGHT OF A COMPOUND SELECTED FROM THE CLASS CONSISTING OF INTRAMOLECULAR COORDINATED BORATE ESTERS REPRESENTED BY THE FORMULAS:
Publications (1)
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US3125526A true US3125526A (en) | 1964-03-17 |
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US3125526D Expired - Lifetime US3125526A (en) | Lubricating greases containing borate |
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Cited By (3)
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US3200074A (en) * | 1963-05-20 | 1965-08-10 | Texaco Inc | Lubricating compositions containing borate ester-amine complexes |
US6008165A (en) * | 1998-07-31 | 1999-12-28 | The Lubrizol Corporation | Alcohol borate esters and borated dispersants to improve bearing corrosion in engine oils |
US6010986A (en) * | 1998-07-31 | 2000-01-04 | The Lubrizol Corporation | Alcohol borate esters to improve bearing corrosion in engine oils |
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US2961443A (en) * | 1957-04-10 | 1960-11-22 | Ethyl Corp | Organic compounds of boron |
US3007873A (en) * | 1959-06-25 | 1961-11-07 | Shell Oil Co | Stable mineral oil compositions |
US3020307A (en) * | 1959-12-23 | 1962-02-06 | Universal Oil Prod Co | Cycloalkenyl borates and preparation thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3200074A (en) * | 1963-05-20 | 1965-08-10 | Texaco Inc | Lubricating compositions containing borate ester-amine complexes |
US6008165A (en) * | 1998-07-31 | 1999-12-28 | The Lubrizol Corporation | Alcohol borate esters and borated dispersants to improve bearing corrosion in engine oils |
US6010986A (en) * | 1998-07-31 | 2000-01-04 | The Lubrizol Corporation | Alcohol borate esters to improve bearing corrosion in engine oils |
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