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
• • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • 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
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained

Definitions

• the polymeric reaction product of an amine with an epihalohydrin compound has been used heretofore as an additive to oils heavier than gasoline or as a means of preventing deposit formation in heat exchangers through which oil is passed. More recently, it has been found that the polymeric reaction product serves to reduce deposit formation in carbureted combustion engines. For these uses, however, apparently the reaction product formed from a monoamine or a diamine with the epihalohydrin compound are substantially equivalent. In contrast, as will be shown by the data in the present application, applicant has found that such equivalence does not prevail for use as an anti-icing agent and particularly in forming a synergistic mixture.
• the present invention relates to a synergistic anti-icing composition of (1) the polymeric reaction product of an aliphatic monoamine with an epihalohydrin compound and (2) a polyhydroxy alcohol.
• the present invention relates to a synergistic anti-icing composition of (1) from about 5% to about by weight of the polymeric reaction product, formed at a temperature of from about 60 F. to about 300 F., of from about 1 to about 2 mole proportions of an aliphatic monoamine with from about 1 to about 1.5 mole proportions of an epihalohydrin compound and (2) from about 95% to about 5% by weight of a polyhydroxy alcohol containing from about 2 to about 50 carbon atoms and from 2 to about 10 hydroxy groups.
• Illustrative preferred amines are primary alkyl amines including dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine, pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine, etc.
• the amine compound is reacted with an epihalohydrin compound.
• Epichlorohydrin is preferred.
• Other epichlorohydrin compounds include 1,2-epoxy-4-chlorobutane, 2,3-epoxy-4-chlorobutane, 1,2- epoxy-S-chloro-pentane, 2,3 epoxy-S-chloropentane, etc.
• the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed.
• epidihalohydrin compounds may be utilized. It is understood that the different epihalohydrin compounds are not necessarily equivalent and that, as hereinbefore set forth, epichlorohydrin is preferred.
• the amine is reacted with the epihalohydrin compound in a mole ratio of from about 1 to about 2 mole proportions of amine and from about 1 to about 1.5 mole proportions of epihalohydrin compound.
• the amine and epichlorohydrin preferably are reacted in substantially equal mole proportions.
• the reaction of amine and epihalohydrin is effected in any suitable manner.
• the desired quantity of amine and epihalohydrin compound may be charged to a reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step wise.
• the epihalohydrin compound may be charged to the reaction zone and the amine is added step wise, with stirring.
• the reaction of epichlorohydrin with the second or later portions of the amine is effected at a higher temperature than with the first portion of the amine.
• the reaction preferably is effected in the presence of a suitable solvent and particularly a hydroxylic solvent.
• a solution of the amine in a solvent and a separate solution of the epihalohydrin compound in a solvent are prepared and these solutions then are commingled in the manner hereinbefore set forth, at least one of the solvents being hydroxylic.
• Any suitable solvent may be employed and preferably comprises an alcohol including ethanol, propanol, butanol, etc., 2-propanol being particularly desirable.
• Other hydroxylic solvents comprise glycols including ethylene glycol, propylene glycol, etc., glycerol or other polyhydric solvents.
• reaction of amine compound and epihalohydrin compound is effected at any suitable temperature, which generally will be within the range of from about 60 to about 300 F. and preferably is in the range of from about 120 to about 185 F.
• this reaction is effected by heating an epichlorohydrin solution in dilute alcohol at refluxing conditions, with stirring, gradually adding the amine thereto, and continuing the heating, preferably at a higher temperature, until the reaction is completed, or the reverse order of adding the reactants may be employed.
• the organic halide salt which inherently is formed, is converted to an inorganic salt, to thereby liberate the free amine for further reaction to form the desired polymeric product.
• This may be effected in any suitable manner and generally is accomplished by reacting the primary reaction product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc. to form the corresponding metal halide.
• the reaction to form the metal halide is effected at a temperature within the range of from about 130 to about 212 F. and preferably from about 165 to about 195 F.
• the inorganic base preferably is added in at least two steps, with intervening heating and reacting, so that organic halide formed after the first addition of inorganic base is in turn reacted to liberate the free amine.
• the product at this stage of manufacture may be withdrawn from the reaction zone and filtered or otherwise treated to remove the inorganic halide. Generally however, it is preferred to perform the next step in the same reaction zone without removing the inorganic halide.
• the inorganic halide is inert and, therefore, its presence is not objectionable.
• the primary reaction product of the amine compound and epihalohydrin compound is now further heated and reacted in order to form the desired linear polymeric reaction product. This further heating and reacting is at a temperature of from about 130 to about 212 F. and preferably from about 165 to about 195 F.
• the inorganic halide salt is removed in any suitable manner, including filtering, centrifugal separation, etc. In some cases, it may be of advantage to effect the filtration at an elevated temperature, which may range from about 95 to about 160 F. or more.
• the polymeric reaction product will have from 2 to 20 and preferably from 3 to recurring units.
• the reaction products will range from liquids to solids and, when desired, may be prepared as a solution in a suitable solvent for ease in handling and using.
• a preferred solvent is an aromatic hydrocarbon including benzene, toluene, xylene, ethylbenzene, diethylbenzene, cumene, etc., or a mixed solvent such as naphtha, kerosene, xylene tower bottoms, etc.
• all or a portion of the aromatic solvent desired in the final product may be used as a solvent during the reaction, in addition to the hydroxylic solvent, and the aromatic solvent is allowed to remain in the final product.
• the polymeric reaction prodnot is used in admixture with a polyhydroxy alcohol.
• polyhydroxy alcohol is the commercially available hexylene glycol which is 2,4-dihydroxy-2-methylpentane.
• Other polyhydroxy alcohols include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, other hexylene glycols as, for example, 1,6-dihydroxyhexane, 2,6-dihydroxyhexane, etc., heptylene glycol, octylene glycol, etc., diethylene glycol, dipropylene glycol, dibutylene glycol, tributylene glycol, etc., dihydroxycyclohexane as, for example, 1,4-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, l,Z-dihydroxycyclohexane, etc., glycerol, 1,2,3-butanetriol, pentanetriol, hexanetriol, heptanetriol, erythritol, etc.
• the polyhydroxy alcohol is a dihydroxy alcohol containing from 2 to 8 carbon atoms and may be of straight or branched chain. However, it is understood that the polyhydroxy alcohol may contain 3 or more hydroxy groups, generally not above about 10 hydroxy groups, as well as being of aliphatic or cyclic in configuration.
• the polyhydroxy alcohol is an alkylene oxide addition product of a polyol.
• the alkylene oxide may comprise ethylene oxide and preferably propylene oxide, although it may comprise butylene oxide, amylene oxide, hexylene oxide etc.
• the polyol may comprise ethylene glycol, propylene glycol, butylene glycol, amylene glycol, hexylene glycol, etc., trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc.
• Triols include pentane triol, hexane triol, heptane triol, octane triol, etc.
• Other polyols may contain from 4 to 10 hydroxyl groups and thus will include the carbohydrates, including particularly sorbitol.
• a number of the polyhydroxy alcohols prepared via alkylene oxide addition are available commercially.
• One of these is a polyoxypropylene polyol available commercially as NIAX LET-240 and is prepared by the reaction of a hexane triol with propylene oxide. Analysis shows the product to have a hydroxy number of 234.6, which corresponds to about 10 moles of propylene oxide per mole of hexane triol. Accordingly, this polyhydroxy alcohol contains an average of 36 carbon atoms and 3 hydroxyl groups.
• Another such product is available commercially as NIAX LHT-550 and is believed to be the mixed polyol resulting from the propylene oxide addition to a mixture of hexane triol and sorbitol. This polyhydroxy alcohol is said to have a hydroxyl number of about 550, an acid number of 0.2 maximum and a specific gravity 20/20 of 1.0910.
• polyhydroxy alcohols prepared via alkylene oxide addition conveniently are obtained commercially, when desired these may be prepared in any suitable manner.
• a polyhydroxy hydrocarbon is reacted with an alkylene oxide, including particularly ethylene oxide and propylene oxide, in molar ratios to produce the oxyalkylated polyhydroxy hydrocarbon containing the number of oxyalkane groups desired. These may range from 1 to 20 and preferably from 5 to 15.
• the oxyalkylation is effected in any suitable manner and generally will be conducted at a temperature of from about room temperature to about 350 F. and more particularly from about 200 F.
• a catalyst such as sodium hydroxide, potassium hydroxide, tertiary amine, quaternary hydroxide, etc.
• a catalyst such as sodium hydroxide, potassium hydroxide, tertiary amine, quaternary hydroxide, etc.
• the catalyst may be omitted and the reaction is effected in the presence of water.
• Superatmospheric pressure may be employed, which may range from 10 to 1000 pounds or more.
• a mixture of polyhydroxy alcohols is employed.
• Illustrative mixtures include a mixture comprising from to by weight of hexylene glycol and 5% to 15% by weight of glycerol, a mixture of 75% to 95% by weight of ethylene glycol and 5% to 25% by weight of erythritol, etc.
• a mixture of monoamines and/or of epihalohydrin compounds may be used in preparing the polymeric reaction product.
• the polymeric reaction product and polyhydroxy alcohol will be used in suitable proportions, which may range from about to about 95% and preferably from to 90% by weight of the polymeric reaction product and from about 95 to about 5% and preferably from 90% to 10% by weight of the polyhydroxy alcohol.
• the amount of total anti-icing composition to be added to the gasoline will be sufficient to effect improved deicing.
• the concentration should be as low as practicable and may range from 0.0001% to 0.05% by weight and preferably is within the range of from about 0.002% to about 0.01% by weight of the fuel, based on the mixed polymeric reaction product and polyhydroxy alcohol exclusive of solvent when employed. While each of the polyamine and the polyhydroxy alcohol may be added separately to the fuel, it generally is pre ferred to prepare a composition of the polymeric reaction product and polyhydroxy alcohol in the proper concentrations and to add this composition to the fuel in the desired amount.
• the mixture of polymeric reaction product and polyhydroxy alcohol may be prepared as a solution in a suitable solvent which may comprise a paraffinic, aromatic and/ or naphthenic naphtha or gasoline.
• a suitable solvent which may comprise a paraffinic, aromatic and/ or naphthenic naphtha or gasoline.
• the solvent may comprise an aromatic or paraffinic hydrocarbon, including benzene, toluene, xylene, ethylbenzene, etc., pentane, hexane, heptane, octane, etc.
• the polymeric reaction product and hexylene glycol will comprise from about 10% to about 90% and preferably from about 25% to about 75% of the solution.
• the synergistic composition of the present invention may be used in any gasoline.
• Commercial gasolines generally comprise a mixture of two or more of cracked gasoline, hydrocracked gasoline, reformed gasoline, alkylate, isoparafiins, aromatics, etc., and in some cases may contain straight run gasoline, coker distillate, etc.
• the synergistic composition of the present invention may be used along with other additives incorporated in gasoline. These may include antioxidant, metal deactivator, tetra-alkyl lead, detergent, dye, etc. When desired, one or more of these additional additives may be admixed with the composition of the present invention and marketed and used in this manner.
• a polymeric reaction product is prepared by the reaction of one mole proportion of epichlorohydrin with one mole proportion of hydrogenated tallow amine.
• the hydrogenated tallow amine comprises a mixture which predominates in alkyl amines containing 16 to 18 carbon atoms per alkyl group although they contain a small amount of alkyl group having 14 carbon atoms.
• the reaction is effected by first forming a solution of 2 moles of epichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. of xylene and 200 cc. of 2-propanol.
• a separate solution of 2 moles of the hydrogenated tallow amine is prepared in an equal volume of xylene.
• One mole of the latter solution is gradually added to the epichlorohydrin solution, with stirring and heating at l30140 F. for about 2.5 hours, after which another mole of the hydrogenated tallow amine is added gradually to the reaction mixture, stirred and reacted at 175 F. for about 2.5 hours.
• One mole of sodium hydroxide then is added with stirring and heating at 185195 F. for 3 /2 hours, after which another mole of sodium hydroxide is added to the mixture, stirred and reacted at 185-195 F. for about 1 hour.
• Example II It will be noted that in Example I the first mole of tallow amine is reacted with epichlorohydrin at F. and then the second mole of tallow amine is reacted at the higher temperature of F. When effecting the reaction in this manner, the polymeric product will have a total of about 12 recurring units. However, when the reaction of all of the constituents is effected at substantially the same temperature, the reaction product will contain 5 or less recurring units. A specific preparation was calculated to comprise 4 recurring units and a molecular weight of about 1400.
• EXAMPLE IV A synergistic mixture was prepared by mixing the polymeric reaction product prepared as described in Example I with hexylene glycol. The polymeric reaction product previously was formed as a 50% solution in naphtha. The synergistic mixture contained 50% of the polymeric reaction product solution (25% by weight of active ingredient) and 50% by weight of hexylene glycol.
• the anti-icing properties were determined in a carburetor icing demonstrating apparatus consisting of a vacuum pump equipped so that cool moisture-saturated air from an ice tower is drawn through a simulated carburetor.
• the gasoline sample passes from a fuel reservoir through a flow meter into the carburetor at a rate of 1.4 lb./hr.
• the air from the ice tower is passed at a flow rate of 14.4 lb./hr. at a temperature of 40 F.
• the manifold vacuum is 9.5 in. Hg at the start and 12.5 at the end of the test. Evaporation of the gasoline in the carburetor further cools the cold moist air, with resulting ice formation on the throttle plate.
• the time in seconds is measured until a drop of 3 in. Hg vacuum occurs, which indicates stalling conditions.
• the fuel used in this example is a commercial gasoline which, without anti-icing additive, reached stalling conditions within about 15 seconds.
• the gasoline used in this example was of summer grade and has a slightly lower vapor pressure than winter grade fuels. This accounts for the fact that the icing time was about 15 seconds rather than about 8 seconds which normally is encountered with the winter grade gasoline.
• the stalling condition was 109.5 seconds which compares to the 68 seconds obtained when using an equal concentration of the polymeric reaction product active ingredient.
• the icing time is increased by 41.5 seconds, which is a considerable improvement and demonstrates the strong synergistic effect obtained by using the mixture of ingredients.
• EXAMPLE V The synergistic mixture of this example is 50% by weight of the polymeric reaction product solution, prepared as described in Example I (25% by weight of active ingredient) and 50% by weight of NIAX LHT-240.
• this polyhydroxy alcohol is the propylene oxide addition product to hexane triol.
• the NIAX LHT-240 when used alone, gave the stalling conditions of 15.6 seconds, 17.8 seconds and 18.4 seconds at concentrations of 25, 50 and 100 p.p.m.
• the mixture of 50% polymeric reaction product of Example I in 50% solution (25% active ingredient) and 50% by weight of NIAX LHT-240 gave stalling conditions of 45.5 seconds and 162.8 seconds at concentrations of 25 and 50 p.p.m. respectively.
• the 162.8 seconds is compared to the sum of the 17.8 seconds obtained when using 50 p.p.m. of NIAX LHT-240 and with the 68 seconds obtained when using 50 p.p.m. (25 p.p.m. active ingredient) of the polymeric reaction product solution.
• a stalling time of 162.8 seconds was obtained which is about double the expected stalling time and dramatically demonstrates the strong synergistic elfect obtained by using the mixture.
• EXAMPLE VI As hereinbefore set forth, the synergistic effect obtained when using the polymeric reaction product appears to apply when a monoamine is used as a reactant.
• a polymeric reaction product was prepared in substantially the same manner as described in Example I except that the amine used was N-tallow-1,3-diaminopropane.
• a 50% solution of this polymeric reaction product increased the stalling time from about 16 seconds in the absence of the additive to 28.3 and 35.9 seconds, respectively, at concentrations of polymeric reaction product solutions (25 and 50 p.p.m. active ingredient) of 50 and 100 p.p.m.
• Synergistic anti-icing composition of (1) from about 5% to about 95% by weight of the polymeric reaction product, formed at a temperature of from about F. to about 300 F., of from about 1 to about 2 mole proportions of an aliphatic monoamine containing from about 4 to about 40 carbon atoms with from about 1 to about 1.5 mole proportions of an epihalohydrin compound selected from the group consisting of epichlorohydrin, 1,2-epoxy-4-chlorobutane, 2,3-epoxy-5-chloropentane, and (2) from about to about 5% by weight of a polyhydroxy alcohol, which is an alkylene oxide addition product to a polyol.
• composition of claim 1 in which said monoamine contains from about 12 to about 30 carbon atoms.
• composition of claim 1 in which said monoamine is hydrogenated tallow amine is hydrogenated tallow amine.
• composition of claim 1 in which said polyhydroxy alcohol is the propylene oxide addition product to hexane triol.

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)
• Compositions Of Macromolecular Compounds (AREA)
• Liquid Carbonaceous Fuels (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22362898

Family Applications (1)

Country Status (7)

Cited By (4)

• 1971
  • 1971-02-16 US US00115693A patent/US3756795A/en not_active Expired - Lifetime
• 1972
  • 1972-02-08 CA CA134,191A patent/CA944561A/en not_active Expired
  • 1972-02-10 DE DE2206201A patent/DE2206201C3/de not_active Expired
  • 1972-02-14 FR FR7204812A patent/FR2125440B1/fr not_active Expired
  • 1972-02-15 IT IT48351/72A patent/IT949734B/it active
  • 1972-02-15 GB GB687172A patent/GB1370711A/en not_active Expired
  • 1972-02-16 JP JP47015714A patent/JPS5036642B1/ja active Pending

Also Published As

Similar Documents

Legal Events