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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/12—Esters of phosphoric acids with hydroxyaryl 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

Definitions

• This invention is directed to novel alkanol amine salts of alkyl acid phosphates and to improved gasoline compositions containing alkanol amine salts of alkyl acid phosphates as additives.
• a common occurrence in the operation of an internal combustion engine is frequent engine stalling in climates where high humidity is common with temperatures between about 30 F. and 60 F.
• This stalling is attributed to the formation of ice particles in the carburetor, especially on the throttle plate and surrounding body walls.
• the formation of ice in the carburetor is caused by a temperature reduction in the metal parts of the carburetor as the fuel vaporizes. This lower metal temperature in turn causes the moisture in the air coming into the carburetor to condense and freeze at the edge of the throttle plate and on the air bleeds of the carburetor. Ice formation at the edge of the throttle plate reduces the flow of air to the engine thereby causing the engine to stall.
• ice formation on the air bleeds or venturi causes the engine to stall from excessively rich mixtures of gasoline.
• Ice formation also occurs in the emulsion tube type carburetor which is used extensively in foreign-make cars.
• This type of carburetor comprises an emulsion tube in which the air and gasoline are mixed, metered and then carbureted. Ice initially forms at the air correction inlet of the emulsion tube and eventually causes the engine to stall.
• Frequent engine stalling also results from operating conditions existing in heavy stop-and-go trafiic when the engine is often operating at idling speeds.
• the reason for the engine to stall in such traflic is due mainly to accumulation of foreign materials on the walls of the carburetor throttle body which is below the closed portion of the throttle plate. Foreign materials are able to enter the carburetor at idling speeds because the air filter at such speeds is relatively ineffective. Most contaminants or foreign materials which enter the carburetor at idling speeds are those thrown out of the engine through the crankcase blowby. These contaminants remain trapped under the hood while the car is stopped and easily enter the carburetor while the engine is idling.
• the present invention is directed to novel salts of primary alkyl acid orthophosphates wherein each esterifying alkyl group contains 8 to 16 carbon atoms and an alkanol amine having either the structure RRNGHzCH-CH:
• R and R may be hydrogen, alkyl, cycloalkyl, phenyl and alkyl phenyl wherein R and R have a sum total of from 8 to 24 carbon atoms, or
• R" is an alkyl, cycloalkyl, phenyl, or aralkyl hydrocarbon radical of from 6 to 25 carbon atoms and R' is either a hydroxy ethyl or hydroxy propyl radical.
• the present invention is also directed to a normally liquid hydrocarbon distillate fuel containing as an antistall additive an effective amount of the hereinbefore described alkanol amine salt.
• the amine salts of the present invention may be prepared according to any of the methods known to the art.
• the amine salt may be prepared by neutralizing the alkyl acid phosphate with the amine. Normally a molecule of amine is used for each molecule of the phosphate to produce a salt exerting a substantially neutral pH.
• the prefered salt of this invention is the bis(2-hydroxyethyl) n-dodecyl amine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate which is commonly referred to as the C alkyl diethanolamine salt of the mixed monoand di-tridecyl acid phosphate.
• N-(2,3-dihydroxypropyl) tert.-dodecylamine salt of an approximately equimolar mixture of dioxo-tridecyl hydrogen phosphate and mono-oxotridecyl dihydrogen phosphate the bis(Z-hydroxyethyl) cocoa amine salt of an approximately equimolar mixture of di-oxo-octyl hydrogen phosphate and mono-oxo-octyl dihydrogen phosphate
• bis(Z-hydroxyethyl) cocoa amine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate the bis(Z-hydroxyethyl) cocoa amine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate.
• the primary alkyl acid esters of orthophosphoric acid (acid phosphates) will be understood to be those esters in which only 1 or 2 of the three acidic hydrogen atoms of orthophosphoric acid have been replaced by alkyl groups, i.e., the monoalkyl dihydrogen phosphates and the dialkyl hydrogen phosphates.
• esters may be obtained according to the general methods of the art which involve reacting an alcohol with phosphorus pentoxide (P 0 From about 2 to about 4 moles of the alcohol maybe used per mole of P 0 Preferably, about 3 moles of the alcohol per mole of P 0 will be used to yield approximately equimolar mixtures of the monoand dialkyl esters of orthophosphoric acid, that is, from about 40 to about 60 mole percent of the monoalkyl esters and the remainder of the dialkyl esters. These mixtures of monoand dialkyl esters are preferred for reasons of economy, but other mixtures, as well as the monoalkyl esters and dialkyl esters individually, may also be used in forming the amine salts of this invention.
• the esters can be separated from the mixtures in which they are prepared by conventional means known in the art.
• the alcohol is a branched or straight-chain primary alkanol having 8 to 16 carbon atoms or a mixture of two or more straight or branched chains or mixtures of straight and branched chain alkanols.
• the branched chain alkanols are preferably those made by the well-known Oxo-process from 00, H and a branched chain olefin such as the C -C monoolefinic polymers and interpolymers of propylene and butylene, as described, for example, in US. Patents 2,824,836 and 2,884,379.
• Examples of preferred xo-alcohols that may be used are isooctyl alcohol from the propylene-butylene dimer, branched tridecyl primary alcohols from triisobutylene and from tetrapropylene, and the branched hexadecyl primary alcohols from pentapropylene.
• branched chain primary alkanols that can be used are those that may be prepared by alkaline condensation of two primary alkanols, having the structure RCH CH OH wherein -R is an alkyl of from 2 to 6 carbon atoms, to produce primary alkanols branched in the 2-position such as RCH OH CHRCH OH
• 2-hexyldecanol-l is produced by heating noctanol with caustic and zinc dust
• 2-ethylhexanol-l is prepared from butanol-l, as more fully described in U.S. Patent 2,457,866.
• the branched alcohols may also be prepared by the conventional aldolization of suitable aldehydes followed by hydrogenation.
• straightchain primary al-kanols are readily available commercially.
• straight-chain alcohols are octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol and hexadecanol.
• the preferred alkyl acid phosphates utilized in this invention are the monoand dialkyl acid phosphates wherein the alkyl group is either isooctyl, 2-ethylhexyl, tridecyl or hexadecyl.
• the amines which are utilized to produce the novel salts of the alkyl acid phosphates of this invention are alkanol amines of two diiferent classifications.
• the first class designated as (A), has the following structural formula OH H wherein R and R can be hydrogen, alkyl, cycloalkyl, phenyl, or alkylphenyl.
• R and R can be hydrogen, alkyl, cycloalkyl, phenyl, or alkylphenyl.
• the total number of carbon atoms present in the IR and R substituents must be from 8 to 24.
• alkyl and cycloalkyl radicals are ethyl, butyl, hexyl, n-octyl, tert.-octyl, ndodecyl, tert.-dodecyl, hexadecyl, the mixed C to C tertiary-alkyl fractions, cyclohexyl, cyclooctyl and cyclodecyl.
• alkylphenyl radicals are p-octylphenyl, p-decylphenyl, and p-dodecylphenyl.
• the alkanol amines of this class may be obtained by any of the methods known in the art. For example, they are easily obtained by the reaction of the appropriate amine, RRNH, with 3-chloropropanediol-l,2,
• the preferred amines of this class are the amines wherein R is hydrogen and R is n-dodecyl, tert.-dodecyl, and tert.-C -C alkyl, or wherein both R and R are butyl radicals.
• the second class of amines designated as class (B), has the following structural formula RII,N( ,RIII)2 wherein R" is an alkyl, cycloalkyl, phenyl, or aralkyl hydrocarbon radical of from 6 to 25 carbon atoms such as octyl, isooctyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, the mixed C to C alkyl fractions from cocoa amine, cyclohexyl, cyclodecyl, cyclooctadecyl, phenyl, or octylbenzyl, hexylbenzyl, decylbenzyl and octadecylbenzyl.
• R is an alkyl, cycloalkyl, phenyl, or aralkyl hydrocarbon radical of from 6
• R' is either a hydroxy ethyl radical or hydroxy propyl radical.
• This class of alkanol amines is easily prepared by the reaction of one mole of the appropriate amine, R N'H with 2 moles of ethylene oxide or propylene oxide.
• R' is hydroxy ethyl
• R'Cl alkyl or aralkyl chloride
• diethanol amine [HN(CH CH OH)
• R" is n-dodecyl, octadecyl, cyclohexyl, octadecylbenzyl or derived from a naturally occurring fatty oil having 8 to 18 carbon atoms such as coconut oil.
• the amount of the alkanol amine salt of the alkyl ester phosphate added to the gasoline is not critical as long as the amount is sufficient to improve the anti-stalling characteristics of the gasoline.
• the preferred amount of the salt added to the gasoline is from about 0.0003% to about 0.02% by weight based on the weight of the distillate fuel.
• gasoline compositions of this invention may contain all the additives incorporated in modern gasoline in addition to the subject alkanol amine phosphate salts.
• additives as anti-knock agents, anti-oxidants, dyes, and metal deactivators do not effect the performance of the salts of this invention and are compatible in gasoline with the subject anti-stalling additive.
• the salt When the salt is to be used as an anti-stalling additive in gasoline, it is preferred to dissolve the salt in a solvent such as methanol, kerosene, or xylene in sufficient concentration to make a 50 to by weight solution of the salt.
• a solvent such as methanol, kerosene, or xylene
• Such a concentrate provides a convenient means for handling the salt and facilitates the blending of the Salt composition into the base gasoline.
• the mixture was stirred for a few hours at 6070 C., completing the mixing and neutralizing reactions, thereby forming the N-(2,3-dihydroxypropyl) tert.-dodecylamine salt of an approximately equimolar mixture of di-oxo-tridecyl hydrogen phosphate and mono-oxo-tridecyl dihydrogen phosphate.
• reaction mass was diluted with kerosene to provide an 80% by weight solution of said neutralized product.
• a lower alcohol such as methanol may be employed as diluent to provide a highly fluid additive for distillate fuels.
• the amine may be added in the neutralization step as a kerosene or methanol solution, whereby the above salt product is obtained directly as a freely mobile solution, e.g., 80% by weight in the diluent.
• the method used to prepare the alkyl acid phosphates of this invention results in a mixture of the monoand dihydrogen phosphates, it is most preferred commercially to use this mixture in the preparation of the amine salts.
• the resulting alkanol amine salt mixture can then be used directly as a gasoline additive.
• specific alkanol amine salts of this invention are prepared by first separating the monohydrogen phosphate from the dihydrogen phosphate, and thereafter reacting the isolated acid phosphate with a specific alkanol amine.
• the separation of .the monohydrogen phosphate from the dihydrogen phosphate is accomplished by conventional techniques.
• the di-oxo-tridecyl hydrogen phosphate is separated and recovered from the mono oxo tridecyl hydrogen phosphate of this example by techniques used and described in US. Patents 2,818,421 and 2,854,468.
• the separated di-oxo-tridecyl hydrogen phosphate is then reacted with N-(2,3-dihydroxypropyl)tert. dodecylamine to form the corresponding amine salt free from significant amounts of the amine salt of the dihydrogen phosphate.
• the amine salt of the dihydrogen phosphate is similarly prepared by reacting the mono'oxo-tridecyl dihydrogen phosphate with N (2,3 dihydroxypropyl)tert. dodecylamine.
• Do. phenyl... CH2OH(OH3)OH Do. n-dodecyL. OH2CH(GHB)OH
• Tridecyl and isooctyl in this table refer to those groups present in oxo-tridecyl and oxo-octyl alcohols.
• the anti-stalling properties of the alkanol amine phosphate salts of the present invention were demonstrated in a 6-cylinder Chrysler engine having a horsepower rating of 86 at 3400 r.p.m. and a displacement of 216.5 cu. in.
• Two types of carburetors were employed in the tests, (a) a throttle plate carburetor and (b) an emulsion tube type.
• the test conditions were as follows:
• Carburetor Type Throttle Emulsion Plate Tube Intake air F 38-40 34-36 Relative humidity, percent 98-100 98-100 Engine load, horsepower--. 10 15 Engine speed, r p m l 1, 500 3 l, 500 Idle speed, r.p.m 350 Fuel temp. to carburetor, F 50-55 50-55 I At high speed. 1 Initially.
• Throttle plate carburetor The operating time of the engine was varied at the conditions described above, using the time required for stalling as a measure of the fuels tendency to cause or prevent stalling due to carburetor icing. All runs were started after soaking the throttle plate with methanol for 0.5 minute at a temperature of 40 F. The operating time selected for the engine depended on the ice-forming tendencies of the fuel. Operating times at the 1500 r.p.m. engine speed were usually in the 0.5-1.5 minute range for uninhibited base fuels. At the end of the 1500 r.p.m. portion of the operating cycle, the throttle was cut back to idle position.
• the anti-stall rating or stall time of a gasoline was defined as the longest 1500 r.p.m. run (to the nearest 0.25 minute) followed by a complete 30 second idle period without stalling. A stall time of 3 or more minutes was considered excellent performance.
• novel alkanol amine salts of the present invention are also very eflective in the use with the con- Comparison tests under the same operating conditions as described above were made to illustrate the eifect of various unsubstituted amine phosphate salts on engine stalling. The results are set forth in Table III below.
• alkanol amine salts of the present invention have shown superiority over the unsubstituted amine salts in tests with the conventional throttle plate carburetor. For example, using a commercial gasoline where 10 represented bright and shiny and 0 represented very heavy black deposits. The base fuel used was the same as that used for the anti-icing tests described above.
• Comparative inspection of the leaflets from the carburetor after the engine was operated on the base gasoline with those leaflets from the carburetor after the engine was operated on gasoline containing an additive of the present invention demonstrates the effective cleaning power of the subject additives. Results of these comparahaving a mid-boiling point of 231 F. as the base fuel, tive tests are showninT able IV below.
• a stall time of 3 minutes in the throttle plate carburetor was reached by using 0.008 wt. percent (80% active ingredient) of the 2-ethyl hexylamine salt of tridecyl acid phosphate, While only 0.0016 -wt. percent (80% active ingredient) of the n-dodecyldiethanol amine salt of tridecyl acid phosphate was required to obtain the same stall time of 3 minutes in the throttle plate carburetor.
• the alkanol amine salts of the present invention also exhibit excellent carburetor detergency properties. Although the detergency test, as described below, was carried out with a throttle plate carburetor, it is also applicable to an engine with an emulsion tube carburetor.
• Carburetor detergency test The carburetor detergency properties of the alkanol amine phosphate salts of the present invention may be demonstrated using a Lausen test engine equipped with a Tillotsen carburetor modified by inserting removable leaflets around the throttle plate. Throughout the test, a portion of the exhaust gases of a second single cylinder engine running at a constant 2500 r.p.m. was introduced into the test carburetor. The test engine was cycled one minute at open throttle under dynamometer load and then for two minutes at idle of 1100:100 r.p.m. for a period of two hours.
• a salt of a tridecyl acid orthophosphate and N-(2,3- dihydroxypropyl) tert.-dodecylamine 1.
• a salt of a tridecyl acid orthophosphate and bis(2- hydroxyethyl) n-dodecylamine 1.
• a salt of a tridecyl acid orthophosphate and bis(2- hydroxyethyl) cocoa amine 4.

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• 1965
  • 1965-01-13 US US425329A patent/US3428713A/en not_active Expired - Lifetime
  • 1965-06-12 DE DE1545502A patent/DE1545502C3/de not_active Expired
  • 1965-06-14 FR FR20682A patent/FR1451313A/fr not_active Expired
  • 1965-06-15 GB GB2524365A patent/GB1053193A/en not_active Expired
• 1967
  • 1967-10-19 US US676619A patent/US3505044A/en not_active Expired - Lifetime

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