US3649229A - Liquid hydrocarbon fuels containing high molecular weight mannich bases - Google Patents
Liquid hydrocarbon fuels containing high molecular weight mannich bases Download PDFInfo
- Publication number
- US3649229A US3649229A US885995A US3649229DA US3649229A US 3649229 A US3649229 A US 3649229A US 885995 A US885995 A US 885995A US 3649229D A US3649229D A US 3649229DA US 3649229 A US3649229 A US 3649229A
- Authority
- US
- United States
- Prior art keywords
- liquid hydrocarbon
- hydrocarbon combustion
- combustion fuel
- fuel
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
Definitions
- This invention relates to liquid hydrocarbon combustion fuels. More particularly, the invention relates to liquid hydrocarbon combustion fuels having detergency properties imparted thereto by incorporating therein a reaction product of the Mannich base type made by using a high molecular weight alkyl-substituted hydroxyaromatic compound.
- liquid hydrocarbon combustion fuels such as fuel oils and gasolines
- gasolines for example, in operational use tend to deposit sludge and varnish at various points in the power system, including carburetor and intake valves. It is desirable, therefore to find a means for improving liquid hydrocarbon fuels by lessening their tendancy to leave such deposits.
- a liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency and antirust properties thereto of an additive composition
- an additive composition comprising the condensation product of (l a high molecular weight alkyl-substituted hydroxy-aromatic compound wherein said alkyl has a molecular weight of from about 600 to about 3,000, (2) an amine, which contains an HN group and (3) an aldehyde, wherein the respective molar ratio of reactants is l:0.l-l:0. 1 -l0.
- the additive compositions utilizable in this invention may be made from (I) a high molecular weight alkyl-substituted phenol, wherein the alkyl substituent has a molecular weight of from about 600 to about 3,000, preferably from about 750 to about 1,200, (2) an aldehyde and (3) an amine which contains an I-IN group, i.e'., an active hydrogen, wherein the respective molar ratio of reactants is as already stated.
- R is a hydrocarbon or substituted hydrocarbon radical
- R is a polyalkylene compound wherein the repeating alkyl unit may be from C to C x is an integer from 1 to 2
- y is an integer from 0 to 2
- z is an integer from 1 to 2.
- high molecular weight alkyl substituted phenols contemplated by the present invention are polypropylphenol, polybutylphenol, polyamylphenol and similarly substituted phenols.
- high molecular weight alkyl substituted compounds of resorcinol, hydroquinone, catechol, eresol, xylenol, amyl phenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenol resins, methylhydroxydiphenyl, guiaeol, alpha and beta naphthol, alpha and beta methylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol, phenylmethylnaphthol, phenanthrol, monemethyl ether and catechol, phenoxyphenol, chlorophenol, hydroxyphenyl sulfides and the like may benzophenyl substituted
- Aldehydes contemplated by the present invention are the aliphatic aldehydes, typified by formaldehyde (such as trioxymethylene) aeetaldehyde, and aldol (B-hydroxy butyraldehyde); aromatic aldehydes, representative of which is benzaldehyde; heterocyelic aldehydes, such as furfural; etc.
- the aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like; in short, any substituent which does not take a major part in the reaction. Preference, however, is given to the aliphatic aldehydes, formaldehyde being particularly preferred.
- the amines contemplated herein are those which contain an amino group characterized by the presence of at least one active hydrogen atom. Such amines may contain only primary amino groups, only secondary amino groups, or both primary and secondary groups.
- Typical amines are the polyalkylpolyamines, ethylenediamine, propylenediamine, polyalkene polyamines (e.g., diethylene triamine, triethylene tetramine); the aromatic amines 0-, mand p-phenylene diamine, diamino naphthalenes; the acid substituted polyalkylpolyamines, N- acctyl tetraethylenepentamine, and the corresponding formylpropionyl-, butyryl-, and the like N-substituted compounds; and the corresponding eyelized compounds formed therefrom, such as the N-alkyl amines of imidazolidine and pyrimidine.
- Secondary heterocyclic amines which are suitable are those characterized by attachment of a hydrogen atom to a nitrogen atom in the heterocyclic group.
- Representative of the amines contemplated herein are morpholine, thiomorpholine, pyrrole, pyrroline, pyrrolidine, indole, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, piperidine, phenoxazine, phenthiazine and their substituted analogs.
- Substituent groups attached to the carbon atoms of these amines are typified by alkyl, aryl, alkaryl, aralkyl, cycloalkyl, and amino compounds referred to above.
- amine shall include the product obtained by reacting an alkenyl succinic anhydride of the formula or alkenyl suecinic acid of the formula with the amines of the foregoing paragraph. See US. Pat. No. 3,346,493.
- R is an alkylene group.
- the alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein,
- the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention.
- alkenyl suecinic acid anhydride when used herein, it must be clearly understood that it embraces the alkenyl suceinie acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated, as set forth hereinbefore.
- alkenyl succinic acid anhydride component examples include ethenyl succinic acid anhydride; ethenyl suecinie acid; ethyl suceinie acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl suceinic acid anhydride; 1,2-dichloropentyl suceinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentyl succinic acid anhydride; 2,3-
- tiimethylbutenyl succinic acid anhydride 3.3-dimethylbutenyl iUCCllllC acid; l.2-dibromo-2-ethylbutyl SUCCll'llC acid; heptenyl succmic acid anhydride; l...-diiodooctyl succinic acid; octenyl succinic acid anhydride; diisobutenyl succmic acid anlhydride; .Z-methylheptenyl succmic acid anhydride; 4-ethylliexenyl succinic acid; l-isopropylphentenyl succmic acid anlnydride; nonenyl succinic acid anhydride'.
- alkenyl suci.:inic acid anhydrides having from about eight to about 35. and preferably. from about nine to about 18 carbon atoms in the alkenyl group thereof. are most advantageously employed in the novel additive compositions.
- Methods for preparing the alkenyl succinic acid anhydrides are well known to those Familiar with the art. the most feasible method comprising the reaction of an olefin with maleic acid anhvdride.
- more .letailed description of the alkenyl succinic acid anhydrides iuitable for use in the additive compositions of the present iniention and their preparation. is disclosed in [1.5. Pat. No. 2.638.450. issued May 12..953.
- the polyalkyl phenols of this invention may be made by reacting 0.1 to moles of a phenol with l mole of a polyalkylene in the presence of an alkylating catalyst.
- an alkylating catalyst such as Bl ⁇ i including the etherate. phenolate or phosphate complexes
- BF or HCl gas such as Bl ⁇ i including the etherate. phenolate or phosphate complexes
- AlCl at 80 to 250 C.
- This process is particuiarly effective when conducted by reacting l to 1.5. or especially 1.25 moles. of phenol to l mole of a polyalkylene compound in the presence of a BF phenolate at about l50 C.
- the product is conveniently dissolved in an aromatic solvent and then washed with water to remove unreacted components. Upon filtration and removal of the aromatic solvent bv distilla- H011. the product. a clear. viscous oil. remains.
- the preparation of the high molecular weight alkyl-sub- :itituted phenols used in this invention may be illustrated by the preparation of polypropylphenol from phenol and polypropylene with a BF 2C H OH-catalyst. For example. the following was charged into a SO-gallon glass-lined Pfaudler iltettle:
- the mixture was heated and stirred for 4 hours at 300 F.. then it was cooled down to [75 F. and 14 kg. toluene. 3.4 kg. butyl alcohol and 34 kg. distilled water were added to wash but the Bland the unreacted phenol. After that. the mixture in the kettle was washed with 5 percent aqueous KOl-l solution to remove any remaining phenol. then with 5 percent aqueous KCL solution to neutralize the unreacted KOH and finally three times with distilled water until neutral to litmus at a temperature in the vicinity of 150 F.
- the washed mixture was filtered through a Sparkler ii-lorizontal plate filter using pound of Hyflo filter aid tdiatomaceous earth) and then the toluene and butyl alcohol were stripped off under vacuum (-40 mm.) at 300 F.
- the product. a clear. brown. viscous oil. gave the following analysis;
- he high molecular weight alkyl-substituted phenol used in his invention may be prepared by any other suitable means.
- the additive composition i.e.. the aforementioned reaction product. is added to the fuel in a small amount to attain the objects hereinbefore discussed.
- the additive com- TJOSlIlOl'l may vary from about 1 to about 200. and. preferably. from about 1 to about 25. pounds per thousand barrels of fuel; )r. in corresponding terms of percent. by weight.
- the concen tration of additive composition may vary from about 0.00025 :0 about 0.l. and preferably. from about 0.00025 to about 3.01 percent. by weight. ot'the fuel.
- the apparatus consisted of a l-liter. four-necked reaction flask equipped with a mechanical stirrer. reflux condenser. thermometer. dropping funnel and later. a nitrogen inlet tube.
- the polypropylphenol with the mineral oil and .iimethylamine were charged to the flask at a temperature of 30 C. and the solution of formaldehyde was added dropwise through the dropping funnel with continuous stirring. After one hour. the temperature was raised to C. and held there for 3 hours while the dropping funnel was replaced by an .nlet tube and nitrogen gas was passed through. The mixture. after adding 100 cc. toluene and 50 cc. butyl alcohol. was washed three times with hot water until neutral to litmus to remove the unreacted amine and formaldehyde. The solution was filtered and stripped under vacuum (5-10 mm.) in a nitrogen atmosphere to 200 C. The product was a clear. orange oil with the following analysis:
- the apparatus consisted of a 500 ml. four-necked reaction flask equipped with a mechanical stirrer, reflux condenser, thermometer, dropping funnel and later, a nitrogen inlet tube.
- EXAMPLE 3 This example illustrates the Mannich reaction of polypropylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2:1:2). The following reactants were employed:
- the apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later, a nitrogen inlet tube.
- the polypropylphenol and paraformaldehyde were charged to the flask at a temperature of 70 C. and the tetraethylenepentamine was added dropwise through the dropping funnel with stirring.
- the reaction mixture was stirred and heated to C. in the presence of nitrogen and held at this temperature for 4 hours. During this time, 34 cc. water was evolved (theory 36 cc.).
- the product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay (a diatomaceous clay filter aid).
- EXAMPLE 4 This example illustrates the Mannich reaction of polybutylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2: l :2). The following reactants were employed:
- Tetraethylenepentamine 15 g. Paral'ormaldehyde 5 g. Polybutylphenol (M.W. i000) 200 g.
- EXAMPLE 5 This example illustrates the Mannich reaction of polypropylphenol with N-acetyl-tetraethylenepentamine and paraforrnaldehyde (ratio 2:1:2). The following reactants were employed:
- the apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer and later, a nitrogen inlet tube.
- the polypropylphenol and N-acetyl-tetraethylenepentamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly in a period of A hour.
- the reaction mixture was heated and stirred in the presence of nitrogen to 200 C. and held at this temperature for 4 hours. During this time, 30 cc. water was evolved (theory 30 cc.).
- the product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay, and a clear, brown viscous oil was obtained with the following analysis:
- EXAMPLE6 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 110.75: 1 The following reactants were employed:
- the apparatus consisted of a -liter. four-necked reaction flask equipped with a mechanical stirrer. thermometer. reflux condenser and later a Dean-Stark water takeoff was added to the condenser.
- the polypropylphenol and diethylenetriamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly over a period of 50 minutes.
- the reaction mixture was stirred and heated to 120 C. and held there for 2 hours. At this point. a Dean-Stark water takeoff was added. nitrogen gas was introduced and the temperature raised to 150 C. and held there for 2 /2 hours. During this time. 30 cc. water was evolved (theory 30 cc.).
- the mixture was stripped under vacuum (5-10 mm.) for 1 hour at 150 C. and 50 g. unreacted amine was recovered.
- the product was a clear. brown viscous oil which gave the followung analysis:
- Polypropylphcnol sulfide (50% Promor
- the apparatus was the same as in Example 6.
- the polypropylphenol sulfide mixture (50% Promor No. 5) and diethylenetriamine were charged to the flask at room temperature and the paraformaldehyde was added slowly over a period of minutes.
- the reaction mixture was stirred and heated to 180 C. for 3% hours.
- the mixture in the flask was stripped under vacuum (5-l0mm.) at I80 C. and some unreacted amine was recovered.
- the product. a dark brown oil gave the following analysis:
- EXAMPLE 8 The example illustrates the Mannich reaction of wax phenol, where the wax has an average of about 24 carbon atoms, with diethylenetrlamlneand para formaldehyde (ratio :0.75:1 The following reactants were employed:
- the setup consisted of a 2-liter, four-necked reaction flask with a mechanical stirrer, thermometer and condenser
- the wax-phenol, Promor Oil No. 5 and diethylenetriamine were charged to the flask at a temperature of about 50 C., and the paraformaldehyde was added slowly in a period of 1 hour.
- the reaction mixture was refluxed for 1 hour.
- Nitrogen gas was introduced and the water was removed at a temperature of l30-l50 C. in a period of 1V2 hours. Then vacuum was applied (10 mm. Hg) for 1% hours at 150 C. After filtratron, a brown oil was obtained which had the following analyits:
- EXAMPLE 9 This example illustrates the Mannich reaction of ,polypropylphenol with diethylenetriamine and paraformaldehyde (ratio l:0.6:2). The following reactants were em- :Jloyed:
- the setup consisted of a l2-liter, four-necked reaction flask equipped with a mechanical stirrer, condenser, thermometer mo a nitrogen inlet tube.
- EXAMPLE l0 This example illustrates the preparation of monosuccinimide of dodecenyl-succinic anhydride with diethylenetriamine. The following reactants were employed:
- the setup consisted of a 3-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later a nitrogen inlet tube.
- EXAMPLE 1 1 This example illustrates the Mannich reaction of (ratio 1:1 1.5). The following reactants were employed:
- the setup consisted of a 5 -lit efifour-necked flask with a mechanical stirrer, thermometer, nitrogen inlet tube and condenser.
- EXAMPLE 12 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 1:0.612) (similar to Example 9 but higher molecular weight polypropylphenol was used). The following reactants were employed:
- Polypropylphenol polypropylene M.W.
- the additive compositions of the present invention impart valuable properties, as hereinbefore indicated, to liquid hydrocarbon combustion fuels, including the distillate fuels, i.e., gasolines and fuel oils.
- the fuel oils that may be improved in accordance with the present invention are hydrocarbon fractions having an initial boiling point of at least about 100 F. and an end-boiling point no higher than about 750 F., and boiling substantially continuously throughout their distillation range.
- Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straight run distillate fractions.
- the distillate fuel oils can be straight run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight run distillate fuel oils, naphthas and the like, with cracked distillate stocks.
- fuel oils can be treated in accordance with well-known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
- distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like.
- the principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 100 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
- Contemplated among the fuel oils are Nos. 1, 2, and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels.
- the domestic fuel oils generally conform to the specifications set forth in A.S.T.M. Specifications D396-48T.
- Specifications for diesel fuels are defined in A.S.T.M. Specification D975-48T.
- Typical jet fuels are defined in Military Specification MlL-F-5624B.
- the gasolines that are improved by the additive compositions of this invention are mixtures of hydrocarbons having an initial boiling point falling between about F. and about F. and an end-boiling point falling between about 250 F. and about 450 F.
- motor gasoline can be straight run gasoline or, as is more usual, it can be a blend of two or more cuts of materials including straight run stock, catalytic or thermal reformate, cracked stock, alkylated natural gasoline, and aromatic hydrocarbons. 7
- CARBURETOR DETERGENCY TEST IN GASOLINE [Inhibitors blended in a fuel comprising 40% TCC gasoline, 40% reformate and 20% light alkylate approximately 85-415 F.
- a liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency properties thereto of an additive composition
- an additive composition comprising the condensation product of l a high molecular weight sulfur free alkylsubstituted hydroxyaromatic compound wherein the alkyl has ti molecular weight of from about 600 to about 3.000.
- liquid hydrocarbon combustion fuel of claim 1 wherein the said condensation product comprises from 1 to about 200 pounds per thousand barrels offuel.
- liquid hydrocarbon combustion fuel of claim 1 will) iii lib
- the said condensatidrfiart iFct comprises from 1 to mom 25 pounds per thousand barrels of fuel.
- liquid hydrocarbon combustion fuel of claim 1 wherein the molecular weight of the alkyl substituent is from about 750 to about [200.
- liquid hydrocarbon combustion fuel of claim 1 vnerein the alkyl-substituted hydroxyaromatic compound is in alkyl-substituted phenol.
- liquid hydrocarbon combustion fuel of claim 1 wherein said aldehyde is selected from the group consisting of T'ormaldehyde and paraformaldehyde.
- liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of polyalkylpolyamines. polyalkenylpolyamines, aromatic amines carboxylic acid-substituted polyalkylpolyamines, and the succinimide formed from any one of these with an olefinic iuccinic acid or anhydride.
- liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of iiimethylamine. dimethylaminopropylamine, tetraethylenepentamine, N-acetyl-tetraethylenepentamine, diethylenetriamine and the monosuccinimide prepared from clodecenyl succinic anhydride and diethylenetriamine.
- liquid hydrocarbon combustion fuel of claim 1 wherein said alkyl-substituted hydroxyaromatic compound is selected from the group consisting of polypropyl phenol and polybutyl phenol.
- liquid hydrocarbon combustion fuel of claim I wherein said alkyl-substituted hydroxyaromatic compound is polypropyl phenol from polypropylene having a molecular weight of 825, said amine is diethylenetriamine, and said aldehyde is paraformaldehyde and the said respective molar Notice of Adverse Decision in Interference 0 Patent No. 3,6L9,229, F. P. Otto,
Abstract
Reaction products obtained from high molecular weight alkylsubstituted hydroxyaromatic compounds, amines and aldehydes are detergency improvers for liquid hydrocarbon fuels.
Description
United States Patent Otto Mar. 14, 1972 [54] LIQUID HYDROCARBON FUELS 2,459,112 1/1949 Oberright ..252/51.5 R CONTAINING HIGH MOLECULAR 2,684,293 7/1954 Hill et al. 44/73 X WEIGHT MANNICH BASES 2,962,442 11/1960 Andress..... 44/73 X 2,984,550 5/1961 Chamot ..44/73 X [72] Inventor: Ferdinand P. Otto, woodbury, NJ. 3,368,972 2/1968 Otto ..252/5l.5 R
3,413,347 11/1968 Worrell ..252/5l.5 R [73] Ass'gnee' Cwpmm 3,416,903 12/1968 Eckert et a1. ..44/73 [22] Filed: Dec. 17, 1969 Primary ExaminerDaniel E. Wyman [21] APPLNO" 885995 AssistantExaminer-W. J. Shine Attorney-Oswald G. Hayes, Andrew L. Gaboriault, Raymond [52] U.S. Cl ..44/73, 252/392 W. Barclay and Claude E. Setliff [51] Int. Cl. ..Cl011/22 [58] Field of Search ..44/73; 233/392 [57] ABSTRACT Reaction products obtained from high molecular weight alkyl- [56] References cued substituted hydroxyaromatic compounds, amines and a1- UNITED STATES PATENTS dehydes are detergency improvers for liquid hydrocarbon fuels. 2,348,638 5/1944 Mikeska et a1 ..44/73 X 2,364,502 12/ 1944 Zimmer et al ..44/73 X 10 Claims, N0 Drawings LIQUID HYDROCARBON FUELS CONTAINING HIGH MOLECULAR WEIGHT MANNICH BASES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to liquid hydrocarbon combustion fuels. More particularly, the invention relates to liquid hydrocarbon combustion fuels having detergency properties imparted thereto by incorporating therein a reaction product of the Mannich base type made by using a high molecular weight alkyl-substituted hydroxyaromatic compound.
2. Discussion Of The Prior Art It is well known to those in this art that liquid hydrocarbon combustion fuels, such as fuel oils and gasolines, tend to exhibit certain deleterious characteristics, either after long periods of storage or under actual operational conditions. Gasolines, for example, in operational use tend to deposit sludge and varnish at various points in the power system, including carburetor and intake valves. It is desirable, therefore to find a means for improving liquid hydrocarbon fuels by lessening their tendancy to leave such deposits.
US. Pat. No. 3,368,972 discloses the use of Mannich base products in lubricating oils as detergency agents. However, there is no teaching therein or suggestion therefrom that such products can be used in fuels.
SUMMARY OF THE INVENTION In accordance with this invention, there is provided a liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency and antirust properties thereto of an additive composition comprising the condensation product of (l a high molecular weight alkyl-substituted hydroxy-aromatic compound wherein said alkyl has a molecular weight of from about 600 to about 3,000, (2) an amine, which contains an HN group and (3) an aldehyde, wherein the respective molar ratio of reactants is l:0.l-l:0. 1 -l0.
DESCRIPTION OF SPECIFIC EMBODIMENTS In general aspect, the additive compositions utilizable in this invention may be made from (I) a high molecular weight alkyl-substituted phenol, wherein the alkyl substituent has a molecular weight of from about 600 to about 3,000, preferably from about 750 to about 1,200, (2) an aldehyde and (3) an amine which contains an I-IN group, i.e'., an active hydrogen, wherein the respective molar ratio of reactants is as already stated.
The reaction involved in preparing the high molecular weight phenol may be depicted as follows:
(OH) x (OH) x (R)? IR (RI) 1 wherein R is a hydrocarbon or substituted hydrocarbon radical, R is a polyalkylene compound wherein the repeating alkyl unit may be from C to C x is an integer from 1 to 2, y is an integer from 0 to 2 and z is an integer from 1 to 2. Use of this product to form the Mannich bases will become apparent from the Examples set forth hereinafter.
Representative high molecular weight alkyl substituted phenols contemplated by the present invention are polypropylphenol, polybutylphenol, polyamylphenol and similarly substituted phenols. For example, in place of phenol, high molecular weight alkyl substituted compounds of resorcinol, hydroquinone, catechol, eresol, xylenol, amyl phenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenol resins, methylhydroxydiphenyl, guiaeol, alpha and beta naphthol, alpha and beta methylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol, phenylmethylnaphthol, phenanthrol, monemethyl ether and catechol, phenoxyphenol, chlorophenol, hydroxyphenyl sulfides and the like may be used.
Aldehydes contemplated by the present invention are the aliphatic aldehydes, typified by formaldehyde (such as trioxymethylene) aeetaldehyde, and aldol (B-hydroxy butyraldehyde); aromatic aldehydes, representative of which is benzaldehyde; heterocyelic aldehydes, such as furfural; etc. The aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like; in short, any substituent which does not take a major part in the reaction. Preference, however, is given to the aliphatic aldehydes, formaldehyde being particularly preferred.
The amines contemplated herein are those which contain an amino group characterized by the presence of at least one active hydrogen atom. Such amines may contain only primary amino groups, only secondary amino groups, or both primary and secondary groups. Typical amines are the polyalkylpolyamines, ethylenediamine, propylenediamine, polyalkene polyamines (e.g., diethylene triamine, triethylene tetramine); the aromatic amines 0-, mand p-phenylene diamine, diamino naphthalenes; the acid substituted polyalkylpolyamines, N- acctyl tetraethylenepentamine, and the corresponding formylpropionyl-, butyryl-, and the like N-substituted compounds; and the corresponding eyelized compounds formed therefrom, such as the N-alkyl amines of imidazolidine and pyrimidine. Secondary heterocyclic amines which are suitable are those characterized by attachment of a hydrogen atom to a nitrogen atom in the heterocyclic group. Representative of the amines contemplated herein are morpholine, thiomorpholine, pyrrole, pyrroline, pyrrolidine, indole, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, piperidine, phenoxazine, phenthiazine and their substituted analogs. Substituent groups attached to the carbon atoms of these amines are typified by alkyl, aryl, alkaryl, aralkyl, cycloalkyl, and amino compounds referred to above.
It is also contemplated that the term amine" shall include the product obtained by reacting an alkenyl succinic anhydride of the formula or alkenyl suecinic acid of the formula with the amines of the foregoing paragraph. See US. Pat. No. 3,346,493.
In the above formulae, R is an alkylene group. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein, The alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl suecinic acid anhydride is used herein, it must be clearly understood that it embraces the alkenyl suceinie acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated, as set forth hereinbefore. Nonlimiting examples of the alkenyl succinic acid anhydride component are ethenyl succinic acid anhydride; ethenyl suecinie acid; ethyl suceinie acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl suceinic acid anhydride; 1,2-dichloropentyl suceinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentyl succinic acid anhydride; 2,3-
tiimethylbutenyl succinic acid anhydride; 3.3-dimethylbutenyl iUCCllllC acid; l.2-dibromo-2-ethylbutyl SUCCll'llC acid; heptenyl succmic acid anhydride; l...-diiodooctyl succinic acid; octenyl succinic acid anhydride; diisobutenyl succmic acid anlhydride; .Z-methylheptenyl succmic acid anhydride; 4-ethylliexenyl succinic acid; l-isopropylphentenyl succmic acid anlnydride; nonenyl succinic acid anhydride'. I-propylhexenyl IiUCClnlC acid anhydride; decenyl succinic acid: decenyl suciainic acid anhydride'. S-methyl-2-isopropyl-hexenyl succmic .icid anhydride; l.2-dibromo-Z-ethyloctenyl succinic acid anliydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1.2-dichloroundecyl succinic acid; 3-ethyl-2- t-butylpentenyl succinic acid anhydride: tetrapropenyl suci.:inic acid anhydride'. tetrapropenyl succinic acid; triisobutenyl succinic acid anhydride'. Z-propyl-noneyl succinic acid anliydride; 3-butyloctenyl succinic acid anhydride; tridecenyl :succinic acid anhydride'. tetradecenyl succinic acid anhydride; lhexadecenyl succinic acid anhydride; sulfurized octadecenyl iiuccinic acid; octadecyl succinic acid anhydride; l.2- dibromo-Z-meihylpentadecenyl succmic acid anhydride; 8- propylpentadecyl,succinic acid anhydride; eicosenyl succmic acid anhydride; l.2-dichloroZ-methylnonadecenyl succinic acid anhydride; E-octyldodecenyl SUCClDlC acid; [.2- iiliiodotetracosenyl succinic acid anhydride; hexacosenyl suctZlnlC acid; hexacosenyl succmic acid anhydride; and hentriacontenyl succinic acid anhydride. In general. alkenyl suci.:inic acid anhydrides having from about eight to about 35. and preferably. from about nine to about 18 carbon atoms in the alkenyl group thereof. are most advantageously employed in the novel additive compositions. Methods for preparing the alkenyl succinic acid anhydrides are well known to those Familiar with the art. the most feasible method comprising the reaction of an olefin with maleic acid anhvdride. more .letailed description of the alkenyl succinic acid anhydrides iuitable for use in the additive compositions of the present iniention and their preparation. is disclosed in [1.5. Pat. No. 2.638.450. issued May 12..953.
The polyalkyl phenols of this invention may be made by reacting 0.1 to moles of a phenol with l mole of a polyalkylene in the presence of an alkylating catalyst. such as Bl} i including the etherate. phenolate or phosphate complexes), BF or HCl gas. AlCl at 80 to 250 C. This process is particuiarly effective when conducted by reacting l to 1.5. or especially 1.25 moles. of phenol to l mole of a polyalkylene compound in the presence of a BF phenolate at about l50 C. The product is conveniently dissolved in an aromatic solvent and then washed with water to remove unreacted components. Upon filtration and removal of the aromatic solvent bv distilla- H011. the product. a clear. viscous oil. remains.
The preparation of the high molecular weight alkyl-sub- :itituted phenols used in this invention may be illustrated by the preparation of polypropylphenol from phenol and polypropylene with a BF 2C H OH-catalyst. For example. the following was charged into a SO-gallon glass-lined Pfaudler iltettle:
.34 kg. (42.5 moles) polypropylene (M.W.=800) .5 kg. (42.5 moles percent excess) phenol 13.25 kg. BF 2C H OH 26 percent BF (585 g. BF
The mixture was heated and stirred for 4 hours at 300 F.. then it was cooled down to [75 F. and 14 kg. toluene. 3.4 kg. butyl alcohol and 34 kg. distilled water were added to wash but the Bland the unreacted phenol. After that. the mixture in the kettle was washed with 5 percent aqueous KOl-l solution to remove any remaining phenol. then with 5 percent aqueous KCL solution to neutralize the unreacted KOH and finally three times with distilled water until neutral to litmus at a temperature in the vicinity of 150 F.
The washed mixture was filtered through a Sparkler ii-lorizontal plate filter using pound of Hyflo filter aid tdiatomaceous earth) and then the toluene and butyl alcohol were stripped off under vacuum (-40 mm.) at 300 F. The product. a clear. brown. viscous oil. gave the following analysis;
active hydrogen (Zerevitinov determination);
lieory nmoles Ch /g. l Hound iilo. 0.85
tield based on the active H analysis= 76.5%.
Ihromatographic clay separation 73.5% yield.
"he high molecular weight alkyl-substituted phenol used in his invention may be prepared by any other suitable means.
"The additive composition. i.e.. the aforementioned reaction product. is added to the fuel in a small amount to attain the objects hereinbefore discussed. In general. the additive com- TJOSlIlOl'l may vary from about 1 to about 200. and. preferably. from about 1 to about 25. pounds per thousand barrels of fuel; )r. in corresponding terms of percent. by weight. the concen tration of additive composition may vary from about 0.00025 :0 about 0.l. and preferably. from about 0.00025 to about 3.01 percent. by weight. ot'the fuel.
he following examples and comparative data are intended :0 illustrate the novel additive compositions of the present invention and to demonstrate their effectiveness in improving "he properties of liquid hydrocarbon combustion fuels. It will 5e understood. of course. that it is not intended the invention we limited to the particular compositions shown or to the ioerations or manipulations involved. Various other additive compositions. and other fuels. can be utilized. as those skilled .n the art will readily appreciate.
EXAMPLE l This example illustrates the Mannich reaction of polypropylphenol with dimethylamine and formaldehyde. The "ollowing reactants were employed:
"nlvpropyl henol lM.W 000.
The apparatus consisted of a l-liter. four-necked reaction flask equipped with a mechanical stirrer. reflux condenser. thermometer. dropping funnel and later. a nitrogen inlet tube.
The polypropylphenol with the mineral oil and .iimethylamine were charged to the flask at a temperature of 30 C. and the solution of formaldehyde was added dropwise through the dropping funnel with continuous stirring. After one hour. the temperature was raised to C. and held there for 3 hours while the dropping funnel was replaced by an .nlet tube and nitrogen gas was passed through. The mixture. after adding 100 cc. toluene and 50 cc. butyl alcohol. was washed three times with hot water until neutral to litmus to remove the unreacted amine and formaldehyde. The solution was filtered and stripped under vacuum (5-10 mm.) in a nitrogen atmosphere to 200 C. The product was a clear. orange oil with the following analysis:
Theory: active hydrogen. 0.41 mmoles CH /g.; oxygen, 0.89%; total nitrogen. 0.55%; basic nitrogen. 0.55%. Found: active hydrogen. 0.35 mmoles CH /g.; oxygen, 0.68%; total nitrogen. 0.45%; basic nitrogen. 0.47%.
I EXAMPLE 2 This example illustrates the Mannich reaction of polypropylphenol with dimethylaminopropylamine and formaldehyde. The following reactants were employed:
Polypropylphenol (M.W. 900,
active H'=0.85) 50 g. Mineral oil 50 g. Dimethylaminopropylamine (M.W. I02) l2 g. 37% aqueous formaldehyde 50 g. Xylene l50 cc.
/CH; l CHZO HZNCHZCHgCH N OH A CHzNHCH CHgCHgN H2O The apparatus consisted of a 500 ml. four-necked reaction flask equipped with a mechanical stirrer, reflux condenser, thermometer, dropping funnel and later, a nitrogen inlet tube.
The polypropylphenol with the mineral oil and dimethylaminopropylamine were charged to the flask at room temperature and the solution of formaldehyde was added dropwise through the dropping funnel during a half hour period with continuous stirring. A cloudy mixture was formed, the temperature rose to 50 C. and 150 cc. xylene was added while the dropping funnel was replaced by an inlet tube and nitrogen gas was passed through. The mixture was refluxed for 3 hours and after cooling down was washed with hot water to remove the unreacted amine until neutral to litmus. Then the xylene was stripped off under vacuum (5-10 mm.) at 200 C. The product, a clear, light brown oil gave the following analysis:
Theory: total nitrogen, 1.08%; basic nitrogen, 1.08%. Found: total nitrogen, 0.91%; basic nitrogen, 0.89%.
EXAMPLE 3 This example illustrates the Mannich reaction of polypropylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2:1:2). The following reactants were employed:
Poiypropylphenol (M.W. 900,
act. H'=0.85) 2,200 g. Tetraethylenepentamine 187 g. Pural'ormaldehyde 59.4 g.
The apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later, a nitrogen inlet tube.
The polypropylphenol and paraformaldehyde were charged to the flask at a temperature of 70 C. and the tetraethylenepentamine was added dropwise through the dropping funnel with stirring. The reaction mixture was stirred and heated to C. in the presence of nitrogen and held at this temperature for 4 hours. During this time, 34 cc. water was evolved (theory 36 cc.). The product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay (a diatomaceous clay filter aid).
The filtrate was a clear, brown, viscous oil with the following analysis:
Percent theory: total nitrogen, 2.86; basic nitrogen, 2.86. Percent found: total nitrogen, 2.61; basic nitrogen, 2.31.
EXAMPLE 4 This example illustrates the Mannich reaction of polybutylphenol with tetraethylenepentamine and paraformaldehyde (ratio 2: l :2). The following reactants were employed:
Tetraethylenepentamine 15 g. Paral'ormaldehyde 5 g. Polybutylphenol (M.W.= i000) 200 g.
The same procedure was followed as in Example 3. The final product was a clear, brown, viscous oil with the following analysis:
Percent theory: total nitrogen, 2.50; basic nitrogen, 2.50. Percent found: total nitrogen, 2.42; basic nitrogen, 1.90.
EXAMPLE 5 This example illustrates the Mannich reaction of polypropylphenol with N-acetyl-tetraethylenepentamine and paraforrnaldehyde (ratio 2:1:2). The following reactants were employed:
Polypropylphenol (M.W. 900,
act. H=0.85) 2,000 g. N-acetyl-tetraethylenepentamine 196 g. Paraformaldehyde 50 g,
The apparatus consisted of a 5-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer and later, a nitrogen inlet tube.
The polypropylphenol and N-acetyl-tetraethylenepentamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly in a period of A hour. The reaction mixture was heated and stirred in the presence of nitrogen to 200 C. and held at this temperature for 4 hours. During this time, 30 cc. water was evolved (theory 30 cc.). The product was filtered hot by suction through an electrically heated Buchner funnel containing a layer of Hyflo clay, and a clear, brown viscous oil was obtained with the following analysis:
Percent theory: total nitrogen, 2.30; basic nitrogen, 1.84. Percent found: total nitrogen, 2,43; basic nitrogen, 1.70.
EXAMPLE6 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 110.75: 1 The following reactants were employed:
Polypropylphenol (M.W. 900,
act. H=0.85) 2,200 g. Diethylenetriamine 144.43 g. Paraformaldehyde 55 g.
The apparatus consisted of a -liter. four-necked reaction flask equipped with a mechanical stirrer. thermometer. reflux condenser and later a Dean-Stark water takeoff was added to the condenser. The polypropylphenol and diethylenetriamine were charged to the flask at a temperature of 60 C. and the paraformaldehyde was added slowly over a period of 50 minutes. The reaction mixture was stirred and heated to 120 C. and held there for 2 hours. At this point. a Dean-Stark water takeoff was added. nitrogen gas was introduced and the temperature raised to 150 C. and held there for 2 /2 hours. During this time. 30 cc. water was evolved (theory 30 cc.). The mixture was stripped under vacuum (5-10 mm.) for 1 hour at 150 C. and 50 g. unreacted amine was recovered. The product was a clear. brown viscous oil which gave the followung analysis:
Percent theory: total nitrogen, 1.62; basic nitrogen. 1.62.
Percent found: total nitrogen. 1.65; basic nitrogen. 1.60.
EXAMPLE? This example illustrates the Mannich reaction of polypropylphenol sulfide with diethylenetriamine and paraformaldehyde. The following reactants were employed:
Polypropylphcnol sulfide (50% Promor The apparatus was the same as in Example 6. The polypropylphenol sulfide mixture (50% Promor No. 5) and diethylenetriamine were charged to the flask at room temperature and the paraformaldehyde was added slowly over a period of minutes. The reaction mixture was stirred and heated to 180 C. for 3% hours. The mixture in the flask was stripped under vacuum (5-l0mm.) at I80 C. and some unreacted amine was recovered. The product. a dark brown oil gave the following analysis:
Percent theory: Total nitrogen, 0.77
Percent found: Total nitrogen, 0.69
EXAMPLE 8 The example illustrates the Mannich reaction of wax phenol, where the wax has an average of about 24 carbon atoms, with diethylenetrlamlneand para formaldehyde (ratio :0.75:1 The following reactants were employed:
.1-14) Wax phenol Z6l g. liethyleneinamine (M.W 103) 25.5 g. "maformuldehyde (MAN 10) 10 g. romor Oil No. 5 (for 509; all dilution) 290 g.
The setup consisted of a 2-liter, four-necked reaction flask with a mechanical stirrer, thermometer and condenser The wax-phenol, Promor Oil No. 5 and diethylenetriamine were charged to the flask at a temperature of about 50 C., and the paraformaldehyde was added slowly in a period of 1 hour. The reaction mixture was refluxed for 1 hour. Nitrogen gas was introduced and the water was removed at a temperature of l30-l50 C. in a period of 1V2 hours. Then vacuum was applied (10 mm. Hg) for 1% hours at 150 C. After filtratron, a brown oil was obtained which had the following analyits:
Percent found: Total nitrogen, 1.82.
EXAMPLE 9 This example illustrates the Mannich reaction of ,polypropylphenol with diethylenetriamine and paraformaldehyde (ratio l:0.6:2). The following reactants were em- :Jloyed:
olvpropylphenol (M.W. 825.
lct. Hfll75) 4000 g. Jiethylenetriamine (M.W. 103) 185 g. Paral'ormaldehyde 180 g. romor Oil No. S (for 25 1' oil dilution) i433 g.
The setup consisted ofa l2-liter, four-necked reaction flask equipped with a mechanical stirrer, condenser, thermometer mo a nitrogen inlet tube.
The mixture of polypropylphenol, diethylenetriamine and Promor Oil No. 5 were charged in the flask and paraformaldehyde was added slowly in a period of 3 hours at a temperature of 70-90 C. The mixture was refluxed for 2 hours and :he water was removed with nitrogen gas at a temperature of 00-l50 C. in 1 hour. Then vacuum was applied (5 mm. Hg) r'or 2 hours at 150 C. and a clear, brown viscous oil was obamed containing 25 oil which gave the following analysis:
Percent theory: total nitrogen, [.30. Percent found: total nitrogen, 1.30.
EXAMPLE l0 This example illustrates the preparation of monosuccinimide of dodecenyl-succinic anhydride with diethylenetriamine. The following reactants were employed:
.Jodecenyl-succmic anhydride (2 moles) MW. 266) 533 g. Diethylenetriamine (2 moles +10% excess) M.W. 103) 227 llylene 400 g.
The setup consisted ofa 3-liter, four-necked reaction flask equipped with a mechanical stirrer, reflux condenser with a Dean-Stark water takeoff, thermometer, dropping funnel and later a nitrogen inlet tube.
The diethylenetriamine and xylene were charged into the flask and dodecenyl-succinic anhydride was added dropwise in 2 hours at a temperature from 50 C. up to C. Water was removed by refluxing with nitrogen gas for 1% hours at C. (about 55 cc.) and then the mixture was stripped under vacuum (5 mm. Hg) for 1% hours at 150 C. to remove the unreacted amine. A clear, very viscous product was obtained with the following analysis:
Percent theory: total nitrogen, 11.5. Percent found: total nitrogen, 10.56.
EXAMPLE 1 1 This example illustrates the Mannich reaction of (ratio 1:1 1.5). The following reactants were employed:
Polypropylphenol (active H=0.8) 1500 g. Dodecenybsuccinimitle-diethylenetriamine (Ex. 462 g. Paral'ormaldehyde 54 g. Promor Oil No.5 ((012257: oil dilution) 660 g..
The setup consisted of a 5 -lit efifour-necked flask with a mechanical stirrer, thermometer, nitrogen inlet tube and condenser.
The polypropylphenol, dodecenyl-succinimide and Promor Oil No. 5 were charged in the flask and paraformaldehyde was added slowly in a period of 2% hours at a temperature of 8090 C., then the water was removed with nitrogen gas at first under light vacuum and then the mixture was stripped under 5-10 mm. Hg. vacuum for 3 hours at 150 C. A total of 23 cc. water was removed (theory 22 cc. water). The final product was a clear, viscous oil containing 25% Promor No. 5which gave the following analysis:
Percent theory: nitrogen, 1.85. Percent found: nitrogen, 1.77.
EXAMPLE 12 This example illustrates the Mannich reaction of polypropylphenol with diethylenetriamine and paraformaldehyde (ratio 1:0.612) (similar to Example 9 but higher molecular weight polypropylphenol was used). The following reactants were employed:
Polypropylphenol (polypropylene M.W.
I120. active H=0.76) 2000 g. Diethylenetriamine (M.W. 103) 93.8 g. Parat'ormaldehyde 91.8 g. Promor Oil No. 5 (for 2571 oil dilution) 712.0 g.
Percent found: total nitrogen, l .49.
The additive compositions of the present invention impart valuable properties, as hereinbefore indicated, to liquid hydrocarbon combustion fuels, including the distillate fuels, i.e., gasolines and fuel oils. Accordingly, the fuel oils that may be improved in accordance with the present invention are hydrocarbon fractions having an initial boiling point of at least about 100 F. and an end-boiling point no higher than about 750 F., and boiling substantially continuously throughout their distillation range. Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straight run distillate fractions. The distillate fuel oils can be straight run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well-known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
The distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like. The principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 100 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
Contemplated among the fuel oils are Nos. 1, 2, and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels. The domestic fuel oils generally conform to the specifications set forth in A.S.T.M. Specifications D396-48T. Specifications for diesel fuels are defined in A.S.T.M. Specification D975-48T. Typical jet fuels are defined in Military Specification MlL-F-5624B.
The gasolines that are improved by the additive compositions of this invention, are mixtures of hydrocarbons having an initial boiling point falling between about F. and about F. and an end-boiling point falling between about 250 F. and about 450 F. As is well known in the art, motor gasoline can be straight run gasoline or, as is more usual, it can be a blend of two or more cuts of materials including straight run stock, catalytic or thermal reformate, cracked stock, alkylated natural gasoline, and aromatic hydrocarbons. 7
The utility of the Mannich products of this invention as additives for fuels has been shown by a number of comparative tests conducted on the fuel alone and on the fuel blended with minor amounts of the Mannich products described in the preceding examples. Both bench tests and engine tests were employed. Carburetor Detergency Test The deposit-forming tendencies of a fuel are determined in an 8-hour engine test. This accelerated test, when run on fuels that contain no detergents, produces an amount of deposit equivalent to the amount observed in 4,000 miles of operation in field tests on taxicab fleets. A six-cylinder Chevrolet engine is equipped with notched rings to increase the amount of flowby and with a glass throttle body section. The engine is operated for 8 hours, using the fuel under test, at alternate idling and running cycles. In the idle cycle, the engine is run at idling speed of 400 rpm. with no load, for 5 minutes. Then for 1 minute, the engine is run at a speed of 2,500 rpm. under a load of 30 BPI-I and at 9.4 in. of mercury manifold pressure. During the running cycle, the blowby and part of the exhaust are released into the carburetor air intake during the idling cycle. After 8 hours operation at alternate run and idle, the carburetor is examined and rated as to the amount of deposit in the throttle throat. In the rating scale, a rating of 0 (zero) indicates a clean carburetor; l--trace deposits; 2=light deposits; 3=medium deposits; and 4=heavy deposits.
CARBURETOR DETERGENCY TEST IN GASOLINE [Inhibitors blended in a fuel comprising 40% TCC gasoline, 40% reformate and 20% light alkylate approximately 85-415 F.
boiling range. 3 cc./gallon offuel of tetraethyllead is present] these contain same nitrogen content ditto Rust Test In Gasoline The rusting characteristics of gasoline were determined in a Static Rust Test, which simulates conditions encountered in storage vessels. The gasoline used was the same as that used in the Carburetor Detergency Test. The test used was ASTM D- 665 except that the temperature was 80 F. instead of F. and the time was 48 hours instead of 24 hours.
The results of this test were as follows.
MODIFIED ASTM RUST TEST D-665 The unhibited gasoline had a rating of 80% rusting in both specimens.
While the present invention has been described with illustrative embodiments. it should be understood that modificalions and variations may be resorted to without departing from the spirit and scope of the invention as will be understood by those skilled in this art.
lclaim:
l. A liquid hydrocarbon combustion fuel containing an amount sufficient to impart improved detergency properties thereto of an additive composition comprising the condensation product of l a high molecular weight sulfur free alkylsubstituted hydroxyaromatic compound wherein the alkyl has ti molecular weight of from about 600 to about 3.000. (2) an amine which contains an amino group having at least one active hydrogen atom and (3) an aldehyde wherein the respective molar ratio of reactants is 1:0. ll0:0.1 -10.
2. The liquid hydrocarbon combustion fuel of claim 1 wherein the said condensation product comprises from 1 to about 200 pounds per thousand barrels offuel.
i. The liquid hydrocarbon combustion fuel of claim 1 will) iii lib
wherein the said condensatidrfiart iFct comprises from 1 to mom 25 pounds per thousand barrels of fuel.
ll, The liquid hydrocarbon combustion fuel of claim 1 wherein the molecular weight of the alkyl substituent is from about 750 to about [200.
5. The liquid hydrocarbon combustion fuel of claim 1 vnerein the alkyl-substituted hydroxyaromatic compound is in alkyl-substituted phenol.
ti. The liquid hydrocarbon combustion fuel of claim 1 wherein said aldehyde is selected from the group consisting of T'ormaldehyde and paraformaldehyde.
l. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of polyalkylpolyamines. polyalkenylpolyamines, aromatic amines carboxylic acid-substituted polyalkylpolyamines, and the succinimide formed from any one of these with an olefinic iuccinic acid or anhydride.
8. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of iiimethylamine. dimethylaminopropylamine, tetraethylenepentamine, N-acetyl-tetraethylenepentamine, diethylenetriamine and the monosuccinimide prepared from clodecenyl succinic anhydride and diethylenetriamine.
9. The liquid hydrocarbon combustion fuel of claim 1 wherein said alkyl-substituted hydroxyaromatic compound is selected from the group consisting of polypropyl phenol and polybutyl phenol.
10. The liquid hydrocarbon combustion fuel of claim I wherein said alkyl-substituted hydroxyaromatic compound is polypropyl phenol from polypropylene having a molecular weight of 825, said amine is diethylenetriamine, and said aldehyde is paraformaldehyde and the said respective molar Notice of Adverse Decision in Interference 0 Patent No. 3,6L9,229, F. P. Otto,
In Interference No. 98,623 invoivin LIQUID HYDROCARBON FUELS CONTAINING HIGH MOLECU- LAR \VEIGHT MANNICH BASES, final judgment adverse to the patentee Oct. 6, 1975, as to claims 1, 2, 3, 4:, 5, 6, 7, 8 and 9.
was rendered [Ofi'im'al Gazette Febmm'y 10, 1976.]
Claims (9)
- 2. The liquid hydrocarbon combustion fuel of claim 1 wherein the said condensation product comprises from 1 to about 200 pounds per thousand barrels of fuel.
- 3. The liquid hydrocarbon combustion fuel of claim 1 wherein the said condensation product comprises from 1 to about 25 pounds per thousand barrels of fuel.
- 4. The liquid hydrocarbon combustion fuel of claim 1 wherein the molecular weight of the alkyl substituent is from about 750 to about 1,200.
- 5. The liquid hydrocarbon combustion fuel of claim 1 wherein the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted phenol.
- 6. The liquid hydrocarbon combustion fuel of claim 1 wherein said aldehyde is selected from the group consisting of formaldehyde and paraformaldehyde.
- 7. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of polyalkylpolyamines, polyalkenylpolyamines, aromatic amines, carboxylic acid-substituted polyalkylpolyamines, and the succinimide formed from any one of these with an olefinic succinic acid or anhydride.
- 8. The liquid hydrocarbon combustion fuel of claim 1 wherein said amine is selected from the group consisting of dimethylamine, dimethylaminopropylamine, tetraethylenepentamine, N-acetyl-tetraethylenepentamine, diethylenetriamine and the monosuccinimide prepared from dodecenyl succinic anhydride and diethylenetriamine.
- 9. The liquid hydrocarbon combustion fuel of claim 1 wherein said alkyl-substituted hydroxyaromatic compound is selected from the group consisting of polypropyl phenol and polybutyl phenol.
- 10. The liquid hydrocarbon combustion fuel of claim 1 wherein said alkyl-substituted hydroxyaromatic compound is polypropyl phenol from polypropylene having a molecular weight of 825, said amine is diethylenetriamine, and said aldehyde is paraformaldehyde, and the said respective molar ratio is 1:0.6:2.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US88599569A | 1969-12-17 | 1969-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3649229A true US3649229A (en) | 1972-03-14 |
Family
ID=25388150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US885995A Expired - Lifetime US3649229A (en) | 1969-12-17 | 1969-12-17 | Liquid hydrocarbon fuels containing high molecular weight mannich bases |
Country Status (1)
Country | Link |
---|---|
US (1) | US3649229A (en) |
Cited By (189)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3877889A (en) * | 1973-11-07 | 1975-04-15 | Lubrizol Corp | Liquid hydrocarbon fuels containing Mannich bases or derivatives thereof |
US3948619A (en) * | 1971-11-30 | 1976-04-06 | Ethyl Corporation | Gasoline composition |
US3994698A (en) * | 1972-02-29 | 1976-11-30 | Ethyl Corporation | Gasoline additive concentrate composition |
US4025316A (en) * | 1974-11-06 | 1977-05-24 | Exxon Research And Engineering Company | Mannich base reaction products useful as liquid hydrocarbon additives |
US4038044A (en) * | 1975-09-12 | 1977-07-26 | E. I. Du Pont De Nemours And Company | Gasoline additive compositions comprising a combination of diamine and polyamine mannich bases |
US4038043A (en) * | 1975-09-12 | 1977-07-26 | E. I. Du Pont De Nemours And Company | Gasoline additive compositions comprising a combination of monoamine and polyamine mannich bases |
US4054422A (en) * | 1975-09-12 | 1977-10-18 | E. I. Du Pont De Nemours & Company | Mannich bases containing tertiary amines and fuel compositions containing said mannich bases |
US4083699A (en) * | 1974-11-19 | 1978-04-11 | Mobil Oil Corporation | Polyoxyethylene polyamine Mannich base products and use of same in fuels and lubricants |
US4140492A (en) * | 1977-09-26 | 1979-02-20 | Exxon Research & Engineering Co. | Borated derivatives of oil-soluble Mannich bases in combination with coadditive hydrocarbons are flow improvers for middle distillate fuel oils |
US4153564A (en) * | 1978-04-24 | 1979-05-08 | Mobil Oil Corporation | Nitrogen-containing compounds and lubricant compositions containing same |
US4172707A (en) * | 1975-09-12 | 1979-10-30 | E. I. Du Pont De Nemours & Company | Mannich bases containing tertiary amines |
JPS54144405A (en) * | 1978-05-01 | 1979-11-10 | Chevron Res | Lubricating oil additive*its manufacture and lubricating oil composition |
US4454059A (en) * | 1976-11-12 | 1984-06-12 | The Lubrizol Corporation | Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants |
DE3405822A1 (en) * | 1984-02-17 | 1985-08-22 | Chevron Research Co., San Francisco, Calif. | Method for reducing fouling in heat exchangers |
US4659338A (en) * | 1985-08-16 | 1987-04-21 | The Lubrizol Corporation | Fuel compositions for lessening valve seat recession |
US4804389A (en) * | 1985-08-16 | 1989-02-14 | The Lubrizol Corporation | Fuel products |
US4820432A (en) * | 1987-07-24 | 1989-04-11 | Exxon Chemical Patents Inc. | Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions |
US4828742A (en) * | 1987-07-24 | 1989-05-09 | Exxon Chemical Patents, Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
EP0317353A2 (en) | 1987-11-19 | 1989-05-24 | Exxon Chemical Patents Inc. | Use of oil soluble dispersant additives in oleaginous compositions |
US4913830A (en) * | 1987-07-24 | 1990-04-03 | Exxon Chemical Patents Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
US4925983A (en) * | 1986-11-12 | 1990-05-15 | The Lubrizol Corporation | Boronated compounds |
WO1990006982A1 (en) * | 1988-12-21 | 1990-06-28 | The Lubrizol Corporation | Fuel stabilizer composition |
EP0376563A1 (en) * | 1988-12-30 | 1990-07-04 | Mobil Oil Corporation | Mannich base deposit control additives and fuel compositions containing same |
US4971711A (en) * | 1987-07-24 | 1990-11-20 | Exxon Chemical Patents, Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
US4997594A (en) * | 1985-10-25 | 1991-03-05 | The Lubrizol Corporation | Compositions, concentrates, lubricant compositions, fuel compositions and methods for improving fuel economy of internal combustion engines |
US5047069A (en) * | 1989-07-27 | 1991-09-10 | Petrolite Corporation | Antioxidants for liquid hydrocarbons |
US5160350A (en) * | 1988-01-27 | 1992-11-03 | The Lubrizol Corporation | Fuel compositions |
US5207939A (en) * | 1990-08-23 | 1993-05-04 | Mobil Oil Corporation | Dihydrocarbyl substituted phenylenediamine-derived phenolic products as antioxidants |
EP0558835A1 (en) | 1992-01-30 | 1993-09-08 | Albemarle Corporation | Biodegradable lubricants and functional fluids |
US5248315A (en) * | 1990-11-15 | 1993-09-28 | Euron S.P.A. | Detergent additive for fuels |
US5266081A (en) * | 1991-10-18 | 1993-11-30 | Mobil Oil Corporation | Multifunctional ashless dispersants |
US5370810A (en) * | 1988-02-29 | 1994-12-06 | Exxon Chemical Patents Inc. | Polyepoxide modified adducts or reactants and oleaginous compositions containing same PT-696 |
US5430105A (en) * | 1992-12-17 | 1995-07-04 | Exxon Chemical Patents Inc. | Low sediment process for forming borated dispersant |
US5498809A (en) * | 1992-12-17 | 1996-03-12 | Exxon Chemical Patents Inc. | Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives |
EP0707058A1 (en) | 1994-10-13 | 1996-04-17 | AGIP PETROLI S.p.A. | Fuel composition |
EP0713908A1 (en) | 1994-11-22 | 1996-05-29 | Ethyl Corporation | Power transmission fluids |
US5554310A (en) * | 1992-12-17 | 1996-09-10 | Exxon Chemical Patents Inc. | Trisubstituted unsaturated polymers |
US5561095A (en) * | 1994-03-31 | 1996-10-01 | Exxon Chemical Patents Inc. | Supported lewis acid catalysts for hydrocarbon conversion reactions |
US5565128A (en) * | 1994-10-12 | 1996-10-15 | Exxon Chemical Patents Inc | Lubricating oil mannich base dispersants derived from heavy polyamine |
US5607890A (en) * | 1994-03-31 | 1997-03-04 | Exxon Chemical Patents Inc. | Supported Lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions |
EP0769546A2 (en) | 1995-10-18 | 1997-04-23 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
US5634951A (en) * | 1996-06-07 | 1997-06-03 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
US5663470A (en) * | 1993-05-20 | 1997-09-02 | Exxon Chemical Patents Inc. | "Heterogeneous lewis acid-type catalysts" |
US5667539A (en) * | 1992-10-05 | 1997-09-16 | Exxon Chemical Patents Inc. | Oleaginous compositions |
EP0827999A1 (en) * | 1996-09-05 | 1998-03-11 | BP Chemicals (Additives) Limited | Detergents for hydrocarbon fuels |
US5789335A (en) * | 1994-03-31 | 1998-08-04 | Exxon Chemical Patents Inc. | Supported Lewis acid catalysts for hydrocarbon conversion reactions |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US5814111A (en) * | 1995-03-14 | 1998-09-29 | Shell Oil Company | Gasoline compositions |
EP0870819A2 (en) * | 1997-04-10 | 1998-10-14 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
US6034184A (en) * | 1998-06-23 | 2000-03-07 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: Mannich reaction products |
US6054539A (en) * | 1998-07-31 | 2000-04-25 | Mobil Oil Corporation | Selectively hydrogenated polymer compositions: polybutadiene-isoprene-polybutadiene |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
EP1010747A1 (en) * | 1998-12-18 | 2000-06-21 | Ethyl Corporation | High-amine mannich dispersants for compression-ignition fuels |
US6103676A (en) * | 1998-06-23 | 2000-08-15 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: hydroformylation/reductive amination reaction products |
US6162768A (en) * | 1990-01-16 | 2000-12-19 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: free radically initiated direct grafting reaction products |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
US6176886B1 (en) | 1999-08-31 | 2001-01-23 | Ethyl Corporation | Middle distillate fuels with enhanced lubricity comprising the reaction product of a phenol formaldehyde resin, an aldehyde and an amino alcohol |
US6215033B1 (en) | 1998-12-11 | 2001-04-10 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: blends with lower molecular weight components |
US6228817B1 (en) | 1990-01-16 | 2001-05-08 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers |
US6248702B1 (en) | 1990-01-16 | 2001-06-19 | Mobil Oil Corporation | Dispersant and dispersant viscosity index improvers from selectively hydrogenated aryl-substituted olefin containing diene copolymers |
US6270539B1 (en) * | 1999-08-31 | 2001-08-07 | Ethyl Corporation | Mannich dispersants with enhanced lubricity |
US6306802B1 (en) | 1994-09-30 | 2001-10-23 | Exxon Chemical Patents Inc. | Mixed antioxidant composition |
US6319881B1 (en) | 1998-06-23 | 2001-11-20 | Exxonmobil Oil Corporation | Haze free oil additive compositions containing dispersants from selectively hydrogenated diene copolymers |
WO2002002485A1 (en) * | 2000-07-06 | 2002-01-10 | Basf Aktiengesellschaft | Dispersant compositions comprising novel emulsifiers for water in oil emulsions |
WO2002090471A2 (en) * | 2001-05-04 | 2002-11-14 | The Lubrizol Corporation | Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof |
EP1229100A3 (en) * | 2001-02-02 | 2003-02-19 | Ethyl Corporation | Secondary amine mannich detergents |
US20030079399A1 (en) * | 2001-09-14 | 2003-05-01 | Malfer Dennis J. | Fuels compositions for direct injection gasoline engines |
US20030122104A1 (en) * | 2001-02-12 | 2003-07-03 | Dober Chemical Corporation | Liquid replacement systems |
US20030173251A1 (en) * | 2000-12-22 | 2003-09-18 | Antonio Gutierrez | Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions |
US6627584B2 (en) | 2002-01-28 | 2003-09-30 | Ethyl Corporation | Automatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids |
US20040091654A1 (en) * | 2001-08-24 | 2004-05-13 | Fleetguard, Inc. | Controlled release of additives in cooling systems |
US20040147410A1 (en) * | 2003-01-15 | 2004-07-29 | Milner Jeffrey L | Extended drain, thermally stable, gear oil formulations |
US6797021B2 (en) | 2000-10-05 | 2004-09-28 | Indian Oil Corporation Limited | Process of preparation of novel mannich bases from hydrogenated and distilled cashew nut shell liquid (CNSL) for use as additive in liquid hydrocarbon fuels |
US6827750B2 (en) | 2001-08-24 | 2004-12-07 | Dober Chemical Corp | Controlled release additives in fuel systems |
US6835218B1 (en) | 2001-08-24 | 2004-12-28 | Dober Chemical Corp. | Fuel additive compositions |
US20050019236A1 (en) * | 2001-08-24 | 2005-01-27 | Harold Martin | Controlled release of additives in fluid systems |
US6860241B2 (en) | 1999-06-16 | 2005-03-01 | Dober Chemical Corp. | Fuel filter including slow release additive |
US20050065043A1 (en) * | 2003-09-23 | 2005-03-24 | Henly Timothy J. | Power transmission fluids having extended durability |
US20050070446A1 (en) * | 2003-09-25 | 2005-03-31 | Ethyl Petroleum Additives, Inc. | Boron free automotive gear oil |
US20050070445A1 (en) * | 2003-09-30 | 2005-03-31 | Nelson Kenneth D. | Stable colloidal suspensions and lubricating oil compositions containing same |
US20050101494A1 (en) * | 2003-11-10 | 2005-05-12 | Iyer Ramnath N. | Lubricant compositions for power transmitting fluids |
US20050101496A1 (en) * | 2003-11-06 | 2005-05-12 | Loper John T. | Hydrocarbyl dispersants and compositions containing the dispersants |
US20050143265A1 (en) * | 2003-12-31 | 2005-06-30 | Loper John T. | Hydrocarbyl dispersants including pendant polar functional groups |
US20050181959A1 (en) * | 2004-02-17 | 2005-08-18 | Esche Carl K.Jr. | Lubricant and fuel additives derived from treated amines |
EP1568759A2 (en) | 2004-02-27 | 2005-08-31 | Afton Chemical Corporation | Power transmission fluids |
US20050202979A1 (en) * | 2004-03-10 | 2005-09-15 | Ethyl Petroleum Additives, Inc. | Power transmission fluids with enhanced extreme pressure characteristics |
US20050268538A1 (en) * | 2004-06-03 | 2005-12-08 | Malfer Dennis J | Reaction of phenols with intermediate triazines |
US20060003905A1 (en) * | 2004-07-02 | 2006-01-05 | Devlin Cathy C | Additives and lubricant formulations for improved corrosion protection |
US20060025313A1 (en) * | 2004-07-29 | 2006-02-02 | Chevron Oronite Company Llc | Lubricating oil composition for internal combustion engines |
US20060025314A1 (en) * | 2004-07-28 | 2006-02-02 | Afton Chemical Corporation | Power transmission fluids with enhanced extreme pressure and antiwear characteristics |
US7001531B2 (en) | 2001-08-24 | 2006-02-21 | Dober Chemical Corp. | Sustained release coolant additive composition |
US20060196107A1 (en) * | 2005-03-04 | 2006-09-07 | Malfer Dennis J | Cyclic mannich products |
US20060217273A1 (en) * | 2005-03-23 | 2006-09-28 | Nubar Ozbalik | Lubricating compositions |
US20060223716A1 (en) * | 2005-04-04 | 2006-10-05 | Milner Jeffrey L | Tractor fluids |
US20060264339A1 (en) * | 2005-05-19 | 2006-11-23 | Devlin Mark T | Power transmission fluids with enhanced lifetime characteristics |
US20060277819A1 (en) * | 2005-06-13 | 2006-12-14 | Puri Suresh K | Synergistic deposit control additive composition for diesel fuel and process thereof |
US20060277820A1 (en) * | 2005-06-13 | 2006-12-14 | Puri Suresh K | Synergistic deposit control additive composition for gasoline fuel and process thereof |
US20070023325A1 (en) * | 2005-08-01 | 2007-02-01 | Sarvesh Kumar | Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof |
US20070042917A1 (en) * | 2005-07-12 | 2007-02-22 | Ramanathan Ravichandran | Amine Tungstates and Lubricant Compositions |
EP1757673A1 (en) | 2005-08-23 | 2007-02-28 | Chevron Oronite Company LLC | Lubricating oil composition for internal combustion engines |
US20070111906A1 (en) * | 2005-11-12 | 2007-05-17 | Milner Jeffrey L | Relatively low viscosity transmission fluids |
US20070123437A1 (en) * | 2005-11-30 | 2007-05-31 | Chevron Oronite Company Llc | Lubricating oil composition with improved emission compatibility |
WO2007127836A1 (en) | 2006-04-26 | 2007-11-08 | R.T. Vanderbilt Company, Inc. | Antioxidant synergist for lubricating compositions |
WO2007131104A1 (en) | 2006-05-05 | 2007-11-15 | R. T. Vanderbilt Company, Inc. | Antioxidant additive for lubricant compositions, comprising organotungstate, diarylamine and organomolybdenum compounds |
US20080015127A1 (en) * | 2006-07-14 | 2008-01-17 | Loper John T | Boundary friction reducing lubricating composition |
US20080015125A1 (en) * | 2006-07-14 | 2008-01-17 | Devlin Mark T | Lubricant compositions |
US20080015124A1 (en) * | 2006-07-14 | 2008-01-17 | Devlin Mark T | Lubricant composition |
US20080040968A1 (en) * | 2006-08-17 | 2008-02-21 | Malfer Dennis J | Fuel additive compounds and method of making the compounds |
US20080051305A1 (en) * | 2006-08-28 | 2008-02-28 | Devlin Mark T | Lubricant composition |
US20080064616A1 (en) * | 2004-10-25 | 2008-03-13 | Huntsman Petrochemical Corporation | Fuel And Oil Detergents |
US20080119377A1 (en) * | 2006-11-22 | 2008-05-22 | Devlin Mark T | Lubricant compositions |
US20080274921A1 (en) * | 2007-05-04 | 2008-11-06 | Ian Macpherson | Environmentally-Friendly Lubricant Compositions |
US20080296234A1 (en) * | 2001-08-24 | 2008-12-04 | Dober Chemical Corporation | Controlled release of microbiocides |
EP2009082A2 (en) | 2007-06-20 | 2008-12-31 | Chevron Oronite Company LLC | Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine |
US20090011963A1 (en) * | 2007-07-06 | 2009-01-08 | Afton Chemical Corporation | Truck fleet fuel economy by the use of optimized engine oil, transmission fluid, and gear oil |
US20090029888A1 (en) * | 2005-07-12 | 2009-01-29 | Ramanathan Ravichandran | Amine tungstates and lubricant compositions |
US20090031614A1 (en) * | 2007-08-01 | 2009-02-05 | Ian Macpherson | Environmentally-Friendly Fuel Compositions |
EP2025737A1 (en) | 2007-08-01 | 2009-02-18 | Afton Chemical Corporation | Environmentally-friendly fuel compositions |
US20090071067A1 (en) * | 2007-09-17 | 2009-03-19 | Ian Macpherson | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
US20090156445A1 (en) * | 2007-12-13 | 2009-06-18 | Lam William Y | Lubricant composition suitable for engines fueled by alternate fuels |
EP2077315A1 (en) | 2007-12-20 | 2009-07-08 | Chevron Oronite Company LLC | Lubricating oil compositions containing a tetraalkyl-napthalene-1,8 diamine antioxidant |
EP2077316A2 (en) | 2007-12-17 | 2009-07-08 | Infineum International Limited | Lubricant compositions with low HTHS for a given SAE viscosity grade |
EP2078745A1 (en) | 2007-12-20 | 2009-07-15 | Chevron Oronite Company LLC | Lubricating oil compositions comprising a molybdenum compound and a zinc dialkyldithiophosphate |
US20090233822A1 (en) * | 2008-03-11 | 2009-09-17 | Afton Chemical Corporation | Ultra-low sulfur clutch-only transmission fluids |
US20090233823A1 (en) * | 2008-03-11 | 2009-09-17 | Volkswagen Aktiengesellschaft | Method for lubricating a clutch-only automatic transmission component requiring lubrication |
DE102009012567A1 (en) | 2008-03-11 | 2009-10-01 | Afton Chemical Corp. | Clutch-only transmission fluid useful for lubrication comprises oil formulated with additive components having metal detergent, phosphorus-based wear preventative, phosphorylated and boronated dispersant, sulfurized extreme pressure agent |
US20090294345A1 (en) * | 2008-05-27 | 2009-12-03 | Dober Chemical Corporation | Controlled release of microbiocides |
US20090304868A1 (en) * | 2008-05-27 | 2009-12-10 | Dober Chemical Corporation | Controlled release cooling additive composition |
US20090301968A1 (en) * | 2008-05-27 | 2009-12-10 | Dober Chemical Corporation | Devices and methods for controlled release of additive compositions |
US20100029527A1 (en) * | 2008-07-31 | 2010-02-04 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
US7883638B2 (en) | 2008-05-27 | 2011-02-08 | Dober Chemical Corporation | Controlled release cooling additive compositions |
US20110190185A1 (en) * | 2010-02-03 | 2011-08-04 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
WO2011096920A1 (en) | 2010-02-03 | 2011-08-11 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
WO2011126642A2 (en) | 2010-03-31 | 2011-10-13 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
WO2011126641A2 (en) | 2010-03-31 | 2011-10-13 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
CN102953064A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Mannich base corrosion-retarding neutralizer and preparation method thereof |
US8425772B2 (en) | 2006-12-12 | 2013-04-23 | Cummins Filtration Ip, Inc. | Filtration device with releasable additive |
EP2698418A1 (en) * | 2012-08-17 | 2014-02-19 | Afton Chemical Corporation | Calcium neutral and overbased mannich and anhydride adducts as detergents for engine oil lubricants |
US8716202B2 (en) | 2010-12-14 | 2014-05-06 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US8933001B2 (en) | 2010-03-31 | 2015-01-13 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US8993496B2 (en) | 2010-03-31 | 2015-03-31 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
EP2933320A1 (en) | 2014-04-17 | 2015-10-21 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
US9249091B2 (en) | 2011-12-27 | 2016-02-02 | Chevron Oronite Company Llc | Post-treated sulfurized salt of an alkyl-substituted hydroxyaromatic composition |
EP2990469A1 (en) | 2014-08-27 | 2016-03-02 | Afton Chemical Corporation | Lubricant composition suitable for use in gasoline direct injection engines |
US9528071B2 (en) | 2015-02-13 | 2016-12-27 | Chevron Oronite Technology B.V. | Lubricating oil compositions with enhanced piston cleanliness |
US9528074B2 (en) | 2015-02-13 | 2016-12-27 | Chevron Oronite Technology B.V. | Lubricating oil compositions with enhanced piston cleanliness |
WO2017011689A1 (en) | 2015-07-16 | 2017-01-19 | Afton Chemical Corporation | Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition |
US9677026B1 (en) | 2016-04-08 | 2017-06-13 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
US9701921B1 (en) | 2016-04-08 | 2017-07-11 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
WO2017146867A1 (en) | 2016-02-25 | 2017-08-31 | Afton Chemical Corporation | Lubricants for use in boosted engines |
WO2017192202A1 (en) | 2016-05-05 | 2017-11-09 | Afton Chemical Corporaion | Lubricant compositions for reducing timing chain stretch |
WO2017192217A1 (en) | 2016-05-05 | 2017-11-09 | Afton Chemical Corporation | Lubricants for use in boosted engines |
WO2018101282A1 (en) | 2016-11-30 | 2018-06-07 | Chevron Japan Ltd. | Lubricating oil compositions for motorcycles |
WO2018111726A1 (en) | 2016-12-16 | 2018-06-21 | Afton Chemical Corporation | Multi-functional olefin copolymers and lubricating compositions containing same |
WO2018136137A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance |
WO2018136138A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition |
WO2018136136A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition |
US10214703B2 (en) | 2015-07-16 | 2019-02-26 | Afton Chemical Corporation | Lubricants with zinc dialkyl dithiophosphate and their use in boosted internal combustion engines |
EP3476923A1 (en) | 2017-10-25 | 2019-05-01 | Afton Chemical Corporation | Dispersant viscosity index improvers to enhance wear protection in engine oils |
US10280383B2 (en) | 2015-07-16 | 2019-05-07 | Afton Chemical Corporation | Lubricants with molybdenum and their use for improving low speed pre-ignition |
US10336959B2 (en) | 2015-07-16 | 2019-07-02 | Afton Chemical Corporation | Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition |
US10377963B2 (en) | 2016-02-25 | 2019-08-13 | Afton Chemical Corporation | Lubricants for use in boosted engines |
US10421922B2 (en) | 2015-07-16 | 2019-09-24 | Afton Chemical Corporation | Lubricants with magnesium and their use for improving low speed pre-ignition |
EP3560966A2 (en) | 2018-04-25 | 2019-10-30 | Afton Chemical Corporation | Multifunctional branched polymers with improved low-temperature performance |
EP3578625A1 (en) | 2018-06-05 | 2019-12-11 | Afton Chemical Corporation | Lubricant composition and dispersants therefor having a beneficial effect on oxidation stability |
WO2020174454A1 (en) | 2019-02-28 | 2020-09-03 | Afton Chemical Corporation | Lubricating compositions for diesel particulate filter performance |
US10836976B2 (en) | 2018-07-18 | 2020-11-17 | Afton Chemical Corporation | Polymeric viscosity modifiers for use in lubricants |
EP3812445A1 (en) | 2019-10-24 | 2021-04-28 | Afton Chemical Corporation | Synergistic lubricants with reduced electrical conductivity |
EP3858954A1 (en) | 2020-01-29 | 2021-08-04 | Afton Chemical Corporation | Lubricant formulations with silicon-containing compounds |
EP3954753A1 (en) | 2020-08-12 | 2022-02-16 | Afton Chemical Corporation | Polymeric surfactants for improved emulsion and flow properties at low temperatures |
WO2022094557A1 (en) | 2020-10-30 | 2022-05-05 | Afton Chemical Corporation | Engine oils with low temperature pump ability |
EP4067463A1 (en) | 2021-03-30 | 2022-10-05 | Afton Chemical Corporation | Engine oils with improved viscometric performance |
US11479736B1 (en) | 2021-06-04 | 2022-10-25 | Afton Chemical Corporation | Lubricant composition for reduced engine sludge |
EP4098723A1 (en) | 2021-06-04 | 2022-12-07 | Afton Chemical Corporation | Lubricating compositions for a hybrid engine |
WO2023004265A1 (en) | 2021-07-21 | 2023-01-26 | Afton Chemical Corporation | Methods of reducing lead corrosion in an internal combustion engine |
EP4124648A1 (en) | 2021-07-31 | 2023-02-01 | Afton Chemical Corporation | Engine oil formulations for low timing chain stretch |
US11572523B1 (en) | 2022-01-26 | 2023-02-07 | Afton Chemical Corporation | Sulfurized additives with low levels of alkyl phenols |
WO2023141399A1 (en) | 2022-01-18 | 2023-07-27 | Afton Chemical Corporation | Lubricating compositions for reduced high temperature deposits |
WO2023159095A1 (en) | 2022-02-21 | 2023-08-24 | Afton Chemical Corporation | Polyalphaolefin phenols with high para-position selectivity |
WO2023212165A1 (en) | 2022-04-27 | 2023-11-02 | Afton Chemical Corporation | Additives with high sulfurization for lubricating oil compositions |
EP4282937A1 (en) | 2022-05-26 | 2023-11-29 | Afton Chemical Corporation | Engine oil formluation for controlling particulate emissions |
EP4306624A1 (en) | 2022-07-14 | 2024-01-17 | Afton Chemical Corporation | Transmission lubricants containing molybdenum |
EP4310162A1 (en) | 2022-07-15 | 2024-01-24 | Afton Chemical Corporation | Detergent systems for oxidation resistance in lubricants |
EP4317369A1 (en) | 2022-08-02 | 2024-02-07 | Afton Chemical Corporation | Detergent systems for improved piston cleanliness |
US11912955B1 (en) | 2022-10-28 | 2024-02-27 | Afton Chemical Corporation | Lubricating compositions for reduced low temperature valve train wear |
US11926804B1 (en) | 2023-01-31 | 2024-03-12 | Afton Chemical Corporation | Dispersant and detergent systems for improved motor oil performance |
WO2024073304A1 (en) | 2022-09-27 | 2024-04-04 | Afton Chemical Corporation | Lubricating composition for motorcycle applications |
EP4357442A1 (en) | 2022-09-21 | 2024-04-24 | Afton Chemical Corporation | Lubricating composition for fuel efficient motorcycle applications |
US11970671B2 (en) | 2022-07-15 | 2024-04-30 | Afton Chemical Corporation | Detergent systems for oxidation resistance in lubricants |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2348638A (en) * | 1940-11-26 | 1944-05-09 | Standard Oil Dev Co | Fuel composition |
US2364502A (en) * | 1941-12-30 | 1944-12-05 | Standard Oil Dev Co | Fuel compositions |
US2459112A (en) * | 1945-07-06 | 1949-01-11 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2684293A (en) * | 1952-01-22 | 1954-07-20 | Ethyl Corp | Stabilized tetraethyllead compositions |
US2962442A (en) * | 1957-01-03 | 1960-11-29 | Socony Mobil Oil Co Inc | Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same |
US2984550A (en) * | 1956-09-06 | 1961-05-16 | Nalco Chemical Co | Color stabilization of petroleum oils and compositions therefor |
US3368972A (en) * | 1965-01-06 | 1968-02-13 | Mobil Oil Corp | High molecular weight mannich bases as engine oil additives |
US3413347A (en) * | 1966-01-26 | 1968-11-26 | Ethyl Corp | Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines |
US3416903A (en) * | 1967-12-26 | 1968-12-17 | Texaco Inc | Thermally stable fuel compositions |
-
1969
- 1969-12-17 US US885995A patent/US3649229A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2348638A (en) * | 1940-11-26 | 1944-05-09 | Standard Oil Dev Co | Fuel composition |
US2364502A (en) * | 1941-12-30 | 1944-12-05 | Standard Oil Dev Co | Fuel compositions |
US2459112A (en) * | 1945-07-06 | 1949-01-11 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2684293A (en) * | 1952-01-22 | 1954-07-20 | Ethyl Corp | Stabilized tetraethyllead compositions |
US2984550A (en) * | 1956-09-06 | 1961-05-16 | Nalco Chemical Co | Color stabilization of petroleum oils and compositions therefor |
US2962442A (en) * | 1957-01-03 | 1960-11-29 | Socony Mobil Oil Co Inc | Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same |
US3368972A (en) * | 1965-01-06 | 1968-02-13 | Mobil Oil Corp | High molecular weight mannich bases as engine oil additives |
US3413347A (en) * | 1966-01-26 | 1968-11-26 | Ethyl Corp | Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines |
US3416903A (en) * | 1967-12-26 | 1968-12-17 | Texaco Inc | Thermally stable fuel compositions |
Cited By (274)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3948619A (en) * | 1971-11-30 | 1976-04-06 | Ethyl Corporation | Gasoline composition |
US3994698A (en) * | 1972-02-29 | 1976-11-30 | Ethyl Corporation | Gasoline additive concentrate composition |
US3877889A (en) * | 1973-11-07 | 1975-04-15 | Lubrizol Corp | Liquid hydrocarbon fuels containing Mannich bases or derivatives thereof |
US4025316A (en) * | 1974-11-06 | 1977-05-24 | Exxon Research And Engineering Company | Mannich base reaction products useful as liquid hydrocarbon additives |
US4083699A (en) * | 1974-11-19 | 1978-04-11 | Mobil Oil Corporation | Polyoxyethylene polyamine Mannich base products and use of same in fuels and lubricants |
US4172707A (en) * | 1975-09-12 | 1979-10-30 | E. I. Du Pont De Nemours & Company | Mannich bases containing tertiary amines |
US4038044A (en) * | 1975-09-12 | 1977-07-26 | E. I. Du Pont De Nemours And Company | Gasoline additive compositions comprising a combination of diamine and polyamine mannich bases |
US4038043A (en) * | 1975-09-12 | 1977-07-26 | E. I. Du Pont De Nemours And Company | Gasoline additive compositions comprising a combination of monoamine and polyamine mannich bases |
US4054422A (en) * | 1975-09-12 | 1977-10-18 | E. I. Du Pont De Nemours & Company | Mannich bases containing tertiary amines and fuel compositions containing said mannich bases |
US4454059A (en) * | 1976-11-12 | 1984-06-12 | The Lubrizol Corporation | Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants |
US4140492A (en) * | 1977-09-26 | 1979-02-20 | Exxon Research & Engineering Co. | Borated derivatives of oil-soluble Mannich bases in combination with coadditive hydrocarbons are flow improvers for middle distillate fuel oils |
US4153564A (en) * | 1978-04-24 | 1979-05-08 | Mobil Oil Corporation | Nitrogen-containing compounds and lubricant compositions containing same |
JPS54144405A (en) * | 1978-05-01 | 1979-11-10 | Chevron Res | Lubricating oil additive*its manufacture and lubricating oil composition |
DE3405822A1 (en) * | 1984-02-17 | 1985-08-22 | Chevron Research Co., San Francisco, Calif. | Method for reducing fouling in heat exchangers |
US4659338A (en) * | 1985-08-16 | 1987-04-21 | The Lubrizol Corporation | Fuel compositions for lessening valve seat recession |
US4804389A (en) * | 1985-08-16 | 1989-02-14 | The Lubrizol Corporation | Fuel products |
US4997594A (en) * | 1985-10-25 | 1991-03-05 | The Lubrizol Corporation | Compositions, concentrates, lubricant compositions, fuel compositions and methods for improving fuel economy of internal combustion engines |
US5358651A (en) * | 1985-10-25 | 1994-10-25 | The Lubrizol Corporation | Compositions, concentrates, lubricant compositions, fuel composition and methods for improving fuel economy of internal combustion engines |
US4925983A (en) * | 1986-11-12 | 1990-05-15 | The Lubrizol Corporation | Boronated compounds |
US5583099A (en) * | 1986-11-12 | 1996-12-10 | The Lubrizol Corporation | Boronated compounds |
US4820432A (en) * | 1987-07-24 | 1989-04-11 | Exxon Chemical Patents Inc. | Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions |
US4828742A (en) * | 1987-07-24 | 1989-05-09 | Exxon Chemical Patents, Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
US4913830A (en) * | 1987-07-24 | 1990-04-03 | Exxon Chemical Patents Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
US4971711A (en) * | 1987-07-24 | 1990-11-20 | Exxon Chemical Patents, Inc. | Lactone-modified, mannich base dispersant additives useful in oleaginous compositions |
EP0317353A2 (en) | 1987-11-19 | 1989-05-24 | Exxon Chemical Patents Inc. | Use of oil soluble dispersant additives in oleaginous compositions |
US5160350A (en) * | 1988-01-27 | 1992-11-03 | The Lubrizol Corporation | Fuel compositions |
US5370810A (en) * | 1988-02-29 | 1994-12-06 | Exxon Chemical Patents Inc. | Polyepoxide modified adducts or reactants and oleaginous compositions containing same PT-696 |
US5482519A (en) * | 1988-02-29 | 1996-01-09 | Exxon Chemical Patents Inc. | Polyepoxide modified adducts or reactants and oleaginous compositions containing same |
WO1990006982A1 (en) * | 1988-12-21 | 1990-06-28 | The Lubrizol Corporation | Fuel stabilizer composition |
EP0376563A1 (en) * | 1988-12-30 | 1990-07-04 | Mobil Oil Corporation | Mannich base deposit control additives and fuel compositions containing same |
US5047069A (en) * | 1989-07-27 | 1991-09-10 | Petrolite Corporation | Antioxidants for liquid hydrocarbons |
US6248702B1 (en) | 1990-01-16 | 2001-06-19 | Mobil Oil Corporation | Dispersant and dispersant viscosity index improvers from selectively hydrogenated aryl-substituted olefin containing diene copolymers |
US6162768A (en) * | 1990-01-16 | 2000-12-19 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: free radically initiated direct grafting reaction products |
US6228817B1 (en) | 1990-01-16 | 2001-05-08 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers |
US5312461A (en) * | 1990-08-23 | 1994-05-17 | Mobil Oil Corporation | Dihydrocarbyl substituted phenylenediamine-derived phenolic products as antioxidants |
US5207939A (en) * | 1990-08-23 | 1993-05-04 | Mobil Oil Corporation | Dihydrocarbyl substituted phenylenediamine-derived phenolic products as antioxidants |
US5248315A (en) * | 1990-11-15 | 1993-09-28 | Euron S.P.A. | Detergent additive for fuels |
US5266081A (en) * | 1991-10-18 | 1993-11-30 | Mobil Oil Corporation | Multifunctional ashless dispersants |
EP0558835A1 (en) | 1992-01-30 | 1993-09-08 | Albemarle Corporation | Biodegradable lubricants and functional fluids |
US5667539A (en) * | 1992-10-05 | 1997-09-16 | Exxon Chemical Patents Inc. | Oleaginous compositions |
US5554310A (en) * | 1992-12-17 | 1996-09-10 | Exxon Chemical Patents Inc. | Trisubstituted unsaturated polymers |
US5498809A (en) * | 1992-12-17 | 1996-03-12 | Exxon Chemical Patents Inc. | Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives |
US5430105A (en) * | 1992-12-17 | 1995-07-04 | Exxon Chemical Patents Inc. | Low sediment process for forming borated dispersant |
US5663130A (en) * | 1992-12-17 | 1997-09-02 | Exxon Chemical Patents Inc | Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives |
US6030930A (en) * | 1992-12-17 | 2000-02-29 | Exxon Chemical Patents Inc | Polymers derived from ethylene and 1-butene for use in the preparation of lubricant disperant additives |
US5874380A (en) * | 1993-05-20 | 1999-02-23 | Exxon Chemical Patents Inc. | Heterogeneous lewis acid-type catalysts |
US5663470A (en) * | 1993-05-20 | 1997-09-02 | Exxon Chemical Patents Inc. | "Heterogeneous lewis acid-type catalysts" |
US5607890A (en) * | 1994-03-31 | 1997-03-04 | Exxon Chemical Patents Inc. | Supported Lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions |
US5561095A (en) * | 1994-03-31 | 1996-10-01 | Exxon Chemical Patents Inc. | Supported lewis acid catalysts for hydrocarbon conversion reactions |
US5648580A (en) * | 1994-03-31 | 1997-07-15 | Exxon Chemical Patents Inc. | Supported lewis acid catalysts for hydrocarbon conversion reactions |
US5780563A (en) * | 1994-03-31 | 1998-07-14 | Exxon Chemical Patents Inc | Supported lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions |
US5789335A (en) * | 1994-03-31 | 1998-08-04 | Exxon Chemical Patents Inc. | Supported Lewis acid catalysts for hydrocarbon conversion reactions |
US6306802B1 (en) | 1994-09-30 | 2001-10-23 | Exxon Chemical Patents Inc. | Mixed antioxidant composition |
US5565128A (en) * | 1994-10-12 | 1996-10-15 | Exxon Chemical Patents Inc | Lubricating oil mannich base dispersants derived from heavy polyamine |
EP0707058A1 (en) | 1994-10-13 | 1996-04-17 | AGIP PETROLI S.p.A. | Fuel composition |
EP0713908A1 (en) | 1994-11-22 | 1996-05-29 | Ethyl Corporation | Power transmission fluids |
US5814111A (en) * | 1995-03-14 | 1998-09-29 | Shell Oil Company | Gasoline compositions |
EP0769546A2 (en) | 1995-10-18 | 1997-04-23 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
EP0811672A3 (en) * | 1996-06-07 | 1998-02-04 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
EP0811672A2 (en) * | 1996-06-07 | 1997-12-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
AU728980B2 (en) * | 1996-06-07 | 2001-01-25 | Afton Chemical Intangibles Llc | Additives for minimizing intake valve deposits, and their use |
US5634951A (en) * | 1996-06-07 | 1997-06-03 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
US6468948B1 (en) | 1996-06-17 | 2002-10-22 | Infineum Usa L.P. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
US6117198A (en) * | 1996-09-05 | 2000-09-12 | The Lubrizol Corporation | Detergents for hydrocarbon fuels |
EP0827999A1 (en) * | 1996-09-05 | 1998-03-11 | BP Chemicals (Additives) Limited | Detergents for hydrocarbon fuels |
EP0870819A3 (en) * | 1997-04-10 | 1999-06-16 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
EP0870819A2 (en) * | 1997-04-10 | 1998-10-14 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
US6103676A (en) * | 1998-06-23 | 2000-08-15 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: hydroformylation/reductive amination reaction products |
US6034184A (en) * | 1998-06-23 | 2000-03-07 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: Mannich reaction products |
US6319881B1 (en) | 1998-06-23 | 2001-11-20 | Exxonmobil Oil Corporation | Haze free oil additive compositions containing dispersants from selectively hydrogenated diene copolymers |
US6054539A (en) * | 1998-07-31 | 2000-04-25 | Mobil Oil Corporation | Selectively hydrogenated polymer compositions: polybutadiene-isoprene-polybutadiene |
US6215033B1 (en) | 1998-12-11 | 2001-04-10 | Mobil Oil Corporation | Dispersants and dispersant viscosity index improvers from selectively hydrogenated polymers: blends with lower molecular weight components |
SG87849A1 (en) * | 1998-12-18 | 2002-04-16 | Ethyl Corp | High-amine mannich dispersants for compression-ignition fuels |
EP1010747A1 (en) * | 1998-12-18 | 2000-06-21 | Ethyl Corporation | High-amine mannich dispersants for compression-ignition fuels |
EP1568757A1 (en) * | 1998-12-18 | 2005-08-31 | Ethyl Corporation | High-amine mannich dispersants for compression-ignition fuels |
US6860241B2 (en) | 1999-06-16 | 2005-03-01 | Dober Chemical Corp. | Fuel filter including slow release additive |
US6270539B1 (en) * | 1999-08-31 | 2001-08-07 | Ethyl Corporation | Mannich dispersants with enhanced lubricity |
US6176886B1 (en) | 1999-08-31 | 2001-01-23 | Ethyl Corporation | Middle distillate fuels with enhanced lubricity comprising the reaction product of a phenol formaldehyde resin, an aldehyde and an amino alcohol |
WO2002002485A1 (en) * | 2000-07-06 | 2002-01-10 | Basf Aktiengesellschaft | Dispersant compositions comprising novel emulsifiers for water in oil emulsions |
US6913660B2 (en) | 2000-07-06 | 2005-07-05 | Basf Aktiengesellschaft | Dispersant compositions comprising novel emulsifiers for water in oil emulsions |
US6797021B2 (en) | 2000-10-05 | 2004-09-28 | Indian Oil Corporation Limited | Process of preparation of novel mannich bases from hydrogenated and distilled cashew nut shell liquid (CNSL) for use as additive in liquid hydrocarbon fuels |
US20030173251A1 (en) * | 2000-12-22 | 2003-09-18 | Antonio Gutierrez | Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions |
US6855674B2 (en) | 2000-12-22 | 2005-02-15 | Infineum International Ltd. | Hydroxy aromatic Mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions |
EP1229100A3 (en) * | 2001-02-02 | 2003-02-19 | Ethyl Corporation | Secondary amine mannich detergents |
US6800103B2 (en) | 2001-02-02 | 2004-10-05 | Ethyl Corporation | Secondary amine mannich detergents |
US20030122104A1 (en) * | 2001-02-12 | 2003-07-03 | Dober Chemical Corporation | Liquid replacement systems |
WO2002090471A2 (en) * | 2001-05-04 | 2002-11-14 | The Lubrizol Corporation | Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof |
US20040168364A1 (en) * | 2001-05-04 | 2004-09-02 | Macduff Malcolm G.J. | Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof |
WO2002090471A3 (en) * | 2001-05-04 | 2003-11-27 | Lubrizol Corp | Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof |
US20070241042A1 (en) * | 2001-08-24 | 2007-10-18 | Dober Chemical Corporation | Controlled release of additives in fluid systems |
US20090283466A1 (en) * | 2001-08-24 | 2009-11-19 | Cummins Filtration Ip Inc. | Controlled release of additives in fluid systems |
US20050019236A1 (en) * | 2001-08-24 | 2005-01-27 | Harold Martin | Controlled release of additives in fluid systems |
US20040091654A1 (en) * | 2001-08-24 | 2004-05-13 | Fleetguard, Inc. | Controlled release of additives in cooling systems |
US6827750B2 (en) | 2001-08-24 | 2004-12-07 | Dober Chemical Corp | Controlled release additives in fuel systems |
US7001531B2 (en) | 2001-08-24 | 2006-02-21 | Dober Chemical Corp. | Sustained release coolant additive composition |
US7591279B2 (en) | 2001-08-24 | 2009-09-22 | Cummins Filtration Ip Inc. | Controlled release of additives in fluid systems |
US20080296234A1 (en) * | 2001-08-24 | 2008-12-04 | Dober Chemical Corporation | Controlled release of microbiocides |
US8109287B2 (en) | 2001-08-24 | 2012-02-07 | Cummins Filtration Ip, Inc. | Controlled release of additives in fluid systems |
US7581558B2 (en) | 2001-08-24 | 2009-09-01 | Cummins Filtration Ip Inc. | Controlled release of additives in fluid systems |
US20070000831A1 (en) * | 2001-08-24 | 2007-01-04 | Fleetguard, Inc. | Controlled release of additives in cooling systems |
US6835218B1 (en) | 2001-08-24 | 2004-12-28 | Dober Chemical Corp. | Fuel additive compositions |
US7938277B2 (en) | 2001-08-24 | 2011-05-10 | Dober Chemical Corporation | Controlled release of microbiocides |
US20030079399A1 (en) * | 2001-09-14 | 2003-05-01 | Malfer Dennis J. | Fuels compositions for direct injection gasoline engines |
US6627584B2 (en) | 2002-01-28 | 2003-09-30 | Ethyl Corporation | Automatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids |
US7888299B2 (en) | 2003-01-15 | 2011-02-15 | Afton Chemical Japan Corp. | Extended drain, thermally stable, gear oil formulations |
US20040147410A1 (en) * | 2003-01-15 | 2004-07-29 | Milner Jeffrey L | Extended drain, thermally stable, gear oil formulations |
US20050065043A1 (en) * | 2003-09-23 | 2005-03-24 | Henly Timothy J. | Power transmission fluids having extended durability |
US20070054813A1 (en) * | 2003-09-25 | 2007-03-08 | Chip Hewette | Boron free automotive gear oil |
US20050070446A1 (en) * | 2003-09-25 | 2005-03-31 | Ethyl Petroleum Additives, Inc. | Boron free automotive gear oil |
US7884058B2 (en) | 2003-09-30 | 2011-02-08 | Chevron Oronite Company Llc | Stable colloidal suspensions and lubricating oil compositions containing same |
US20050070445A1 (en) * | 2003-09-30 | 2005-03-31 | Nelson Kenneth D. | Stable colloidal suspensions and lubricating oil compositions containing same |
US20050101496A1 (en) * | 2003-11-06 | 2005-05-12 | Loper John T. | Hydrocarbyl dispersants and compositions containing the dispersants |
EP2230292A1 (en) | 2003-11-10 | 2010-09-22 | Afton Chemical Corporation | Methods of lubricating transmissions |
US20100279901A1 (en) * | 2003-11-10 | 2010-11-04 | Iyer Ramnath N | Methods for providing steel-on-steel friction and/or steel-on-paper friction with lubricant compositions for power transmitting fluids |
US20050101494A1 (en) * | 2003-11-10 | 2005-05-12 | Iyer Ramnath N. | Lubricant compositions for power transmitting fluids |
US9267093B2 (en) | 2003-11-10 | 2016-02-23 | Afton Chemical Corporation | Methods for providing steel-on-steel friction and/or steel-on-paper friction with lubricant compositions for power transmitting fluids |
US20080009426A1 (en) * | 2003-11-10 | 2008-01-10 | Iyer Ramnath N | Lubricant Compositions and Methods Comprising Dispersant and Detergent |
US20050143265A1 (en) * | 2003-12-31 | 2005-06-30 | Loper John T. | Hydrocarbyl dispersants including pendant polar functional groups |
US7214649B2 (en) | 2003-12-31 | 2007-05-08 | Afton Chemical Corporation | Hydrocarbyl dispersants including pendant polar functional groups |
US7645728B2 (en) | 2004-02-17 | 2010-01-12 | Afton Chemical Corporation | Lubricant and fuel additives derived from treated amines |
US20050181959A1 (en) * | 2004-02-17 | 2005-08-18 | Esche Carl K.Jr. | Lubricant and fuel additives derived from treated amines |
US7947636B2 (en) | 2004-02-27 | 2011-05-24 | Afton Chemical Corporation | Power transmission fluids |
EP1568759A2 (en) | 2004-02-27 | 2005-08-31 | Afton Chemical Corporation | Power transmission fluids |
US20050192185A1 (en) * | 2004-02-27 | 2005-09-01 | Saathoff Lee D. | Power transmission fluids |
US20050202979A1 (en) * | 2004-03-10 | 2005-09-15 | Ethyl Petroleum Additives, Inc. | Power transmission fluids with enhanced extreme pressure characteristics |
US7384434B2 (en) * | 2004-06-03 | 2008-06-10 | Afton Chemical Corporation | Reaction of phenols with intermediate triazines |
US20050268538A1 (en) * | 2004-06-03 | 2005-12-08 | Malfer Dennis J | Reaction of phenols with intermediate triazines |
US20060003905A1 (en) * | 2004-07-02 | 2006-01-05 | Devlin Cathy C | Additives and lubricant formulations for improved corrosion protection |
US20060025314A1 (en) * | 2004-07-28 | 2006-02-02 | Afton Chemical Corporation | Power transmission fluids with enhanced extreme pressure and antiwear characteristics |
US7875576B2 (en) | 2004-07-29 | 2011-01-25 | Chevron Oronite Company Llc | Lubricating oil composition for internal combustion engines |
US20060025313A1 (en) * | 2004-07-29 | 2006-02-02 | Chevron Oronite Company Llc | Lubricating oil composition for internal combustion engines |
US20080064616A1 (en) * | 2004-10-25 | 2008-03-13 | Huntsman Petrochemical Corporation | Fuel And Oil Detergents |
US20060196107A1 (en) * | 2005-03-04 | 2006-09-07 | Malfer Dennis J | Cyclic mannich products |
US20060217273A1 (en) * | 2005-03-23 | 2006-09-28 | Nubar Ozbalik | Lubricating compositions |
US8557752B2 (en) | 2005-03-23 | 2013-10-15 | Afton Chemical Corporation | Lubricating compositions |
US20060223716A1 (en) * | 2005-04-04 | 2006-10-05 | Milner Jeffrey L | Tractor fluids |
US20060264339A1 (en) * | 2005-05-19 | 2006-11-23 | Devlin Mark T | Power transmission fluids with enhanced lifetime characteristics |
US20060277820A1 (en) * | 2005-06-13 | 2006-12-14 | Puri Suresh K | Synergistic deposit control additive composition for gasoline fuel and process thereof |
US20060277819A1 (en) * | 2005-06-13 | 2006-12-14 | Puri Suresh K | Synergistic deposit control additive composition for diesel fuel and process thereof |
US20070042917A1 (en) * | 2005-07-12 | 2007-02-22 | Ramanathan Ravichandran | Amine Tungstates and Lubricant Compositions |
US8080500B2 (en) | 2005-07-12 | 2011-12-20 | King Industries, Inc. | Amine tungstates and lubricant compositions |
US20090029888A1 (en) * | 2005-07-12 | 2009-01-29 | Ramanathan Ravichandran | Amine tungstates and lubricant compositions |
US20080194440A1 (en) * | 2005-07-12 | 2008-08-14 | Ramanathan Ravichandran | Amine tungstates and lubricant compositions |
US7820602B2 (en) | 2005-07-12 | 2010-10-26 | King Industries, Inc. | Amine tungstates and lubricant compositions |
US8222180B2 (en) | 2005-08-01 | 2012-07-17 | Indian Oil Corporation Limited | Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof |
US20070023325A1 (en) * | 2005-08-01 | 2007-02-01 | Sarvesh Kumar | Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof |
EP1757673A1 (en) | 2005-08-23 | 2007-02-28 | Chevron Oronite Company LLC | Lubricating oil composition for internal combustion engines |
US20070111906A1 (en) * | 2005-11-12 | 2007-05-17 | Milner Jeffrey L | Relatively low viscosity transmission fluids |
US20070123437A1 (en) * | 2005-11-30 | 2007-05-31 | Chevron Oronite Company Llc | Lubricating oil composition with improved emission compatibility |
US7981846B2 (en) | 2005-11-30 | 2011-07-19 | Chevron Oronite Company Llc | Lubricating oil composition with improved emission compatibility |
WO2007127836A1 (en) | 2006-04-26 | 2007-11-08 | R.T. Vanderbilt Company, Inc. | Antioxidant synergist for lubricating compositions |
WO2007131104A1 (en) | 2006-05-05 | 2007-11-15 | R. T. Vanderbilt Company, Inc. | Antioxidant additive for lubricant compositions, comprising organotungstate, diarylamine and organomolybdenum compounds |
US7879775B2 (en) | 2006-07-14 | 2011-02-01 | Afton Chemical Corporation | Lubricant compositions |
US20080015127A1 (en) * | 2006-07-14 | 2008-01-17 | Loper John T | Boundary friction reducing lubricating composition |
US20080015125A1 (en) * | 2006-07-14 | 2008-01-17 | Devlin Mark T | Lubricant compositions |
US7902133B2 (en) | 2006-07-14 | 2011-03-08 | Afton Chemical Corporation | Lubricant composition |
US20080015124A1 (en) * | 2006-07-14 | 2008-01-17 | Devlin Mark T | Lubricant composition |
US20080040968A1 (en) * | 2006-08-17 | 2008-02-21 | Malfer Dennis J | Fuel additive compounds and method of making the compounds |
US7833953B2 (en) | 2006-08-28 | 2010-11-16 | Afton Chemical Corporation | Lubricant composition |
US20080051305A1 (en) * | 2006-08-28 | 2008-02-28 | Devlin Mark T | Lubricant composition |
US20080119377A1 (en) * | 2006-11-22 | 2008-05-22 | Devlin Mark T | Lubricant compositions |
US8425772B2 (en) | 2006-12-12 | 2013-04-23 | Cummins Filtration Ip, Inc. | Filtration device with releasable additive |
US20080274921A1 (en) * | 2007-05-04 | 2008-11-06 | Ian Macpherson | Environmentally-Friendly Lubricant Compositions |
EP2420553A1 (en) | 2007-05-04 | 2012-02-22 | Afton Chemical Corporation | Environmentally-Friendly Lubricant Compositions |
EP2017329A1 (en) | 2007-05-04 | 2009-01-21 | Afton Chemical Corporation | Environmentally-Friendly Lubricant Compositions |
US20100152078A1 (en) * | 2007-05-04 | 2010-06-17 | Ian Macpherson | Environmentally-friendly lubricant compositions |
EP2009082A2 (en) | 2007-06-20 | 2008-12-31 | Chevron Oronite Company LLC | Synergistic lubricating oil composition containing a mixture of a nitro-substituted diarylamine and a diarylamine |
US20090011963A1 (en) * | 2007-07-06 | 2009-01-08 | Afton Chemical Corporation | Truck fleet fuel economy by the use of optimized engine oil, transmission fluid, and gear oil |
EP2025737A1 (en) | 2007-08-01 | 2009-02-18 | Afton Chemical Corporation | Environmentally-friendly fuel compositions |
US20090031614A1 (en) * | 2007-08-01 | 2009-02-05 | Ian Macpherson | Environmentally-Friendly Fuel Compositions |
US20090071067A1 (en) * | 2007-09-17 | 2009-03-19 | Ian Macpherson | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
EP2072611A1 (en) | 2007-12-13 | 2009-06-24 | Afton Chemical Corporation | Lubricant composition suitable for engines fueled by alternate fuels |
US20090156445A1 (en) * | 2007-12-13 | 2009-06-18 | Lam William Y | Lubricant composition suitable for engines fueled by alternate fuels |
EP2077316A2 (en) | 2007-12-17 | 2009-07-08 | Infineum International Limited | Lubricant compositions with low HTHS for a given SAE viscosity grade |
EP2078745A1 (en) | 2007-12-20 | 2009-07-15 | Chevron Oronite Company LLC | Lubricating oil compositions comprising a molybdenum compound and a zinc dialkyldithiophosphate |
US20100331224A1 (en) * | 2007-12-20 | 2010-12-30 | Boffa Alexander B | Lubricating Oil Compositions Comprising A Molybdenum Compound And A Zinc Dialkyldithiophosphate |
EP2077315A1 (en) | 2007-12-20 | 2009-07-08 | Chevron Oronite Company LLC | Lubricating oil compositions containing a tetraalkyl-napthalene-1,8 diamine antioxidant |
US20090233823A1 (en) * | 2008-03-11 | 2009-09-17 | Volkswagen Aktiengesellschaft | Method for lubricating a clutch-only automatic transmission component requiring lubrication |
US8703669B2 (en) | 2008-03-11 | 2014-04-22 | Afton Chemical Corporation | Ultra-low sulfur clutch-only transmission fluids |
US8546311B2 (en) | 2008-03-11 | 2013-10-01 | Volkswagen Aktiengesellsschaft | Method for lubricating a clutch-only automatic transmission component requiring lubrication |
US20090233822A1 (en) * | 2008-03-11 | 2009-09-17 | Afton Chemical Corporation | Ultra-low sulfur clutch-only transmission fluids |
DE102009012567A1 (en) | 2008-03-11 | 2009-10-01 | Afton Chemical Corp. | Clutch-only transmission fluid useful for lubrication comprises oil formulated with additive components having metal detergent, phosphorus-based wear preventative, phosphorylated and boronated dispersant, sulfurized extreme pressure agent |
DE102009001301A1 (en) | 2008-03-11 | 2009-09-24 | Volkswagen Ag | Method for lubricating a component only for the clutch of an automatic transmission, which requires lubrication |
US8702995B2 (en) | 2008-05-27 | 2014-04-22 | Dober Chemical Corp. | Controlled release of microbiocides |
US20090301968A1 (en) * | 2008-05-27 | 2009-12-10 | Dober Chemical Corporation | Devices and methods for controlled release of additive compositions |
US8591747B2 (en) | 2008-05-27 | 2013-11-26 | Dober Chemical Corp. | Devices and methods for controlled release of additive compositions |
US20090304868A1 (en) * | 2008-05-27 | 2009-12-10 | Dober Chemical Corporation | Controlled release cooling additive composition |
US20090294345A1 (en) * | 2008-05-27 | 2009-12-03 | Dober Chemical Corporation | Controlled release of microbiocides |
US7883638B2 (en) | 2008-05-27 | 2011-02-08 | Dober Chemical Corporation | Controlled release cooling additive compositions |
US7943796B2 (en) | 2008-07-31 | 2011-05-17 | Chevron Oronise Company LLC | Lubricating oil additive and lubricating oil composition containing same |
US20100029527A1 (en) * | 2008-07-31 | 2010-02-04 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
WO2010014829A2 (en) | 2008-07-31 | 2010-02-04 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
US8354566B2 (en) | 2010-02-03 | 2013-01-15 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
US20110190185A1 (en) * | 2010-02-03 | 2011-08-04 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
US8183192B2 (en) | 2010-02-03 | 2012-05-22 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
WO2011096920A1 (en) | 2010-02-03 | 2011-08-11 | Chevron Oronite Company Llc | Lubricating oil additive and lubricating oil composition containing same |
US8993496B2 (en) | 2010-03-31 | 2015-03-31 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
WO2011126641A2 (en) | 2010-03-31 | 2011-10-13 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
WO2011126642A2 (en) | 2010-03-31 | 2011-10-13 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
US9150811B2 (en) | 2010-03-31 | 2015-10-06 | Cherron Oronite Company LLC | Method for improving copper corrosion performance |
US8901050B2 (en) | 2010-03-31 | 2014-12-02 | Chevron Oronite Company Llc | Method for improving copper corrosion performance |
US8933001B2 (en) | 2010-03-31 | 2015-01-13 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
US8716202B2 (en) | 2010-12-14 | 2014-05-06 | Chevron Oronite Company Llc | Method for improving fluorocarbon elastomer seal compatibility |
CN102953064B (en) * | 2011-08-19 | 2014-11-12 | 中国石油天然气股份有限公司 | Mannich base corrosion-retarding neutralizer and preparation method thereof |
CN102953064A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Mannich base corrosion-retarding neutralizer and preparation method thereof |
US9249091B2 (en) | 2011-12-27 | 2016-02-02 | Chevron Oronite Company Llc | Post-treated sulfurized salt of an alkyl-substituted hydroxyaromatic composition |
US9206373B2 (en) | 2012-08-17 | 2015-12-08 | Afton Chemical Corporation | Calcium neutral and overbased mannich and anhydride adducts as detergents for engine oil lubricants |
EP2698418A1 (en) * | 2012-08-17 | 2014-02-19 | Afton Chemical Corporation | Calcium neutral and overbased mannich and anhydride adducts as detergents for engine oil lubricants |
US9657252B2 (en) | 2014-04-17 | 2017-05-23 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
EP2933320A1 (en) | 2014-04-17 | 2015-10-21 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
EP2990469A1 (en) | 2014-08-27 | 2016-03-02 | Afton Chemical Corporation | Lubricant composition suitable for use in gasoline direct injection engines |
US9528071B2 (en) | 2015-02-13 | 2016-12-27 | Chevron Oronite Technology B.V. | Lubricating oil compositions with enhanced piston cleanliness |
US9528074B2 (en) | 2015-02-13 | 2016-12-27 | Chevron Oronite Technology B.V. | Lubricating oil compositions with enhanced piston cleanliness |
WO2017011689A1 (en) | 2015-07-16 | 2017-01-19 | Afton Chemical Corporation | Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition |
US10214703B2 (en) | 2015-07-16 | 2019-02-26 | Afton Chemical Corporation | Lubricants with zinc dialkyl dithiophosphate and their use in boosted internal combustion engines |
EP3943581A1 (en) | 2015-07-16 | 2022-01-26 | Afton Chemical Corporation | Lubricants with tungsten and their use for improving low speed pre-ignition |
US10550349B2 (en) | 2015-07-16 | 2020-02-04 | Afton Chemical Corporation | Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition |
US10421922B2 (en) | 2015-07-16 | 2019-09-24 | Afton Chemical Corporation | Lubricants with magnesium and their use for improving low speed pre-ignition |
US10336959B2 (en) | 2015-07-16 | 2019-07-02 | Afton Chemical Corporation | Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition |
US10280383B2 (en) | 2015-07-16 | 2019-05-07 | Afton Chemical Corporation | Lubricants with molybdenum and their use for improving low speed pre-ignition |
WO2017146867A1 (en) | 2016-02-25 | 2017-08-31 | Afton Chemical Corporation | Lubricants for use in boosted engines |
EP3613831A1 (en) | 2016-02-25 | 2020-02-26 | Afton Chemical Corporation | Lubricants for use in boosted engines |
US10377963B2 (en) | 2016-02-25 | 2019-08-13 | Afton Chemical Corporation | Lubricants for use in boosted engines |
US9677026B1 (en) | 2016-04-08 | 2017-06-13 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
US9701921B1 (en) | 2016-04-08 | 2017-07-11 | Afton Chemical Corporation | Lubricant additives and lubricant compositions having improved frictional characteristics |
EP3228684A1 (en) | 2016-04-08 | 2017-10-11 | Afton Chemical Corporation | Lubricant compositions having improved frictional characteristics and methods of use thereof |
EP3243892A1 (en) | 2016-04-08 | 2017-11-15 | Afton Chemical Corporation | Lubricant compositions having improved frictional characteristics and methods of use thereof |
WO2017192217A1 (en) | 2016-05-05 | 2017-11-09 | Afton Chemical Corporation | Lubricants for use in boosted engines |
WO2017192202A1 (en) | 2016-05-05 | 2017-11-09 | Afton Chemical Corporaion | Lubricant compositions for reducing timing chain stretch |
US10323205B2 (en) | 2016-05-05 | 2019-06-18 | Afton Chemical Corporation | Lubricant compositions for reducing timing chain stretch |
US11155764B2 (en) | 2016-05-05 | 2021-10-26 | Afton Chemical Corporation | Lubricants for use in boosted engines |
WO2018101282A1 (en) | 2016-11-30 | 2018-06-07 | Chevron Japan Ltd. | Lubricating oil compositions for motorcycles |
WO2018111726A1 (en) | 2016-12-16 | 2018-06-21 | Afton Chemical Corporation | Multi-functional olefin copolymers and lubricating compositions containing same |
WO2018136137A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance |
US10370615B2 (en) | 2017-01-18 | 2019-08-06 | Afton Chemical Corporation | Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition |
US10443011B2 (en) | 2017-01-18 | 2019-10-15 | Afton Chemical Corporation | Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition |
US10443558B2 (en) | 2017-01-18 | 2019-10-15 | Afton Chemical Corporation | Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance |
WO2018136138A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition |
WO2018136136A1 (en) | 2017-01-18 | 2018-07-26 | Afton Chemical Corporation | Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition |
EP3476923A1 (en) | 2017-10-25 | 2019-05-01 | Afton Chemical Corporation | Dispersant viscosity index improvers to enhance wear protection in engine oils |
US10513668B2 (en) | 2017-10-25 | 2019-12-24 | Afton Chemical Corporation | Dispersant viscosity index improvers to enhance wear protection in engine oils |
US11098262B2 (en) | 2018-04-25 | 2021-08-24 | Afton Chemical Corporation | Multifunctional branched polymers with improved low-temperature performance |
EP3560966A2 (en) | 2018-04-25 | 2019-10-30 | Afton Chemical Corporation | Multifunctional branched polymers with improved low-temperature performance |
US11760953B2 (en) | 2018-04-25 | 2023-09-19 | Afton Chemical Corporation | Multifunctional branched polymers with improved low-temperature performance |
EP3578625A1 (en) | 2018-06-05 | 2019-12-11 | Afton Chemical Corporation | Lubricant composition and dispersants therefor having a beneficial effect on oxidation stability |
US10836976B2 (en) | 2018-07-18 | 2020-11-17 | Afton Chemical Corporation | Polymeric viscosity modifiers for use in lubricants |
WO2020174454A1 (en) | 2019-02-28 | 2020-09-03 | Afton Chemical Corporation | Lubricating compositions for diesel particulate filter performance |
EP3812445A1 (en) | 2019-10-24 | 2021-04-28 | Afton Chemical Corporation | Synergistic lubricants with reduced electrical conductivity |
US11066622B2 (en) | 2019-10-24 | 2021-07-20 | Afton Chemical Corporation | Synergistic lubricants with reduced electrical conductivity |
EP3858954A1 (en) | 2020-01-29 | 2021-08-04 | Afton Chemical Corporation | Lubricant formulations with silicon-containing compounds |
EP3954753A1 (en) | 2020-08-12 | 2022-02-16 | Afton Chemical Corporation | Polymeric surfactants for improved emulsion and flow properties at low temperatures |
WO2022094557A1 (en) | 2020-10-30 | 2022-05-05 | Afton Chemical Corporation | Engine oils with low temperature pump ability |
EP4067463A1 (en) | 2021-03-30 | 2022-10-05 | Afton Chemical Corporation | Engine oils with improved viscometric performance |
US11479736B1 (en) | 2021-06-04 | 2022-10-25 | Afton Chemical Corporation | Lubricant composition for reduced engine sludge |
EP4098723A1 (en) | 2021-06-04 | 2022-12-07 | Afton Chemical Corporation | Lubricating compositions for a hybrid engine |
WO2023004265A1 (en) | 2021-07-21 | 2023-01-26 | Afton Chemical Corporation | Methods of reducing lead corrosion in an internal combustion engine |
EP4124648A1 (en) | 2021-07-31 | 2023-02-01 | Afton Chemical Corporation | Engine oil formulations for low timing chain stretch |
WO2023141399A1 (en) | 2022-01-18 | 2023-07-27 | Afton Chemical Corporation | Lubricating compositions for reduced high temperature deposits |
US11572523B1 (en) | 2022-01-26 | 2023-02-07 | Afton Chemical Corporation | Sulfurized additives with low levels of alkyl phenols |
WO2023147258A1 (en) | 2022-01-26 | 2023-08-03 | Afton Chemical Corporation | Sulfurized additives with low levels of alkyl phenols |
WO2023159095A1 (en) | 2022-02-21 | 2023-08-24 | Afton Chemical Corporation | Polyalphaolefin phenols with high para-position selectivity |
WO2023212165A1 (en) | 2022-04-27 | 2023-11-02 | Afton Chemical Corporation | Additives with high sulfurization for lubricating oil compositions |
EP4282937A1 (en) | 2022-05-26 | 2023-11-29 | Afton Chemical Corporation | Engine oil formluation for controlling particulate emissions |
EP4306624A1 (en) | 2022-07-14 | 2024-01-17 | Afton Chemical Corporation | Transmission lubricants containing molybdenum |
EP4310162A1 (en) | 2022-07-15 | 2024-01-24 | Afton Chemical Corporation | Detergent systems for oxidation resistance in lubricants |
US11970671B2 (en) | 2022-07-15 | 2024-04-30 | Afton Chemical Corporation | Detergent systems for oxidation resistance in lubricants |
EP4317369A1 (en) | 2022-08-02 | 2024-02-07 | Afton Chemical Corporation | Detergent systems for improved piston cleanliness |
EP4357442A1 (en) | 2022-09-21 | 2024-04-24 | Afton Chemical Corporation | Lubricating composition for fuel efficient motorcycle applications |
WO2024073304A1 (en) | 2022-09-27 | 2024-04-04 | Afton Chemical Corporation | Lubricating composition for motorcycle applications |
US11912955B1 (en) | 2022-10-28 | 2024-02-27 | Afton Chemical Corporation | Lubricating compositions for reduced low temperature valve train wear |
US11926804B1 (en) | 2023-01-31 | 2024-03-12 | Afton Chemical Corporation | Dispersant and detergent systems for improved motor oil performance |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3649229A (en) | Liquid hydrocarbon fuels containing high molecular weight mannich bases | |
US3658707A (en) | Fuel oil and lubricating oil compositions | |
EP0008953B1 (en) | Fuel containing novel detergent | |
US4083699A (en) | Polyoxyethylene polyamine Mannich base products and use of same in fuels and lubricants | |
US3368972A (en) | High molecular weight mannich bases as engine oil additives | |
US3443918A (en) | Gasoline composition | |
US4134846A (en) | Multipurpose hydrocarbon fuel and lubricating oil additive mixture | |
US5207939A (en) | Dihydrocarbyl substituted phenylenediamine-derived phenolic products as antioxidants | |
EP0902824B1 (en) | Fuel additives | |
AU619957B2 (en) | Middle distillate fuel having improved storage stability | |
US4144034A (en) | Polyether-maleic anhydride reaction product containing motor fuel composition | |
JPS5920712B2 (en) | liquid hydrocarbon fuel composition | |
US6488723B2 (en) | Motor fuel additive composition and method for preparation thereof | |
US4456454A (en) | Mannich reaction product for motor fuels | |
US4144036A (en) | Detergent fuel composition | |
US4670021A (en) | Detergent and corrosion inhibiting additive and motor fuel composition containing same | |
US4643737A (en) | Polyol-acid anhydride-N-alkyl-alkylene diamine reaction product and motor fuel composition containing same | |
US5039310A (en) | Polyether substituted mannich bases as fuel and lubricant ashless dispersants | |
JPH02300292A (en) | Additive for fuel or lubricating oil | |
US3133800A (en) | Glycol borate amine salts as gasoline additives | |
US4054422A (en) | Mannich bases containing tertiary amines and fuel compositions containing said mannich bases | |
US5266081A (en) | Multifunctional ashless dispersants | |
US3655560A (en) | Fuels and lubricants containing aminoguanidine antioxidants | |
US4981493A (en) | ORI-Inhibited and deposit-resistant motor fuel composition | |
US4322220A (en) | Multipurpose hydrocarbon fuel and lubricating oil additive |