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
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers

Definitions

• R is an aliphatic hydrocarbon radical having from about 8 to 20 carbon atoms and R is hydrogen or an acyl radical derived from a fatty acid having from about 8 to 20 carbons, at least one but not more than two of said R' substituents being an acyl radical.
• a class of partial esters of polyethoxylated N-hydrocarbyl-substituted 1,3-propanediamine compounds are provided as carburetor detergents when employed in a liquid hydrocarbon fuel for an internal combustion engine. These compounds, which are characterized by having a relatively long hydrocarbon radical attached to a nitrogen atom, as well as having one or two ester groups in the basic structure, appear to be unique in their detergency properties. Similar compounds in which all of the hydroxy groups have been esterified are essentially ineffective as carburetor detergents.
• Polyethoxylated N 7 hydrocarbon-substituted 1,3-propanediamine compounds which are precursors of the partial esters employed inithe present invention, are susceptible to extraction by the tank water bottoms present in fuel distribution systems, ,making ;it difficult to maintainan efiective concentration of the additive in the fuel composition. 7
• the fuel composition of -the invention prevents or mitigates the problem of deposits lay down in the carbu- Patented Oct. 9, 1973 retor of an internal combustion engine.
• a gasoline of the invention is employed in a carburetor which already has a substantial build-up of deposits from prior operations, a rather severe test of the detergency property of a fuel composition, this gasoline is very effective for removing substantial amounts of the pre-formed deposits.
• R is an aliphatic hydrocarbon radical having from 8 to 20 carbon atoms and R' is hydrogen or an acyl radical derived from a fatty acid having from about 8 to 20 carbon atoms, at least one but not more than two of said R' substituents being an acyl radical.
• a preferred embodiment of the invention is the monoester and diester in which least one but not more than two of said R sub stituents represents an acryl radical having from about 16 to 18 carbon atoms and R is an aliphatic hydrocarbon radical having from 16 to 18 carbon atoms.
• esters of a polyethoxylated N hydrocarbyl-1,3-pr0panediamine there is criticality in the structure of an ester of a polyethoxylated N hydrocarbyl-1,3-pr0panediamine in order to provide an effective carburetor detergent.
• the full esters that is, the triesters of polyethoxylated N-hydrocarbyl-1,3-propanediamine, are essentially ineffective as carburetor detergents when added to gasoline.
• the monoand diesters of these compounds exhibit unusual effectiveness for removing carburetor deposits.
• the monoand diesters of the prescribed polyethoxyated N-hydroxycarbyl-1,3-propanediamine are prepared by reacting 1 to 2 moles of a suitable fatty acid with approximately 1 mole of a polyethoxylated N-hydrocarbyl1,3- propanediamine. This reaction is preferably conducted in an inert solvent. While the reaction temperature is not critical, it is preferred to conduct the esterification at a temperature ranging from about to 210 C. with the particularly preferred temperature of reaction being from to 200 C. The reaction is continued until the amount of the water of esterification collected indicates that the reaction has been completed or substantially complete.
• the following examples illustrate the preparation of partial esters employed in the fuel composition of the invention.
• EXAMPLE IV 48.3 grams (0.091 mole) of N-tallow-N,N', -tris-2- EXAMPLE V 532.0 grams (1.0 mole) of N-tallow-N,N',N-tris-2- hydroxyethyl-1,3-propanediamine, 574 grams (2.0 moles) of a fatty acid mixture consisting principally of linoleic and oleic acids were combined in 350 milliliters of xylene. The reaction mixture was aseotrope distilled to a pot temperature of 180 C. and allowed to reflux at this temperature for about 3 hours. While the water of esterification was collected. After this time the reaction temperature was raised to 200 C.
• the diesterified product amounting to 1068 grams, was obtained as a 88 wt. percent solution in xylene.
• the xylene solution gave an OH No. of 71 as compared to the theoretical of 47.
• partial esters which are eifective as detergents in the gasoline compositions of the invention include the monoand diesters of the following diamines:
• a -tris,-2-hydroxyethyl-1,3-propane- '-tris-2-hydroxyethyl-1,3-propane ---.nonanoie-, decanoic, tetradecanoic, pentanoic; hexadecanoic and heptadecanoic.
• the prescribed monoand diesters of N-C hydrocarbyl N,N',N-2-hydroxyethyl-1,3-propanediamine are employed in the gasoline fuel .composition in a concentration to provide effective-carburetor detergent properties,
• the esterstare employed .in 7 a concentration ranging from about 0.0004 to 0.1 weight percent with a preferred concentration ranging from about 0100110004 and amost preferred" concentration ranging from 0.002 to 0.005 weight percent.
• the base fuel will consist of a mixture of hydrocarbons in the gasoline boiling range, i.e., boiling from about 75 to 450 Ff'The hydrocarbon components can consist of paraffinimnaphthenic, aromatic and olefinic hydrocarbons.
• This gasoline can be obtained naturally or it can be produced by thermal or catalytic cracking and/ or reforming of petroleum hydrocarbons.
• the base fuel will generally have a Research Octane Number above 85 and up to about 102 Withthe preferred range being from about 90 to 100. p 1
• the prescribed partial esters .of N-hydrocarbyl tris hydroxyethyl-1,3-propanediamine additive were tested for effectiveness in the carburetor detergency test.
• This test is run on Chevrolet V 8 eng irie mounted on a test stand using a modified four-barrel C3.Ibl1IClO1-*
• the two secondary barrels of the carburetor are sealed and the feed to each of the primary barrels-arranged so that the de-i tergent additive fuel can run inone barrel and the ref; erence fuel run in the other.
• the primary carburetor barrels were also modified to contain removable aluminum inserts in the throttle plate area so that the deposits formed on the inserts couldbe conveniently weighed.
• the first procedure,--;des ignated I the engine is run for a periodof time, usually 24 or 48 hours, using the base fuel as the feed to bothbarrels with engineblow-by circulated to the air inlet of the carburetor. The weight of the deposits onboth sleeves is determined-and recorded. The engine is then cycled for '24 additional hours with base fuel being fed-to one-barrel and the additive fuel to the other and no .blow-by to .the carburetor air irdet.
• the inserts are then removed-from the-carburetor and weighed to determine the difference between the pera formances of the additive and non-additive fuels for removing preformed deposits.
• the aluminum inserts After the aluminum inserts have been cleaned, they are replaced in the carburetor and the process repeated with the'fuel feeds-intothecarburetor reversed in order to minimize difierences'infuel distribution and carburetor" construction.
• the results obrun for a-period' of time; usually' 24 to 48 hours, using" the base'fue'l as the feed to both barrelswith engine blow-byeirculat'ed' to'the air inlet of the carburetor.
• the weight of the deposits-on both sleeves is determined and recorded.
• the engine is then cycled'f'or 24 additional hours with base fnelcontaining a recognized commercial additive at a'concerit'ra'tion of 50 ptb. being fed to one barrel and the additive fuel to the other.
• blow-by is circulated to the air inlet of the carburetor.
• the inserts are'then removed from" the carburetor and weighed to determine thediiference between the per formances 'of the additive and commercial detergent fuels for removing preformed deposits.
• After the aluminum ins'erts have been cleaned," -they are replaced in the carburetor'arid' the process repeated with the fuel feeds into the carburetor reversed in order to minimize differences in fuel distribution and carburetor construction.
• the results obtained in the two runs are averaged and the elfectiveness of the reference fuel and of the additive fuels for removing deposits expressed in percents.
• the base fuel employed in the following examples was a premium grade gasoline having an octane number of about 99.2 and containing 3 cc. of tetraethyl lead per gallon.
• This gasoline consisted of about 25.5 percent aromatic hydrocarbons, 95 percent olefinic hydrocarbons and 65 percent parafiinic hydrocarbons and boiled in the range from about 90 F. to 370 F.
• Fuel compositions of the invention were tested in the Chevrolet Carburetor Detergent Test and the results set forth in Table I below.
• the percent effectiveness reported is the difference obtained by subtracting the percent eifectiveness of the reference fuel from the percent effectiveness of the additive fuel.
• Runs 1, 2, 3, 4, 5 and 7 illustrate the surprising effectiveness of the prescribed partial esters as carburetor detergent in motor fuel compositions.
• Run 6 wherein the fully esterified tristearate ester of N-tallow-N,N,N' tris 2 hydroxyethyl-1,3-propanediamine was employed in the gasoline composition, was essentially ineffective as a carburetor detergent.
• the fuels of the invention may contain any additive conventionally employed in gasoline. Tetraalkyl lead, antiknock additives, dyes, corrosion inhibitors, anti-oxidants and the like can be beneficially employed without materially affecting the detergent additive of the invention.
• 3,502,451 which disclosure is incorporated in this application, in combination with the detergent of the present invention are particularly effective multifunctional fuels, compositions containing polypropylene and polyisobutylene of 80 to 1100 molecular weight at from about 0.025 to 0.1 volume percent being preferred.
• a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing from about 0.0004 to 0.1 weight percent of a partial ester of a polyethoxylated N-hydrocarbyl-1,3-propanediamine having the formula:
• R is an aliphatic hydrocarbon radical having from about 8 to 20 carbon atoms and R is hydrogen or an acyl radical derived from a fatty acid having from 8 to 20 carbon atoms, at least one but not more than two of said R substituents being an acyl radical.
• a motor fuel composition according to claim 1 containing from about 0.001 to 0.04 weight percent of said partial ester.
• a motor fuel composition according to claim 1 containing from about 0.002 to 0.005 weight percent of said partial ester.
• a motor fuel composition of claim 1 which additionally contain from about 0.01 to 0.20 volume percent of (l) a polymer of a C to C unsaturated hydrocarbon (2) a copolymer of a C to C unsaturated hydrocarbon, or (3) the corresponding hydrogenated polymer or copolymer, said polymer or copolymer having a molecular weight in the range from about 500 to 3,500.
• a motor fuel composition according to claim 1 containing from about 0.025 to 0.1 volume percent of polypropylene having a molecular weight ranging from about 800 to 1100.
• a motor fuel composition according to claim 1 containing from about 0.025 to 0.1 volume percent of polyisobutylene having a molecular weight ranging from about 800 to 1100.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22935733

Family Applications (1)

Country Status (8)

Cited By (8)

Families Citing this family (1)

• 1972
  • 1972-04-26 US US00247645A patent/US3764281A/en not_active Expired - Lifetime
• 1973
  • 1973-04-03 GB GB1578273A patent/GB1383273A/en not_active Expired
  • 1973-04-10 CA CA168,359A patent/CA987494A/en not_active Expired
  • 1973-04-13 DE DE2318634A patent/DE2318634A1/de active Pending
  • 1973-04-23 JP JP48045232A patent/JPS4923207A/ja active Pending
  • 1973-04-24 IT IT23363/73A patent/IT984097B/it active
  • 1973-04-25 SE SE7305816A patent/SE379369B/xx unknown
  • 1973-04-26 FR FR7315094A patent/FR2182121B1/fr not_active Expired

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