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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained

Definitions

• ABSTRACT Fuels with improved dispersancy, anti-icing and rust inhibiting properties contain a compound prepared by the Mannich reaction between a hydroxy-substituted aromatic compound, usually an alkylphenol in which the alkyl group contains at least about six carbon atoms; formaldehyde or a reversible polymer thereof; and a hydroxyalkyl-substituted amine such as diethanolamine. Also useful as additives are the epoxide adducts of such compounds.
• This invention relates to novel liquid hydrocarbon fuels having excellent dispersancy and anti-icing and rust inhibiting properties. More particularly, it relates to compositions comprising a major amount of a liquid hydrocarbon fuel and, dissolved or substantially stably dispersed therein, a minor amount of at least one Mannich base or derivative thereof as specifically described hereinafter.
• a principal object of the present invention is to provide improved liquid hydrocarbon fuels for internal combustion engines and the like.
• a further object is to provide fuels with advantageous dispersancy and rust inhibition properties and decreased susceptibility to icing at low temperatures.
• a further object is to provide fuels containing improved additives which impart thereto the properties described above.
• R is a monoor polyhydroxy-substituted aromatic, alkylaromatic or (substituted alkyl)aromatic radical;
• R is hydrogen or a lower alkyl or hydroxysubstituted lower alkyl radical;
• R is a hydroxysubstituted lower alkyl radical or 1 R R4N/ R is a lower alkylene radical;
• R is hydrogen or a lower alkyl or hydroxy-substituted lower alkyl radical;
• R is a hydroxy-substituted lower alkyl radical;
• x is the valence of K.
• R is a hydroxy-substituted aromatic radical or the like.
• R may be derived from compounds such as phenol, catechol, resorcinol, a-naphthol or B-naphthol.
• Alkylaromatic radicals derived from these compounds are particularly preferred, especially monoalkylaromatic radicals in which the alkyl group contains at least about six and preferably up to about 100 carbon atoms.
• substituted alkyl groups are considered fully equivalent to the alkyl groups for the purpose of this invention.
• substituted in this sense is meant alkyl groups containing substituents which do not alter significantly their character or reactivity. Examples are:
• R is a monohydroxy-substituted alkylaromatic radical in which the alkyl group contains about lO-2O carbon atoms.
• the integer x is usually 1 or 2 (though it maybe as large as the number of aromatic carbon atoms not otherwise substituted) and is preferably 1; that is, the preferred additive compounds are mono(Mannich bases) of the aromatic or similar materials previously described.
• each of R and R is a hydroxy-substituted lower alkyl radical, the term lower alkyl as used herein referring to alkyl radicals containing seven carbon atoms or less.
• these radicals are hydroxyethyl radicals. Any valences of the nitrogen atom which are not satisfied by such radicals are satisfied by hydrogen or lower alkyl.
• R is wherein R is a lower alkylene (usually an ethylene) radical; R is hydrogen or a lower alkyl or hydroxysubstituted lower alkyl radical and is usually a hydroxyethyl radical; R is a hydroxy-substituted lower alkyl and usually a hydroxyethyl radical.
• R is a hydroxyalkyl-substituted alkylene diamines such as 2-( 2- aminoethylamino)ethanol.
• the Mannich bases used in the fuel compositions of this invention are conveniently prepared by the Mannich reaction between a suitable hydroxyaromatic compound or the like, formaldehyde or a reversible polymer thereof (e.g., paraformaldehyde, trioxane), and an amine of the formula
• a suitable hydroxyaromatic compound or the like formaldehyde or a reversible polymer thereof (e.g., paraformaldehyde, trioxane)
• the reaction may be effected at a temperature between room temperature and about 225C., usually about 50200C., with the amounts of the reagents being such as to provide a mole ratio of hydroxyaromatic compound to formaldehyde to amine ranging from about 1:1:1 to about 1:3:3.
• an inert diluent such as an aliphatic or aromatic hydrocarbon (e.g., petroleum fractions, toluene, xylene), to facilitate the reaction.
• an inert diluent such as an aliphatic or aromatic hydrocarbon (e.g., petroleum fractions, toluene, xylene)
• Suitable methods for preparation of the Mannich bases are described in U.S. Pat. Nos. 2,033,092 and 3,297,597, the disclosures of which are incorporated by reference herein.
• adducts of at least one epoxide with one or more Mannich bases as described above. Such adducts frequently impart demulsification properties to the fuels in addition to the properties previously described.
• the epoxide used for preparing the adduct may be, for example, ethylene oxide, propylene oxide, glycidyl ethers, butyl epoxystearate or an epoxide prepared from a commercially available a-olefin mixture in which the olefins contain about 11-14 carbon atoms. Lower alkylene oxides, especially ethylene and propylene oxide, are preferred.
• Preparation of the Mannich base-epoxide adducts is accomplished by merely mixing the epoxide with the Mannich base, up to about 20 moles of epoxide being used per mole of Mannich base, and maintaining at a suitable temperature (usually about 25-125C.) for a period of time sufficient to enable the reaction to take place.
• a suitable temperature usually about 25-125C.
• EXAMPLE 1 A solution of 798 parts (3 moles) of tetrapropenesubstituted phenol in 900 parts of xylene is heated to 100C., and 462 parts (4.5 moles) of diethanolamine is added. The mixture is further heated to 120C. and 198 parts (6 moles) of paraformaldehyde is added slowly so as to minimize foaming. After paraformaldehyde addition is complete, the mixture is heated to 140C. for hours while water is removed by distillation. It is then filtered to yield a 40% solution in xylene of the desired Mannich base; the solution contains 2.65% nitrogen.
• EXAMPLE 2 A solution of 798 parts (3 moles) of tetrapropenesubstituted phenol in 989 parts of xylene is heated to 100C., and 598 parts (4.5 moles) of diisopropanolamine is added. The mixture is heated to 120C. and 198 parts (6 moles) of paraformaldehyde is added slowly. The temperature is raised to 210C. and held there for 8 hours with removal of water by distillation. Upon filtration, there is obtained a 60% solution in xylene of the desired product. The solution contains 2.13% nitrogen.
• EXAMPLE 4 A solution of 1257 parts (3 moles) of a polyisobutene-substituted phenol (wherein the polyisobutene substituent has a molecular weight of about 300) in 1321 parts of xylene is heated to C., and 630 parts (6 moles) of diethanolamine is added followed by 198 parts (6 moles) of paraformaldehyde (added slowly to minimize foaming). The mixture is heated to 145C. for 9 hours as water is removed by distillation, and is then filtered to yield a 60% solution in xylene of the desired Mannich base; the solution contains 2.49% nitrogen.
• EXAMPLE 5 A solution of 625 parts (0.5 mole) of a polyisobutenyl phenol having a molecular weight of about 1000 in 489 parts of mineral oil is heated to C., and 25 parts (0.75 mole) of paraformaldehyde is added slowly. The mixture is heated to 160C. for 4 hours as water is removed by distillation, and is then cooled to 90C. and 79 parts (0.75 mole) of diethanolamine is added. The temperature is raised to 120C. and an additional 33 parts (1 mole) of paraformaldehyde is added. The temperature is raised to 160C. and maintained there for 6 hours as water is removed by distillation. The mixture is then filtered to yield a 60% solution'in mineral oil of the desired Mannich base; the solut on contains 0.7% nitrogen.
• EXAMPLE 6 A solution of 910 parts (4.74 moles) of heptylphenol in 1358 parts of xylene is heated to 80C., and 997 parts (9.48 moles) of diethanolamine is added. The mixture is heated to 1 10C. and 313 parts (9.48 moles) of paraformaldehyde is added slowly. The mixture is then heated to C. as water is removed by azeotropic distillation. The residue is cooled and filtered to yield the desired product as a 60% solution in xylene containing 3.93% nitrogen.
• EXAMPLE 7 A mixture of 423 parts (1.59 moles) of the product of Example 1 and 205 parts of xylene is heated to 100C., and 185 parts (318 moles) of propylene oxide is added. The mixture is heated at 100C. for 16 hours and is then stripped at C./10 mm. Xylene is added to produce a 60% solution of the product therein, which after filtration contains 4.9% hydroxyl.
• the fuel compositions of the present invention contain in addition to the Mannich base or derivative thereof described hereinabove, a major proportion of a normally liquid hydrocarbon fuel, usually a petroleum distillate fuel such as an aviation or motor gasoline, diesel fuel or fuel oil as defined by ASTM Specification D396. Particularly preferred is gasoline, that is,
• the Mannich base is dissolved or substantially stably dispersed in the fuel. It will usually be dissolved therein, but the invention includes fuel compositions (especially those comprising residual fuels) which are stable dispersions (e.g., sols or similar colloids).
• the amount of Mannich base employed is sufficient to disperse solids, inhibit icing or inhibit rust formation; this amount is usually about 1l0,000 and preferably 4-1000 parts (by weight) per million parts of final composition.
• the Mannich bases may be incorporated in the fuel simply by mixing them therewith at the desired concentration. Alternatively, they may be dissolved first in a combustible solvent, particularly a hydrocarbon solvent having a boiling point below about 250C. such as naphtha, benzene, toluene, xylene, gasoline or light mineral oil to obtain a fluid concentrate containing up to about 80% of the Mannich base, and the concentrate may then be added to the fuel to obtain the final fuel composition.
• a combustible solvent particularly a hydrocarbon solvent having a boiling point below about 250C.
• a hydrocarbon solvent having a boiling point below about 250C.
• the fuel of this invention may contain other additives known to those skilled in the art.
• additives include anti-knock agents such as tetraalkyl lead compounds; lead scavengers such as the haloalkanes; deposit preventers or modifiers such as the triaryl phosphates; dyes; antioxidants such as 2,6-di-tertiary-butyl- 4-methylphenol; auxiliary rust inhibitors such as alkylated succinic acids; auxiliary dispersants such as the reaction products of polyalkylene polyamines with alkylated succinic acids; bacteriostatic agents; gum inhibitors; metal deactivators; upper cylinder lubricants; demulsifiers; dehazers; and the like.
• anti-knock agents such as tetraalkyl lead compounds
• lead scavengers such as the haloalkanes
• deposit preventers or modifiers such as the triaryl phosphates
• dyes such as 2,6-di-tertiary
• a typical fuel composition of this invention comprises gasoline (which may be leaded or unleaded) containing the following additives, all parts being parts by weight per million parts of the final composition:
• a composition comprising a major amount of a liquid hydrocarbon fuel and, dissolved or substantially stably dispersed therein, a minor amount sufficient to improve dispersancy, anti-icing or rust inhibiting properties thereof of at least one compound of the formula wherein R is a monoor polyhydroxy-substituted aromatic, alkyl-aromatic or (substituted alkyl)aromatic radical; R is hydrogen or a lower alkyl or hydroxysubstituted lower alkyl radical; R is a hydroxysubstituted lower alkyl radical or R is a lower alkylene radical; R is hydrogen or a lower alkyl or hydroxy-substituted lower alkyl radical; R is a hydroxy-substituted lower alkyl radical; and x is the valence of R; with the proviso that the substituents on said substituted radicals do not alter significantly their character or reactivity.
• R is a monohydroxy-substituted monoalkylaromatic radical in which the alkyl group contains at least about 6 carbon atoms.
• composition according to claim 2 wherein the alkyl group in R contains about 10-20 carbon atoms.
• composition according to claim 6 wherein the alkyl group in R is a tetrapropenyl group.
• a composition comprising a major amount of a liquid hydrocarbon fuel and, dissolved or substantially stably dispersed therein, a minor amount sufficient to improve dispersancy, anti-icing or rust inhibiting properties thereof of at least one adduct of at least one epoxide with one or more compounds of the formula 1 R CH2N R wherein R is a monoor poIyhydroxy-substituted aromatic, alkylaromatic or (substituted alkyl)aromatic radical; R is hydrogen or a lower alkyl or hydroxysubstituted lower alkyl radical; R is a hydroxysubstituted lower alkyl radical or R is a lower alkylene radical; R is hydrogen or a lower alkyl or hydroxy-substituted lower alkyl radical; R is a hydroxy-substituted lower alkyl radical; and x is the valence of R; the mole ratio of said epoxide to said compound of the formula R2 R CH N being up to
• composition according to claim 9. wherein the epoxide is ethylene or propylene oxide, and alkyl group in R contains about lO-20 carbon atoms, and x is 1 or 2.
• composition according to claim 10 wherein the epoxide is propylene oxide and the alkyl group in R is a tetrapropenyl group.

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• 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)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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Cited By (19)

Citations (6)

Family Cites Families (2)

• 1973
  • 1973-11-07 US US413488A patent/US3877889A/en not_active Expired - Lifetime
• 1974
  • 1974-10-24 GB GB4605174A patent/GB1460330A/en not_active Expired
  • 1974-10-29 CA CA212,584A patent/CA999433A/en not_active Expired
  • 1974-10-29 AU AU74807/74A patent/AU7480774A/en not_active Expired
  • 1974-11-05 IT IT53861/74A patent/IT1023157B/it active
  • 1974-11-05 FR FR7436707A patent/FR2249947B1/fr not_active Expired
  • 1974-11-06 DE DE19742452722 patent/DE2452722A1/de active Granted
  • 1974-11-06 JP JP49127931A patent/JPS5920712B2/ja not_active Expired

Patent Citations (6)

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