US2642452A - Synthetic lubricating oil - Google Patents
Synthetic lubricating oil Download PDFInfo
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- US2642452A US2642452A US65986A US6598648A US2642452A US 2642452 A US2642452 A US 2642452A US 65986 A US65986 A US 65986A US 6598648 A US6598648 A US 6598648A US 2642452 A US2642452 A US 2642452A
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- esters
- viscosity
- olefin
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- 239000010689 synthetic lubricating oil Substances 0.000 title claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- OKLGKGPAZUNROU-YUMQZZPRSA-N 2-amino-2-deoxyisochorismic acid Chemical class N[C@@H]1[C@@H](OC(=C)C(O)=O)C=CC=C1C(O)=O OKLGKGPAZUNROU-YUMQZZPRSA-N 0.000 claims 1
- 239000000314 lubricant Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002480 mineral oil Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 7
- 239000004435 Oxo alcohol Substances 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 238000006641 Fischer synthesis reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- -1 pour depressants Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
-
- 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
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
-
- 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
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- 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
- C10N2040/12—Gas-turbines
-
- 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
- C10N2040/12—Gas-turbines
- C10N2040/13—Aircraft turbines
Definitions
- This invention relates to a new class of compounds which have been found to be particularly suitable for use as synthetic lubricants because of their low pour point, high viscosity index and unusually good load carrying properties. These compounds have also been found to be useful as addition agents for mineral lubricating oils, in which they serve as improvers of the load carrying properties of th same.
- lubricant art considerable progress has been realized in recent years in the production of lubricants characterized by oneor more specific properties and adapted for particular uses. In the main, this progress can be attributed to two developments: the first, new refining procedures, and the second, addition agents-capable 01 imparting particular properties to available lubricants.
- viscosity index improvers and pour depressants are added to automotive lubricants to render the lubricants more adaptable to Wide changes in temperature conditions, while other agents are added to improve the load carrying properties of a lubricant which is to be employed, for example, under extreme pressure conditions.
- Esters represent one class of materials which have attracted unusual interest as synthetic lubricants. In general, they are characterized by higher viscosity indices and lower pour points than mineral oils of corresponding viscosity. The esters described in the present specification have been found to exhibit very low pour points, high viscosity indices and, in addition, unusually good 4 Claims. (Cl. 260461) load carrying properties. Lubricants possessing such properties are of special value in the lubrication of engines which are subjected to high temperatures such as combustion turbine engines, particularly those of the prop-jet type.
- Mineral oil lubricants containing added viscosity index improvers, thickeners or otherhighly nonvolatileadditives are undesirable for use in such 'tions with Type I olefins both normal and isoengines because of the tendency to leave a residue which would accumulate and interfere with theof branched chain structure, being derived from a primary monohydric aliphatic alcohol obtained as a product of the Oxo synthesis.
- the 0x0 process may be described as the catalytic reaction of mono-olefins with carbon monoxide and hydrogen at a temperature of 300-350 F. and under a pressure of about 3000 lbs/sq. in. toform aldehydes and the subsequent hydrogenation of the aldehydes to form primary alcohols.
- Cobalt catalysts are employed in the reaction of the olefin with carbon monoxide and hydrogen, and conventional hydrogenation catalysts are employed for the reduction of the aldehydes.
- one mol of olefin reacts with one mol of carbon monoxide and one mol of hydrogen to form an aldehyde containing one more carbon atom 'per molecule than the olefin, according to the reaction:
- the aldehydes thus formed may be hydrogenated to the corresponding primary alcohols, according to the reaction:
- esters having properties which make them suitable for use as lubrieating oils it is desirable to employ alcohols which are chiefly of a branched chain structure, and accordingly it is desirable to employ as starting materialsolefins or olefin mixtures which contain not more than 20% of Type I oleflns having a straight chain hydrocarbon radical.
- the olefins may be of any type, provided they are essentially of chain length from C7 to C19, which will produce alcohols of the C8 to C20 range.
- OX alcohols useful in accordance with the present invention
- a large variety of olefin-containing commercial products may be employed.
- a C1 fraction isolated from the product of the polymerization of propylene or a mixture of C3 or C4 olefins may be employed in themeduction of C8 Oxo alcohols, since the fraction contains no more than a trace of diolefins and the unsaturated hydrocarbon content of the. same consists almost entirely of monoolefins, largely tertiary.
- Diisobutylene produced by the cold acid polymerization of isobutylene, maybe employed in the production of C9 Oxo alcohols.
- olefins For the production of alcohols having 12 to 14 carbon atoms a convenient source of olefins is a Fischer synthesis product, boiling above about 350 R, which, after treatment with bauxite, contains about 50% of mono-olefins of which not more than a trace consists of Type 1 straight chain olefins. This product may be fractionated to narrow the range of carbon content in the alcohol product. 7
- the alcohols formed by applying the 0x0 process to the olefinic materials described above will naturally consist of complex mixtures, and the exact composition of many of these products is not known.
- the C8 Oxo alcohols obtained from the propylene polymers described above have been found to comprise a mixture of isomers having, on the average, two alkyl side groups along a carbon chain 4 to 6 carbon atoms in length.
- the Oxo nonyl alcohol product formed from commercial diisobutylene prepared by the cold acid polymerization of isobutylene consists of 3,5,5-trimethylhexanol-l, 2-isopropyl-3,3-dimethylbutanol-l, and 2,2,4,4-tetramethylpentanol-l.
- the phosphate esters of the present invention may be conveniently prepared by contacting about three molecular proportions of a suitable Oxo alcohol or mixture of Oxoalcohols With one molecular proportion of phosphorus oxychloride in the presence of a suitable medium such as.
- Cs O-xo alcohol for example, was prepared from a C7 fraction of a product of the polymerization of C3 and C4 olefins. The olefinic content of this fraction consists of not more than 4% of Type I olefins.
- the C9 Oxo alcohol was preparedfrom commercial diisobutylene consisting of about of Type III and 20% of Type In the following table are shown a number of properties of the 0x0 alcohols employed in preparing the esters:
- Almen Machine Kinematic Viscosity Weights Carried ASTM I (Gradual Loading) Alcohol Reacted with Pour ASTM Viscosity P001: Point Slope Index F. 210 F
- Alone Mineral Oil 1 1 conventionally refined Coastalnaphthenic oil of 42 seconds Saybolt viscosity at 210 F. The unblended mineral oil carried only two weights on the Almen machme.
- the mineral lubricating oil base stocks which may be improved in load-carrying capacity by the addition of the new compounds of the present invention may be derived from the various types of crude petroleum and many consist of distillates or blends of various kinds which have been refined by any of the conventional methods. Synthetic oils may also be used, such as those obtained by the polymerization of olefins or by the hydrogenation of coal or its products.
- the :base oils may vary considerably in viscosity and other properties depending upon the particular use for which they are desired.
- addition agents such as thickeners, pour depressants, antioxidants, dyes, etc.
- thickeners such as thickeners, pour depressants, antioxidants, dyes, etc.
- esters are also useful as plasticizers for synthetic resins, e. g., of the polyvinyl chloride or vinyl chloride-vinyl acetate copolymer type, and for synthetic rubbers, e. g., of the Buna N type.
- a synthetic lubricating oil having an ASTM pour point below about 35 F., a viscosity index above about 125, a viscosity at 210 F. of at least 3.0 centistokes and a flash point of at least 450 F., said oil consisting predominantly of Ca to C14 ,weight of the mineral oil.
- composition according to claim 1 in whic the alkyl groups are Ca groups.
- composition according to claim 1 in which the alkyl groups are derived from a C9 O-xo alcohol obtained by OX0 synthesis from diisobutylene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Description
Patented June 16, 1953 UNITED S ATES PATENT OFFICE field, N. J., assignors to Standard Oil Development Company, a, corporation of Delaware "N Drawing. Application December 17, 1948, Serial No. 65,986
This invention relates to a new class of compounds which have been found to be particularly suitable for use as synthetic lubricants because of their low pour point, high viscosity index and unusually good load carrying properties. These compounds have also been found to be useful as addition agents for mineral lubricating oils, in which they serve as improvers of the load carrying properties of th same. In the, lubricant art, considerable progress has been realized in recent years in the production of lubricants characterized by oneor more specific properties and adapted for particular uses. In the main, this progress can be attributed to two developments: the first, new refining procedures, and the second, addition agents-capable 01 imparting particular properties to available lubricants. Thus, viscosity index improvers and pour depressants are added to automotive lubricants to render the lubricants more adaptable to Wide changes in temperature conditions, while other agents are added to improve the load carrying properties of a lubricant which is to be employed, for example, under extreme pressure conditions.
Recently, in an effort to obtain superior lubricants endowed with specific and superior characteristics, a new field has been explored, namely, the synthesis of lubricants from various materials. Esters represent one class of materials which have attracted unusual interest as synthetic lubricants. In general, they are characterized by higher viscosity indices and lower pour points than mineral oils of corresponding viscosity. The esters described in the present specification have been found to exhibit very low pour points, high viscosity indices and, in addition, unusually good 4 Claims. (Cl. 260461) load carrying properties. Lubricants possessing such properties are of special value in the lubrication of engines which are subjected to high temperatures such as combustion turbine engines, particularly those of the prop-jet type. Mineral oil lubricants containing added viscosity index improvers, thickeners or otherhighly nonvolatileadditives are undesirable for use in such 'tions with Type I olefins both normal and isoengines because of the tendency to leave a residue which would accumulate and interfere with theof branched chain structure, being derived from a primary monohydric aliphatic alcohol obtained as a product of the Oxo synthesis. The 0x0 process may be described as the catalytic reaction of mono-olefins with carbon monoxide and hydrogen at a temperature of 300-350 F. and under a pressure of about 3000 lbs/sq. in. toform aldehydes and the subsequent hydrogenation of the aldehydes to form primary alcohols. This process was first developed in Germany and first described in this country in the Roelen U.-S. Patent 2,327,066, granted August 17, 1943. Cobalt catalysts are employed in the reaction of the olefin with carbon monoxide and hydrogen, and conventional hydrogenation catalysts are employed for the reduction of the aldehydes. In the presence of the cobalt catalyst, one mol of olefin reacts with one mol of carbon monoxide and one mol of hydrogen to form an aldehyde containing one more carbon atom 'per molecule than the olefin, according to the reaction:
The aldehydes thus formed may be hydrogenated to the corresponding primary alcohols, according to the reaction:
In the present specification a number of different types of olefins will be referred to, and for convenience these may be defined by the following formulas, in which R, R, etc., represent alkyl radials:
Type I: RGH=CH2 Type II: ROH=CHR Type III: R-O=CHz Type IV: RC=CHR" RI RI! In'the reactions of the 0x0 process, described above, there is no invariable point of attack on the olefinic double bond, and in the case of reacalcohols are formed. However, with all of the other types of olefins defined above branched chain alcohols greatly predominate in the products. For the production of esters having properties which make them suitable for use as lubrieating oils it is desirable to employ alcohols which are chiefly of a branched chain structure, and accordingly it is desirable to employ as starting materialsolefins or olefin mixtures which contain not more than 20% of Type I oleflns having a straight chain hydrocarbon radical. Except for this limitation the olefins may be of any type, provided they are essentially of chain length from C7 to C19, which will produce alcohols of the C8 to C20 range.
For the commercial production. of OX alcohols useful in accordance with the present invention a large variety of olefin-containing commercial products may be employed. For example, a C1 fraction isolated from the product of the polymerization of propylene or a mixture of C3 or C4 olefins may be employed in themeduction of C8 Oxo alcohols, since the fraction contains no more than a trace of diolefins and the unsaturated hydrocarbon content of the. same consists almost entirely of monoolefins, largely tertiary. Diisobutylene, produced by the cold acid polymerization of isobutylene, maybe employed in the production of C9 Oxo alcohols. For the production of alcohols having 12 to 14 carbon atoms a convenient source of olefins is a Fischer synthesis product, boiling above about 350 R, which, after treatment with bauxite, contains about 50% of mono-olefins of which not more than a trace consists of Type 1 straight chain olefins. This product may be fractionated to narrow the range of carbon content in the alcohol product. 7
The alcohols formed by applying the 0x0 process to the olefinic materials described above will naturally consist of complex mixtures, and the exact composition of many of these products is not known. The C8 Oxo alcohols obtained from the propylene polymers described above have been found to comprise a mixture of isomers having, on the average, two alkyl side groups along a carbon chain 4 to 6 carbon atoms in length. The Oxo nonyl alcohol product formed from commercial diisobutylene prepared by the cold acid polymerization of isobutylene consists of 3,5,5-trimethylhexanol-l, 2-isopropyl-3,3-dimethylbutanol-l, and 2,2,4,4-tetramethylpentanol-l.
The phosphate esters of the present invention may be conveniently prepared by contacting about three molecular proportions of a suitable Oxo alcohol or mixture of Oxoalcohols With one molecular proportion of phosphorus oxychloride in the presence of a suitable medium such as.
benzene. When phosphorus oxychloride is employed it may be desirable to have present a were prepared by methods which have been described above. Cs O-xo alcohol, for example, was prepared from a C7 fraction of a product of the polymerization of C3 and C4 olefins. The olefinic content of this fraction consists of not more than 4% of Type I olefins. The C9 Oxo alcohol was preparedfrom commercial diisobutylene consisting of about of Type III and 20% of Type In the following table are shown a number of properties of the 0x0 alcohols employed in preparing the esters:
Ca Ca il-l2 012-13 13-14 Hydroxyl No 408 373 317 260 269 Carbonyl No 4 4 7 7 1 Saponification No. 13 11 8 l9 8 Acid N0 0. 2 O. 1 0. 3 0. 1 '0. 06
The above described alcohols were each reacted With phosphorus oxychloride to form phosphate esters, the following procedure being followed in each case: A mixture of one gram mol of the alcohol, 1.1 gram mols of pyridine, and 92 ml. of benzene was cooled to -5 C., and then 51.1 g. /3 mol) of POCb was dropped in at such a rate that the temperature did not exceed 10 C. When the addition was complete, the mixture was refluxed for two hours, after which 150 ml. of water was added and the benzene layer separated. The latter was washed several times with water or with dilute aqueous alkali until it was neutral. After drying over a desiccant such as Drierite (anhydrous C'aSOe), the solvent was distilled off at 5 mm. pressure and a bath temperature of ZOO-225 C. (In this process an excess of alcohol may be employed if desired.)
In the table below areshown properties of the phosphate esters, prepared as described above, which indicate their particular suitability for use as synthetic lubricants.
. Almen Machine Kinematic Viscosity Weights Carried ASTM I (Gradual Loading) Alcohol Reacted with Pour ASTM Viscosity P001: Point Slope Index F. 210 F Alone Mineral Oil 1 1 conventionally refined Coastalnaphthenic oil of 42 seconds Saybolt viscosity at 210 F. The unblended mineral oil carried only two weights on the Almen machme.
basic substance such as pyridine to absorb the hydrogen chloride produced in the reaction. A typical method suitable for preparing any of the compounds of the present invention will be described in detail below.
Data will be given below showing properties of five typical examples of trialkyl phosphates illustrating the present invention. The alcohols The above data indicate that the materials testedpossess an uncommonly low pour point, high viscosity index and high load-carrying characteristics, and since these materials have a viscosity within the lubricating oil range they are of particular interest as synthetic lubricants. In addition to the use of these materials along as synthetic lubricants, they are valuable for employed in the preparation of these esters 7 improving the film strength and oiliness proper-- ties of mineral oils with which they are blended. For this purpose, they are preferably blended in proportions ranging from 1% to by column of the above table show the usefulness of these compounds when blended with a mineral oil. Ihe tin-blended mineral oil employed in these tests was capable of carrying only two weights on the Almen machine under similar conditions of test.
The mineral lubricating oil base stocks which may be improved in load-carrying capacity by the addition of the new compounds of the present invention may be derived from the various types of crude petroleum and many consist of distillates or blends of various kinds which have been refined by any of the conventional methods. Synthetic oils may also be used, such as those obtained by the polymerization of olefins or by the hydrogenation of coal or its products. The :base oils may vary considerably in viscosity and other properties depending upon the particular use for which they are desired.
If desired, other known addition agents, such as thickeners, pour depressants, antioxidants, dyes, etc., may be added to the mineral oil composition prepared in accordance with the present invention.
The above described esters are also useful as plasticizers for synthetic resins, e. g., of the polyvinyl chloride or vinyl chloride-vinyl acetate copolymer type, and for synthetic rubbers, e. g., of the Buna N type.
What is claimed is:
1. A synthetic lubricating oil having an ASTM pour point below about 35 F., a viscosity index above about 125, a viscosity at 210 F. of at least 3.0 centistokes and a flash point of at least 450 F., said oil consisting predominantly of Ca to C14 ,weight of the mineral oil. The data in the last highly branched trialkyl esters of phosphoric acid, the ester portions of said phosphoric acid esters being derived from a primary monohydric alcohol boiling below about 450 F. which is obtained by Oxo synthesis wherein there is employed as the olefinic substance a hydrocarbon material whose olefin content consists of not more than 20% by weight based on the total olefin of an olefin of the type RI-IC CHz where R is a straight chain saturated aliphatic hydrocarbon radical.
2. A composition according to claim 1 in whic the alkyl groups are Ca groups.
3. A composition according to claim 1 in which the alkyl groups are derived from a C9 O-xo alcohol obtained by OX0 synthesis from diisobutylene.
4. A composition according to claim 1 in which the alkyl groups are derived from a 012-013 O-xo alcohol.
LOUIS A. MIKESKA. PAUL V. SMITH, J R.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Aiken et al.: J. Polymer Sci., vol. 2, pp. 178- 198 (1947).
Claims (1)
1. A SYNTHETIC LUBRICATING OIL HAVING AN ASTM POUR POINT BELOW ABOUT -35* F., A VISCOSITY INDEX ABOVE ABOUT 125, A VISCOSITY AT 210* F. OF AT LEAST 3.0 CENTISTOKES AND A FLASH POINT OF AT LEAST 450* F., SAID OIL CONSISTING PREDOMINANTLY OF C8 TO C14 HIGHLY BRANCHED TRIALKYL ESTERS OF PHOSPHORIC ACID, THE ESTER PORTIONS OF SAID PHOSPHORIC ADIC ESTERS BEING DERIVED FROM A PRIMARY MONOHYDRIC ALCOHOL BOILING BELOW ABOUT 450* F. WHICH IS OBTAINED BY OXO SYNTHESIS WHEREIN THERE IS EMPLOYED AS THE OLEFINIC SUBSTANCE A HYDROCARBON MATERIAL WHOSE OLEDIN CONTENT CONSISTS OF NOT MORE THAN 20% BY WEIGHT BASED ON THE TOTAL OLEFIN OF AN OLEFIN OF THE TYPE RHC=CH2 WHERE R IS A STRAIGHT CHAIN SATURATED ALIPHATIC HYDROCARBON RADICAL.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL75191D NL75191C (en) | 1948-12-17 | ||
US65986A US2642452A (en) | 1948-12-17 | 1948-12-17 | Synthetic lubricating oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US65986A US2642452A (en) | 1948-12-17 | 1948-12-17 | Synthetic lubricating oil |
Publications (1)
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US2642452A true US2642452A (en) | 1953-06-16 |
Family
ID=22066509
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US65986A Expired - Lifetime US2642452A (en) | 1948-12-17 | 1948-12-17 | Synthetic lubricating oil |
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US (1) | US2642452A (en) |
NL (1) | NL75191C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2989386A (en) * | 1958-09-24 | 1961-06-20 | Exxon Research Engineering Co | Gasolines containing combustion chamber deposit modifiers |
US6066753A (en) * | 1997-09-12 | 2000-05-23 | Clariant Gmbh | Mixtures of long-chain alkyl phosphates |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1993552A (en) * | 1933-02-14 | 1935-03-05 | Du Pont | Preparation of esters of polybasic acids |
US2005619A (en) * | 1934-11-10 | 1935-06-18 | Du Pont | Esters of acids of phosphorus |
US2285853A (en) * | 1934-02-23 | 1942-06-09 | Du Pont | Lubrication |
US2327066A (en) * | 1938-09-19 | 1943-08-17 | Roelen Otto | Production of oxygenated carbon compounds |
US2340331A (en) * | 1935-04-02 | 1944-02-01 | Lubri Zol Corp | Lubrication |
US2406802A (en) * | 1942-02-18 | 1946-09-03 | Carbide & Carbon Chem Corp | 2-ethylhexyl phosphates |
US2490283A (en) * | 1947-02-03 | 1949-12-06 | Shell Dev | Addition of carbonmonoxide-hydrogen to unsaturated compounds |
US2507055A (en) * | 1947-10-15 | 1950-05-09 | Gulf Oil Corp | Addition agents for mineral oils and compositions containing the same |
US2517916A (en) * | 1947-12-15 | 1950-08-08 | Du Pont | Branched chain acyclic aldehydes and alcohols and their preparation |
US2549270A (en) * | 1948-07-19 | 1951-04-17 | Shell Dev | Lubricant and hydraulic fluid composition |
-
0
- NL NL75191D patent/NL75191C/xx active
-
1948
- 1948-12-17 US US65986A patent/US2642452A/en not_active Expired - Lifetime
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1993552A (en) * | 1933-02-14 | 1935-03-05 | Du Pont | Preparation of esters of polybasic acids |
US2285853A (en) * | 1934-02-23 | 1942-06-09 | Du Pont | Lubrication |
US2005619A (en) * | 1934-11-10 | 1935-06-18 | Du Pont | Esters of acids of phosphorus |
US2340331A (en) * | 1935-04-02 | 1944-02-01 | Lubri Zol Corp | Lubrication |
US2327066A (en) * | 1938-09-19 | 1943-08-17 | Roelen Otto | Production of oxygenated carbon compounds |
US2406802A (en) * | 1942-02-18 | 1946-09-03 | Carbide & Carbon Chem Corp | 2-ethylhexyl phosphates |
US2490283A (en) * | 1947-02-03 | 1949-12-06 | Shell Dev | Addition of carbonmonoxide-hydrogen to unsaturated compounds |
US2507055A (en) * | 1947-10-15 | 1950-05-09 | Gulf Oil Corp | Addition agents for mineral oils and compositions containing the same |
US2517916A (en) * | 1947-12-15 | 1950-08-08 | Du Pont | Branched chain acyclic aldehydes and alcohols and their preparation |
US2549270A (en) * | 1948-07-19 | 1951-04-17 | Shell Dev | Lubricant and hydraulic fluid composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2989386A (en) * | 1958-09-24 | 1961-06-20 | Exxon Research Engineering Co | Gasolines containing combustion chamber deposit modifiers |
US6066753A (en) * | 1997-09-12 | 2000-05-23 | Clariant Gmbh | Mixtures of long-chain alkyl phosphates |
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