US3303130A - Lubricant compositions containing organo mercaptoalkyl borates - Google Patents
Lubricant compositions containing organo mercaptoalkyl borates Download PDFInfo
- Publication number
- US3303130A US3303130A US506127A US50612765A US3303130A US 3303130 A US3303130 A US 3303130A US 506127 A US506127 A US 506127A US 50612765 A US50612765 A US 50612765A US 3303130 A US3303130 A US 3303130A
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- United States
- Prior art keywords
- borate
- mono
- tri
- organo
- mercaptoalkyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 38
- -1 organo mercaptoalkyl borates Chemical class 0.000 title description 131
- 239000000314 lubricant Substances 0.000 title description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 34
- 230000001050 lubricating effect Effects 0.000 claims description 28
- 239000010687 lubricating oil Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 description 29
- 125000000962 organic group Chemical group 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- WSIANCUTPULNMY-UHFFFAOYSA-N C(CCCCCCCCCCC)SCCOB(OCCSCCCCCCCCCCCC)OCCSCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)SCCOB(OCCSCCCCCCCCCCCC)OCCSCCCCCCCCCCCC WSIANCUTPULNMY-UHFFFAOYSA-N 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- WWOWUKPIQFKJRO-UHFFFAOYSA-N tris(2-sulfanylethyl) borate Chemical compound SCCOB(OCCS)OCCS WWOWUKPIQFKJRO-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010688 mineral lubricating oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- 208000032544 Cicatrix Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000037387 scars Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- SYCNGJXKLSBITB-UHFFFAOYSA-N 1-benzylsulfanylethanol Chemical compound CC(O)SCC1=CC=CC=C1 SYCNGJXKLSBITB-UHFFFAOYSA-N 0.000 description 1
- TUADVWCHTOAKQA-UHFFFAOYSA-N 1-butylsulfanylethanol Chemical compound CCCCSC(C)O TUADVWCHTOAKQA-UHFFFAOYSA-N 0.000 description 1
- NUTVORGGYDQIDD-UHFFFAOYSA-N 1-ethylsulfanylethanol Chemical compound CCSC(C)O NUTVORGGYDQIDD-UHFFFAOYSA-N 0.000 description 1
- XUIZXGCLXPMKRL-UHFFFAOYSA-N 1-phenylsulfanylethanol Chemical compound CC(O)SC1=CC=CC=C1 XUIZXGCLXPMKRL-UHFFFAOYSA-N 0.000 description 1
- AAFKOWOILUBVJH-UHFFFAOYSA-N 1-propylsulfanylethanol Chemical compound CCCSC(C)O AAFKOWOILUBVJH-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- XBCDECDLTNTPSZ-UHFFFAOYSA-N 1-sulfanylheptan-1-ol Chemical compound CCCCCCC(O)S XBCDECDLTNTPSZ-UHFFFAOYSA-N 0.000 description 1
- AKIZPWSPNKVOMT-UHFFFAOYSA-N 1-sulfanylhexan-1-ol Chemical compound CCCCCC(O)S AKIZPWSPNKVOMT-UHFFFAOYSA-N 0.000 description 1
- PDXOPTFTOFXXSU-UHFFFAOYSA-N 1-sulfanylpentan-1-ol Chemical compound CCCCC(O)S PDXOPTFTOFXXSU-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XHTPZOANPACIRY-UHFFFAOYSA-N B(OCCCS)(OCCCS)OCCCSCCCCCCCCCCCCCCCC Chemical compound B(OCCCS)(OCCCS)OCCCSCCCCCCCCCCCCCCCC XHTPZOANPACIRY-UHFFFAOYSA-N 0.000 description 1
- FSUGIMWJMJFJMC-UHFFFAOYSA-N B(OCCS)(OCCSCC)OCCSCC Chemical compound B(OCCS)(OCCSCC)OCCSCC FSUGIMWJMJFJMC-UHFFFAOYSA-N 0.000 description 1
- XYRKEMRHUCQELX-UHFFFAOYSA-N CSCCOB(OCCSC)OCCSC Chemical compound CSCCOB(OCCSC)OCCSC XYRKEMRHUCQELX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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 Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric 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
- 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
Definitions
- This invention relates to an improved lubricant for use in internal combustion engines and more particularly to a lubricating composition having improved extreme pressure and antiwear characteristics.
- a lubricating composition having improved antiwear and load-carrying characteristics can be obtained by incorporating into a lubricating oil a small amount of an organo mercaptoalkyl borate having the general formula wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkary-l, aralky-l and cycloaikyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16, inclusive.
- the R substituents may be either alike or different. From the standpoint of ease in preparation, it is preferred to employ those compounds where the R groups are of the same kind.
- radicals which we intend to include with respect to R in the above formula are as follows: hydrogen; methyl; ethyl; propyl; isopropyl; n butyl; sec-buty-l; tertiary butyl; amyl; hexyl; heptyl; n-octyl; isooctyl; nonyl; decyl; undecyl; dodecyl; tridecyl; tetradecyl; pentadecyl; 'hexadecyl; pheny-l; l-naphthyl; Z-naphthyl; o-, m-, and p-tolyl; m-, and p-xylyl; methylnaphthyl; dimethylnaphthyl; tri-, tetra-, penta-, and hexamethylnaphthyl;
- organo substituents of the organo mercaptoalkyl borates can be selected from a variety of the organic radicals mentioned above on the basis of their ability to impart oil-solubility to the compounds.
- Specific examples of some of the organo mercaptoalkyl borates represented by the above formula are tri (mercaptoethy hborate tri(methylmercaptoethyl)borate tri(ethylmercaptoethyl borate tri(propy-lrnercaptoethyl)borate tri (butylmercaptoethyl borate tri( hexylmercaptoethylyb orate tri octylmercaptoethyl borate tri( decylmercaptoethyl borate tri( dodecylmerc aptoethyl) borate tri (hexadecylmercaptoet-hyl borate tri (phenylmercaptoethyl borate tri(nap
- organo mercaptoalkyl borates having the general formula B(OCH CH SR) wherein R is hydrogen or an alkyl radical containing from 1 to 12-carbon atoms form a preferred group of compounds. Especially good results are obtained, for example, with tri(mercaptoethyl)borate and tri(dodecylmercaptoethyl) borate.
- the amount of the organo mercaptoalkyl borate compound employed may vary over wide limits depending upon the particular compound employed, the type of base oil in which the compound is incorporated and the severity of the conditions to which the ultimate composition is subjected. In general, however, we use an amount between about 0.5 and 10 percent by weight based on the weight of the oil. Good results are obtained with about 1 to about 5 percent by weight of the organo mercaptoalkyl borate compound. In any event, the organo mercaptoalkyl borate is employed in an amount sufficient to improve the antiwear and extreme pressure characteristics of the oil to which the compound is added. When used in amounts of about 0.5 to about 10 percent by weight, the organo mercaptoalkyl borate also serves as an oxidation inhibitor.
- the organo mercaptoalkyl borates can be prepared according to known chemical procedures. Neither the compounds per se nor their method of preparation constitutes any portion of this invention.
- the organo mercaptoalkyl borates for example, can be prepared by reacting boric acid with one or more of the appropriate thioalcohols under reflux conditions in a suitable solvent such as a liquid hydrocrabon, e.g., benzene, toluene or the like. The reaction is continued until the theoretical amount of Water is formed. Theoretically, complete reaction of the boric acid and alcohol requires 3 moles of the alcohol for each mole of boric acid. Thus, the reaction is theoretically complete when 3 moles of Water are formed for each mole of boric acid used.
- the heating process is discontinued and the solvent evaporated from the product. No catalyst is required.
- the reaction of the boric acid and thioalcohol occurs readily at temperatures in the range of about 40 to about 200 C. The reaction is preferably conducted at atmospheric pressure. It will be recognized that when organo mercapotalkyl borates with the same organic radicals are desired, a single thioalcohol is employed. When organo mercaptoalkyl borates with different organic radicals are desired, two or more thioalcohols may be utilized separately or as mixtures thereof. In any event, the total amount of alcohol employed to eifect esterification should be sufficient to replace the three hydrogen atoms of the boric acid.
- Suitable thioalcohols for use as starting materials include organo mercaptoalkanols such as mercaptoethanol, methylmercaptoethanol, ethylmercaptoethanol, propylmercaptoethanol, butylmercaptoethanol, octylmercaptoethanol, dodecylrnercaptoethanol, hexadecylmercaptoeth a n o l phenylmercaptoethanol, tolylmercaptoethanol, benzylmercaptoethanol, cyclohexylmercaptoethanol, mercaptopropanol, methyl'mercaptopropanol, mercaptobutanol, mercaptopentanol, mercaptohexanol, mercaptoheptanol,
- organo mercaptoalkanols such as mercaptoethanol, methylmercaptoethanol, ethylmercaptoethanol, propylmercaptoethanol, buty
- Example 1 A mixture of 6.2 grams (0.1 mole) of boric acid, 23.4 grams (0.3 mole) of 2-mercaptoethanol and 100 ml. of
- benzene was refluxed at about 80 C. in a flask connected to a reflux condenser by means of a Dean-Stark trap.
- Example 11 A mixture of 76.2 grams (2.34 moles) of 2-n-d0- decylmercaptoethanol, 48.8 grams (0.78 mole) of boric acid and one liter of toluene was refluxed at about 110 C. in a flask connected to a reflux condenser by means of a Dean-Stark trap. The water which formed during the reaction was collected as a toluene azeotrope. When 43 ml. of water was collected (theory is 42.2 ml.), the reaction was terminated, the solution filtered and the toluene removed under reduced pressure. The product thus obtained was a clear liquid which solidified slowly to a wax on standing. The product weighed 582 grams a (99+% yield). Elemental analysis of the product shows it to compare favorably with the theoretical analysis of tri(2-dodecylmercaptoethyl)borate.
- the lubricating oil to which the organo mercaptoalkyl borate is added to form a lubricating composition having' improved antiwear and extreme pressure characteristics can be any oil of lubricating viscosity such as refined or semirefined parafiinic, naphthenic or asphalt base oil.
- Hydrotreated mineral oils because of their improved stability over untreated oils are especially prefered lubricating bases for preparing lubricants to be used under moderately elevated temperatures. When temperatures in the order of 400 F. and above are to be encountered, synthetic oils of lubricating viscosity form a preferred class of lubricating oil bases to which the organo mercaptoalkyl borate is added.
- synthetic lubricating oils such as polymerized oleflns, organic esters such as di-Z-ethylhexyl sebacate and di-Z-ethylhexyl azelate and the like can also be used as the base oil to form a lubricating composition in accordance with the invention.
- a blend of oils of suitable viscosity can be employed instead of a single oil, by means of which any desired viscosity can be secured.
- the lubricating composition of our invention can contain minor amounts of other agents normally added to lubricating oils for a specific purpose such as a dispersant, a detergent, a pour point depressant, a thickener,
- lubricating composition can also contain oiliness and other extreme pressure agents and antioxidants to further enhance the lubricating characteristics if desired.
- the additives disclosed herein can be added to the lubricating oil base directly or in the form of an oil concentrate in an amount to give the desired concentration in the final 6 lubricating composition. Slight heating of the mixture may be advantageously employed to facilitate blending of the additives in the com-position.
- test lubricant at a level of 2 mm.
- Iball can be rotated from a motor drive at 600, 1200 or 1800 r.p.m. Each test is run with new steel .balls.
- a test is run on a lubricant at a specific load, temperature, speed and time. Lubricating properties are evaluated from an examination of (1) the scars on the clean surfaces of the three stationary balls, the two maximum right angle diameters of each wear scar being measured to the closest 0.01 millimeter and averaged and (2) the load in kilograms at which seizure occurs.
- a more complete description of the machine and test method are given in the Naval Research Laboratory Report entitled A Study of the Four Ball Wear Machine, by W. C. Clinton, NRL Report 3709, September 1950.
- compositions E and F also show improved viscosity indices after the 48 hour test.
- Tri(methylmetcaptoethyl)borate Tri(nony1 phenylmercaptoethyl)- borate Dl(mercaptoethyl) mono(methylmercaptoethyl) borate Iri(phenylmercaptobutybborate- Mouo(mereaptoethyl) ditethylmercaptoethybborate 'Iri(mercaptohexadecybborate
- lubricating compositions of the invention also have improved resistance to oxidation.
- a lubricating composition comprising a major amount of a lubricating oil and a small amount, sufficient to improve the antiwear and load-carrying characteristics of the oil, of an organo rnercaptoalkyl borate having the general formula S (CI-In) RS(CI-lz)uO-I 3-O(CHz)nSR wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16.
- a lubricating composition comprising a major amount of a lubricating oil and a small amount, suflicient to improve the antiwear and load-carrying characteristics of the oil, of an organo mercaptoethyl borate having the general formula 1 B (OCH CH SR 3 wherein R is selected from the group consisting of hydrogen and an alkyl radical containing 1 to 12 carbon atoms.
- organo mercaptoethyl borate is tri(dodecylmercaptoethyl) borate.
- a lubricating composition comprising a major amount of a mineral lubricating oil and about 0.5 to about 10 percent by Weight of tri(mercapt0ethyl)borate.
- a lubricating composition comprising a major amount of a mineral lubricating oil and about 0.5 to about 10 percent by weight of tri(dodecylmercaptoethyl) borate.
- a lubricating composition comprising a major amount of diisooctyl azelate and about 0.5 to about 10 percent by weight of tri(mercaptoethyl)borate.
- a lubricating composition comprising a major amount of diisooctyl azelate and about 0.5 to about 10 percent by weight of tri(dodecy1mercaptoethyl)borate.
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Description
United States l atent f) 3 383,130 LUBRICANT COMPOSITIONS CONTAINING ORGANO MERCAPTOALKYL BORATES Frederick E. Seypinski, Monroeville, and Harold 0.
Strange, Penn Hills Township, Allegheny County, Pa.,
assignors to Gulf Research 8; Development Company,
Pittsburgh, Pa, a corporation of Delaware No Drawing. Filed Nov. 2, 1965, Ser. No. 506,127
9 Claims. (Cl. 252-463) This invention relates to an improved lubricant for use in internal combustion engines and more particularly to a lubricating composition having improved extreme pressure and antiwear characteristics.
In the design of modern engines, machinery, and the like, the engineer is constantly striving for improvements with respect to compactness, speed, power and acceleration. In achieving these improvements closer tolerances are being employed between adjacent moving surfaces. In order to prevent undue wear and perhaps even seizure of the adjacent surfaces, a lubricating composition is -required which will form a lubricating film between the respective surfaces. The lubricating film must be able to Withstand extremely high pressures without being squeezed from between the surfaces and without being decomposed.
We have discovered that a lubricating composition having improved antiwear and load-carrying characteristics can be obtained by incorporating into a lubricating oil a small amount of an organo mercaptoalkyl borate having the general formula wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkary-l, aralky-l and cycloaikyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16, inclusive. The R substituents may be either alike or different. From the standpoint of ease in preparation, it is preferred to employ those compounds where the R groups are of the same kind.
Specific examples of the radicals which we intend to include with respect to R in the above formula are as follows: hydrogen; methyl; ethyl; propyl; isopropyl; n butyl; sec-buty-l; tertiary butyl; amyl; hexyl; heptyl; n-octyl; isooctyl; nonyl; decyl; undecyl; dodecyl; tridecyl; tetradecyl; pentadecyl; 'hexadecyl; pheny-l; l-naphthyl; Z-naphthyl; o-, m-, and p-tolyl; m-, and p-xylyl; methylnaphthyl; dimethylnaphthyl; tri-, tetra-, penta-, and hexamethylnaphthyl; o-, m-, and p-ethylphenyl; o-, m-, and p-propylphenyl; o-, m-, and p-butylphenyl; o-, m-, and p-amylphenyl; o-, m-, and p-hexylphenyl; o-, m-, and p-heptylphenyl; 0-, n1-, and p-octy-lphenyl; 0-, m-, and p-nonylphenyl; diethylphenyl; dipropylphenyl; dibutylphenyl; diamylphenyl; triethylphenyl; tripropylphenyl; tetraethylphenyl; pentaethylpheny-l; benzyl; phenethyl; gamma-phenylpropyl; naphthylethyl; o-, m-, and p-methylbenzyl; 0-, 111-, and p-methylphenethyl; cyclopentyl; cyclohexyl; cyclooctyl; methylcyclohexyl; and the like.
The organo substituents of the organo mercaptoalkyl borates can be selected from a variety of the organic radicals mentioned above on the basis of their ability to impart oil-solubility to the compounds. Specific examples of some of the organo mercaptoalkyl borates represented by the above formula are tri (mercaptoethy hborate tri(methylmercaptoethyl)borate tri(ethylmercaptoethyl borate tri(propy-lrnercaptoethyl)borate tri (butylmercaptoethyl borate tri( hexylmercaptoethylyb orate tri octylmercaptoethyl borate tri( decylmercaptoethyl borate tri( dodecylmerc aptoethyl) borate tri (hexadecylmercaptoet-hyl borate tri (phenylmercaptoethyl borate tri(naphthylmercaptoethyl) borate tri (tolylmercaptoethyl borate tri (ethylphenylmercaptoethyl) borate tri nonylphenylmercaptoethyl borate tri benzylme-rcaptoethyl) borate tri (cyclohexylmercaptoethyl borate di mercaptoethyl) mono (-methylmercaptoethyl) borate di mercaptoethyl) mono (ethylmerc aptoethyl borate di(mercaptoethyl) mono(propylmercaptoethyl)borate di mercaptoethyl) mono(butylmercaptoethyl) borate di (mercaptoethyl) mono(hexylmercaptoethyl) borate di (rnercaptoethyl) mon o( octylmercaptoethyl) borate di (me-rcaptoethyl) mono( do decylmercaptoethyl borate di (rnercaptoet'hyl) mono( hexadecylmercaptoethyl) borate di(mercaptoethyl) mono( phenylmercaptoethyl borate di merca-ptoethyl) mono(tolylmercaptoethyl) borate di mercaptoethyl) mono(nonylphenylmercaptoethyl) borate di (merc aptoethyl) di (mercaptoethyl) borate mono(mercaptoethyl) di-( met'hylmercaptoethyl)borate mono(mercaptoethyl) di (ethylmercaptoethyl) borate mono( mercaptoethyl) di propylmercaptoet-hyl) borate mono( mercaptoethyl) di (butyl-mercaptoethyl) borate mono(mercaptoethyl) di (hexylmercaptoethyl) borate mono(mercaptoethyl) di (octylmercaptoethyl borate mono(mercaptoethyl) di(dodecylmercaptoethyl)borate mono mercaptoethyl) di (hexadecylmercaptoethyl) borate mono mercaptoethyl) di phenylmerc aptoethyl )-b0rate mono (mercaptoethyl) di (tolylme-rcaptoethyl) borate mono(mercaptoethyl) di (nonylphenylmercaptoethyl) borate mono(mercaptoethy-l) di(benzylmercaptoethyl) borate mono (mercaptoethyl) di cyclohexylmercaptoethyl) borate tri mercaptopropyl borate tri (methylmercaptopropyl borate tri ethylmercaptopropyl borate tri (propylmercaptopropyl borate tri butylmercaptopropyl borate tri (hexylmercaptopropyl borate tri octylmercaptopropyl borate tri decylmercaptopropyl) borate tri dodecylmercaptopropyl borate tri(hexadecylmercaptopropyl borate tri(phenylmercaptopropyl borate tri( naphthylmercaptopropyl borate tri( tolylmercaptopropyl) borate tri(ethylphenylmercaptopropyl borate tri(nonylphenylmercaptopropyl borate tri( benzylmercaptopropyl borate tri(cyclohexylmercaptopropyl) borate di (mercaptopropyl) mono methylmercaptopropyl borate di(mercaptopropyl) mono (ethylmercaptopropyl borate di (mercaptopropyl) mono pr-opylmercaptopropyl borate di(mercaptopropyl) mono butylmercaptopropyl borate di (mercaptopropyl) mono hexylmercaptopropyl borate di(mercaptopropyl) mono octylmercaptopropyl) borate di(mercaptopropyl) mono dodecylmercaptopropyl)borate di(mercaptopropyl) mono (hexadecylmercaptopropyl) borate di(mercaptopropyl) mono (phenylmercaptopropyl borate di(mercaptopropyl) mono (tolylmercaptopropyl) borate mono (benzyl-mercaptoethyl borate mono (eyelohexy-lmercaptoethyl) di(mercaptopropyl) mono(nonylphenylmercaptopropyl) borate di(mercaptopr-op'yl) mono(benzylmercaptopropyl)borate di mercaptopropyl) mono cyclohexylmercaptopropyl) borate mono (mercaptopropyl) di(methylmercaptopropyl)borate mono (mercaptopropyl) di ethylmercaptopropyl borate mono mercaptopropyl) di propylmercaptopropyl borate mono (mercaptopropyl) di butylmercaptopropyl borate mono mercaptopropyl) di hexylmercaptopropyl )borate mono (mercaptopropyl) di octylrnercaptopropyl borate mono(mercaptopropy1) di(dodecylmercaptoprpyl)borate mono (mercaptopr-opyl) di(hexadecylmercaptopropyl) borate mono (mercaptopropyl) di (phenylmercaptopropyl) borate mon0(mercaptopropyl) di(tolylmercaptopropyl)borate mono (mercaptopropyl) di nonylphenylmercaptopropyl) borate mono (mercaptop ropyl) di benzylmercaptopropyl borate mono(mercaptopropyl) di(cyclohexylmercaptopropyl) borate tri(mercaptobutyl)borate tri methylmercaptobutyl borate tri (ethylmercaptobutyl) borate tri(propylmercaptobutyl)borate tri butylmercaptobutyl borate tri(hexylmercaptobutyl)borate tri(octylmercaptobutyl)borate tri(decylmercaptobutyl)borate tri(dodecylmercaptobutyl)borate tri(hexadecylmercaptobutyl)borate tri(phenylmercaptobutyl)borate tri( naphthylmercaptobutyl borate tri(tolylmercaptobutyl)borate tri ethylphenylmercaptobutyl borate tri(nonylphenylmercaptobutyl)borate tri(benzylmercaptobutyl)borate tri(cyclohexylmercaptobutyl)borate di(rnercaptobutyl) mono(methylmercaptobutyl)borate di mercaptobutyl) mono (ethylmercaptobutyl) borate di(mercaptobutyl) mono (propylmercaptobutyl)borate di(mercaptobutyl) mono(butylmercaptobutyl)borate di mercaptobutyl) mono (hexylmercaptobutyl borate di mercaptobutyl) mono octylmercaptobutyl borate di(mercaptobutyl) mono(dodecylmercaptobutyl)borate di (mercaptobutyl) mono (hexadecylmercaptobutyl') borate di(mercaptobutyl) mono(phenylmercaptobutyl)borate di(mercapt-obutyl) mono(tolylmercapt0butyl)borate di(mercaptobutyl) mono(nonylphenylmercaptobutyl) borate di(mercaptobuty1) mono(benzylmercaptobutyl)borate di(mercaptobutyl) mono(cyclohexylmercaptobutyl) borate mono (mercaptobutyl) di (methylmercapt-obutyl borate mono (mercaptobutyl) di ethylmercaptobutyl borate mono(mercaptobutyl) di(propylmercaptobutyl)borate mono(mercaptobutyl) di(butylmercaptobutyl)borate mono(mercaptobutyl) di(hexylmercaptobutyl)borate mono (mercaptobutyl) di octylmercaptobutyl borate mono mercaptobutyl) di (dodecylmercaptobutyl borate mono(n1ercaptobutyl) di(hexadecylmercaptobutyl)borate mono(mercaptobutyl) di(phenylmercaptobutyl)borate mono (mercaptobutyl) di(tolylmercaptobutyl borate mono(mercaptobutyl) di(nonylphenylmercaptobutyl) borate mono (mercaptobutyl) di (benzylmercaptobutyl borate mono(mercaptobutyl) di(cyclohexylmercaptobutyl)borate tri(mercaptoamyl)borate tri(mercaptohexyl)borate tri(mercaptoheptyl)borate tri(mercaptooctyl)borate tri(mercaptononyl)borate tri(mercaptodecyl)borate tri( mercaptoundecyl borate tri(mercaptododecyl)borate 4 tri(mercaptotridecyl)borate tri(mercaptotetradecyl)borate tri(mercaptopentadecyl)borate tri (mercaptohexadecyl borate While all of the organo mercaptoalkyl borates mentioned hereinabove can be employed for improving the antiwear and load-carrying characteristics of an oil, it is not to be implied that all such compounds serve with equal efficiency. Those organo mercaptoalkyl borates having the general formula B(OCH CH SR) wherein R is hydrogen or an alkyl radical containing from 1 to 12-carbon atoms form a preferred group of compounds. Especially good results are obtained, for example, with tri(mercaptoethyl)borate and tri(dodecylmercaptoethyl) borate.
The amount of the organo mercaptoalkyl borate compound employed may vary over wide limits depending upon the particular compound employed, the type of base oil in which the compound is incorporated and the severity of the conditions to which the ultimate composition is subjected. In general, however, we use an amount between about 0.5 and 10 percent by weight based on the weight of the oil. Good results are obtained with about 1 to about 5 percent by weight of the organo mercaptoalkyl borate compound. In any event, the organo mercaptoalkyl borate is employed in an amount sufficient to improve the antiwear and extreme pressure characteristics of the oil to which the compound is added. When used in amounts of about 0.5 to about 10 percent by weight, the organo mercaptoalkyl borate also serves as an oxidation inhibitor.
The organo mercaptoalkyl borates can be prepared according to known chemical procedures. Neither the compounds per se nor their method of preparation constitutes any portion of this invention. The organo mercaptoalkyl borates, for example, can be prepared by reacting boric acid with one or more of the appropriate thioalcohols under reflux conditions in a suitable solvent such as a liquid hydrocrabon, e.g., benzene, toluene or the like. The reaction is continued until the theoretical amount of Water is formed. Theoretically, complete reaction of the boric acid and alcohol requires 3 moles of the alcohol for each mole of boric acid. Thus, the reaction is theoretically complete when 3 moles of Water are formed for each mole of boric acid used. When the theoretical amount of water is collected, the heating process is discontinued and the solvent evaporated from the product. No catalyst is required. The reaction of the boric acid and thioalcohol occurs readily at temperatures in the range of about 40 to about 200 C. The reaction is preferably conducted at atmospheric pressure. It will be recognized that when organo mercapotalkyl borates with the same organic radicals are desired, a single thioalcohol is employed. When organo mercaptoalkyl borates with different organic radicals are desired, two or more thioalcohols may be utilized separately or as mixtures thereof. In any event, the total amount of alcohol employed to eifect esterification should be sufficient to replace the three hydrogen atoms of the boric acid. While we have disclosed a method of preparing the organo mercaptoalkyl borates by reacting boric acid with the appropriate thioalcohol or mixture of thioalcohols, other methods of preparing the organo mercaptoaikyl borates can be employed without deviating from the scope of the invention provided the resulting esters have the general formula disclosed hereinabove. Suitable thioalcohols for use as starting materials include organo mercaptoalkanols such as mercaptoethanol, methylmercaptoethanol, ethylmercaptoethanol, propylmercaptoethanol, butylmercaptoethanol, octylmercaptoethanol, dodecylrnercaptoethanol, hexadecylmercaptoeth a n o l phenylmercaptoethanol, tolylmercaptoethanol, benzylmercaptoethanol, cyclohexylmercaptoethanol, mercaptopropanol, methyl'mercaptopropanol, mercaptobutanol, mercaptopentanol, mercaptohexanol, mercaptoheptanol,
fnercaptooctanol,
Example 1 A mixture of 6.2 grams (0.1 mole) of boric acid, 23.4 grams (0.3 mole) of 2-mercaptoethanol and 100 ml. of
benzene was refluxed at about 80 C. in a flask connected to a reflux condenser by means of a Dean-Stark trap.
The water which formed during the reaction was collected as a benzene azeotrope. When 5.2 ml. of water was col- 'lected (theory is 5.4 ml.), the reaction was terminated and the benzene was stripped off under reduced pressure. The product thus obtained was a clear liquid weighing 23.4 grams (96% yield). Elemental analysis of the product shows it to compare favorably with the theoretical analysis of tri(2-mercaptoethyl)borate as follows:
Percent by weight for B(OCH CH SH) Found: Carbon, 28.0; hydrogen, 6.1; sulfur, 37.5; boron, 4.4. Theoretical: Carbon, 29.8; hydrogen, 6.2; sulfur, 39.8; boron, 4.5.
Example 11 A mixture of 76.2 grams (2.34 moles) of 2-n-d0- decylmercaptoethanol, 48.8 grams (0.78 mole) of boric acid and one liter of toluene was refluxed at about 110 C. in a flask connected to a reflux condenser by means of a Dean-Stark trap. The water which formed during the reaction was collected as a toluene azeotrope. When 43 ml. of water was collected (theory is 42.2 ml.), the reaction was terminated, the solution filtered and the toluene removed under reduced pressure. The product thus obtained was a clear liquid which solidified slowly to a wax on standing. The product weighed 582 grams a (99+% yield). Elemental analysis of the product shows it to compare favorably with the theoretical analysis of tri(2-dodecylmercaptoethyl)borate.
Percent by weight for B(OCH CH SC H Found: Carbon, 65.91; hydrogen, 10.80; boron, 1.47. Theoretical: Carbon, 67.5; hydrogen, 11.65; boron, 1.47.
The lubricating oil to which the organo mercaptoalkyl borate is added to form a lubricating composition having' improved antiwear and extreme pressure characteristics can be any oil of lubricating viscosity such as refined or semirefined parafiinic, naphthenic or asphalt base oil. Hydrotreated mineral oils, because of their improved stability over untreated oils are especially prefered lubricating bases for preparing lubricants to be used under moderately elevated temperatures. When temperatures in the order of 400 F. and above are to be encountered, synthetic oils of lubricating viscosity form a preferred class of lubricating oil bases to which the organo mercaptoalkyl borate is added. Thus, synthetic lubricating oils such as polymerized oleflns, organic esters such as di-Z-ethylhexyl sebacate and di-Z-ethylhexyl azelate and the like can also be used as the base oil to form a lubricating composition in accordance with the invention. If desired, a blend of oils of suitable viscosity can be employed instead of a single oil, by means of which any desired viscosity can be secured.
The lubricating composition of our invention can contain minor amounts of other agents normally added to lubricating oils for a specific purpose such as a dispersant, a detergent, a pour point depressant, a thickener,
-a corrosion inhibitor, a viscosity index improver, an
antifoamant, a rust inhibitor, a dye and the like. The
lubricating composition can also contain oiliness and other extreme pressure agents and antioxidants to further enhance the lubricating characteristics if desired.
To prepare an improved lubricating composition the additives disclosed herein can be added to the lubricating oil base directly or in the form of an oil concentrate in an amount to give the desired concentration in the final 6 lubricating composition. Slight heating of the mixture may be advantageously employed to facilitate blending of the additives in the com-position.
To demonstrate the effectiveness of the organo mercaptoalkyl borates of the type described hereinabove, we have conducted comparative tests, the results of which are listed in Table I, with a mineral lubricating oil alone and with the same oil blended with representative organo mercaptoalkyl borates. The mineral oil employed had the following typical inspection:
Gravity, API 32.2 Viscosity, SUS Sec.:
F. 153.0 210 F. 44.0 Flash OC, F. 440 Fire 00, F. 490
In illustrating the improved antiwear and load-carrying characteristics, tests were made using the four-ball wear test. In conducting this test, a four ball wear test machine was employed. In this machine, three steel balls are securely fastened in contact with each other in a horizontal plane in a cup. A fourth steel ball in a rotating spindle is placed so that it is entirely supported by the other three balls forming -a pyramid. The test cup is placed on a stage which can move vertically to facilitate loading. The stage rests on a calibrated fulcrum so that specific weights may be applied to force the three balls in the cup to contact the rotating fourth ball at a predetermined pressure. The cup holding the three balls also contains the test lubricant at a level of 2 mm. above the stationary balls, thus assuring an adequate supply of lubricant at the contact points. A fixed oil temperature is maintained by a relay system connected to a thermocouple in the cup and a heater in the stage. The fourth Iball can be rotated from a motor drive at 600, 1200 or 1800 r.p.m. Each test is run with new steel .balls. I
A test is run on a lubricant at a specific load, temperature, speed and time. Lubricating properties are evaluated from an examination of (1) the scars on the clean surfaces of the three stationary balls, the two maximum right angle diameters of each wear scar being measured to the closest 0.01 millimeter and averaged and (2) the load in kilograms at which seizure occurs. A more complete description of the machine and test method are given in the Naval Research Laboratory Report entitled A Study of the Four Ball Wear Machine, by W. C. Clinton, NRL Report 3709, September 1950.
In illustrating the improved antiwear and load-carrying characteristics of compositions of the invention by the four ball wear test, the movable ball was rotated at 1800 r.p.m. for one hour while maintaining the test lubricant at 250 F Separate one hour tests were conducted using new steel balls at loads of 10 to 50 kilograms unless seizure was encountered. At the end of each test, wear scars were measured. The advantageous wear properties of the oil containing an additive of the invent-ion as compared with the base oil are illustrated by the data set forth in Table I.
1 Seizure.
7 It is apparent from the data in Table I that a lulbricating composition containing an organo mercaptoalkyl borate in accordance with the invention has substantially improved antiwear and load carrying characteristics as determined by the fourball wear tests.
and acid number. The compositions of the invention (Compositions E and F) also show improved viscosity indices after the 48 hour test.
Specific examples of other compositions within the scope of the invention are set forth in Table III.
Organo mereaptoalkyl borate:
Tri(methylmetcaptoethyl)borate Tri(nony1 phenylmercaptoethyl)- borate Dl(mercaptoethyl) mono(methylmercaptoethyl) borate Iri(phenylmercaptobutybborate- Mouo(mereaptoethyl) ditethylmercaptoethybborate 'Iri(mercaptohexadecybborate In addition to improved antiwear and load carrying characteristics, lubricating compositions of the invention also have improved resistance to oxidation. In order to demonstrate the effectiveness of the organomercaptoalkyl borates of the type described hereinabove as antioxidants in lubricating oils, we have conducted comparative oxidation tests with representative lubricating oils alone and with the same lubricating oils blended with representative organo mrcaptoa l kyl borates. The oxidation test was conducted by bubbling air at a rate of one liter per hour through approximately milliliters of test luibricant contained in a glass tube inserted into an aluminum block heated to 347 F. (175 C.). The duration of the test was 48 hours; The viscosity of the test lubricant and its acid number were determined at the beginning and the conclusion of each test. The percent increase in viscosity and the increase in acid number of the lubricant during the test is indicative of the oxidation stability of the test lubricant at a temperature of 347 F. under accelerated oxidizing conditions.
The results of comparative tests on a lubricating oil alone, and the same lubricating oil with an organo mercaptoalkyl borate are shown in Table II.
TABLE 11 Percent by Weight Composition D E F Diisooctyl azelate 100 99. 0 99. 0 Tri(mercaptoethyl)borate (Example I) 1.0 Trxiffodecylmercaptoethyl)borate (Example 1 0 Oxidation Test (Air flow, 1 1/l1r.):
Viscosity, cs. at 100 F.:
Initial 12. 66 12. 66 12. 28 After 48-hour test 1 22. 79 1 13.00 1 12. 55 Increase 10. 13 0. 34 0. 27 Percent Increase in Viscosity 80 2. 7 2. 2 Viscosity Index:
Initial 166 153 163 After 48-hour test 1 142 1 168 1 165 Change in viscosity index. 24 +15 +2 Acid Number (ASTM D 974):
Initial 0. 7 0.07 0.06 After 48-hour test 1 28.68 1 1. 82 1 1. 12 Increase 28. 61 1. 75 1. 06
1 Average of 2 tests.
The data in Table II clearly show that a lubricating oil normally tending to undergo oxidational changes at an elevated temperature has improved resistance to oxidational changes when a small amount of an organo mercaptoalkyl borate is present. The lubricating oils containing the tri(mercaptoethyl)borate and tri(dodecylmercaptoethyl) borate have very little increase in viscosity Although the invention has been described particularly with reference to lubricating oil compositions, it will be recognized that other lubricating compositions including oils thickened to the consistency of a grease areincluded by the invention.
While our invention has been described with reference to various specific examples and embodiments, it will be understood that the invention is not limited to such examples and embodiments and may be variously practiced within the scope of the claims hereinafter made.
We claim: I
1. A lubricating composition comprising a major amount of a lubricating oil and a small amount, sufficient to improve the antiwear and load-carrying characteristics of the oil, of an organo rnercaptoalkyl borate having the general formula S (CI-In) RS(CI-lz)uO-I 3-O(CHz)nSR wherein R is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16.
2. The lubricating composition of claim 1 wherein the organo mercaptoalkyl borate is present in an amount of about 0.5 to 10 percent by weight.
3. A lubricating composition comprising a major amount of a lubricating oil and a small amount, suflicient to improve the antiwear and load-carrying characteristics of the oil, of an organo mercaptoethyl borate having the general formula 1 B (OCH CH SR 3 wherein R is selected from the group consisting of hydrogen and an alkyl radical containing 1 to 12 carbon atoms.
4. The lubricating composition of claim 3 wherein the organo mercaptoethyl borate is tri(InercaptoethyD'borate.
5. The lubricating composition of claim 3 wherein the organo mercaptoethyl borate is tri(dodecylmercaptoethyl) borate.
6. A lubricating composition comprising a major amount of a mineral lubricating oil and about 0.5 to about 10 percent by Weight of tri(mercapt0ethyl)borate.
7. A lubricating composition comprising a major amount of a mineral lubricating oil and about 0.5 to about 10 percent by weight of tri(dodecylmercaptoethyl) borate.
8. A lubricating composition comprising a major amount of diisooctyl azelate and about 0.5 to about 10 percent by weight of tri(mercaptoethyl)borate.
9. A lubricating composition comprising a major amount of diisooctyl azelate and about 0.5 to about 10 percent by weight of tri(dodecy1mercaptoethyl)borate.
References Cited by the Examiner UNITED STATES PATENTS 10/1950 Rogers et a1. 252-463 9/1959 Ramsden 260-462 OTHER REFERENCES Organoboron Chemistry, Howard Steinberg, Interscience Publishers, New York, vol. 1, 1964, p. 27.
DANIEL E. WYMAN, Primary Examiner.
L. G. XIARHOS, Assistant Examiner.
Claims (1)
1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF A LUBRICATING OIL AND A SMALL AMOUNT, SUFFI CIENT TO IMPROVE THE ANTIWEAR AND LOAD-CARRYING CHARACTERISTICS OF THE OIL, OF AN ORGANO MERCAPTOALKYL BORATE HAVING THE GENERAL FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US506127A US3303130A (en) | 1965-11-02 | 1965-11-02 | Lubricant compositions containing organo mercaptoalkyl borates |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US506127A US3303130A (en) | 1965-11-02 | 1965-11-02 | Lubricant compositions containing organo mercaptoalkyl borates |
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| Publication Number | Publication Date |
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| US3303130A true US3303130A (en) | 1967-02-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US506127A Expired - Lifetime US3303130A (en) | 1965-11-02 | 1965-11-02 | Lubricant compositions containing organo mercaptoalkyl borates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3303130A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USB328210I5 (en) * | 1967-04-13 | 1975-01-28 | ||
| US4115286A (en) * | 1977-05-31 | 1978-09-19 | Phillips Petroleum Company | Lubricant antiwear additives containing sulfur and boron |
| US4209410A (en) * | 1976-04-28 | 1980-06-24 | Phillips Petroleum Company | Lubricants |
| FR2515185A1 (en) * | 1981-10-26 | 1983-04-29 | Chevron Res | |
| US4394278A (en) * | 1981-05-26 | 1983-07-19 | Mobil Oil Corporation | Friction reducing additives and compositions thereof |
| US4465605A (en) * | 1982-10-18 | 1984-08-14 | Mobil Oil Corporation | Borated polyhydroxyalkyl sulfides and lubricants containing same |
| US4689162A (en) * | 1984-10-12 | 1987-08-25 | Ciba-Geigy Corporation | Boron-containing compounds |
| US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
| WO1999035218A1 (en) * | 1998-01-09 | 1999-07-15 | Infineum Usa L.P. | Lubricant compositions |
| US6277794B1 (en) | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
| US20060105922A1 (en) * | 2004-10-21 | 2006-05-18 | R. T. Vanderbilt Company, Inc. | Hydroxyalkyldithiocarbamate borate esters |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2526506A (en) * | 1947-10-29 | 1950-10-17 | Standard Oil Dev Co | Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers |
| US2904570A (en) * | 1956-03-27 | 1959-09-15 | Metal & Thermit Corp | Hydrocarbontin derivatives of trismercapto borate esters |
| US3108966A (en) * | 1960-08-23 | 1963-10-29 | Texaco Inc | Lubricant containing copper corrosion inhibitor |
| US3125527A (en) * | 1964-03-17 | Synergistic combination of extreme pres- |
-
1965
- 1965-11-02 US US506127A patent/US3303130A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3125527A (en) * | 1964-03-17 | Synergistic combination of extreme pres- | ||
| US2526506A (en) * | 1947-10-29 | 1950-10-17 | Standard Oil Dev Co | Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers |
| US2904570A (en) * | 1956-03-27 | 1959-09-15 | Metal & Thermit Corp | Hydrocarbontin derivatives of trismercapto borate esters |
| US3108966A (en) * | 1960-08-23 | 1963-10-29 | Texaco Inc | Lubricant containing copper corrosion inhibitor |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USB328210I5 (en) * | 1967-04-13 | 1975-01-28 | ||
| US3914275A (en) * | 1967-04-13 | 1975-10-21 | Olin Corp | Borate esters prepared by successive reactions of boric acid with glycol |
| US4209410A (en) * | 1976-04-28 | 1980-06-24 | Phillips Petroleum Company | Lubricants |
| US4115286A (en) * | 1977-05-31 | 1978-09-19 | Phillips Petroleum Company | Lubricant antiwear additives containing sulfur and boron |
| US4394278A (en) * | 1981-05-26 | 1983-07-19 | Mobil Oil Corporation | Friction reducing additives and compositions thereof |
| FR2515185A1 (en) * | 1981-10-26 | 1983-04-29 | Chevron Res | |
| US4465605A (en) * | 1982-10-18 | 1984-08-14 | Mobil Oil Corporation | Borated polyhydroxyalkyl sulfides and lubricants containing same |
| US4689162A (en) * | 1984-10-12 | 1987-08-25 | Ciba-Geigy Corporation | Boron-containing compounds |
| US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
| WO1999032588A1 (en) * | 1997-12-18 | 1999-07-01 | Infineum Usa L.P. | Antiwear agents for lubricating compositions |
| US6028210A (en) * | 1997-12-18 | 2000-02-22 | Exxon Chemical Patents, Inc. | Process for making sulfur boron antiwear agents for lubricating compositions |
| CN1103807C (en) * | 1997-12-18 | 2003-03-26 | 英菲诺姆美国公司 | Anti-wear agents for lubricating compositions |
| WO1999035218A1 (en) * | 1998-01-09 | 1999-07-15 | Infineum Usa L.P. | Lubricant compositions |
| US6277794B1 (en) | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
| US20060105922A1 (en) * | 2004-10-21 | 2006-05-18 | R. T. Vanderbilt Company, Inc. | Hydroxyalkyldithiocarbamate borate esters |
| US20060106243A1 (en) * | 2004-10-21 | 2006-05-18 | R. T. Vanderbilt Company, Inc. | Hydroxyalkyldithiocarbamate esters |
| US7544644B2 (en) | 2004-10-21 | 2009-06-09 | R.T. Vanderbilt, Inc. | Hydroxyalkyldithiocarbamate borate esters |
| US7589226B2 (en) | 2004-10-21 | 2009-09-15 | R.T. Vanderbilt Company, Inc. | Hydroxyalkyldithiocarbamate esters |
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