US2833715A - Lubricant compositions - Google Patents
Lubricant compositions Download PDFInfo
- Publication number
- US2833715A US2833715A US537588A US53758855A US2833715A US 2833715 A US2833715 A US 2833715A US 537588 A US537588 A US 537588A US 53758855 A US53758855 A US 53758855A US 2833715 A US2833715 A US 2833715A
- Authority
- US
- United States
- Prior art keywords
- oil
- amine
- fatty acids
- reaction product
- unsaturated fatty
- 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
- 239000000203 mixture Substances 0.000 title claims description 37
- 239000000314 lubricant Substances 0.000 title description 9
- 239000003921 oil Substances 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 239000007795 chemical reaction product Substances 0.000 claims description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims description 31
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 30
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 22
- 239000010687 lubricating oil Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 230000001050 lubricating effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 43
- -1 amine salt Chemical class 0.000 description 34
- 239000000654 additive Substances 0.000 description 26
- 239000002253 acid Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 15
- 239000003599 detergent Substances 0.000 description 13
- 239000000470 constituent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 229910052788 barium Inorganic materials 0.000 description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 9
- 239000000539 dimer Substances 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- 201000006747 infectious mononucleosis Diseases 0.000 description 9
- 239000013638 trimer Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 5
- 235000020778 linoleic acid Nutrition 0.000 description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001296 Malleable iron Inorganic materials 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
- C10M2223/121—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy of alcohols or phenols
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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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- This invention pertains to improved lubricant'compositions and in particular to internal combustion engine lubricant compositions which inhibit corrosion, rusting and the pitting and/or wear of the operating parts of the engine.
- valve-lifters for smoother and more efficient engine operation.
- the lifters ride on the cam shaft converting the rotary motion of the cam into a reciprocating motion, which in turn opens and .closes the valves.
- the bottom of the valve-lifter is known as the cam follower.
- the hydraulic part of the valve-lifter functions by means of a plunger on the inside of the valve lifter barrel, together with a ball-check and a spring.
- larger valves, high valve spring pressures and camshafts which produce more rapid valve opening and closing are employed.
- lubricant for internal combustion engines which is improved with respect to oxidation stability, detergency, and dispersant powers.
- a further object of the invention is to provide a method of reducing or eliminating the sticking of hydraulic valve-lifters, the pitting and/or wear of cam followers, and the corrosion of bearings in internal combustion engines.
- Another object is to provide a oil, i. e, an oil having a Saybolt Universal viscosity above about 80 seconds at 100 F., containing between about 0.002 and 10% of a neutralized phosphomsand sulfurcontaining detergent-type lubricating oil additive, between about 0.001 and 5% of an amine salt of the polymerization products of unsaturated fatty acids.
- the detergenttype additive may be one such as an alkaline earth metal, e. g. barium, neutralized reaction product of a phosphorus sulfide and a hydrocarbon such as butylene polymers, including those additives which have excess basicity.
- the amine employed in forming the salts of the polymerized fatty acids is an oil-soluble aliphatic monoamine such as octadecyl amine.
- the polymerization products of the unsaturated fatty acids, e. g. linoleic acid, have a molecular weight between about 400 and 2000.
- the detergent-type lubricating oil additive used is one which contains phosphorus and sulfur.
- the function of this type of additive is to inhibit the formation of sludge and/or varnish-like products which are deposited in the engine and/or about the valves and rings of the engine.
- Detergent additives of this type are usually used in amounts of from about 0.002 to about 10%, and preferably from about 0.01% to about 5%.
- phosphorusand sulfur-containing addition agents are. the neutralized reaction products of a phosphorus sulfide and a hydrocarbon, an alcohol, a ketone, an amine or an ester.
- the neutralized reaction products of a phosphorus sulfide such as a phosphorus penta-sulfide, and a hydrocarbon (note U. S. 2,3l6,082) are preferred.
- the preferred hydrocarbon used for reactionwith the phosphorus sulfide is a mono-olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefin hydrocarbons, such as propylene, butylenes, amylenes or copolymers thereof.
- mono-olefin hydrocarbons such as propylene, butylenes, amylenes or copolymers thereof.
- Such polymers maybe obtained by the polymerization of mono-olefins of less than 6 carbon atoms in the presence of a catalyst, such even as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or' other similar halide catalysts of the Friedel-Crafts type.
- the polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000.
- Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing monoand isomono-olefins, such as butylene and isobutylene at a temperature of from about 80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel- Crafts type, such as for example, boron fluoride, aluminum chloride, and the like.
- a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline can be used.
- Parafinic hydrocarbons such as bright stock residuums, lubricating oil distillates, waxes, and the like can be reacted with phosphorus sulfide. Olefins having 16 to 30 carbon atoms or higher may be reacted with the phosphorus sulfide.
- Other hydrocarbons that can be reacted with a phosphorus sulfide are aromatic hydrocarbons such as benzene, naphthalene, diphenyl, alkylated aromatic hydrocarbons such as benzene having alkyl substituents containing preferably at least 8 carbon atoms, and the like.
- the phosphorus sulfide-hydrocarbon reaction product can be readily obtained by reacting a phosphorus sulfide, for example P 8 with the hydrocarbon at a temperature of from about 200 F. to about 500 F., and preferably from about 200 F. to about 400 F., using from about 1% to about 50%, and preferably from about 5% to about 25% of the phosphorus sulfide in the reaction. It is advantageous to maintain a non-oxidizing atmosphere, such as for example, an atmosphere of nitrogen above the reaction mixture. Usually, it is preferable to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification becomes.
- reaction product can be further treated with steam at an elevated temperature of from about 100 F. to about 600 F.
- the phosphorus sulfide-hydrocarbon reaction product normally shows a titratable acidity which is neutralized by treatment with a basic reagent.
- neutralized reaction product of a phosphorus sulfide and a hydrocarbon as used herein means a phosphorus sulfide-hydrocarbon reaction product having at least 1% of its titratable acidity neutralized by the reaction with a basic reagent.
- the phosphorus sulfide-hydrocarbon reaction product when neutralized with a basic reagent containing a metal constituent is characterized by the presence or retention of the metal constituent of the basic reagent.
- neutralized reaction product of a phosphorus sulfide and hydrocarbon also includes those products which contain the metal constituent in excess of the amount stoichiometrically necessary to replace the acidic hydrogens contained in the phosphorus sulfidehydrocarbon reaction product.
- Such compounds which have this excess amount of metal constituent are known in the art as having excess basicity. They have also been called highly basic, as well as, compounds which have an alkaline reserve which serves to neutralize the acids which are formed in the oxidation of the gasoline and/or sulfur compounds contained therein and/ or lubricating oil.
- the highly basic detergents also have improved detergent and dispersant properties. All of such terms have been used to describe those neutralization products which contain an amount of metal in excess of that required to form the normal neutralization products of the acidic phosphorus sulfide-hydrocarbon reaction product.
- those detergent additives which have excess basicity may contain between 0.5 and 5 moles of the metal constituent per mole of phosphorus contained in the phosphorus sulfide-hydrocarbon reaction product; the particular amount varies with the acidity of the reaction product of phosphorus sulfide and a hydrocarbon, the valence of the metal constituent, and the degree of basicity desired.
- the metal constituent is barium
- the normal neutralization products may contain up to about 3 parts of barium per part of phosphorus by weight in the neutralized phosphorus sulfide-hydrocarbon reaction product. If a product having excess basicity is desired then a weight ratio of between about 4 and 15 parts e. g.
- reaction product can be treated with solid alkaline compounds such as KOH, NaOI-I, Na CO CaO, BaO, Ba(OH) Na S, and the like, at an elevated temperature of from about F. to about 600 F.
- solid alkaline compounds such as KOH, NaOI-I, Na CO CaO, BaO, Ba(OH) Na S, and the like
- Neutralized reaction products containing a heavy metal constituent such as for example, tin, titanium, aluminum, chromium, cobalt, zinc, iron, and the like, can be obtained by reacting a salt of the desired heavy metal with the phosphorus sulfide-hydrocarbon reaction product which has been treated with a basic reagent such as abovedescribed.
- the amine uscd in forming the amine salt of the polymerization products of unsaturated fatty acids are aliphatic mono-amines.
- the amines are of the oil-soluble type. They may have between 8 and 24 carbon atoms.
- Particularly suitable aliphatic amines are the primary mono-amines such as for example, octadecyl amine.
- the aliphatic hydrocarbon radical may have either a straight'or branched chain.
- Aliphatic polyamine salts of the polymerization products of the unsaturated fatty acids are not sufficiently soluble in the oil.
- the amines used may be chemically pure products or of a commercial quality.
- Suitable primary aliphatic mono-amines may be obtained by converting the fatty acids, derived from natural fatty acid glycerides, and the nitrilcs and then reducing the nitriles, for example at temperatures below C. and under alkaline conditions, principally to the primary amines.
- the aliphatic amines usually contain from about 8 to about 18 carbon atoms.
- Suitable amines are the products manufactured according to this general procedure and sold under the trade name Armeen, such as Armeen 8, Armeen 10D, Armeen 14, Airncen 16, Armeen 18 (the Armeens contain a mixture of amines, the principal constituent of. which has the number of These additives which have carbon atoms indicated after the trade name Armeen).
- Armeen such as Armeen 8, Armeen 10D, Armeen 14, Airncen 16, Armeen 18
- Armeens contain a mixture of amines, the principal constituent of. which has the number of These additives which have carbon atoms indicated after the trade name Armeen).
- Other aliphatic mono-amines which may be employed are the Primenes. These are mixtures of substantially primary amines having molecular weights of from about 185 to 350, and whose alkyl chains are branched.
- the polymerization products of the unsaturated fatty acids, from which are formed the amine salts are those such as may be obtained by the polymerization of natural or synthetic mono-carboxylic acids which generally will have 16 to 26 carbon atoms, most frequently 18 carbon atoms, but if synthetic unsaturated fatty acids are used they may have a lesser or greater number of carbon atoms.
- Examples of the natural fatty acids are those such as linoleic, linolenic, ricinoleic (which upon heating forms linoleic acid), linoleaidic, elaidolinolenic, 'eleostearic, arachidonic, eicosatrienoic, cetoleic, docosatrienoic and the like.
- the free fatty acids can be polymerized either thermally or with the assistance of catalysts. A method of thermally polymerizing free fatty acids (see U. S.
- 2,482,761 consists of hydrolyzing a fat or an oil, adding a small portion of water, andheating in a pressure vessel until substantially all of the diand tri-unsaturated fatty acids present polymerize. The resultant product is then heated at a reduced pressure to distill olf vaporizable constituents, leaving behind the polymerized unsaturated fatty acids.
- the polymerization reaction is carried out at a temperature of about 300 to 360 C. for about 3 to 8 hours at a pressure vary- 'ing between 75 and 500 p. s. i. g.
- the polymerization product may consist of monomers, dimers, trimers, and higher polymers of the unsaturated fatty acids.
- the various fats or oils which may be hydrolyzed to produce the free fatty acids used in the above thermal polymerization are those such as sardine oil, linseed oil, soybean oil, castor oil, peanut oil, palm oil, olive oil, cottonseed oil, sunflower seed oil, and the like.
- Another method of preparing the polymerized fatty acids consists of subjecting fats and oils such as have been listed supra (without previous hydrolysis) to a thermal or catalytic polymerization to cause polymerization of the esters of the unsaturated carboxylic acids to the dimers, trimers, and higher polymerization products thereof, followed by hydrolysis to yield the corresponding polymers of the acids.
- a large source of the polymerized unsaturated fatty acids are those residual acids obtained by methanolysis (see U. S. 2,450,940) of the semi-drying or drying type oils such as castor oil, soybean oil, and others listed supra, polymerizing the methyl esters, removing unpolymerized compounds, saponifying the residual esters and freeing polymerized acids therefrom.
- the products of catalytic polymerization of semi-drying oils such as the BF polymerization products of soybean oil, cottonseed oil, or the like also produce polymers suitable for use in the invention.
- the mixture of high molecular weight unsaturated fatty acids comprises monomers, dimers, trimers and higher polymers in the ratio of from about 45% to about 55% of a monomers and dimers fraction having a molecular weight in the range of from about 300 to 600, and from about 45% to about 55% of a trimers and higher polymer fraction having a molecular weight in excess of 600.
- the fatty acid polymers result in part from a thermal polymerization of fatty acid type 6 constituents of the castor oil, and in part from other reactions, such asthe inter-molecular esterification, of such acid to form high molecular weight products.
- the acid mixture which is mainly amixture of polymeric long chain polybasic carboxylic acids, is further characterized by the following specifications:
- a fatty acid mixture such as above described is marketed under the trade name D-50 Acids, and also as VR-l Acids.
- the polymerization products of the unsaturated fatty acids may have a molecular weight between about 400 and 2000. Those polymers having a molecular weight higher than about 500, and especially those having molecular weights averaging about 800 or higher are particularly preferred for use in this invention.
- the polymerization products may consist primarily of dimers and trimers of linoleic acid, for example Emery 955 dimer acid which contains 85% of the dimer, 12% of the trimer, and 3% of the monomer of linoleic acid may be used.
- Especially preferred polymerized unsaturated acids are the polymerization products of acids such as linoleic acid having a molecular weight between about 400 and 2000, wherein the polymerization products consist of more than about 40% of the trimer and higher molecular weight polymers of linoleic acid with the remainder consisting primarily of monomers and dimers of linoleic acid.
- the amine salts may be prepared by reacting, under carefully controlled, non-dehydrating conditions, i. e. below about 200 F., the amine and the polymerization products of the unsaturated fatty acids. Care must be taken in the preparation of such salts inasmuch as prolonged exposure to temperatures higher than about 200 F. results in the formation of amides upon separating out water.
- the amine salts may be preformed by effecting the reaction in a volatile solvent which is then distilled from the amine salt, or it may be prepared in a hydrocarbon oil.
- the amine salts may be formed in situ in the lubricating oil composition by adding thereto the reactants i. e. the amine and the polymerization products of the unsaturated fatty acids.
- the phosphorusand sulfur-containing detergent-type additive and the amine salt of the polymerization products of unsaturated fatty acids can be added individually to the lubricating oil base or they can be pre-mixed (preferably together with the detergent-type additive) in the desired proportions and the resultant mixture then added to the lubricating oil base.
- Concentrations of a suitable oil base containing more than 10%, for example up to 50% or more, of the detergent-type additive, alone or in combination with more than about 5%, for example up to 25% or more, of the amine salt can be used for blending with the hydrocarbon oils in the proportions desired for the particular conditions of use to provide a finished valve-lifters .weremade.
- the tests made to determine" the anti-pitting and anti-wear properties of the oil is known as the L-S-S test. established by the General Motors Re search Division. The test is made on a 1953 Chevrolet power glide engine equipped with chilled iron lifters, forged steel cams, steel rocker arm shafts, malleable iron rocker arms and operating at 3150 R. P. M. with a load of 30 brake horsepower, an oil sump temperature of 255 F and a water outlet temperature of 200 F. Dual valve springs are installed to give an assembled static valve spring load of 240 pounds at.0.330 inchvalve opening. The test is continued for 24 hours at the end of which the cam followers are inspected for pitting and over-all wear.
- compositions A and B were composed of the following:
- Sample 3 shows that when the amine salt, prepared from Emery 955 Acid and Primene JMR octadecylamine, is used in the oil, only two lifters are pitted;
- Sample 6 shows that when the amine salt, prepared from D Acid and Armeen T which consists of the technical mixture of amines prepared from tallow, is used in the oil, it enables the oil to pass the L-S-S test and allows only 1 cam follower to-become pitted. This is accom- 1 plished when using only one-third as much of the antipitting additive as was employed in Sample 5.
- the test employed is called the modified Indiana hydraulic valve lifter rust test. This test is carried out in a Chevrolet power-glide engine opcrating at 2500, R. P. M. and a load of 45 B. H. P. with an. oil temperature of F. and a water temperature of 85-95" F. The test engine is operated at these conditions for 20 hours with a 4 hour running and 4 hour off cycle. At the end of 20 hours the dipstick, rocker arm shaft and valve lifters are inspected for rust. Valve lifters free of. rust are rated 10 and. badly rusted lifters are rated 1.
- oils obtained by thepolymerization of olefins synthetic lubrieating oils of'the alkylene oxide type, for example, Ucon Oils, and the polycarboxylic acid ester type oils such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc. may be used.
- composition of claim 1 wherein the basic reagent is an alkaline earth metal compound.
- composition of claim 1 in which the unsaturated fatty acid is linoleic acid
- composition of claim 1 wherein the polymerization products of the unsaturated fatty acids consist of more than about 40% of the trimer and higher molecular weight polymers, the remainder being essentially monomers and dimers of the unsaturated fatty acids.
- composition of claim 1 wherein the amine is a primary octadecyl amine.
- composition of claim 1 which also contains between 0.001 and 5% of an oil-soluble aliphatic monoamine.
- a lubricating oil composition having improved valve lifter anti-pitting and anti-wear properties comprising a major proportion of a lubricating mineral oil base, between about 0.002 and of a barium-containing neutralized reaction product of a phosphorus sulfide and a butylene polymer, said neutralized reaction product having excess basicity, between about 0.05 and 2% of an amine salt of the polymerization products of linoleic acid, said amine being an oil-soluble aliphatic primary mono- 10.
- An addition agent for formulating a lubricatingv oil composition which has improved valve lifters antipitting and anti-wear properties, said agent comprising a concentrated solution of a mineral oil containing more than 10% of a phosphorus sulfide-hydrocarbon reaction product which has been neutralized with a basic reagent and more than about 5% of an amine salt of the polymerization products of those unsaturated fatty acids which I have from 16 to 26 carbon atoms per molecule, said amine being an oil-soluble aliphatic mono-amine and said polymerization products having a molecular weight between about 400 and 2000, said concentrated solution being capable of dilution with a lubricating mineral oil base to form a homogeneous mixture containing between about 0.002 and 10% of the neutralized phosphorus sulfide-hydrocarbon reaction product and between about 0.001 and 5% of the amine salt.
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
United States Patent LUBRICANT CGMPOSITIONS Norman E. Lemmon, Whiting, Ind., and Ellis K. Fields,
Chicago, Ill., assignors to Standard Oil Company, Chicage, 11]., a corporation of Indiana N 0 Drawing. Application September 29, 1955 Serial No. 537,588
Claims. (Cl. 25232.7)
This invention pertains to improved lubricant'compositions and in particular to internal combustion engine lubricant compositions which inhibit corrosion, rusting and the pitting and/or wear of the operating parts of the engine.
Many modern automobile engines are designed with hydraulic valve-lifters for smoother and more efficient engine operation. In the operation of hydraulic valvelifters, the lifters ride on the cam shaft converting the rotary motion of the cam into a reciprocating motion, which in turn opens and .closes the valves. The bottom of the valve-lifter is known as the cam follower. The hydraulic part of the valve-lifter functions by means of a plunger on the inside of the valve lifter barrel, together with a ball-check and a spring. To obtain higher efficiency and greater horsepower, larger valves, high valve spring pressures and camshafts which produce more rapid valve opening and closing are employed. In the operation of such engines, greatly increased pressures are encountered where the camshaft lobes come into contact with the faces of the valve-lifters resulting in excessive and severe cam and lifter wear as well as pitting of the cam followers. This wear and/ or pitting cannot be adequately inhibited by most present-day internal combustion engine crank-case lubricants. Surprisingly, the type of anti-wear properties which will inhibit piston'ring and/ or cylinder wear are not necessarily the same as the antiwear properties necessary to prevent cam and lifter wear and/ or pitting; hence many lubricants which are elfective in inhibiting ring and cylinder wear are ineffective in preventing cam and lifter wear. A further complicating factor in this problem is caused by the materials used in making the camshaft and valve-lifters since different metals and metal combinations are used for this purpose in the various engines. Furthermore, because of the small clearances between the plunger and the barrel of hydraulic valve-lifters, extremely small amounts of deposits such as varnish and/ or rusting may cause sticking of the valve-lifter. Hence, it is essential for good engine operation to provide a lubricant which will, in addition.
to inhibit wear and/ or pitting, also inhibit the formation of varnish and/ or rusting in the valve-lifter. I
It is an object of this invention to provide a lubricant composition which will be substantially free of any tendency to cause valve lifter sticking and/or rusting and which will have improved cam follower anti-pitting and anti-wear properties. lubricant for internal combustion engines which is improved with respect to oxidation stability, detergency, and dispersant powers. A further object of the invention is to provide a method of reducing or eliminating the sticking of hydraulic valve-lifters, the pitting and/or wear of cam followers, and the corrosion of bearings in internal combustion engines. Other objects and advantages will become apparent from the following description thereof.
In accordance with the herein described invention, the
above objects can be attained by incorporating in a viscous Another object is to provide a oil, i. e, an oil having a Saybolt Universal viscosity above about 80 seconds at 100 F., containing between about 0.002 and 10% of a neutralized phosphomsand sulfurcontaining detergent-type lubricating oil additive, between about 0.001 and 5% of an amine salt of the polymerization products of unsaturated fatty acids. The detergenttype additive may be one such as an alkaline earth metal, e. g. barium, neutralized reaction product of a phosphorus sulfide and a hydrocarbon such as butylene polymers, including those additives which have excess basicity. The amine employed in forming the salts of the polymerized fatty acids is an oil-soluble aliphatic monoamine such as octadecyl amine. The polymerization products of the unsaturated fatty acids, e. g. linoleic acid, have a molecular weight between about 400 and 2000. a
While the polymerization pro-ducts of unsaturated fatty acids improve the anti-wear, anti-pitting, and anti-rusting properties of the lubricant containing the detergent additive, the improvement is often insufficient and the oxidation stability of the oil is reduced. This causes an increase in the erosion in the bearing surfaces ..of the internal combustion engine. It has been found that these deficiencies in the use of the polymerization products of the unsaturated fatty acids can be eliminated by employing the aliphatic mono-amine salts thereof.
It has also been found thatthe pitting and/or wear, as well as the rusting problem, occurring in hydraulic valve lifters is markedly increased when using a neutral-l i zed phosphorous-and sulfur-containing detergent-type-additive which has an excess basicity. These highly basic detergent additives i. e. those which contain a metal constituent in excess of that stoichiometrically necessary to neutralize the acidic hydrogen atoms, are being'used to an increasing extent since they furnish an alkaline're-.
serve which neutralizes acid compounds formed in the oxidation of gasoline or oil and also provide improved detergent and dispersant power. It appears that the prob-l lem of pitting, wear, and/ or rusting increases as the amount of excess basicity of the detergent additive increases. It has been discovered that the amine salts of the polymerization products of the unsaturated fattyacids are effective in greatly reducing or eliminating completely this aggravated problem. The presence of between about 0.001 and 5% of an oil soluble aliphatic mono-amine in the lubricating oil composition which contains the detergent additive and the amine salt of the polymerization products of the unsaturated fatty acids, improves the antirust properties of the lubricating oil composition further. I
The detergent-type lubricating oil additive used is one which contains phosphorus and sulfur. The function of this type of additive is to inhibit the formation of sludge and/or varnish-like products which are deposited in the engine and/or about the valves and rings of the engine. Detergent additives of this type are usually used in amounts of from about 0.002 to about 10%, and preferably from about 0.01% to about 5%. Among the phosphorusand sulfur-containing addition agents are. the neutralized reaction products of a phosphorus sulfide and a hydrocarbon, an alcohol, a ketone, an amine or an ester. Of the phosphorus sulfide reaction product a'dditives, the neutralized reaction products of a phosphorus sulfide, such as a phosphorus penta-sulfide, and a hydrocarbon (note U. S. 2,3l6,082) are preferred.
The preferred hydrocarbon used for reactionwith the phosphorus sulfide is a mono-olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefin hydrocarbons, such as propylene, butylenes, amylenes or copolymers thereof. Such polymers maybe obtained by the polymerization of mono-olefins of less than 6 carbon atoms in the presence of a catalyst, such even as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or' other similar halide catalysts of the Friedel-Crafts type.
The polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing monoand isomono-olefins, such as butylene and isobutylene at a temperature of from about 80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel- Crafts type, such as for example, boron fluoride, aluminum chloride, and the like. In the preparation of these polymers, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline can be used.
Parafinic hydrocarbons such as bright stock residuums, lubricating oil distillates, waxes, and the like can be reacted with phosphorus sulfide. Olefins having 16 to 30 carbon atoms or higher may be reacted with the phosphorus sulfide. Other hydrocarbons that can be reacted with a phosphorus sulfide are aromatic hydrocarbons such as benzene, naphthalene, diphenyl, alkylated aromatic hydrocarbons such as benzene having alkyl substituents containing preferably at least 8 carbon atoms, and the like.
The phosphorus sulfide-hydrocarbon reaction product can be readily obtained by reacting a phosphorus sulfide, for example P 8 with the hydrocarbon at a temperature of from about 200 F. to about 500 F., and preferably from about 200 F. to about 400 F., using from about 1% to about 50%, and preferably from about 5% to about 25% of the phosphorus sulfide in the reaction. It is advantageous to maintain a non-oxidizing atmosphere, such as for example, an atmosphere of nitrogen above the reaction mixture. Usually, it is preferable to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification becomes. necessary; however, an excess amount of phosphorus sulfide can be used and separated from the product by filtration or by dilution with a hydrocarbon solvent, such as hexane, filtering and subsequently removing the solvent by suitable means, such as by distillation. If desired, the reaction product can be further treated with steam at an elevated temperature of from about 100 F. to about 600 F.
The phosphorus sulfide-hydrocarbon reaction product normally shows a titratable acidity which is neutralized by treatment with a basic reagent. The term neutralized reaction product of a phosphorus sulfide and a hydrocarbon as used herein means a phosphorus sulfide-hydrocarbon reaction product having at least 1% of its titratable acidity neutralized by the reaction with a basic reagent. The phosphorus sulfide-hydrocarbon reaction product when neutralized with a basic reagent containing a metal constituent is characterized by the presence or retention of the metal constituent of the basic reagent.
The term neutralized reaction product of a phosphorus sulfide and hydrocarbon also includes those products which contain the metal constituent in excess of the amount stoichiometrically necessary to replace the acidic hydrogens contained in the phosphorus sulfidehydrocarbon reaction product. Such compounds which have this excess amount of metal constituent are known in the art as having excess basicity. They have also been called highly basic, as well as, compounds which have an alkaline reserve which serves to neutralize the acids which are formed in the oxidation of the gasoline and/or sulfur compounds contained therein and/ or lubricating oil. The highly basic detergents also have improved detergent and dispersant properties. All of such terms have been used to describe those neutralization products which contain an amount of metal in excess of that required to form the normal neutralization products of the acidic phosphorus sulfide-hydrocarbon reaction product.
In general those detergent additives which have excess basicity may contain between 0.5 and 5 moles of the metal constituent per mole of phosphorus contained in the phosphorus sulfide-hydrocarbon reaction product; the particular amount varies with the acidity of the reaction product of phosphorus sulfide and a hydrocarbon, the valence of the metal constituent, and the degree of basicity desired. For example when the metal constituent is barium, the normal neutralization products may contain up to about 3 parts of barium per part of phosphorus by weight in the neutralized phosphorus sulfide-hydrocarbon reaction product. If a product having excess basicity is desired then a weight ratio of between about 4 and 15 parts e. g. 5 parts of barium per part of phosphorus in the phosphorus sulfide-hydrocarbon reaction product should be used. excess basicity may conveniently be made by neutralizing the acidic phosphorus sulfide-hydrocarbon reaction product with an amount of basic reagent inexcess of that necessary to replace the acidic hydrogen atoms contained therein. Prior to neutralization the reaction product can be hydrolyzed and clayed to remove inorganic acids of phosphorusas described in U. S. 2,688,612 issued to R. W. Watson September 7, 1954.
The neutralized phosphorus sulfide-hydrogen reaction product can be obtained by treating the acidic reaction product with a suitable basic compound, such as hydroxide, carbonate, oxide, or sulfide of an alkali or alkaline earth. metal, such as for example, potassium hydroxide, sodium hydroxide, sodium sulfide, and calcium oxide,'lime, barium hydroxide, barium oxide, etc. The neutralization of the phosphorus sulfide-hydrocarbon reaction product is carried out preferably in a non-oxidizing atmosphere by contacting the acidic reaction product either as such or dissolved in a suitable solvent, such as naphtha with a solution of the basic agent. As an alternative method the reaction product can be treated with solid alkaline compounds such as KOH, NaOI-I, Na CO CaO, BaO, Ba(OH) Na S, and the like, at an elevated temperature of from about F. to about 600 F. Neutralized reaction products containing a heavy metal constituent, such as for example, tin, titanium, aluminum, chromium, cobalt, zinc, iron, and the like, can be obtained by reacting a salt of the desired heavy metal with the phosphorus sulfide-hydrocarbon reaction product which has been treated with a basic reagent such as abovedescribed.
The amine uscd in forming the amine salt of the polymerization products of unsaturated fatty acids are aliphatic mono-amines. The amines are of the oil-soluble type. They may have between 8 and 24 carbon atoms. Particularly suitable aliphatic amines are the primary mono-amines such as for example, octadecyl amine. The aliphatic hydrocarbon radical may have either a straight'or branched chain. Aliphatic polyamine salts of the polymerization products of the unsaturated fatty acids are not sufficiently soluble in the oil.
In forming the amine salt with a single amine or a mixture of amines, the amines used may be chemically pure products or of a commercial quality. Suitable primary aliphatic mono-amines may be obtained by converting the fatty acids, derived from natural fatty acid glycerides, and the nitrilcs and then reducing the nitriles, for example at temperatures below C. and under alkaline conditions, principally to the primary amines. Depending upon the fatty acid used, the aliphatic amines usually contain from about 8 to about 18 carbon atoms. Suitable amines are the products manufactured according to this general procedure and sold under the trade name Armeen, such as Armeen 8, Armeen 10D, Armeen 14, Airncen 16, Armeen 18 (the Armeens contain a mixture of amines, the principal constituent of. which has the number of These additives which have carbon atoms indicated after the trade name Armeen). Other aliphatic mono-amines which may be employed are the Primenes. These are mixtures of substantially primary amines having molecular weights of from about 185 to 350, and whose alkyl chains are branched.
The polymerization products of the unsaturated fatty acids, from which are formed the amine salts, are those such as may be obtained by the polymerization of natural or synthetic mono-carboxylic acids which generally will have 16 to 26 carbon atoms, most frequently 18 carbon atoms, but if synthetic unsaturated fatty acids are used they may have a lesser or greater number of carbon atoms. Examples of the natural fatty acids are those such as linoleic, linolenic, ricinoleic (which upon heating forms linoleic acid), linoleaidic, elaidolinolenic, 'eleostearic, arachidonic, eicosatrienoic, cetoleic, docosatrienoic and the like. The free fatty acids can be polymerized either thermally or with the assistance of catalysts. A method of thermally polymerizing free fatty acids (see U. S. 2,482,761) consists of hydrolyzing a fat or an oil, adding a small portion of water, andheating in a pressure vessel until substantially all of the diand tri-unsaturated fatty acids present polymerize. The resultant product is then heated at a reduced pressure to distill olf vaporizable constituents, leaving behind the polymerized unsaturated fatty acids. The polymerization reaction is carried out at a temperature of about 300 to 360 C. for about 3 to 8 hours at a pressure vary- 'ing between 75 and 500 p. s. i. g. The polymerization product may consist of monomers, dimers, trimers, and higher polymers of the unsaturated fatty acids. The various fats or oils which may be hydrolyzed to produce the free fatty acids used in the above thermal polymerization are those such as sardine oil, linseed oil, soybean oil, castor oil, peanut oil, palm oil, olive oil, cottonseed oil, sunflower seed oil, and the like.
Another method of preparing the polymerized fatty acids consists of subjecting fats and oils such as have been listed supra (without previous hydrolysis) to a thermal or catalytic polymerization to cause polymerization of the esters of the unsaturated carboxylic acids to the dimers, trimers, and higher polymerization products thereof, followed by hydrolysis to yield the corresponding polymers of the acids. A large source of the polymerized unsaturated fatty acids are those residual acids obtained by methanolysis (see U. S. 2,450,940) of the semi-drying or drying type oils such as castor oil, soybean oil, and others listed supra, polymerizing the methyl esters, removing unpolymerized compounds, saponifying the residual esters and freeing polymerized acids therefrom. The products of catalytic polymerization of semi-drying oils such as the BF polymerization products of soybean oil, cottonseed oil, or the like also produce polymers suitable for use in the invention.
It should be understood that while various polymerized unsaturated fatty acids maybe used, they do not all provide the same effect, and indeed there may be pronounced differences when used in the composition of this invention. A highly preferred source of the polymerized unsaturated fatty acids is obtained as a byproduct still residue in the manufacture of sebacic acid by the dry distillation of castor oil in the presence of sodium hydroxide. A method of obtaining such byproduct still residues in the manufacture of sebacic acid is described in U. S. 2,470,849 issued to W. E. Hanson May 24, 1949. The mixture of high molecular weight unsaturated fatty acids comprises monomers, dimers, trimers and higher polymers in the ratio of from about 45% to about 55% of a monomers and dimers fraction having a molecular weight in the range of from about 300 to 600, and from about 45% to about 55% of a trimers and higher polymer fraction having a molecular weight in excess of 600. The fatty acid polymers result in part from a thermal polymerization of fatty acid type 6 constituents of the castor oil, and in part from other reactions, such asthe inter-molecular esterification, of such acid to form high molecular weight products. The acid mixture, which is mainly amixture of polymeric long chain polybasic carboxylic acids, is further characterized by the following specifications:
Acid N0. 150 to 164 Saponification No. 175 to 186 Free fatty acids percent 75 to 82 Iodine value 44 to Non-saponifiables percent 2.5 to 5 A fatty acid mixture such as above described is marketed under the trade name D-50 Acids, and also as VR-l Acids.
The polymerization products of the unsaturated fatty acids may have a molecular weight between about 400 and 2000. Those polymers having a molecular weight higher than about 500, and especially those having molecular weights averaging about 800 or higher are particularly preferred for use in this invention. The polymerization products may consist primarily of dimers and trimers of linoleic acid, for example Emery 955 dimer acid which contains 85% of the dimer, 12% of the trimer, and 3% of the monomer of linoleic acid may be used. Especially preferred polymerized unsaturated acids are the polymerization products of acids such as linoleic acid having a molecular weight between about 400 and 2000, wherein the polymerization products consist of more than about 40% of the trimer and higher molecular weight polymers of linoleic acid with the remainder consisting primarily of monomers and dimers of linoleic acid.
The amine salts may be prepared by reacting, under carefully controlled, non-dehydrating conditions, i. e. below about 200 F., the amine and the polymerization products of the unsaturated fatty acids. Care must be taken in the preparation of such salts inasmuch as prolonged exposure to temperatures higher than about 200 F. results in the formation of amides upon separating out water. The amine salts may be preformed by effecting the reaction in a volatile solvent which is then distilled from the amine salt, or it may be prepared in a hydrocarbon oil. The amine salts may be formed in situ in the lubricating oil composition by adding thereto the reactants i. e. the amine and the polymerization products of the unsaturated fatty acids. While the use of one mole of the amine per carboxylic acid group contained in the polymerization products of the unsaturated fatty acids is necessary to form the amine salts, if a larger amount of the amine is employed it exists in the free state. Upon the addition of a mixture of the amine salt together with free amine to the lubricating oil improved anti-rust properties are obtained.
The phosphorusand sulfur-containing detergent-type additive and the amine salt of the polymerization products of unsaturated fatty acids can be added individually to the lubricating oil base or they can be pre-mixed (preferably together with the detergent-type additive) in the desired proportions and the resultant mixture then added to the lubricating oil base. Concentrations of a suitable oil base containing more than 10%, for example up to 50% or more, of the detergent-type additive, alone or in combination with more than about 5%, for example up to 25% or more, of the amine salt, can be used for blending with the hydrocarbon oils in the proportions desired for the particular conditions of use to provide a finished valve-lifters .weremade. The tests made to determine" the anti-pitting and anti-wear properties of the oil is known as the L-S-S test. established by the General Motors Re search Division. The test is made on a 1953 Chevrolet power glide engine equipped with chilled iron lifters, forged steel cams, steel rocker arm shafts, malleable iron rocker arms and operating at 3150 R. P. M. with a load of 30 brake horsepower, an oil sump temperature of 255 F and a water outlet temperature of 200 F. Dual valve springs are installed to give an assembled static valve spring load of 240 pounds at.0.330 inchvalve opening. The test is continued for 24 hours at the end of which the cam followers are inspected for pitting and over-all wear.
The effectiveness of the additives for preventing pitting of the cam followers is shown in the table which follows. In obtaining the data presented in this table various additives for preventing pitting and/or wear of the cam followers were added either to OilComposition A of Oil Composition B and the mixtures then evaluated. Oil
Compositions A and B were composed of the following:
Oil Composition A-SAE W-20 oil plus 3.0% of a barium-containing neutralized reaction product of P 8 and a polybutene of about 1000 molecular weight (having a barium to phosphorus weight ratio of approximately 3:1, that is to say having no excess alkalinity or basicity) plus 0.67% of a sulfurized dipentene (35% sulfur) plus 4.6% of a V. I. improver plus p. p. m. anti-foam agent.
Oil Composition B-SAE 5W-20 oil plus 5.5% of a barium-containing neutralized reaction product of P 5 and a polybutene of about l000'molecular. weight (having a barium to phosphorus weight ratio ofabout 5:1, i. e. having excess basicity) plus 0.75%, of a. sulfurized dipentene sulfur) plus 10 p. p. m. antifoam agent. The results show:
L-S5 engine tests 1 Estimated. Samples 1 and 4 show that unless an anti-pitting and'antiwear additive is present in the oil almost all of the cam follower surfaces will be pitted. Sample 4 shows that when the detergent additive has excess basicity, the degree of pitting and/ or wear is increased. Samples 2 and 5 sh'ow that the pitting and/or wear problem is not eliminated merely by using the polymerization products of theun saturated fatty acids (the compositions of the commercial polymerized fatty acids used here have been detailed previously). Sample 3 shows that when the amine salt, prepared from Emery 955 Acid and Primene JMR octadecylamine, is used in the oil, only two lifters are pitted; Sample 6 shows that when the amine salt, prepared from D Acid and Armeen T which consists of the technical mixture of amines prepared from tallow, is used in the oil, it enables the oil to pass the L-S-S test and allows only 1 cam follower to-become pitted. This is accom- 1 plished when using only one-third as much of the antipitting additive as was employed in Sample 5.
An additional series of samples were evaluated to determine the ability of various additives to prevent rusting of the hydraulic valve-lifters. The test employed is called the modified Indiana hydraulic valve lifter rust test. This test is carried out in a Chevrolet power-glide engine opcrating at 2500, R. P. M. and a load of 45 B. H. P. with an. oil temperature of F. and a water temperature of 85-95" F. The test engine is operated at these conditions for 20 hours with a 4 hour running and 4 hour off cycle. At the end of 20 hours the dipstick, rocker arm shaft and valve lifters are inspected for rust. Valve lifters free of. rust are rated 10 and. badly rusted lifters are rated 1.
The oil samples employed in this test were portions of Oil Composition B which was previously described. The effectiveness of different additives for preventing rusting and/ or corrosion in the hydraulic valve-lifters rust shown in the table which follows:
Modified Indiana hydraulic valve lifter rust test Sample 4 shows that it is imperative to employ an additivefor inhibiting the rusting of the valve lifters. Sample 7 indicates that the D-50 Acid reduces the amount of rusting. Best results, however, can be obtained when employing the amine salt (Armeen T was employed) of the polymerized unsaturated fatty acids.
The advantage of employing free amine in the lubrieating oil composition containing the detergent and amine salt of the polymerized unsaturated fatty acids was demonstrated in accelerated rusting tests in Water. The tests demonstrated that the presence of free amine in the oil containing the detergent additive and the amine salt of the polymerization products of the unsaturated fatty acids provided rust protection for twice the length of time as was provided when no free amine was present.
Additional tests evaluating lubricating oils containing different anti-pitting and anti-wear compounds were conducted. L-4 tests which measure the oil stability and insure that the additive does not lower the stability of the oil were made. The L-4 test measures the bearing weight loss. In these tests it was demonstrated that the lubricatingoil containing neutralized phosphorus and sulfurcontaining' detergent additive produces better results in the L-4 test when an octadecyl amine salt of the D-50 Acid was used in place of the 13-50 Acid alone.
While thepresent invention has been described by the use of our additives in petroleum lubricating oils, other lubricating oil bases can be employed. For example oils obtained by thepolymerization of olefins, synthetic lubrieating oils of'the alkylene oxide type, for example, Ucon Oils, and the polycarboxylic acid ester type oils such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc. may be used.
Unless otherwise stated, the percentages stated herein and in the claims are weight percentages.
Although the present invention has been described with reference to specific preferred embodiments thereof, the invention is not to be considered as limited thereto but includes within its scope such modifications and variations as come within the spirit of the appended claims.
Weclaim:
l. A lubricating oil. composition having improved valve lifter anti-pitting and anti-wear properties compris ing a major proportion of a lubricating mineral oil base, between about 0.002 and 10% of a phosphorus sulfide-hydrocarbon reaction product which has been neutralized with a basic reagent, and between about 0.001 and 5% of an amine salt of the polymerization products of those unsaturated fatty acids which have between 16 and 26 carbon atoms per molecule, said amine being an oil soluble aliphatic mono-amine, and said polymerization products having a molecular weight between about 400 and 2000. v
2. The composition of claim 1 wherein the basic reagent is an alkaline earth metal compound.
3. The composition of claim 1 wherein the phosphorus sulfide-hydrocarbon reaction product has been neutralized with a basic barium compound to produce a product having excess basicity.
4. The composition of claim 1 in which the unsaturated fatty acid is linoleic acid,
5. The composition of claim 1 wherein the polymerization products of the unsaturated fatty acids consist of more than about 40% of the trimer and higher molecular weight polymers, the remainder being essentially monomers and dimers of the unsaturated fatty acids.
6. The composition of claim 1 wherein the amine is a primary octadecyl amine.
7. The composition of claim 1 which also contains between 0.001 and 5% of an oil-soluble aliphatic monoamine.
8. A lubricating oil composition having improved valve lifter anti-pitting and anti-wear properties comprising a major proportion of a lubricating mineral oil base, between about 0.002 and of a barium-containing neutralized reaction product of a phosphorus sulfide and a butylene polymer, said neutralized reaction product having excess basicity, between about 0.05 and 2% of an amine salt of the polymerization products of linoleic acid, said amine being an oil-soluble aliphatic primary mono- 10. An addition agent for formulating a lubricatingv oil composition which has improved valve lifters antipitting and anti-wear properties, said agent comprising a concentrated solution of a mineral oil containing more than 10% of a phosphorus sulfide-hydrocarbon reaction product which has been neutralized with a basic reagent and more than about 5% of an amine salt of the polymerization products of those unsaturated fatty acids which I have from 16 to 26 carbon atoms per molecule, said amine being an oil-soluble aliphatic mono-amine and said polymerization products having a molecular weight between about 400 and 2000, said concentrated solution being capable of dilution with a lubricating mineral oil base to form a homogeneous mixture containing between about 0.002 and 10% of the neutralized phosphorus sulfide-hydrocarbon reaction product and between about 0.001 and 5% of the amine salt.
References Cited in the file of this patent UNITED STATES PATENTS Kelso Apr. 6, 1943 Langer Ian. 6, 1953
Claims (1)
1. A LUBRICATING OIL COMPOSITION HAVING IMPROVED VALVE LIFTER ANTI-PITTING AND ANTI-WEAR PROPERTIES COMPRISING A MAJOR PROPORTION OF A LUBRICATING MINERAL OIL BASE, BETWEEN ABOUT 0.002 AND 10% OF A PHOSPHORUS SULFIDE-HYDROCARBON REACTION PRODUCT WHICH HAS BEEN NEUTRALIZED WITH A BASIC REAGENT, AND BETWEEN ABOUT 0.001 AND 5% OF AN AMINE SALT OF THE POLYMERIZATION PRODUCTS OF THOSE UNSATURATED FATTY ACIDS WHICH HAVE BETWEEN 16 AND 26 CARBON ATOMS PER MOLECULE, SAID AMINE BEING AN OIL SOLUBLE ALIPHATIC MONO-AMINE, AND SAID POLYMERIZATION PRODUCTS HAVING A MOLECULAR WEIGHT BETWEEN ABOUT 400 AND 2000.
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US537588A US2833715A (en) | 1955-09-29 | 1955-09-29 | Lubricant compositions |
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US537588A US2833715A (en) | 1955-09-29 | 1955-09-29 | Lubricant compositions |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2975133A (en) * | 1955-04-21 | 1961-03-14 | Gulf Oil Corp | Corrosion-inhibiting mineral oil compositions |
US3113106A (en) * | 1958-06-03 | 1963-12-03 | Standard Oil Co | Rust inhibited lubricants |
US3203896A (en) * | 1962-03-28 | 1965-08-31 | Universal Oil Prod Co | Lubricating composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2316090A (en) * | 1941-12-30 | 1943-04-06 | Standard Oil Co | Lubricant |
US2624708A (en) * | 1950-06-23 | 1953-01-06 | Union Carbide & Carbon Corp | Inhibited polyoxyalkylene glycol fluids |
-
1955
- 1955-09-29 US US537588A patent/US2833715A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2316090A (en) * | 1941-12-30 | 1943-04-06 | Standard Oil Co | Lubricant |
US2624708A (en) * | 1950-06-23 | 1953-01-06 | Union Carbide & Carbon Corp | Inhibited polyoxyalkylene glycol fluids |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2975133A (en) * | 1955-04-21 | 1961-03-14 | Gulf Oil Corp | Corrosion-inhibiting mineral oil compositions |
US3113106A (en) * | 1958-06-03 | 1963-12-03 | Standard Oil Co | Rust inhibited lubricants |
US3203896A (en) * | 1962-03-28 | 1965-08-31 | Universal Oil Prod Co | Lubricating composition |
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