US3072570A - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- US3072570A US3072570A US619957A US61995756A US3072570A US 3072570 A US3072570 A US 3072570A US 619957 A US619957 A US 619957A US 61995756 A US61995756 A US 61995756A US 3072570 A US3072570 A US 3072570A
- Authority
- US
- United States
- Prior art keywords
- phosphorus
- product
- barium
- temperature
- reaction product
- 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
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- 239000000203 mixture Substances 0.000 title claims description 29
- 239000010687 lubricating oil Substances 0.000 title claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 69
- 229910052698 phosphorus Inorganic materials 0.000 claims description 69
- 239000011574 phosphorus Substances 0.000 claims description 69
- 239000000047 product Substances 0.000 claims description 43
- 229930195733 hydrocarbon Natural products 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims description 34
- 229910052788 barium Inorganic materials 0.000 claims description 28
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 28
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims description 16
- 150000001553 barium compounds Chemical class 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- -1 olefin hydrocarbon Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 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
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 230000000007 visual effect Effects 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
-
- 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
-
- 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
-
- 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
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
Definitions
- This invention relates to a novel lubricating oil composition and more particularly pertains to a lubricating oil composition having outstanding deiergency characteristics and corrosion inhibiting propert es.
- oils are not well suited as lubricants for use in internal combustion engines, particularly of the ty e operating under severe conditions, since under such conditions the lubricants are susceptible to deterioration resulting in the development of carbonaceous and/or resinous or similar varnish-like deposits in the engines and on and about the valves and rings of the engine nd under some conditions such oils are not efiective in .ting corrosion of the various com onents of the engine.
- a product having the desired detergency characteristics and corrosion inhibiting properties can be obtained by incorporating in a lubricant composition a minor proportion, from about 0.001 percent to about 10 percent by weight, and preferably from about 0.1 percent to about 5 percent by weight of the product obtained by reacting an olefinic hydrocarbon having a molecular weight of from about 150 to about 50,000, particularly an olefinic polymer of butylene, with from about 1 percent to about 50 percent by Weight, and preferably from about 5 percent to about 25 percent by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F, and preferably from about 300 F.
- Methanol is the preferred alkanol and nonyl phenol or phenol per se are preferred phenols.
- the esterifyng reaction is carried out at a temperature of from about F. to about 350 F. depending upon the hydroxy compound used, for at least about /2 hour and preferably from about 4 to about 6 hours.
- the esterified product is then saponified with at least about 1 mol, and preferably about 2 mols, of a basic barium compound, preferably barium oxide, per mol of phosphorus in the esterified product at a temperature from about 125 F. to about 350 F. and preferably from about 240 F. to about 300 F. for at least about /2 hour and preferably about 2 hours.
- the saponified product can then be contacted with carbon dioxide, if desired, to reduce the excess alkalinity of the product. This reaction is carried out at a temperature of from about 125 F. to about 350 F. preferably from about 240 to 300 F. for a period of time up to about 10 hours and preferably not more than about 2 hours.
- the preferred basic barium compound is barium oxide, although barium hydroxide can be employed.
- the use of the various hydrates of basic barium compounds is to be avoided.
- the alkanols or phenols employed in the reaction are nOt contaminated with water, i.e., only anhydrous alkanols or phenols may be employed.
- the preferred alkanols which can be employed are those having up to about 12 carbon atoms.
- the lower molecular weight alcohols such as methyl, ethyl and isopropyl are particularly preferred, although butanol, hexanol, heptanol, octanol and their various isomers are Well 1 may be used having up to about 20 side chain carbon atoms, either in one side chain or two or more side chains.
- the olefin is reacted with a phosphorus sulfide such as P 8 P 5 P sor other phosphorus sulfides, and preferably phosphorus pentasulfide, P285.
- a phosphorus sulfide such as P 8 P 5 P sor other phosphorus sulfides, and preferably phosphorus pentasulfide, P285.
- the olefinic hydrocarbon constituent in this reaction is preferably a mono olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or iso-mono-olefinic hydrocarbons, such as. propylenes, butylenes and amylenes or the co-polymers obtained by the polymerization of hydrocarbon mixtures containing iso-mono-olefins and monoolefins of less than 6 carbon atoms.
- the polymers can be obtained by the polymerization of these olefins or mixtures of olefins in the presence of a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel- Crafts type.
- a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel- Crafts type.
- olefins suitable for the preparation of the hereindescribed phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 to about 18 carbon atoms, and preferably at least 15 carbon atoms are in a long chain.
- Such olefins can be obtained by the dehydrogenation of parafiins, such as by the cracking of paraflin Wax or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paratfin Waxes.
- the preparation of the barium-containing phosphorus sulfide-olefinic hydrocarbon reaction product is carried out in the following manner.
- the olefinic hydrocarbon such as, for example, an olefinic polymer of the desired molecular weight
- a phosphorus sulfide such as P 8
- the reaction is carried out for from about one to about ten hours or more, and preferably for about 5 hours.
- the phosphorus sulfide-olefinic hydrocarbon reaction can, if desired, be carried out in the presence of a sulfurizing agent such as elemental sulfuror a halide of sulfur.
- a sulfurizing agent such as elemental sulfuror a halide of sulfur.
- the reaction product thus obtained is then preferably diluted with a normally liquid hydrocarbon, generally the same as, or similar to, the hydrocarbon oil in which the finished additive is to be employed, to a total phosphorus content of from about 0.5 percent to about 5 percent, and preferably to a phosphorus content of from about 1 percent to about 2 percent.
- the phosphorus sulfide-olefinic hydrocarbon reaction product preferably oil diluted, is then heated to at least about 125 F., depending upon the particular mono-hydroxy compound used, and is esterified with from about 0.25 to about 3.0 mols, and preferably about 1 mol, per mol of phosphorus in the phosphorus sulfide-olefinic hydrocarbon reaction product, of an alkanol having from 1 to about 12 carbon atoms or phenol or an alkylated phenol.
- the esterification'reaction is carried out for at least about /2 hour and preferably from about 4 to 6 hours. Although the reaction may be continued for as long as hours or more, this is not generally necessary and is uneconomical. Hydrogen sulfide is evolved during the esterification reaction and it can be removed by blowing the reaction mixture with nitrogen; this is not essential, however, but merely tends to speed the reaction.
- the product is saponified with a basic barium compound such as barium oxide.
- a basic barium compound such as barium oxide.
- the amount of barium oxide employed is at least about one mol per mol of phosphorus in the esterifiedproduct.
- a neutral salt will be formed. It is generally preferable, however, and one of the objects of this invention, to form a basic salt having a high barium to phosphorus ratio.
- the temperature is maintained between about F. and 350 F. and preferably between about 240 F. and 300 F. Higher temperatures, of course, increase the reaction rate and are thus desirable.
- the reaction mixture is thus heated for at least about one-half hour and preferably for about two to about six hours.
- the reaction may be continued for as long as ten hours or more but this is generally not necessary and is uneconomical.
- the reaction product can then be filtered in order to remove unreacted components; however, this is not always necessary if the preferred amounts as hereinbefore specified are employed.
- the product can be blown with carbon dioxide to reduce excess alkalinity. Although not necessary, it is sometimes desirable to do so in order to meet certain specifications and to provide an additive mixture with a very high barium to phosphorus ratio and yet being essentially neutral.
- the carbon dioxide blowing step is carried out at a temperature in the range of from about 125 F. to about 350 F. and for convenience generally at the temperature at which the prodnot was saponified.
- Carbon dioxide treating time can vary over wide limits depending upon the degree to which excessive alkalinity is desired to be reduced. Thus the carbon dioxide blow may be carried out for a few minutes, or for as long as 10 hours or more. We have found, however, that contacting with CO for periods longer han about 2 hours has practically negligible effect upon reducing basicity of the product.
- EXAMPLE 2 Same as Example 1 except that after saponification with barium oxide, the product was blown with carbon dioxide for 10 minutes. Thi product contained identical amounts of barium, phosphorus and sulfur but the alkalinity was reduced to 5.3 mg. KOH/ gr.
- EXAMPLE 3 The diluted butylene polymer-P 8 reaction product of Example 1 was reacted with about one'mol of nonyl phenol per mol of phosphorus present in the foregoing reaction product. The temperature of esterification was held between 270 F. and 300 F. for about 5 hours and the reaction mixture was blown with nitrogen throughout this period. The ester was then saponitied with about 2 mols of barium oxide per mol of phosphorus present in the ester at a temperature between 250260 F. for about 3 hours. The product was then blown with carbon dioxide for an additional 2 hours at the same temperature. The final product contained 8.31% barium, 1.39% phosphorus and 1.66% sulfur; having a barium to phosphorus ratio of about 6:1 and an alkalinity of 2.5 mg. KOH/ gr.
- EXAMPLE 4 An additive mixture in accordance with the prior art was prepared as follows.
- the P S -butylene polymer of Example 1 was hydrolyzed in the presence of steam at a temperature or" about 350 F. This product was then diluted with an SAE 20 base oil to a phosphorus content of 1.5 percent and then contacted with fullers earth at a temperature of about 300 F. and filtered.
- the hydrolyzed, clay-contacted product was then neutralized with an excess of barium hydroxide octahydrate at a temperature of about 350 F. and then filtered.
- the product thus obtained had a barium content of 3.04 percent, a phosphorus content of 2.1 percent and less than 0.5 percent sulfur.
- EXAMPLE 5 To demonstrate the necessity of first esterifying and then saponifying, this example is presented wherein methanol and barium oxide are added simultaneously.
- the diluted P S -butylene polymer prepared as described in Example 1 was reacted with about 2 mols of barium oxide (based on phosphorus content of the reaction mixture) in the presence of about 5 mols of methanol (also based on phosphorus content of the reaction mixture) at a temperature of 160-180 F. for about 4 hours.
- the alcohol was then distilled off at about 300 F. and the product was filtered. It contained 5.31% barium, 1.48% phosphorus and 2.89% sulfur; thus having a barium to phosphorus ratio of only about 3.6, indicating barium oxide utilization of only about 50%.
- this example illustrates that esterification prior to saponification is necessary to obtain very high barium to phosphorus ratios.
- EXAMPLE 6 Similar to Example except that nonyl phenol was used instead of methanol.
- the product obtained had a barium to phosphorus ratio of only 4.6 to 1 and was extremely difli'cult to filter. The yield was less than 10% and the product was cloudy.
- compositions provided by our invention due to their high barium to phosphorus ratio, have superior effectiveness as detergents.
- This is demonstrated by the results obtained with the so-called conventional L-l test.
- This test is made on a Caterpillar 1-A-S1 single cylinder Caterpillar engine equipped with new pistons, rings and liners, operating for 480 hours at 100 r.p.m. at a load of 19.8 B.H.P., with an oil sump temperature of 145150 35., and a water outlet temperature of 175-180 F.
- the fuel employed in this test was at the so-called S-l level, containing 1 percent sulfur. This test is designed to measure oil detergency and inspections are made at 120, 240 and 480 hours.
- lubricating oil bases such as hydrocarbon oils, natural or synthetic, such as those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide types, and the polycarboxylic acid ester type oils such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc.
- additives such as anti-oxidants, anti-foaming agents, pour point depressors, extreme pressure agents, anti-wear agents, V.I. improvers, etc. may be incorporated in lubricating oils containing the additive of our invention.
- a lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of a saponified reaction product having a barium to phosphorus content of at least about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F.
- a lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about by weight, of the saponified reaction product having a barium to phosphorus ratio of about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F.
- a lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of the product obtained by reacting under anhydrous conditions a butylene polymer having a molecular weight of from about 150 to about 50,000 with from about 1% to about 50% by weight of phosphorus pentasulfide at a temperature of from about 200 F.
- a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon
- the method of preparing a phosphorus, sulfur and barium containing lubricating oil additive having a high barium to phosphorus ratio and sufiicient sulfur to effectively inhibit corrosion of metal surfaces comprises reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about to about 50,000 with from about 1% to about 50% by Weight of a phosphorus sulfide at a temperature of from about 200 F.
- a mono-hydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about 125 F to about 350 F. for at least about /2
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Description
Patented Jan. 8, 1963 This invention relates to a novel lubricating oil composition and more particularly pertains to a lubricating oil composition having outstanding deiergency characteristics and corrosion inhibiting propert es.
Many oils are not well suited as lubricants for use in internal combustion engines, particularly of the ty e operating under severe conditions, since under such conditions the lubricants are susceptible to deterioration resulting in the development of carbonaceous and/or resinous or similar varnish-like deposits in the engines and on and about the valves and rings of the engine nd under some conditions such oils are not efiective in .ting corrosion of the various com onents of the engine.
It has heretofore been found that certain hydrolyzed reaction products of a phosphorus sulfide and an olefin hydrocarbon such as an olefin polymer, when small amounts to a hydrocarbon oil, are effective in hibiting the formation of varnish, sludge, carbon and like in lubricating oils during use. It has also been found that neutralizing these hydrolyzed reaction products of a phosphorus sulfide and an olefinic hydrocarbon with a basic reagent having a metal constituent, particularly basic barium compounds, provides a compost .on which is effective as a detergent. While general dificulty is encountered in neutralizing such reaction roducts in the manner heretofore practiced, it has been observed that when neutralizing such reaction products with an amount of basic barium compound which would result in a composition having a metal to phosphorous ratio greater than the amount necessary to form a neutral salt greater than about a lzl mol ratio or 4.45 weig t ratio or barium to phosphorus) d ulties are encountered by reason of the formation of gels which make it pr. ticaily impossible to filter the product to remove u ,ted constit ents. It has also been observed that the elds when e i'iploying such methods are quite low. Moreover, in the manutacture of these lubricants containing the neutralized, metal containing hydrolyzed reaction product of a phosphorus sulfide and an olefinic hydrocarbon, a substantial amount of the sulfur introduced therein by the phosphorus'sultide is lost in the hydrolysis. Consequently, under certain conditions these compositions do not ffectively inhibit corrosion of the metal surfaces which they lubricate. Moreover, when preparing such compositions in accordance with the prior art, it has generally bee necessary to treat the product which has been s to hydrolysis to remove undesirable hydrolysis p This is accomplished, for example, by clay treatment.
As more and more fuels h..ving high sulfur contents come into use, particularly in compression-fi tion engines, i.e., diesel engines, it becomes necessary to provide lubricants which have a high metal to phosphorus ratio providing reserve basicity to disperse p icles of c rbon, resin and the like the lubricating oil. it is well-. vn that increasing the metal content, and hence the basic y, of the additive of the type described herein will efiectively increase the ability of the oil to neutralize acids formed by the combustion of the fuel. it is also known that the most economical way of increasing tilfi metal content of the lubricating oil containing additive of the type de scribed herein is to increase the metal to phosphorus ratio of the additive rather than to increase the total amount of additive in the oil to obtain the desired cont nt It has, however, heretofore been impractical to increase the metal to phosphorus ratio substantially without adversely affecting the filterability of the product.
It is an object of our invention to provide a lubricant for internal combustion engines which will have outstanding detergency characteristics and will also inhibit corrosion of metal surfaces. Another object is to provide a method of neutralizing reaction products of a phosphorus sulfide and an olefinic hydrocarbon with a basic barium compound whereby a bright product, free of gel and having a high barium to phosphorus ratio is obtained. it is a further object of our invention to provide a method of preparing a lubricant additive whereby hydrolysis is prevented and the additional process steps to remove undesirable products formed during such hydrolysis are avoided. These and additional objects will become apparent as the description of the invention proceeds.
We have discovered that a product having the desired detergency characteristics and corrosion inhibiting properties can be obtained by incorporating in a lubricant composition a minor proportion, from about 0.001 percent to about 10 percent by weight, and preferably from about 0.1 percent to about 5 percent by weight of the product obtained by reacting an olefinic hydrocarbon having a molecular weight of from about 150 to about 50,000, particularly an olefinic polymer of butylene, with from about 1 percent to about 50 percent by Weight, and preferably from about 5 percent to about 25 percent by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F, and preferably from about 300 F. to about 500 F; esterifying the phosphorus sulfide olefinic hydrocarbon reaction product with from about 0.25 to about 3.0 mols, and preferably about 1 mol, per mol of phosphorus present in the phosphorus sulfideolefinic hydrocarbon reaction product, of an alkanol having from 1 to about 12 carbon atoms or a phenol having up to about 20 side chain carbon atoms. Methanol is the preferred alkanol and nonyl phenol or phenol per se are preferred phenols. The esterifyng reaction is carried out at a temperature of from about F. to about 350 F. depending upon the hydroxy compound used, for at least about /2 hour and preferably from about 4 to about 6 hours. The esterified product is then saponified with at least about 1 mol, and preferably about 2 mols, of a basic barium compound, preferably barium oxide, per mol of phosphorus in the esterified product at a temperature from about 125 F. to about 350 F. and preferably from about 240 F. to about 300 F. for at least about /2 hour and preferably about 2 hours. The saponified product can then be contacted with carbon dioxide, if desired, to reduce the excess alkalinity of the product. This reaction is carried out at a temperature of from about 125 F. to about 350 F. preferably from about 240 to 300 F. for a period of time up to about 10 hours and preferably not more than about 2 hours. It is essential, in order to avoid undesirable hydrolysis of the product during its preparation, that Water is not admitted to the system. Thus, the preferred basic barium compound is barium oxide, although barium hydroxide can be employed. The use of the various hydrates of basic barium compounds is to be avoided. For the same reason, it is likewise essential that the alkanols or phenols employed in the reaction are nOt contaminated with water, i.e., only anhydrous alkanols or phenols may be employed.
As stated hereinbefore, the preferred alkanols which can be employed are those having up to about 12 carbon atoms. By reason of cost and availability, the lower molecular weight alcohols such as methyl, ethyl and isopropyl are particularly preferred, although butanol, hexanol, heptanol, octanol and their various isomers are Well 1 may be used having up to about 20 side chain carbon atoms, either in one side chain or two or more side chains.
In the preparation of the phosphorus sulfide-olefinic hydrocarbon reaction product, the olefin is reacted with a phosphorus sulfide such as P 8 P 5 P sor other phosphorus sulfides, and preferably phosphorus pentasulfide, P285.
The olefinic hydrocarbon constituent in this reaction is preferably a mono olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or iso-mono-olefinic hydrocarbons, such as. propylenes, butylenes and amylenes or the co-polymers obtained by the polymerization of hydrocarbon mixtures containing iso-mono-olefins and monoolefins of less than 6 carbon atoms. The polymers can be obtained by the polymerization of these olefins or mixtures of olefins in the presence of a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel- Crafts type.
Other preferred olefins suitable for the preparation of the hereindescribed phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 to about 18 carbon atoms, and preferably at least 15 carbon atoms are in a long chain. Such olefins can be obtained by the dehydrogenation of parafiins, such as by the cracking of paraflin Wax or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated paratfin Waxes.
In general, the preparation of the barium-containing phosphorus sulfide-olefinic hydrocarbon reaction product, in accordance with the present invention, is carried out in the following manner. The olefinic hydrocarbon such as, for example, an olefinic polymer of the desired molecular weight, is reacted with from about 1 percent to about 50 percent, and preferably from about 5 percent to about 25 percent, of a phosphorus sulfide such as P 8 at a temperature of from about 200 F. to about 600 F. in a non-oxidizing atmosphere such as, for example, an atmosphere of nitrogen. The reaction is carried out for from about one to about ten hours or more, and preferably for about 5 hours. The phosphorus sulfide-olefinic hydrocarbon reaction can, if desired, be carried out in the presence of a sulfurizing agent such as elemental sulfuror a halide of sulfur. The reaction product thus obtained is then preferably diluted with a normally liquid hydrocarbon, generally the same as, or similar to, the hydrocarbon oil in which the finished additive is to be employed, to a total phosphorus content of from about 0.5 percent to about 5 percent, and preferably to a phosphorus content of from about 1 percent to about 2 percent.
The phosphorus sulfide-olefinic hydrocarbon reaction product, preferably oil diluted, is then heated to at least about 125 F., depending upon the particular mono-hydroxy compound used, and is esterified with from about 0.25 to about 3.0 mols, and preferably about 1 mol, per mol of phosphorus in the phosphorus sulfide-olefinic hydrocarbon reaction product, of an alkanol having from 1 to about 12 carbon atoms or phenol or an alkylated phenol. The esterification'reaction is carried out for at least about /2 hour and preferably from about 4 to 6 hours. Although the reaction may be continued for as long as hours or more, this is not generally necessary and is uneconomical. Hydrogen sulfide is evolved during the esterification reaction and it can be removed by blowing the reaction mixture with nitrogen; this is not essential, however, but merely tends to speed the reaction. When the esterification reaction has been completed,
which is indicated when hydrogen sulfide no longer evolves, the product is saponified with a basic barium compound such as barium oxide. The amount of barium oxide employed is at least about one mol per mol of phosphorus in the esterifiedproduct. At a 1:1 ratio of barium to phosphorus, a neutral salt will be formed. It is generally preferable, however, and one of the objects of this invention, to form a basic salt having a high barium to phosphorus ratio. Thus, it is preferable to employ from two to three times the amount of basic barium compound as that necessary to form the neutral salt. t a mol ratio of barium to phosphorus of about 2, the efficiency of barium utilization is maximized and is about Basic barium compound in excess of this amount can be employed without deleterious effect but the eificiency of barium utilization will decrease substantially and hinder filtration of the product after the reaction is completed.
After addition of the basic barium compound to the reaction mixture, the temperature is maintained between about F. and 350 F. and preferably between about 240 F. and 300 F. Higher temperatures, of course, increase the reaction rate and are thus desirable. The reaction mixture is thus heated for at least about one-half hour and preferably for about two to about six hours. The reaction may be continued for as long as ten hours or more but this is generally not necessary and is uneconomical. The reaction product can then be filtered in order to remove unreacted components; however, this is not always necessary if the preferred amounts as hereinbefore specified are employed.
After saponification, the product can be blown with carbon dioxide to reduce excess alkalinity. Although not necessary, it is sometimes desirable to do so in order to meet certain specifications and to provide an additive mixture with a very high barium to phosphorus ratio and yet being essentially neutral. The carbon dioxide blowing step is carried out at a temperature in the range of from about 125 F. to about 350 F. and for convenience generally at the temperature at which the prodnot was saponified. Carbon dioxide treating time can vary over wide limits depending upon the degree to which excessive alkalinity is desired to be reduced. Thus the carbon dioxide blow may be carried out for a few minutes, or for as long as 10 hours or more. We have found, however, that contacting with CO for periods longer han about 2 hours has practically negligible effect upon reducing basicity of the product.
The following examples are illustrative of our invention:
EXAMPLE 1 Butylene polymer (of about 700 molecular weight) was reacted with about 15 percent P S at a temperature of 400 F. in an atmosphere of nitrogen for about 5 hours. This reaction product Was then diluted with an SAE 5 base oil to a phosphorus content of 2.0 percent. The reaction mixture was heated to about 180 F. and about two mols of methyl alcohol per mol of phosphorus was added to form the ester. The end of the reaction was noted when alcohol no longer refluxed and also when hydrogen sulfide evolution ended. About two mols of barium oxide per mol of phosphorus present in the ester was then added to the mixture and the temperature was increased to 240 F. and held at that temperature for 3 hours. The product was then filtered. it contained 9.66% barium, 1.59% phosphorus and 1.6% sulfur; giving a barium to phosphorus ratio of about 6:1. The product had an alkalinity of 33.66 mg. KOH/ gr.
EXAMPLE 2 Same as Example 1 except that after saponification with barium oxide, the product was blown with carbon dioxide for 10 minutes. Thi product contained identical amounts of barium, phosphorus and sulfur but the alkalinity was reduced to 5.3 mg. KOH/ gr.
EXAMPLE 3 The diluted butylene polymer-P 8 reaction product of Example 1 was reacted with about one'mol of nonyl phenol per mol of phosphorus present in the foregoing reaction product. The temperature of esterification was held between 270 F. and 300 F. for about 5 hours and the reaction mixture was blown with nitrogen throughout this period. The ester was then saponitied with about 2 mols of barium oxide per mol of phosphorus present in the ester at a temperature between 250260 F. for about 3 hours. The product was then blown with carbon dioxide for an additional 2 hours at the same temperature. The final product contained 8.31% barium, 1.39% phosphorus and 1.66% sulfur; having a barium to phosphorus ratio of about 6:1 and an alkalinity of 2.5 mg. KOH/ gr.
EXAMPLE 4 An additive mixture in accordance with the prior art was prepared as follows. The P S -butylene polymer of Example 1 was hydrolyzed in the presence of steam at a temperature or" about 350 F. This product was then diluted with an SAE 20 base oil to a phosphorus content of 1.5 percent and then contacted with fullers earth at a temperature of about 300 F. and filtered. The hydrolyzed, clay-contacted product was then neutralized with an excess of barium hydroxide octahydrate at a temperature of about 350 F. and then filtered. The product thus obtained had a barium content of 3.04 percent, a phosphorus content of 2.1 percent and less than 0.5 percent sulfur.
EXAMPLE 5 To demonstrate the necessity of first esterifying and then saponifying, this example is presented wherein methanol and barium oxide are added simultaneously. The diluted P S -butylene polymer prepared as described in Example 1 was reacted with about 2 mols of barium oxide (based on phosphorus content of the reaction mixture) in the presence of about 5 mols of methanol (also based on phosphorus content of the reaction mixture) at a temperature of 160-180 F. for about 4 hours. The alcohol was then distilled off at about 300 F. and the product was filtered. It contained 5.31% barium, 1.48% phosphorus and 2.89% sulfur; thus having a barium to phosphorus ratio of only about 3.6, indicating barium oxide utilization of only about 50%. As pointed out above, this example illustrates that esterification prior to saponification is necessary to obtain very high barium to phosphorus ratios.
EXAMPLE 6 Similar to Example except that nonyl phenol was used instead of methanol. The product obtained had a barium to phosphorus ratio of only 4.6 to 1 and was extremely difli'cult to filter. The yield was less than 10% and the product was cloudy.
As pointed out hereinbefore, the compositions provided by our invention, due to their high barium to phosphorus ratio, have superior effectiveness as detergents. This is demonstrated by the results obtained with the so-called conventional L-l test. This test is made on a Caterpillar 1-A-S1 single cylinder Caterpillar engine equipped with new pistons, rings and liners, operating for 480 hours at 100 r.p.m. at a load of 19.8 B.H.P., with an oil sump temperature of 145150 35., and a water outlet temperature of 175-180 F. The fuel employed in this test was at the so-called S-l level, containing 1 percent sulfur. This test is designed to measure oil detergency and inspections are made at 120, 240 and 480 hours. Piston lands, grooves and liner are inspected for carbon and lacquer. Varnish values are based on a visual rating of from 1 to 10 in which a rating of 10 indicates no varnish and a rating of 1 indicates excessive amounts of varnish. The following compositions were subjected to the L-1 test, results of which are shown in Table 1:
3ccase o l 6 Sample C 6.6% of the product of Example 5 93.4% SAE 30 base oil TABLE 1.-L1 ENGINE TESTHIGH SULFUR FUEL The results shown in Table I for Sample A demonstrate the eifectiveness of our compositions as a detergent. Sample B is typical of the commercially available motor oil detergents and it is apparent that our composition is far superior to Sample B. While the commercially available detergents, exemplified by Sample 13 in Table 1 are very effective as regards detergency characteristics, it is necessary to incorporate with them an additional corrosion inhibitor. This is not necessary when using our composition inasmuch as it exhibits excellent corrosion inhibition properties due to its high sulfur content. Sample C which contains the additive of Example 5 which was prepared by saponification in the presence of methanol is demonstrated to be inferior with respect to detergency to our composition which was prepared by first esterifying the product and then saponifying.
While the present invention has been described by the use of our composition in petroleum lubricating oils, other lubricating oil bases may be employed such as hydrocarbon oils, natural or synthetic, such as those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide types, and the polycarboxylic acid ester type oils such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other of the well known additives, such as anti-oxidants, anti-foaming agents, pour point depressors, extreme pressure agents, anti-wear agents, V.I. improvers, etc. may be incorporated in lubricating oils containing the additive of our invention.
Unless otherwise stated, the percentages stated herein and in the claims are weight percentages.
While we have described our invention by reference to specific embodiments thereof, the same are given by way of illustration. Modifications and variations will be apparent from our description to those skilled in the art.
We claim:
1. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of a saponified reaction product having a barium to phosphorus content of at least about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfideolefinic hydrocarbon reaction product with from about 0.25 to about 3.0 moles per mole of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about F. to about 300 F. for at least about one-half hour, and saponifying the esterified product with from about 2 to 3 moles of a basic barium compound per mole of phosphorus in said esterified product at a temperature of from about 125 to about 350 F. for at least about one-half hour whereby the resulting product is said saponified reaction product having a barium to phosphorus content of at least about 6:1.
2. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about by weight, of the saponified reaction product having a barium to phosphorus ratio of about 6:1 and obtained by reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about 150 to 50,000 with from about 1% to about 50% by weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfideolefinic hydrocarbon reaction product with from about 0.25 to about 3.0 moles per mole of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about side chain carbon atoms at a temperature of from about 125 F. to about 300 F. for about one-half hour, and saponifying the esterified product with from about 2 to 3 moles of a basic barium compound per mole of phosphorus in said esterified product at a temperature of from about 125 to about 350 F. for about one-half hour whereby the resulting product is said saponified reaction product having a barium to phosphorus content of about 6: 1.
3. The lubricant composition of claim 1 wherein said saponified reaction product is contacted with carbon dioxide at a temperature in the range of from about 125 F. to about 350 F.
4. The lubricant composition of claim 1 wherein said olefinic hydrocarbon is a polymer of butylene.
5. The lubricant composition of claim 1 wherein said phosphorus sulfide is phosphorus pentasulfide.
6. The lubricant composition of claim 1 wherein said basic barium compound is barium oxide.
7. The lubricant composition of claim 1 wherein said mono-hydroxy compound is methanol.
8. The lubricant composition of claim 1 wherein said mono-hydroxy compound is nonyl phenol.
9. A lubricant composition comprising a major proportion of a lubricating oil and in combination therewith a minor proportion, from about 0.001% to about 10% by weight, of the product obtained by reacting under anhydrous conditions a butylene polymer having a molecular weight of from about 150 to about 50,000 with from about 1% to about 50% by weight of phosphorus pentasulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus pentasulfide-butylene polymer reaction product with from about 0.25 to about 3.0 mols per mol of phosphorus present in the phosphorus pentasulfide-butylene polymer reaction product of a monohydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about F. to about 350 F. for at least about A2 hours, saponifying the esterified product with from about 2 to about 3 mols of barium oxide per mol of phosphorus in said esterifiedproduct at a temperature of from about 125 F. to about 350 F. for at least about /2 hour, and contacting the saponified reaction product with carbon dioxide at a temperature of from about 125 F. to about 350 F.
10. The method of preparing a phosphorus, sulfur and barium containing lubricating oil additive having a high barium to phosphorus ratio and sufiicient sulfur to effectively inhibit corrosion of metal surfaces which method comprises reacting under anhydrous conditions an olefinic hydrocarbon having a molecular weight of from about to about 50,000 with from about 1% to about 50% by Weight of a phosphorus sulfide at a temperature of from about 200 F. to about 600 F., esterifying the phosphorus sulfide-olefinic hydrocarbon reaction product with from about 0.25 to about 3.0 mols per mol of phosphorus present in the phosphorus sulfide-olefinic hydrocarbon reaction product of a mono-hydroxy compound selected from the group consisting of alkanols having from 1 to about 12 carbon atoms and phenols having up to about 20 side chain carbon atoms at a temperature of from about 125 F to about 350 F. for at least about /2 hour and saponifying the esterified product with from about 2 to about 3 mols of a basic barium compound per mol of phosphorus in the esterified product at a temperature of from about 125 F. to about 350 F. for at least about /2 hour.
11. The method of claim 10 wherein said saponified product is contacted with carbon dioxide at a temperature in the range of from about 125 F. to about 350 F.
12. The method of claim 10 wherein said olefinic hydrocarbon is a polymer of butylene.
13. The method of claim 10 wherein said phosphorus sulfide is phosphorus pentasulfide.
14. The method of claim 10 wherein said basic barium compound is barium oxide. 15. The method of claim 10 wherein said mono-hydroxy compound is methanol.
16. The method of claim 10 wherein said mono-hydroxy compound is nonyl phenol.
References Qited in the file of this patent UNITED STATES PATENTS 2,409,878 May Oct. 22, 1946 2,461,961 Buckmann et al. Feb. 15, 1949 2,767,164 Assert et al. Oct. 16, 1956 2,806,022 Sabol Sept. 10, 1957 2,851,416 Sabol et al. Sept. 9, 1958
Claims (1)
1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL AND IN COMBINATION THEREWITH A MINOR PROPORTION, FROM ABOUT 0.001% TO ABOUT 10% BY WEIGHT, OF A SAPONIFIED REACTION PRODUCT HAVING A BARIUM TO PHOSPHORUS CONTENT OF AT LEAST ABOUT 6:1 AND OBTAINED BY REACTING UNDER ANHYDROUS CONDITIONS AN OLEFINIC HYDROCARBON HAVING A MOLECULAR WEIGHT OF FROM ABOUT 150 TO 50,000 WITH FROM ABOUT 1% TO ABOUT 50% BY WEIGHT OF A PHOSPHORUS SULFIDE AT A TEMPERATURE OF FROM ABOUT 200* F. TO ABOUT 600*F., ESTERIFYING THE PHOSPHORUS SULFIDEOLEFINIC HYDROCARBON REACTION PRODUCT WITH FROM ABOUT 0.25 TO ABOUT 3.0 MOLES PER MOLE OF PHOSPHORUS PRESENT I3IN THE PHOSPHORUS SULFIDE-OLEFINIC HYDROCARBON REACTION PRODUCT OF A MONOHYDROXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKANOLS HAVING FROM 1 TO ABOUT 12 CARBON ATOMS AND PHENOLS HAVING UP TO ABOUT 20 SIDE CHAIN CARBON ATOMS AT A TEMPERATURE OF FROM ABOUT 125*F. TO ABOUT 300*F. FOR AT LEAST ABOUT ONE-HALF HOUR, AND SAPONIFYING THE ESTERIFIED PRODUCT WITH FROM ABOUT 2 TO 3 MOLES OF A BASIC BARIUM COMPOUND PER MOLE OF PHOSPHORUS IN SAID ESTERIFIED PRODUCT AT A TEMPERATURE OF FROM ABOUT 125 TO ABOUT 350*F. FOR AT LEAST ABOUT ONE-HALF HOUR WHEREBY THE RESULTING PRODUCT IS SAID SAPONIFIED REACTION PRODUCT HAVING A BARIUM TO PHOSPHORUS CONTENT OF AT LEAST ABOUT 6:1.
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US619957A US3072570A (en) | 1956-11-02 | 1956-11-02 | Lubricating oil composition |
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Cited By (1)
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US20090060303A1 (en) * | 1995-11-30 | 2009-03-05 | Carl Zeiss Microlmaging Ais, Inc. | Method and apparatus for automated image analysis of biological specimens |
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US2767164A (en) * | 1952-11-03 | 1956-10-16 | Lubrizol Corp | Complexes containing phosporus and sulphur and methods of making same |
US2806022A (en) * | 1955-09-29 | 1957-09-10 | Standard Oil Co | Preparation of metal salts of phosphorus sulfide-hydrocarbon reaction products |
US2851416A (en) * | 1956-01-30 | 1958-09-09 | Standard Oil Co | Lubricating oil composition |
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US2409878A (en) * | 1944-07-15 | 1946-10-22 | Sinclair Refining Co | Lubricating oil |
US2461961A (en) * | 1945-12-29 | 1949-02-15 | Union Oil Co | Lubricating composition |
US2767164A (en) * | 1952-11-03 | 1956-10-16 | Lubrizol Corp | Complexes containing phosporus and sulphur and methods of making same |
US2806022A (en) * | 1955-09-29 | 1957-09-10 | Standard Oil Co | Preparation of metal salts of phosphorus sulfide-hydrocarbon reaction products |
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