WO1985000620A1 - Quaternary deposit control additives - Google Patents
Quaternary deposit control additives Download PDFInfo
- Publication number
- WO1985000620A1 WO1985000620A1 PCT/US1984/001187 US8401187W WO8500620A1 WO 1985000620 A1 WO1985000620 A1 WO 1985000620A1 US 8401187 W US8401187 W US 8401187W WO 8500620 A1 WO8500620 A1 WO 8500620A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- group
- moiety
- polyoxyalkylene
- amine
- Prior art date
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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
-
- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—Amides; Imides
- C10M133/18—Amides; Imides of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2221/043—Polyoxyalkylene ethers with a thioether group
Definitions
- This invention is directed to quaternary salts of various polyether polyamines, to fuel compositions and lubricating oil compositions containing these compounds and to their use as either fuel additives or detergents or dispersancy additives in lubricating oils.
- Typical areas commonly and sometimes seriously burdened by the formation of deposits include carburetor ports, the throttle body and venturies, engine intake valves, combustion chamber, etc. Deposits adversely affect the operation of the vehicle. For example, deposits on the carburetor throttle body and venturies increase the fuel-to-air ratio of the gas mixture to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. The high fuel-air ratio also reduces the gas mileage obtainable from the vehicle.
- OMPI deposit-prone areas of the harmful deposits thereby enhancing engine performance and longevity.
- detergent-type gasoline additives currently available which, to varying degrees, perform these functions.
- this application also relates to lubricating oil compositions containing quaternary poly- ether amine additives which contribute dispersancy and detergency to the compositions.
- Lubricating oil compositions particularly for use in internal combustion engines, have long performed many functions other than simply lubricating moving parts. Modern-day, highly compounded lubricating oil compositions provide anti-wear, anti-oxidant, extreme- pressure and anti-rust protection in addition to maintaining the cleanliness of the engine by detergency and dispersancy. Many lubricating oil additives are wel l-known for accomplishing these functions .
- U.S. Patent No. 4,160,648 discloses deposit control additives comprised of polyoxyalkylene carbamates;
- U.S. Patent Application Serial No. 403,607, filed July 30, 1982 discloses polyether polyamine ethanes as deposit control additives;
- carboxylic and other acid salts, as well as the quaternary salts of basic nitrogen- containing polymers are known in the art as deposit control and/or carburetor detergent additives in fuel compositions. See, for example, U.S. Patent No. 3,468,640. These additives are also known to have improved corrosion inhibition properties relative to the pure basic nitrogen-containing polymers.
- Additives are provided which, when added to fuel or used as fuel concentrates, are effective in maintaining the cleanliness of the engine and its intake systems.
- the additives consist of the quaternary salts of various poly- ether polyamines soluble in hydrocarbon fuel boiling in the gasoline range. These quaternary salts show enhanced dispersancy and corrosion inhibition and therefore serve well as deposit control and/or carburetor dispersants. The nature of the anion in these various salts has also been found to affect their performance.
- the additives When added to lubricating oils, these additives are effective in maintaining the dispersancy of the oil and the efficiency of the engine.
- the additives consist of the quaternary salts of various polyether polyamines soluble in lubricating oil. These quaternary salts show enhanced dispersancy and corrosion inhibition and therefore serve well as lubricating oil dispersant agents. The nature of the anion in these various salts has also been found to affect their performance.
- the quaternary salts of the present invention are comprised of basically three moieties or components: a hydrophobic moiety at one end of the molecule comprising polyoxyalkylene polymer submoieties; a hydrophilic amine moiety at the other end, the basic nitrogen atom of which has been quaternized with an appropriate alkyl halidej and the third moiety, a connecting group serving to unite the hydrophilic and hydrophobic ends of the molecule.
- the polyoxyalkylene moiety comprises at least one oxyalkylene unit of from 2 to 4 carbon atoms and may e terminated or "capped” with a hydrocarbyl group.
- the hydrocarbyl terminating group of the polyoxyalkylene moiety may contain from between 5 to 30 carbon atoms.
- the polyoxyalkylene chain is bonded through a terminal oxygen to the appropriate connecting group which is in turn bonded to an amino nitrogen atom in the amine or polyamine group.
- the polyamine preferably contains from about 2 to about 12 amine nitrogens and from about 2 to about 40 carbon atoms, with a carbon-nitrogen ratio of between 1:1 and 10:1. At least one nitrogen atom is quaternized with a hydrocarbyl halide.
- the compounds have a molecular weight in the range of about 500 to about 2500, and preferably from about 800 to about 1500.
- the hydrocarbyl halides finding use as the quaternizing agents include alkyl groups containing from 1 to 20 carbon atoms and may be or contain aromatic groups such as phenyl or benzyl groups.
- the halides of the alkyl halide group ordinarily consist of chloride, bromide and iodide. Certain of the additives of the present invention are believed to be useful as dispersant additives in lubricating oils as well.
- the present invention herein consists of a fuel additive, a quaternized polyoxyalkylene polyamine or polyether polyamine, and a fuel composition containing a major amount of a liquid hydrocarbon fuel boiling in the gasoline range and from about 30 to about 10,000 ppm of said additive.
- the quaternized polyether polyamine has a molecular weight of from about 500 to about 2500, and preferably from about 800 to about 1500.
- the additive consists of three parts or moieties. The first is the polyether or polyoxyalkylene moiety, which may or may not be hydrocarbyl terminated or "capped”.
- the polyether moiety is bound through the second moiety, a connecting group or linkage to the nitrogen atom of the third moiety, the amine, which is quaternized by an appropriate alkyl halide.
- the polyoxyalkylene moiety and the quaternized amino moiety are selected to provide solubility in the fuel composition, deposit control activity, and corrosion inhibition within a vehicle's fuel system and engine.
- the moieties are selected to provide solubility in a lubri- eating oil composition with dispersant activity and corrosion inhibition properties.
- the moieties are selected to provide solubility in a lubricating oil composition with dispersant activity and corrosion inhibition properties.
- Polyoxyalkylene Moiety The polyoxyalkylene moiety is ordinarily comprised of polyoxyalkylene polymers containing at least one oxyalkylene unit, preferably 1 to 30 units, and more preferably 5 to 30 units, and most preferably 10 to about 25 oxyalkylene units. When polymerized in the polymeriza ⁇ tion reaction, a single type of alkylene oxide may be employed. Copolymers, however, are equally satisfactory and random copolymers are readily prepared. Blocked copolymers of oxyalkylene units also provide satisfactory polyoxyalkylene polymers for the practice of the present invention.
- the polyoxyalkylene moiety may also be terminated or "capped” by a hydrocarbyl terminating group.
- This terminating group may be comprised of an alkyl group of from 5 to about 30 carbon atoms, an aryl group of from 6 to about 30 carbon atoms, an alkaryl group of from 7 to about 30 carbon atoms, an aralkyl group of from 7 to about 30 carbon atoms, or a methylol-substituted alkyl group of from 5 to about 30 carbon atoms.
- the polyoxyalkylene moiety may ordinarily be prepared in a variety of ways, the most common for the practice of the present invention being by the reaction of an appropriate lower alkylene oxide containing from 2 to 4 carbon atoms with an appropriate initiator; for example, chlorohydrin or an alkyl phenol. In the preferred embodi ⁇ ment, ethylene chlorohydrin is used. Copolymers may be readily prepared by contacting the initiator compound with a mixture of alkylene oxides, while the blocked copolymers may be prepared by reacting the initiator first with one alkylene oxide and then another in any order or repetitively under polymerization conditions. As an example, the polyoxyalkylene moiety derived from an alkyl phenol initiated polymerization detailed above is prepared as an alcohol containing a terminal hydroxyl group. The polyether moiety is then attached through the appropriate connecting group to the 01 -7-
- polyamine moiety by a variety of ways, one of which includes reacting the hydroxyl group of the polyoxy-
- resulting polyoxyalk lene alkyl chloride is then reacted with an amine or polyamine to produce the composition to be quaternized, resulting in the composition of the present invention.
- the connecting group joining the polyoxyalkylene moiety with the amine moiety may be any relatively small diradical containing at least one carbon, oxygen, sulfur and/or nitrogen atom, and usually containing up to 12 carbon atoms.
- the connecting group which results and 20. is used in the present composition is ordinarily a func- ⁇ tion of the method by which the compositions are formed and/or by which the components of the polyoxyalkylene moiety and the polyamine moiety are joined together.
- Appropriate connecting groups include: 5 O carbamates -0-C-NH-; Z Z' ethylene -CH 2 -CH 2 - 0 oxyethy lene CH 2 -CH 2 0-)-
- amides -C-NZ-; and methylene -CHZ-; where Z and Z' independently H, or an alkyl group of from 1 to 2 carbon atoms.
- the Amine Moiety of the quaternized polyether amine is derived from ammonia or, more preferably, from a polyamine having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms.
- the polyamine preferably has a carbon to ni ' trogen ratio of from about 1:1 to about 10:1.
- the polyamine may be substituted with a substituent group selected from (A) hydrogen; (B) hydrocarbyl groups from about 1 to about 10 carbon atoms; (C) acyl groups from about 2 to about 10 carbon atoms; and (D) monoketo, monocyano, lower alkyl and lower alkoxy derivatives of (B), (C).
- “Lower”, as used in lower alkyl and lower alkoxy * means a group containing about 1 to 6 carbon atoms.
- “Hydrocarbyl” denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g. aralkyl.
- the substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines.
- the acyl groups falling within the definition of the aforementioned (C) substituents are such as propionyl, acetyl, etc.
- the more preferred substituents are hydrogen, C- ⁇ to Cg alkyls, and C- ⁇ -Cg hydroxyalkyls.
- polyalkylene polyamines including alkylene diamine and substituted polyamines, e.g. alkyl and hydroxyalkyl-substituted poly- alkylene polyamines.
- alkylene groups contain from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms.
- Such groups are exemplified by ethyleneamines and include ethylene diamine, diethylene triamine, di(trimethylene) triamine, dipropylenetriamine, triethylenetetramine, etc.
- Such amines encompass isomers which are the branched-chain polyamines and the previously mentioned substituted poly ⁇ amines, including hydroxy and hydrocarbyl-substituted polyamines.
- polyalkylene polyamines those containing 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms, are especially preferred and the C 2 to C ⁇ alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g. ethylene diamine, tetraethylenepentamine, etc.
- compositions of the present invention are prepared by the quaternization of the polyether poly ⁇ amines using alkyl halides.
- Quaternary ammonium compounds are generally prepared by the reaction of amines with alkyl halides. These compounds have 4 carbon atoms linked directly to a nitrogen atom through covalent bonding. The anion in the original alkylating agent is therefore linked to the nitrogen through an electrovalent bond.
- the compo ⁇ sitions are prepared by reacting the appropriate polyether polyamine with an alkyl halide containing from 1 to
- the alkyl halide may also contain aro- matics such as benzyl, etc.
- the halides utilized in the alkyl halides of the present invention ordinarily consist of chloride, bromide and iodide.
- the anion portion of the quaternized ammonium compounds may also be exchanged for other anions such as acetate, trimethylacetate, alkyl- phenoxide, or hydroxide. These may be generalized as C 2 to C ⁇ 2 carboxylate anions, Cg to C ⁇ phenoxides, or alkyl- substituted phenoxides.
- the polyether polyamines are quaternized by standard quaternizing reactions; that is, mixing appropriate amounts of the amine and the alkyl halide and applying heat.
- a generalized, preferred formula for the quaternized polyether polyamines finding utility in this invention is as follows:
- R an alkyl group of 5 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, alkaryl group of 7 to 30 carbon atoms, aralkyl group of 7 to 30 carbon atoms, or methylol-substituted alkyl group of 5 to 30 carbon atoms;
- R V1 alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups
- Y a halide, a C 2 to C-, carboxylate anion, or a C to C ⁇ Q phenoxide or alkyl-substituted phenoxide.
- the proper concentra ion of the additive in fuel necessary in order to achieve the desired deposit control effect or carburetor detergency is dependent upon a vari ⁇ ety of factors, including type of fuel used, the presence of other detergents .or dispersants, or other additives, etc.
- the range of concentra ion of the additive in the base fuel is from 30 to 10,000 weight ppm, preferably from 30 to 2,000 weight ppm, and most preferably from 100 to 700 ppm of quaternized polyether polyamine per part of base fuel. If other detergents are present, a lesser amount of quaternized polyether polyamine may be used.
- oils which find use in this invention are oils of lubricating viscosity derived from petroleum or synthetic sources. Oils of lubricating viscosity normally have viscosities in the range of 35 to 50,000 Saybolt Universal Seconds (SUS) at 37.8°C, and more usually from about 50 to 10,000 SUS at 37.8°C.
- base oils are naphthenic bases; paraffin bases; mixed-base mineral oils; and synthetic oils, for example, alkylene polymers such as polymers of propylene, butylene, etc.; and mixtures thereof.
- oils besides the subject additives are such additives as dispersants/detergents, rust inhibitors, anti-oxidants, oiliness agents, foam inhibitors, viscosity index improvers, pour point depres ⁇ sants, etc.
- these other additives will be present in amounts of from about 0.5 to 15.0 weight percent of the total composition.
- each of the additives will be present in the range from about 0.01 to 5.0 weight percent of the total composition.
- the quaternized polyether polyamines may be used as concentrates, and could be used as additives to fuels or lubricating oils subsequent to their preparation.
- the weight percent of these additives will usually range from about 0.3 to 50 weight percent.
- the concentrate would ordinarily comprise an inert, stable oleophilic, organic solvent and the carrier of said solvent, boiling in the range of from about 65.6°C to 204.4°C.
- the concentrate will preferably contain from about 10 to about 50 weight percent of the quaternized polyether polyamine compound.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A fuel composition containing 30 to 10,000 ppm of an additive comprising quaternized polyoxyalkylene amine salts of molecular weight 500 to about 2500, the polyoxyalkylene moiety comprising 1 to 30 oxyalkylene units, the units having 2 to 4 carbon atoms and the amine comprising 1 to 12 amine nitrogen atoms and 2 to 40 carbon atoms and having a connecting moiety linking the polyoxyalkylene moiety to the amine moiety. Also disclosed are lubricating oil compositions containing the additive, concentrates of this additive and the composition of the additive itself.
Description
-i-
QUATERNARY DEPOSIT CONTROL ADDITIVES
BACKGROUND OF THE INVENTION
Field of the Invention
This invention is directed to quaternary salts of various polyether polyamines, to fuel compositions and lubricating oil compositions containing these compounds and to their use as either fuel additives or detergents or dispersancy additives in lubricating oils.
Numerous deposit-forming substances are inherent in hydrocarbon fuels. These substances when used in internal combustion engines tend to form deposits on and around areas of the engine contacted by the fuel.
Typical areas commonly and sometimes seriously burdened by the formation of deposits include carburetor ports, the throttle body and venturies, engine intake valves, combustion chamber, etc. Deposits adversely affect the operation of the vehicle. For example, deposits on the carburetor throttle body and venturies increase the fuel-to-air ratio of the gas mixture to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. The high fuel-air ratio also reduces the gas mileage obtainable from the vehicle.
Deposits on the engine intake valves when they get sufficiently heavy, on the other hand, restrict the gas mixture flow into the combustion chamber. This restriction starves the engine of air and fuel and results in a loss of power. Deposits on the valves also increase the probability of valve failure due to burning and improper valve seating. In addition, these deposits may break off and enter the combustion chamber, possibly resulting in mechanical damage to the piston, piston rings, engine head, etc.
The formation of these deposits can be inhibited as well as removed by incorporating an active detergent and/or dispersant into the fuel. These detergents/dispersants function to cleanse these
OMPI
deposit-prone areas of the harmful deposits, thereby enhancing engine performance and longevity. There are numerous detergent-type gasoline additives currently available which, to varying degrees, perform these functions.
Additionally, many corrosion problems are inherent in engine operation, particularly over time. Moisture and oxygen and petroleum fuels in contact with ferrous metals contribute to the formation of corrosion products which may significantly interfere with the smooth operation of a variety of a vehicle's fuel system and engine parts, such as the fuel storage tank, fuel lines and injectors. This corrosion can also be formed or promoted by various other agents including some fuel components, such as acids, and even some deposit control additives. This corrosion, besides interfering with the vehicle's operation which may result in a shortening of the engine life, also contributes to a reduction of the efficiency of the engine. It is therefore very desirable for a fuel composition to possess both deposit control additives which effectively control the deposits in the intake systems and corrosion inhibitors which help prevent corrosive agents from interfering with efficient engine operation. The present invention discloses a new class of compounds which seek to overcome both of these problems.
Likewise, this application also relates to lubricating oil compositions containing quaternary poly- ether amine additives which contribute dispersancy and detergency to the compositions.
Lubricating oil compositions, particularly for use in internal combustion engines, have long performed many functions other than simply lubricating moving parts. Modern-day, highly compounded lubricating oil compositions provide anti-wear, anti-oxidant, extreme- pressure and anti-rust protection in addition to maintaining the cleanliness of the engine by detergency and dispersancy. Many lubricating oil additives are wel l-known for accomplishing these functions .
MPI
Additionally, many corrosion problems are inherent in engine operation, particularly over time. Moisture and oxygen and petroleum fuels in contact with ferrous metals contribute to the formation of corrosion products which may significantly interfere with the smooth operation of the engine. This corrosion can also be formed or promoted by various other agents including some lubricating oil components, such as acids, and even some dispersant additives. This corrosion, besides interfering with the vehicle's operation which may result in a shortening of the engine life, also contributes to a reduction of the efficiency of the engine. It is therefore very desirable for a lubricating oil composition to possess both dispersant additives and corrosion inhibitors. The present invention discloses a new class of compounds which seek to overcome both of these problems. Deposit control additives including polyether amines are disclosed in U.S. Patent No. 3,864,098 and hydrocarbyl polyoxyalkylene polyamines in U.S. Patent No. 4,247,301. U.S. Patent No. 4,160,648 discloses deposit control additives comprised of polyoxyalkylene carbamates; U.S. Patent Application Serial No. 403,607, filed July 30, 1982, discloses polyether polyamine ethanes as deposit control additives; and U.S. Patent Application Serial No. 499,131, filed May 31, 1983, discloses methylol polyether amino ethanes as deposit control additives. Additionally, carboxylic and other acid salts, as well as the quaternary salts of basic nitrogen- containing polymers are known in the art as deposit control and/or carburetor detergent additives in fuel compositions. See, for example, U.S. Patent No. 3,468,640. These additives are also known to have improved corrosion inhibition properties relative to the pure basic nitrogen-containing polymers.
SUMMARY OF THE INVENTION
Additives are provided which, when added to fuel or used as fuel concentrates, are effective in maintaining
the cleanliness of the engine and its intake systems. The additives consist of the quaternary salts of various poly- ether polyamines soluble in hydrocarbon fuel boiling in the gasoline range. These quaternary salts show enhanced dispersancy and corrosion inhibition and therefore serve well as deposit control and/or carburetor dispersants. The nature of the anion in these various salts has also been found to affect their performance.
When added to lubricating oils, these additives are effective in maintaining the dispersancy of the oil and the efficiency of the engine. The additives consist of the quaternary salts of various polyether polyamines soluble in lubricating oil. These quaternary salts show enhanced dispersancy and corrosion inhibition and therefore serve well as lubricating oil dispersant agents. The nature of the anion in these various salts has also been found to affect their performance. The quaternary salts of the present invention are comprised of basically three moieties or components: a hydrophobic moiety at one end of the molecule comprising polyoxyalkylene polymer submoieties; a hydrophilic amine moiety at the other end, the basic nitrogen atom of which has been quaternized with an appropriate alkyl halidej and the third moiety, a connecting group serving to unite the hydrophilic and hydrophobic ends of the molecule.
The polyoxyalkylene moiety comprises at least one oxyalkylene unit of from 2 to 4 carbon atoms and may e terminated or "capped" with a hydrocarbyl group. The hydrocarbyl terminating group of the polyoxyalkylene moiety may contain from between 5 to 30 carbon atoms. Preferably, the polyoxyalkylene chain is bonded through a terminal oxygen to the appropriate connecting group which is in turn bonded to an amino nitrogen atom in the amine or polyamine group. The polyamine preferably contains from about 2 to about 12 amine nitrogens and from about 2 to about 40 carbon atoms, with a carbon-nitrogen ratio of between 1:1 and 10:1. At least one nitrogen atom is quaternized with a hydrocarbyl halide. The compounds have
a molecular weight in the range of about 500 to about 2500, and preferably from about 800 to about 1500. The hydrocarbyl halides finding use as the quaternizing agents include alkyl groups containing from 1 to 20 carbon atoms and may be or contain aromatic groups such as phenyl or benzyl groups. The halides of the alkyl halide group ordinarily consist of chloride, bromide and iodide. Certain of the additives of the present invention are believed to be useful as dispersant additives in lubricating oils as well.
DETAILED DESCRIPTION OF THE INVENTION The present invention herein consists of a fuel additive, a quaternized polyoxyalkylene polyamine or polyether polyamine, and a fuel composition containing a major amount of a liquid hydrocarbon fuel boiling in the gasoline range and from about 30 to about 10,000 ppm of said additive. The quaternized polyether polyamine has a molecular weight of from about 500 to about 2500, and preferably from about 800 to about 1500. The additive consists of three parts or moieties. The first is the polyether or polyoxyalkylene moiety, which may or may not be hydrocarbyl terminated or "capped". The polyether moiety is bound through the second moiety, a connecting group or linkage to the nitrogen atom of the third moiety, the amine, which is quaternized by an appropriate alkyl halide.
As fuel additives, the polyoxyalkylene moiety and the quaternized amino moiety are selected to provide solubility in the fuel composition, deposit control activity, and corrosion inhibition within a vehicle's fuel system and engine. As lubricating oil additives, the moieties are selected to provide solubility in a lubri- eating oil composition with dispersant activity and corrosion inhibition properties.
As lubricating oil additives, the moieties are selected to provide solubility in a lubricating oil composition with dispersant activity and corrosion inhibition properties.
Polyoxyalkylene Moiety The polyoxyalkylene moiety is ordinarily comprised of polyoxyalkylene polymers containing at least one oxyalkylene unit, preferably 1 to 30 units, and more preferably 5 to 30 units, and most preferably 10 to about 25 oxyalkylene units. When polymerized in the polymeriza¬ tion reaction, a single type of alkylene oxide may be employed. Copolymers, however, are equally satisfactory and random copolymers are readily prepared. Blocked copolymers of oxyalkylene units also provide satisfactory polyoxyalkylene polymers for the practice of the present invention. The polyoxyalkylene moiety may also be terminated or "capped" by a hydrocarbyl terminating group. This terminating group may be comprised of an alkyl group of from 5 to about 30 carbon atoms, an aryl group of from 6 to about 30 carbon atoms, an alkaryl group of from 7 to about 30 carbon atoms, an aralkyl group of from 7 to about 30 carbon atoms, or a methylol-substituted alkyl group of from 5 to about 30 carbon atoms.
The polyoxyalkylene moiety may ordinarily be prepared in a variety of ways, the most common for the practice of the present invention being by the reaction of an appropriate lower alkylene oxide containing from 2 to 4 carbon atoms with an appropriate initiator; for example, chlorohydrin or an alkyl phenol. In the preferred embodi¬ ment, ethylene chlorohydrin is used. Copolymers may be readily prepared by contacting the initiator compound with a mixture of alkylene oxides, while the blocked copolymers may be prepared by reacting the initiator first with one alkylene oxide and then another in any order or repetitively under polymerization conditions. As an example, the polyoxyalkylene moiety derived from an alkyl phenol initiated polymerization detailed above is prepared as an alcohol containing a terminal hydroxyl group. The polyether moiety is then attached through the appropriate connecting group to the
01 -7-
polyamine moiety by a variety of ways, one of which includes reacting the hydroxyl group of the polyoxy-
05 alkylene unit with phosgene to form a polyoxyalkylene chloroformate and then reacting the polyoxyalkylene chloroformate with'an amine. Alternatively, the hydroxyl group may be reacted with epichlorohydrin to give a methylol-substituted ethyl chloride end group. The
10 resulting polyoxyalk lene alkyl chloride is then reacted with an amine or polyamine to produce the composition to be quaternized, resulting in the composition of the present invention.
The Connecting Group
15 The connecting group joining the polyoxyalkylene moiety with the amine moiety may be any relatively small diradical containing at least one carbon, oxygen, sulfur and/or nitrogen atom, and usually containing up to 12 carbon atoms. The connecting group which results and 20. is used in the present composition is ordinarily a func-^ tion of the method by which the compositions are formed and/or by which the components of the polyoxyalkylene moiety and the polyamine moiety are joined together. Appropriate connecting groups include: 5 O carbamates -0-C-NH-; Z Z' ethylene -CH2-CH2- 0 oxyethy lene CH2-CH20-)-
CH OH
I 2 methylol ethylene -CH-CH2~ ;
O 0 succinates -0-C II-CH2-CH2-C II-0- ; 5 ethers -0- ; th ioethe rs -S- ; 0 ii carbon ls -C- ;
carbonates -0-C-0-; 0
II esters -C-0-;
amides -C-NZ-; and methylene -CHZ-; where Z and Z' independently = H, or an alkyl group of from 1 to 2 carbon atoms.
The Amine Moiety The amine moiety of the quaternized polyether amine is derived from ammonia or, more preferably, from a polyamine having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms. The polyamine preferably has a carbon to ni'trogen ratio of from about 1:1 to about 10:1. The polyamine may be substituted with a substituent group selected from (A) hydrogen; (B) hydrocarbyl groups from about 1 to about 10 carbon atoms; (C) acyl groups from about 2 to about 10 carbon atoms; and (D) monoketo, monocyano, lower alkyl and lower alkoxy derivatives of (B), (C). "Lower", as used in lower alkyl and lower alkoxy*, means a group containing about 1 to 6 carbon atoms. "Hydrocarbyl" denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g. aralkyl. The substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines. The acyl groups falling within the definition of the aforementioned (C) substituents are such as propionyl, acetyl, etc. The more preferred substituents are hydrogen, C-^ to Cg alkyls, and C-^-Cg hydroxyalkyls. The more preferred polyamines finding use within the scope of the present invention are polyalkylene polyamines, including alkylene diamine and substituted
polyamines, e.g. alkyl and hydroxyalkyl-substituted poly- alkylene polyamines. Preferably the alkylene groups contain from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Such groups are exemplified by ethyleneamines and include ethylene diamine, diethylene triamine, di(trimethylene) triamine, dipropylenetriamine, triethylenetetramine, etc. Such amines encompass isomers which are the branched-chain polyamines and the previously mentioned substituted poly¬ amines, including hydroxy and hydrocarbyl-substituted polyamines. Among the polyalkylene polyamines, those containing 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms, are especially preferred and the C2 to C^ alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g. ethylene diamine, tetraethylenepentamine, etc.
In many instances a single compound will not be used as reactant in the preparation of the compositions of this invention, in particular the polyamine component. That is, mixtures will be used in which one or two compounds will predominate with the average composition indicated. The Quaternized Composition
The final compositions of the present invention are prepared by the quaternization of the polyether poly¬ amines using alkyl halides. Quaternary ammonium compounds are generally prepared by the reaction of amines with alkyl halides. These compounds have 4 carbon atoms linked directly to a nitrogen atom through covalent bonding. The anion in the original alkylating agent is therefore linked to the nitrogen through an electrovalent bond. The compo¬ sitions are prepared by reacting the appropriate polyether polyamine with an alkyl halide containing from 1 to
20 carbon atoms. The alkyl halide may also contain aro- matics such as benzyl, etc. The halides utilized in the alkyl halides of the present invention ordinarily consist of chloride, bromide and iodide. The anion portion of the quaternized ammonium compounds may also be exchanged for
other anions such as acetate, trimethylacetate, alkyl- phenoxide, or hydroxide. These may be generalized as C2 to C^2 carboxylate anions, Cg to C^ phenoxides, or alkyl- substituted phenoxides. The polyether polyamines are quaternized by standard quaternizing reactions; that is, mixing appropriate amounts of the amine and the alkyl halide and applying heat. A generalized, preferred formula for the quaternized polyether polyamines finding utility in this invention is as follows:
Ri Rii Ri Rii Riv
R-O-C1H-C1HO-)— I I iii '© vi Θ n—-1rCH-CH-X-R11 -N . -RV1 Y
Rv
wherein R = an alkyl group of 5 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, alkaryl group of 7 to 30 carbon atoms, aralkyl group of 7 to 30 carbon atoms, or methylol-substituted alkyl group of 5 to 30 carbon atoms;
R1 and RX1 independently = hydrogen, methyl or ethyl; n = 1 to 30, preferably 10 to 25;
X = the connecting group as defined above;
R111 = a chemical bond, an alkylene or hydroxy- substituted alkylene group of 2 to 12 carbon atoms, or ■(•NH-CH2-CH2 χ, where x = 0 to 5;
Rlv and Rv independently = alkyl groups of 1 to
20 carbon atoms, aralkyl group of 7 to 20 carbon atoms, alkaryl group of 7 to 20 carbon atoms, or phenyl;
RV1 = alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups
H of 7 to 20 carbon atoms, phenyl, or -£CH2CH2 χH, where x = 1 to 5; and
Y = a halide, a C2 to C-, carboxylate anion, or a C to C^Q phenoxide or alkyl-substituted phenoxide.
The proper concentra ion of the additive in fuel necessary in order to achieve the desired deposit control effect or carburetor detergency is dependent upon a vari¬ ety of factors, including type of fuel used, the presence of other detergents .or dispersants, or other additives, etc. Generally, however, and in the preferred embodiment, the range of concentra ion of the additive in the base fuel is from 30 to 10,000 weight ppm, preferably from 30 to 2,000 weight ppm, and most preferably from 100 to 700 ppm of quaternized polyether polyamine per part of base fuel. If other detergents are present, a lesser amount of quaternized polyether polyamine may be used.
The oils which find use in this invention are oils of lubricating viscosity derived from petroleum or synthetic sources. Oils of lubricating viscosity normally have viscosities in the range of 35 to 50,000 Saybolt Universal Seconds (SUS) at 37.8°C, and more usually from about 50 to 10,000 SUS at 37.8°C. Examples of such base oils are naphthenic bases; paraffin bases; mixed-base mineral oils; and synthetic oils, for example, alkylene polymers such as polymers of propylene, butylene, etc.; and mixtures thereof.
Usually included in the oils besides the subject additives are such additives as dispersants/detergents, rust inhibitors, anti-oxidants, oiliness agents, foam inhibitors, viscosity index improvers, pour point depres¬ sants, etc. Usually, these other additives will be present in amounts of from about 0.5 to 15.0 weight percent of the total composition. Generally, each of the additives will be present in the range from about 0.01 to 5.0 weight percent of the total composition.
It is also contemplated that the quaternized polyether polyamines may be used as concentrates, and could be used as additives to fuels or lubricating oils subsequent to their preparation. In concentrates, the weight percent of these additives will usually range from about 0.3 to 50 weight percent. The concentrate would ordinarily comprise an inert, stable oleophilic, organic
solvent and the carrier of said solvent, boiling in the range of from about 65.6°C to 204.4°C. The concentrate will preferably contain from about 10 to about 50 weight percent of the quaternized polyether polyamine compound.
The following examples are presented to illustrate a specific embodiment of the practice of this invention and should not be interpreted as a limitation upon the scope of that invention.
EXAMPLES
)
To an ice-cold solution of 55 is ( 0. 724 moles ) dimethyl hydraz ine in 100 mis methylene chloride was added equiva lents )
in 600 mis methylene chloride
at a rate o approx mate y drop/second with vigorous stirring under an atmosphere of nitrogen.
After the addition was complete, the reaction was warmed to room temperature and concentrated in vacuo to afford a slurry. This slurry was dissolved in approxi¬ mately 600 mis of toluene and extracted once with 100 mis of water, once with 100 mis saturated aqueous aHCθ3 and then with water until the washings were neutral (pH paper). The organic layer was dried over anh. MgSO^, filtered and stripped in vacuo to afford 634 gms of a golden oil: Basic nitrogen = 0.67%; total nitrogen = 1.39%; IR (cm-1) 1730 (C=0), 3310 (N-H).
Example 2
The procedure of M. S. Brown [J. Che . and Eng. Data, _12_ (4) 612 (1967)] was followed. To 570 gms (0.326 equivalents) of the polyether dimethyl hydrazine carbamate prepared in Example 1 was added 41 mis (0.658 moles) of methyl iodide dropwise over approximately 10 minutes under an atmosphere of nitrogen with vigorous stirring. The reaction was stirred at room temperature and monitored by IR until all the starting material had reacted (approximately 18 hours). The reaction was then stripped in vacuo to afford an oil: IR 1750 c (C=0).
Example 3 Preparation of
To an ice-cold solution of 300 gms (0.166 moles)
di ethylformamide and 80 is tributylamine was added 11 mis (0.166 moles) methyl iodide dropwise with vigorous stirring under an atmosphere of nitrogen. After the addition, the reaction was heated to 60°C for 1 hour and then allowed to cool to room temperature with stirring overnight. The reaction was then extracted with water until the washings were neutral (pH paper), dried over Na2SO_j and stripped to afford an oil: Basic nitrogen = 0%; IR (cm-1) 1710 (carbamate C=0), 3320 (N-H) .
Example 4 Preparation of
+(Me OAc" C
To 50 gms of the material prepared in Example 3 was added 180 mis n-butanol. This solution was extracted nine times with 50 ml portions of a 5 wt. % aqueous sodium acetate solution. The organic layer was then dried over anh. Na2SO., filtered and stripped to afford a yellow oil: Basic nitrogen = 0.65%; IR (cm~l) 1575 (carboxylate C=0), 1710 (carbamate C=0), 3250 (N-H).
Claims
WHAT IS CLAIMED IS:
1• A fuel composition comprising a major portion of hydrocarbon boiling in the gasoline range, and from 30 to about 10,000 ppm of quaternized polyoxyalkylene amine salts of molecular weight from about 500 to about 2500, said polyoxyalkylene moiety comprising 1 to 30 oxyalkylene units selected from oxyalkylene units having 2 to 4 carbon atoms, said amine moiety comprising from 1 to about 12 amine nitrogen atoms and from about 2 to 40 carbon atoms, and further comprising a connecting moiety linking said polyoxyalkylene moiety and said amine moiety.
2. A fuel composition according to Claim 1 wherein said amine moiety is a polyamine.
3. A fuel composition according to Claim 1 wherein the quaternized amine moiety is quaternized by alkyl halides having from 1 to 20 carbon atoms.
4. A fuel composition according to Claim 3 wherein the halide anions of the alkyl halide are selected from the group consisting of chloride, bromide, and iodide.
5. A fuel composition according to Claim 4 wherein said halide anions may be substituted following quaterni- zation of the quaternized polyoxyalkylene amine salts with a composition selected from the group consisting of: C2 to C-]2 carboxylate anions, Cg to C Q phenoxides, or alkyl- substituted phenoxide anions.
6. A fuel composition according to Claim 1 wherein said connecting moiety is selected from the group consist¬ ing of carbamate, ethylene, oxyethylene, methylol ethyl¬ ene, succinate, ether, thioether, carbonyl, carbonate, ester, amide, and methylene groups.
7. A fuel composition according to Claim 6 wherein said connecting moiety contains from about 1 to about 12 carbon atoms.
8. A fuel composition according to Claim 7 wherein said polyoxyalkylene moiety comprises 10 to about
25 oxyalkylene units.
9. A fuel composition according to Claim 8 wherein said amine moiety contains from about 2 to about 12 amine nitrogen atoms and from about 2 to about 24 carbon atoms.
10. A fuel composition according to Claim 9 wherein said amine moiety comprises C2 to C, alkylene polyamines.
11. A fuel composition according to Claim 1 wherein said quaternized polyoxyalkylene amine salts have a molecular weight of from 800 to 1500.
12. A fuel composition comprising a major portion of hydrocarbon boiling in the gasoline range and from 30 to 10,000 ppm of a trialkyl polyoxyalkylene ammonium salt of molecular weight from about 500 to about 2500, said poly¬ oxyalkylene comprising 1 to 30 oxyalkylene units selected from oxyalkylene units having 2 to 4 carbon atoms, said amine moiety comprising from 1 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms, and further comprising a connecting moiety linking said polyoxyalkylene moiety and said amine moiety.
14. A fuel composition as claimed in Claim 13 wherein the alkyl groups of said trialkyl polyoxyalkylene
05 ammonium salt are selected from the group consisting of alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups of 7 to 20 carbon atoms and phenyl.
10 15. A fuel composition as claimed in Claim 14 wherein said trialkyl groups are methyl groups.
16. A fuel composition comprising a major portion of hydrocarbon boiling in the gasoline range and from 30 to I5 about 10,000 ppm of a fuel additive of the formula:
)11 ,11 )1V
R-O H-CHO)n_1CH-CH-X-R 111 Θ-Ri Θ
20
wherein R = an alkyl group of 5 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, alkaryl group of 7 to 30 carbon atoms, aralkyl group of 7 to 5 30 carbon atoms, or methylol-substituted alkyl group of 5 to 30 carbon atoms;
R1 and R11 independently = hydrogen, methyl or ethyl; n = 1 to 30, preferably 10 to 25;
X = a connecting group selected from the group 0 consisting of:
O carbamates -0-C II-NH-; Z Z'
5 ethylene -C IH2-CIH2-; oxyethylene CH2-CH20 ;
CH2OH methylol ethylene -CH-CH2-;
0 O 0 II succinates -0-C-CH2-CH2-c"°-?
' O PI ethers -0-*, thioethers -S-;
0 carbonyls -C II-;
0 li carbonates -0-C-0-;
esters -C-0-;
amides -C-NZ- ; and methylene -CHZ- ; where Z and Z ' = H , or an alkyl group of from 1 to 2 carbon atoms ;
.1 1 1 = a chemical bond , an alkyle ne or hydroxy- substituted alkylene group of 2 to 12 carbon atoms , or f H-C-^-CH^ , where x = 0 to 5 ;
,ιv and Rv independently = alkyl groups of 1 to
20 carbon atoms, aralkyl group of 7 to 20 carbon atoms, alkaryl group of 7 to 20 carbon atoms, or phenyl;
Rvi _ alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups of 7 to 20 carbon atoms, phenyl, or ■fNH-CH2-CH2*χ, where x = 1 to 5; Y = a halide, a C2 to C, carboxylate anion, or a Cg to C g phenoxide or alkyl-substituted phenoxide.
17. A concentrate comprising an inert, stable oleophilic organic solvent boiling in the range of 65.6°C to 204.4°C and from 10 to 50 weight percent of the compound of Claim 1, 12 or 16.
18. Compounds suitable for additives in internal combustion engines which comprise the minor portion addi¬ tive of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16.
OMPI
19. A lubricating oil composition comprising a major portion of oil of lubricating viscosity and a minor amount of quaternized polyoxyalkylene amine salts of molecular weight from about 500 to about 2500, said polyoxyalkylene moiety comprising 1 to 30 oxyalkylene units selected from oxyalkylene units having 2 to 4 carbon atoms, said amine moiety comprising from 1 to about 12 amine nitrogen atoms and from about 2 to 40 carbon atoms, and further comprising a connecting moiety linking said polyoxyalkylene moiety and said amine moiety.
20. A lubricating oil composition according to Claim 19 wherein said amine moiety is a polyamine.
21. A lubricating oil composition according to Claim 19 wherein the quaternized amine moiety is quaternized by alkyl halides having from 1 to 20 carbon atoms.
22. A lubricating oil composition according to Claim 21 wherein the halide anions of the alkyl halide are selected from the group consisting of chloride, bromide, and iodide.
23. A lubricating oil composition according to Claim 22 wherein said halide anions may be substituted following quaternization of the quaternized polyoxy- alkylene amine salts with a composition selected from the group consisting of: C to C-,2 carboxylate anions, Cg to C3Q phenoxides, or alkyl-substituted phenoxide anions.
24. A lubricating oil composition according to Claim 23 wherein said connecting moiety is selected from the group consisting of carbamate, ethylene, oxyethylene, methylol ethylene, succinate, ether, thioether, carbonyl, carbonate, ester, amide, and methylene groups.
25. A lubricating oil composition according to Claim 24 wherein said connecting moiety contains from about 1 to about 12 carbon atoms.
26. A lubricating oil composition according to Claim 25 wherein said polyoxyalkylene moiety comprises 10 to about 25 oxyalkylene units.
27. A lubricating oil composition according to Claim 26 wherein said amine moiety contains from about 2 to about 12 amine nitrogen atoms and from about 2 to about 24 carbon atoms.
28. A lubricating oil composition according to Claim 27 wherein said amine moiety comprises C2 to C3 aIkylene polyamines.
29. A lubricating oil composition according to
Claim 19 wherein said quaternized polyoxyalkylene amine salts have a molecular weight of from 800 to 1500.
30. A lubricating oil composition comprising a major portion of oil of lubricating viscosity and a minor amount of a trialkyl polyoxyalkylene ammonium salt of molecular weight from about 500 to about 2500, said polyoxyalkylene comprising 1 to 30 oxyalkylene units selected from oxyalkylene units having 2 to 4 carbon atoms, said amine moiety comprising from 1 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms, and further comprising a connecting moiety linking said polyoxyalkylene moiety and said amine moiety.
31. A lubricating oil composition as claimed in Claim 30 wherein said trialkyl polyoxyalkylene ammonium salt is a salt selected from the group consisting of halide salts, C2 to C,2 carboxylate salts, and Cg to C3Q phenoxide or alkyl-substituted phenoxide salts.
32. A lubricating oil composition as claimed in Claim 31 wherein the alkyl groups of said trialkyl polyoxyalkylene ammonium salt are selected from the group consisting of alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups of 7 to 20 carbon atoms and phenyl.
33. A lubricating oil composition as claimed in Claim 32 wherein said trialkyl groups are methyl groups.
34. A lubricating oil composition comprising a major portion of oil of lubricating viscosity and a minor amount of an additive of the formula:
wherein R = an alkyl group of 5 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, alkaryl group of 7 to 30 carbon atoms, aralkyl group of 7 to 30 carbon atoms, or methylol-substituted alkyl group of 5 to 30 carbon atoms; R1 and R11 independently = hydrogen, methyl or ethyl; n = 1 to 30, preferably 10 to 25; X = a connecting group selected from the group consisting of:
0
II carbamates -0-C-NH-;
ethylene -CH2-CH2-; oxyethylene ■CH2-CH20 ;
CH20H methylol ethylene -CH-CH2-; o o ssuucccciinnaatteess - -O0--C-CH2 ethers -0- r thioethers -S-;
O carbonyls -I,
0
II carbonates -0-C-0-;
O esters -C- •0-;
O amides -C II-NZ-; and methylene -CHZ-; where Z and Z' = H, or an alkyl group of from 1 to
2 carbon atoms; R111 = a chemical bond, an alkylene or hydroxy- substituted alkylene group of 2 to 12 carbon atoms, or fNH-CH2-CH2 χ, where x = 0 to 5;
Rlv and Rv independently = alkyl groups of 1 to
20 carbon atoms, aralkyl group of 7 to 20 carbon atoms, alkaryl group of 7 to 20 carbon atoms, or phenyl;
Rvl = alkyl groups of 1 to 20 carbon atoms, aralkyl groups of 7 to 20 carbon atoms, alkaryl groups of 7
H to 20 carbon atoms, phenyl, or fCH2CH2 *χ_i, where x = 1 to 5; and
Y = a halide, a C2 to C^2 carboxylate anion, or a Cg to C Q phenoxide or alk l-substituted phenoxide.
35. A lubricating oil composition according to
Claim 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34 wherein said minor amount of said minor amount composition comprises from about 0.01 to about 10.0 percent by weight of the total composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE8484903020T DE3482122D1 (en) | 1983-07-29 | 1984-07-23 | ADDITIVES FOR REGULATING THE DEPTH OF QUATERNAEREN. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US51850683A | 1983-07-29 | 1983-07-29 | |
US51850583A | 1983-07-29 | 1983-07-29 | |
US518,506 | 1983-07-29 | ||
US518,505 | 1983-07-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1985000620A1 true WO1985000620A1 (en) | 1985-02-14 |
Family
ID=27059487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1984/001187 WO1985000620A1 (en) | 1983-07-29 | 1984-07-23 | Quaternary deposit control additives |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0151621B1 (en) |
DE (1) | DE3482122D1 (en) |
WO (1) | WO1985000620A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0293192A1 (en) * | 1987-05-27 | 1988-11-30 | Exxon Chemical Patents Inc. | Diesel fuel composition |
US4846848A (en) * | 1987-05-08 | 1989-07-11 | Shell Oil Company | Gasoline composition |
EP0404876A1 (en) * | 1988-09-09 | 1991-01-02 | Chevron Res | Long-chain aliphatic hydrocarbyl amine additives having an oxy-carbonyl connecting group. |
EP0486097A1 (en) * | 1990-11-15 | 1992-05-20 | EURON S.p.A. | Process for preparing detergent additive for fuels |
FR2682684A1 (en) * | 1991-10-22 | 1993-04-23 | Rouet Jean | Process for treating paraffinic hydrocarbons |
WO1997012928A1 (en) * | 1995-10-04 | 1997-04-10 | The Dow Chemical Company | Amine capped polyethers and process for producing same |
US5814111A (en) * | 1995-03-14 | 1998-09-29 | Shell Oil Company | Gasoline compositions |
US5817593A (en) * | 1995-06-02 | 1998-10-06 | The Dow Chemical Company | Catalyst and process for producing amines |
EP2589647A1 (en) | 2011-11-04 | 2013-05-08 | Basf Se | Quaternised polyether amines and their use as additives in fuels and lubricants |
WO2014066361A1 (en) * | 2012-10-23 | 2014-05-01 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1270656B (en) | 1994-10-13 | 1997-05-07 | Euron Spa | FUEL COMPOSITION |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3440029A (en) * | 1964-05-20 | 1969-04-22 | Dow Chemical Co | Gasoline containing anti-icing additive |
US3454625A (en) * | 1967-04-03 | 1969-07-08 | Gaf Corp | Novel quaternary ammonium carbamate antistatic agents |
US3468640A (en) * | 1964-09-22 | 1969-09-23 | Chevron Res | Gasoline compositions |
US4040798A (en) * | 1973-07-16 | 1977-08-09 | Rohm And Haas Company | Hydrocarbon compositions containing rust inhibitors |
US4236020A (en) * | 1976-06-21 | 1980-11-25 | Chevron Research Company | Carbamate deposit control additives |
US4247301A (en) * | 1978-06-19 | 1981-01-27 | Chevron Research Company | Deposit control and dispersant additives |
US4261704A (en) * | 1979-06-22 | 1981-04-14 | Basf Wyandotte Corporation | Polyoxyalkylene polyamine detergent compositions |
US4294714A (en) * | 1979-07-25 | 1981-10-13 | Chevron Research Company | Carboxylic acid salt containing deposit control additives and fuel and lube oil compositions containing them |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3486866A (en) * | 1966-01-05 | 1969-12-30 | Petrolite Corp | Quaternary ammonium iodide stabilized fuels |
-
1984
- 1984-07-23 DE DE8484903020T patent/DE3482122D1/en not_active Expired - Fee Related
- 1984-07-23 EP EP19840903020 patent/EP0151621B1/en not_active Expired - Fee Related
- 1984-07-23 WO PCT/US1984/001187 patent/WO1985000620A1/en active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3440029A (en) * | 1964-05-20 | 1969-04-22 | Dow Chemical Co | Gasoline containing anti-icing additive |
US3468640A (en) * | 1964-09-22 | 1969-09-23 | Chevron Res | Gasoline compositions |
US3454625A (en) * | 1967-04-03 | 1969-07-08 | Gaf Corp | Novel quaternary ammonium carbamate antistatic agents |
US4040798A (en) * | 1973-07-16 | 1977-08-09 | Rohm And Haas Company | Hydrocarbon compositions containing rust inhibitors |
US4236020A (en) * | 1976-06-21 | 1980-11-25 | Chevron Research Company | Carbamate deposit control additives |
US4247301A (en) * | 1978-06-19 | 1981-01-27 | Chevron Research Company | Deposit control and dispersant additives |
US4261704A (en) * | 1979-06-22 | 1981-04-14 | Basf Wyandotte Corporation | Polyoxyalkylene polyamine detergent compositions |
US4294714A (en) * | 1979-07-25 | 1981-10-13 | Chevron Research Company | Carboxylic acid salt containing deposit control additives and fuel and lube oil compositions containing them |
Non-Patent Citations (1)
Title |
---|
See also references of EP0151621A4 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4846848A (en) * | 1987-05-08 | 1989-07-11 | Shell Oil Company | Gasoline composition |
WO1988009365A1 (en) * | 1987-05-27 | 1988-12-01 | Exxon Chemical Patents, Inc. | Diesel fuel composition |
EP0293192A1 (en) * | 1987-05-27 | 1988-11-30 | Exxon Chemical Patents Inc. | Diesel fuel composition |
EP0404876A1 (en) * | 1988-09-09 | 1991-01-02 | Chevron Res | Long-chain aliphatic hydrocarbyl amine additives having an oxy-carbonyl connecting group. |
EP0404876A4 (en) * | 1988-09-09 | 1991-04-24 | Chevron Research Company | Long-chain aliphatic hydrocarbyl amine additives having an oxy-carbonyl connecting group |
EP0486097A1 (en) * | 1990-11-15 | 1992-05-20 | EURON S.p.A. | Process for preparing detergent additive for fuels |
FR2682684A1 (en) * | 1991-10-22 | 1993-04-23 | Rouet Jean | Process for treating paraffinic hydrocarbons |
US5814111A (en) * | 1995-03-14 | 1998-09-29 | Shell Oil Company | Gasoline compositions |
US5817593A (en) * | 1995-06-02 | 1998-10-06 | The Dow Chemical Company | Catalyst and process for producing amines |
US5952529A (en) * | 1995-06-02 | 1999-09-14 | The Dow Chemical Company | Catalyst and process for producing amines |
US5789490A (en) * | 1995-10-04 | 1998-08-04 | The Dow Chemical Company | Amine capped polyethers and process for producing same |
WO1997012928A1 (en) * | 1995-10-04 | 1997-04-10 | The Dow Chemical Company | Amine capped polyethers and process for producing same |
EP2589647A1 (en) | 2011-11-04 | 2013-05-08 | Basf Se | Quaternised polyether amines and their use as additives in fuels and lubricants |
WO2013064689A1 (en) | 2011-11-04 | 2013-05-10 | Basf Se | Quaternized polyetheramines and use thereof as additives in fuels and lubricants |
WO2014066361A1 (en) * | 2012-10-23 | 2014-05-01 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
US10202559B2 (en) | 2012-10-23 | 2019-02-12 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
EP3489332A1 (en) * | 2012-10-23 | 2019-05-29 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
US10669496B2 (en) | 2012-10-23 | 2020-06-02 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
US11174444B2 (en) | 2012-10-23 | 2021-11-16 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
Also Published As
Publication number | Publication date |
---|---|
EP0151621A4 (en) | 1986-08-21 |
EP0151621B1 (en) | 1990-05-02 |
DE3482122D1 (en) | 1990-06-07 |
EP0151621A1 (en) | 1985-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4600409A (en) | Quaternary deposit control additives | |
US4604103A (en) | Deposit control additives--polyether polyamine ethanes | |
EP0803515B1 (en) | Process for preparing polyisobutyl hydroxyaromatic compounds | |
US4247301A (en) | Deposit control and dispersant additives | |
US5254138A (en) | Fuel composition containing a quaternary ammonium salt | |
US4191537A (en) | Fuel compositions of poly(oxyalkylene) aminocarbamate | |
US4134846A (en) | Multipurpose hydrocarbon fuel and lubricating oil additive mixture | |
US4288612A (en) | Deposit control additives | |
JP3725588B2 (en) | Otto engine fuel and valve cleaning additive therefor | |
US4197409A (en) | Poly(oxyalkylene)aminocarbomates of alkylene polyamine | |
ES2203891T3 (en) | USE OF ADDITIVE FUEL COMPOSITIONS CONTAINING A POLYETHYL ALCOHOL AND A HYDROCARBILPHENOL. | |
US3658707A (en) | Fuel oil and lubricating oil compositions | |
CA1146965A (en) | Deposit control and dispersant additives | |
US4274837A (en) | Deposit control additives and fuel compositions containing them | |
US4564372A (en) | Quaternary deposit control additives | |
EP0100665B1 (en) | Deposit control additives for hydrocarbon fuels and lubricants for use in internal combustion engines | |
WO1985000620A1 (en) | Quaternary deposit control additives | |
US4294714A (en) | Carboxylic acid salt containing deposit control additives and fuel and lube oil compositions containing them | |
EP0414963A1 (en) | N-subsituted carbamates and their use as fuel additives | |
US4897087A (en) | Diisocyanate derivatives as ashless fuel dispersants and detergents and fuel compositions containing same | |
US4526587A (en) | Deposit control additives-methylol polyether amino ethanes | |
US4259086A (en) | Multipurpose hydrocarbon fuel and lubricating oil additive | |
US4581151A (en) | Quaternary deposit control additives | |
US4527996A (en) | Deposit control additives - hydroxy polyether polyamines | |
EP0590770B1 (en) | Method of preparing an amidoalkanolamine composition for use in fuel compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AL | Designated countries for regional patents |
Designated state(s): AT BE CH DE FR GB LU NL SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1984903020 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1984903020 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1984903020 Country of ref document: EP |