WO1985001956A1 - Additifs de regulation de depot - polyamines de polyether hydroxy - Google Patents

Additifs de regulation de depot - polyamines de polyether hydroxy Download PDF

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Publication number
WO1985001956A1
WO1985001956A1 PCT/US1984/001759 US8401759W WO8501956A1 WO 1985001956 A1 WO1985001956 A1 WO 1985001956A1 US 8401759 W US8401759 W US 8401759W WO 8501956 A1 WO8501956 A1 WO 8501956A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
additive
independently
fuel
lubricating oil
Prior art date
Application number
PCT/US1984/001759
Other languages
English (en)
Inventor
Curtis B. Campbell
Original Assignee
Chevron Research Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chevron Research Company filed Critical Chevron Research Company
Priority to DE8484904244T priority Critical patent/DE3479515D1/de
Publication of WO1985001956A1 publication Critical patent/WO1985001956A1/fr

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
    • 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention is directed to hydroxy polyether polyamines, to fuel compositions and lubricating oil compositions containing these compounds and to their use
  • 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.
  • each engine when new, requires a certain minimum octane fuel in order to operate satisfactorily without pinging and/or knocking. As the engine is operated on any gas ⁇ oline, this minimum octane increases and, in most cases, if the engine is operated in the same fuel for a prolonged period, will reach an equilibrium. This is apparently caused by an amount of deposits in the combustion chamber. Equilibrium is typically reached after 5000 to 15000 miles of automobile operation.
  • octane requirement increase in particular engines used with commercial gasolines will vary at equi- librium from 5 or 6 octane units to as high as 12 or
  • OMPI disclose* lead-containing fuel compositions having reduced ORI properties.
  • the ORI problem is compounded by the fact that the most common method for increasing the octane rating of unleaded gasoline is to increase its aromatic content. This, however, eventually causes an even greater increase in the octane requirement.
  • some of presently used nitrogen-containing compounds used as deposit-control additives and their mineral oil or polymer carriers may also significantly contribute to ORI in engines using unleaded fuels.
  • the second complicating factor relates to oil solubility of the fuel additives.
  • Fuel additives due to their higher boiling point over gasoline itself, tend to accumulate on surfaces in the combustion chamber. This accumulation of the additive eventually finds its way into the lubricating oil via a "blow-by" process. In some cases this process may be of no concern as the fuel additives will be inert and compatible in the oil.
  • the additive is incompatible in the lubrica ⁇ ting oil a serious problem develops as the accumulation of the additive results in an emulsion-like sludge which is detrimental to efficient operation. Therefore, it is particularly desirable that the gasoline additive be oil compatible.
  • the present invention also relates to lubricating oil compositions containing hydroxy polyether polyamines 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 main- taining the cleanliness of the engine by detergency and dispersancy. Many lubricating oil additives are well known for accomplishing these functions. For maintaining engine cleanliness, a well-known class of ashless deter ⁇ gents which have been found to be particularly useful are polyoxyalkylene carbamates.
  • Polyether a ine-type fuel additives for deposit control and lubricating oil dispersancy are well-known but have traditionally been surfactant-type molecules having a large, non-polar hydrophobic end or "tail", for instance, a hydrocarbyl capped polyether moiety, and a polar, hydrophilic amine or polyamine end. Examples of these -type of compositions may be found in U.S. Patent No. 4,247,301; U.S. Patent No. 4,160,648; and applications U.S. Serial Nos. 403,606 and 403,607, Campbell, both filed July 7, 1982 and applications U.S. Serial Nos, 499,131 and 499,132, both filed May 31, 1983.
  • Additives are provided which, when added to fuels or used as fuel concentrates, are effective in cleaning and maintaining the cleanliness of engine intake systems and when added at from about 0.01 to about 10 weight percent to lubricating oil, are effective in providing dispersancy and detergency to the oil.
  • the additives consist of certain fuel and lubricating oil soluble hydroxy polyoxyalkylene amines or polyamines These additives have the following general formula:
  • R' ' has at least 2 carbon atoms
  • compositions may be either mono or polyamines, but polyamines are preferred.
  • the additive compounds have molecular weights of >from about 500 to
  • this invention is based on my discovery that the hydrophobic portion of a polyether polyamine fuel additive may contain an "uncapped" hydroxy1 group, provided that the polyether is a co-polymer and that the portion of the co-polymer having the hydroxyl group has more carbon atoms per unit than the other portion of the block co-polymer.
  • a preferred compound is composed of a block co-polymer in which the hydroxyl-containing portion is composed of pol (butylene glycol) and the other portion is composed of poly(ethylene glycol).
  • R 1 has at least 2 carbon atoms, and that R * ' , R * ' ' and R 1V are H.
  • the compositions are selected to provide solubility in fuel compositions and deposit control activity without contributing to octane require ⁇ ment increase (ORI) .
  • the desired concentration of the additive will vary according to fuel
  • the concentration will be from about 250 parts per million (ppm) by weight to about 5000 ppm by weight.
  • the preferred concentration is from about 300 ppm to 2000 ppm.
  • the additive compositions may be used as concentrates, and could be used 'as additive to fuels subsequent to their prepara ⁇ tion.
  • 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 olephilic organic solvent and the carrier of said solvent boiling in the range of from about 150° to 400°F and the concentrate would preferably contain from about 10 to 50 weight percent of the additive compound.
  • the specific compositions are selected to provide solubility in lubricating oil compositions with dispersant activity, without contributing to depos >it formation in the lubricating oil composition.
  • the addition to the oil of from about 0.01 to about 10 weight percent of an additive of this invention is effective in providing dispersancy and detergency to the oil.
  • 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 37.6°C and more usually from about 50 to 10,000 SUS at 37.6°C.
  • base oils are naphthenic bases, paraffin base and mixed base mineral oils, synthetic oils; for example, alkylene polymers, such as the polymers or propylene, butylene, etc., and mixtures thereof.
  • oils besides the subject additives are such additives as dispersant/detergents, rust inhibitors, antioxidants, 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 weight percent of the total composition.
  • each of the addi- tives will be present in the range from about 0.01 to
  • additive compositions may be used as lubricating oil concentrates, and could be used as additive to lubricating oils subsequent to their preparation.
  • weight percent of these additives will usually range from about 10 to 90 weight percent.
  • the additive compounds can be prepared by a variety of known processes.
  • an appropriate hydroxy-substituted amine containing both the desired amino moiety and the appropriate hydroxy- ter inated alkyl moiety, is first reacted to form an
  • a halohydroxyalkylene preferably chlorohydroxyalkylene is first reacted at the hydroxy terminus with an appropriate alkylene oxide.
  • the halo group is then reacted with an amine or polyamine, preferably in excess to yield the hydroxy poly(oxy- alkylene) amines or polyamines of this invention.
  • Suitable halohydroxyalkylenes include
  • the resulting slurry was heated to approx. 90°C and 100 ml (1.16 moles) of distilled 1,2-epoxybutane was added over 30 minutes. After this addition, the reaction was stirred with heating for 30 minutes and then cooled to room temperature and stirred for 16 hours.
  • the reaction was quenched by adding approx. 200 ml of t-butanol and stirring 30 minutes, followed by approx. 50 ml of water.
  • the reaction was diluted with 300 ml ether and extracted with two 100 ml portions of water.
  • a Waukesha CFR single-cylinder engine is used. The run is carried out for 15 hours, at the end of which time the intake valve is removed, washed with hexane and weighed. The previously determined weight of the clean valve is subtracted from the weight of the valve. The difference between the two weights is the weight of the deposit with a lesser amount of deposit measured connoting a superior additive.
  • the operating conditions of the test are as follows: water jacket temperature 100°C; manifold vacuum of 29.5 cm Hg, intake mixture temperature of 50.2°C; air-fuel ratio of 12; ignition spark timing of 40°BTC; engine speed is 1800 rpm; and the crankcase oil is a commercial 30 oil. The amount of carbonaceous deposit in milligrams on the intake valves is measured and reported in the following Table I.

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  • 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)
  • Lubricants (AREA)

Abstract

Additifs conférant des caractéristiques détergentes et de dispersion à des huiles lubrifiantes, et permettant la régulation des dépôts dans les systèmes d'admission de moteurs lorsque les additifs sont mélangés au carburant. Ces additifs comprennent des amines de polyéther hydroxy de formule générale (I), où R' et R'' indépendamment sont sélectionnés dans le groupe composé d'hydrogène et de groupes alkyle possédant de 1 à 4 atomes de carbone, et où au moins un élément parmi R' et R'' possède au moins 2 atomes de carbone; R''' et RIV indépendamment représentent hydrogène ou méthyle; RV et RVI indépendamment sont hydrogène ou$(3,)$où Z est un nombre entier compris entre 1 et 5, et x et y indépendamment sont des nombres entiers compris entre 1 et 30.
PCT/US1984/001759 1983-10-31 1984-10-30 Additifs de regulation de depot - polyamines de polyether hydroxy WO1985001956A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8484904244T DE3479515D1 (en) 1983-10-31 1984-10-30 Deposit control additives - hydroxy polyether polyamines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US54755883A 1983-10-31 1983-10-31
US54755983A 1983-10-31 1983-10-31
US547,558 1983-10-31
US547,559 1983-10-31

Publications (1)

Publication Number Publication Date
WO1985001956A1 true WO1985001956A1 (fr) 1985-05-09

Family

ID=27068576

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1984/001759 WO1985001956A1 (fr) 1983-10-31 1984-10-30 Additifs de regulation de depot - polyamines de polyether hydroxy

Country Status (3)

Country Link
EP (1) EP0162890B1 (fr)
DE (1) DE3479515D1 (fr)
WO (1) WO1985001956A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255115A1 (fr) * 1986-07-31 1988-02-03 Wynn Oil Company Composition d'additifs pour essence
EP0303862A1 (fr) * 1987-08-21 1989-02-22 Wynn Oil Company Composition d'additif
US5112364A (en) * 1988-08-05 1992-05-12 Basf Aktiengesellschaft Gasoline-engine fuels containing polyetheramines or polyetheramine derivatives
EP0524783A1 (fr) * 1991-07-23 1993-01-27 Oceanfloor Limited Utilisation de compositions d'huile lubrifiante
WO2000020536A1 (fr) * 1998-10-02 2000-04-13 Sanyo Chemical Industries, Ltd. Detergent pour le mazout et composition de mazout
EP1106616A2 (fr) * 1999-12-08 2001-06-13 Institut Francais Du Petrole Dérivés de l'isosorbide utilisables dans des compositions détergentes pour carburants de type essence
US8100095B2 (en) 2006-11-17 2012-01-24 Mcknight James K Combustion devices for powdered fuels and powdered fuel dispersions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3231619A (en) * 1959-12-18 1966-01-25 Jefferson Chem Co Inc Basic primary amino polyether compositions
US4247301A (en) * 1978-06-19 1981-01-27 Chevron Research Company Deposit control and dispersant additives

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030197A (en) * 1960-11-22 1962-04-17 Petrolite Corp Thermally stable distillate fuels
US4251670A (en) * 1977-09-26 1981-02-17 Texaco Inc. Glycol polyether-acrylic acid-amine reaction product for fuel and mineral oils

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3231619A (en) * 1959-12-18 1966-01-25 Jefferson Chem Co Inc Basic primary amino polyether compositions
US4247301A (en) * 1978-06-19 1981-01-27 Chevron Research Company Deposit control and dispersant additives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0162890A4 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255115A1 (fr) * 1986-07-31 1988-02-03 Wynn Oil Company Composition d'additifs pour essence
EP0303862A1 (fr) * 1987-08-21 1989-02-22 Wynn Oil Company Composition d'additif
US5112364A (en) * 1988-08-05 1992-05-12 Basf Aktiengesellschaft Gasoline-engine fuels containing polyetheramines or polyetheramine derivatives
EP0524783A1 (fr) * 1991-07-23 1993-01-27 Oceanfloor Limited Utilisation de compositions d'huile lubrifiante
WO2000020536A1 (fr) * 1998-10-02 2000-04-13 Sanyo Chemical Industries, Ltd. Detergent pour le mazout et composition de mazout
EP1106616A2 (fr) * 1999-12-08 2001-06-13 Institut Francais Du Petrole Dérivés de l'isosorbide utilisables dans des compositions détergentes pour carburants de type essence
FR2802207A1 (fr) * 1999-12-08 2001-06-15 Inst Francais Du Petrole Derives de l'isosorbide utilisables dans des compositions detergentes pour carburants de type essence
EP1106616A3 (fr) * 1999-12-08 2001-10-24 Institut Francais Du Petrole Dérivés de l'isosorbide utilisables dans des compositions détergentes pour carburants de type essence
US6527816B2 (en) 1999-12-08 2003-03-04 Institut Francais Du Petrole Isosorbide derivatives that can be used in detergent compositions for gasoline-type fuels
US8100095B2 (en) 2006-11-17 2012-01-24 Mcknight James K Combustion devices for powdered fuels and powdered fuel dispersions
US9016216B2 (en) 2006-11-17 2015-04-28 James K. McKnight Methods of combustion of powdered fuels and powdered fuel dispersions

Also Published As

Publication number Publication date
EP0162890B1 (fr) 1989-08-23
EP0162890A4 (fr) 1986-08-21
EP0162890A1 (fr) 1985-12-04
DE3479515D1 (en) 1989-09-28

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