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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
• • 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
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
• • 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
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
  • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds

Definitions

• This invention relates to fuel compositions for internal combustion engines, especially gasoline, containing a certain class of organic boron compounds.
• Such compounds have been shown to be effective in these respects but their use has been limited to a varying extent by the relatively high solubility of such compounds in water, and also by the low resistance of such compounds to decomposition through hydrolysis. Such compounds are thus lost from gasoline, at least in part, by the leaching or hydrolyzing action of the free water with which the gasoline invariably comes in contact during commercial storage and handling.
• Another disadvantage of such compounds is that the only ones known to resist hydrolysis and leaching to any material extent contain only small amounts of boron in proportion to the rest of the molecule. Thus relatively large concentrations of such compounds are necessary to achieve a desired concentration of boron in the gasoline.
• a principal object of this invention to provide an improved hydrocarbon fuel composition for internal combustion engines.
• a more particular object of the invention is to provide such a composition which has improved combustion characteristics.
• a further object of the invention is to provide a gasoline composition with improved resistance to surface ignition and less tendency to increase the octane requirement of the engine in which it is used.
• Still another object of the invention is to provide a boron-containing gasoline composition especially resistant to the action of water.
• Another object of the invention is to provide a gasoline composition especially resistant to the action of water and containing a boron additive the boron content of which is especially high.
• Another object of the invention is to provide a boron-containing gasoline composition the boron content of which can be especially high.
• the boron gasoline additives of the present invention are hexa- 2,821,463 Ice Patented Jan. 28, 1958 2 tomic heterocyclic ring compounds or mixtures thereof with normal boiling points no higher than about 500 C.
• the heterocyclic ring of these compounds contains three boron atoms alternating with three nitrogen atoms.
• Each of the nitrogen atoms of the heterocyclic ring is attached directly to a carbon atom in an organic radical with a radical weight of at least 15, and each of the boron atoms of the heterocyclic ring is attached to a hydrogen atom, or to a carbon or nitrogen atom in a radical with a radical weight of at least 15.
• the boron compounds of the gasoline compositions of the invention thus have the general formula:
• X is a hydrogen, or'a radical with a radical weight of at least 15 and attached to the boron atom directly through an atom of an element having an atomic number of from 6m 7 inclusive; and wherein Y is a radical with a radical weight of at least 15 and attached to the nitrogen atom directly through a carbon atom.
• X be an organic radical and that the ring-connecting element of the X radical be carbon. It is also preferred that both X and Y be organic radicals and contain no more than 10 carbon atoms, and especially organic radicals containing no atoms other than carbon, hydrogen and nitrogen. Particularly suitable compounds are those in which X and Y are hydrocarbyl groups containing no more than 5 carbon atoms, and especially no more than 3 carbon atoms. Still better, especially in the case of Y, are such hydrocarbyl groups in which the atom attached to the ring is a secondary or tertiary carbon atom.
• the total of the radical weights of the ring substituents be no greater than 500.
• Particularly advantageous compounds are those which have an especially high boron content, such as those in which the total of the radical weight of the ring substituents is no greater than 300, and preferably no greater than 250.
• the total of the radical weights of the ring substituents of the heterocyclic boron compound should be at least 48, and preferably at least 125.
• heterocyclic boron compounds of the compositions of the invention are generally called borazoles, the name borazole indicating the unsubstituted hexatomic ring compound (BH-NH) and the substituents of the ring being named with N- and/ or 18- prefixes to designate their positions.
• borazoles the compound with the structural formula illustrated above, wherein each X is a methyl group and each Y is an isopropyl group, is called N-triisopropyl-B-trimethylborazole.
• borazoles suitable in the practice of the invention are: N-triphenyl-B-trimethylborazole, N-triphenyl-B-tris(dimethylamino)borazole, N-triphenyl-B-triethylborazole, N-tricyclohexyl-B-trimethylborazole, N-
• N-tris(2-pr0pyl)-B-trichloroborazole was prepared by reaction of isopropylamine with boron trichloride in the presence of triethylamine similar to a procedure used by Jones and Kinney [1. Am. Chem. Soc. '61, 1378 (1939)] for the preparation of N-triphenyl-B-trichloroborazole.
• This and other like compounds are especially suitable for the preparation of the additives of the invention as in the following examples.
• the precipitate was then removed by suction filtration, the solvent removed under reduced pressure, and the product distilled in a Claisen still.
• the product a colorless liquid, B. P. 46 C. (1.1 mm. Hg), weighed 27 grams.
• the material analyzed 15.3% boron as against a theoretical boron content of 15.7% for N-tris(2-propyl)borazole.
• Triethyl borate do Immediate white precipitate plus evolution of heat.
• N-tris(2-propy1)-B-tri- No change for at least N change at 90 methylborazole. 16 hours. for at least 1 our.
• N-tris(2-propyl)borazole do D0.
• the engine was thoroughly cleaned at the beginning of each test on a particular fuel, and operated during the test with a spark advance of 25 BTDC and on a cylic schedule of 1 minute idling and 3 minutes cruise.
• the lubricant used was a common commercial crankcase oil.
• the octane requirement of the engine at full power output was determined at least once a day during each test.
• a base gasoline consisting of a blend of toluene, isooctane, and normal heptane containing sufficient motor mix fluid to supply 3.0 cc. tetraethyl lead per U. S. gallon was tested according to this procedure.
• the octane requirement of the engine leveled off after about 120 hours at 6:1 octane numbers above the octant requirement of the clean engine.
• EXAMPLE 8 The benetfis of the gasoline compositions of the invention in suppressing preignition or wild ping were shown in the engine test designed to measure deposit-induced ignition which is described by Hirschler, McCullough, and Hall, Deposit Induced Ignition Evaluation in Laboratory Engine, a paper presented at the Symposium on Preignition, Society of Automotive Engineers, Atlantic City, June 7-12, 1953.
• the engine used in this test is a CFR anti-knock test engine in which the standard overhead valve cylinder is replaced by L-head cylinder.
• the engine is operated on a cyclic schedule of 50 seconds of idling and 150 seconds at full throttle.
• the engine is equipped with an ionization gap and a surface-ignition counter. It thus differentiates between normal and uncontrolled combustion and counts the number of incidences of the latter.
• This base gasoline has an induction period (average of two tests) of 9.9 hours by ASTM method D-525.
• the induction period of the same base gasoline containing 3.6 grams of N-tn's(2-propyl)-B-trimethylborazole per U. S. gallon (0.4 gram boron per U. S. gallon) was 11.0 hours.
• the induction period of the same base gasoline containing 4.0 grams of N-tris(2-propyl)-B-tris(dimethylamino)borazole per U. S. gallon (0.4 gram boron per U. S. gallon) was over 22 hours.
• the base gasoline, the base gasoline containing 3.6 grams N-tris(2-propyl)-B-tn'- methylborazole per gallon, and the base gasoline containing 4.0 grams N-tris(2-propyl)-B-tris(dimethylamino) borazole per gallon were each added to a separate phase of water and a sandblasted and isopentaneacetone washed drum steel strip was suspended into each gasoline sample so as to extend through the interface and into the water phase. The strips were observed and their appearance recorded periodically as follows, each system being maintained at normal room temperature:
• EXAMPLE 11 A gasoline containing from 0.005 to 1.0 gram of boron, per U. S. gallon, in the form of N-trimethyl-B-trimethylborazole, when tested according to the procedures of Examples 5, 6, 7, and 8, shows remarkable benefits with respect to resistance to the action of water, reduction of E octane requirement increase and suppression of surface ignition.
• the effective concentrations of these compounds in the gasoline compositions can be very small.
• the concentration of compound should not be greater than sufficient to supply a boron content of about 1.0 gram per U. S. gallon, or preferably, about 0.5 gram per U. S. gallon.
• a preferred concentration of compound is that suflicient to supply a boron content of from about 0.2 to about 0.4 gram per U. S. gallon.
• the gasoline compositions of the invention can, and ordinarily will, contain other additives, such as the common commercial additives, for example anti-detonants, such as tetraethyl lead, iron carbonyl, dicyclopentadienyl iron and derivatives thereof, Xylidene and N-methylaniline, lead scavengers, such as ethylene dibromide and ethylene dichloride, dyes, spark plug antifoulants such as tricresyl phosphate, dimethyl xylyl phosphate and diphenyl cresyl phosphate and diphenyl cresyl phosphate, other deposit modifiers such as other boron compounds and lower alkyl phosphates and phosphites, oxidation inhibitors such as N,N- disecondary butyl P phenylenediamine, N n-butyl-paminophenol and 2,6 -ditertiarybutyl-4-methylphenol
• anti-detonants such as
• a gasoline composition consisting essentially of hydrocarbons boiling within the gasoline range and containing from about 0.005 to about 1.0 gram of boron, per U. S. gallon, in the form of a borazole compound boiling not higher than about 500 C. and having the formula:
• each X isselected from the group consisting of hydrogen and an organic radical having a radical atomic weight of at least and attached to a ring boron atom through an atom of an element having an atomic number of from 6 to 7 inclusive, and wherein each Y is an organic radical having a radical atomic weight of at least 15 and attached to a ring nitrogen atom directly through a carbon atom.
• each Y is an organic radical containing from 1 to 10 carbon atoms.
• each Y is a hydrocarbyl radical containing from 1 to 5 carbon atoms.
• a gasoline composition in accordance with claim 3, wherein the borazole compound is N-tris (2-propyl) borazole.
• a gasoline composition consisting essentially of hydrocarbons boiling within the gasoline range and containing from about 0.005 to about 1.0 gram of boron, per U. S. gallon, in the form of a borazole compound boiling not higher than about 500 C. and having the formula:
• each X is an organic radical having a radical atomic weight of at least 15 and attached to a ring boron atom through an atom of an element having an atomic number from 6 to 7 inclusive
• each Y is an organic radical having a radical atomic weight of at least 15 and attached to a ring nitrogen atom directly through a carbon atom.
• each X and each Y is a hydrocarbyl radical containing from 1 to 5 carbon atoms.
• borazole compound is N-tris(2-propyl)-B- tris (dimethylamino borazole.
• a gasoline composition in accordance with claim 7, wherein the borazole compound is N-tris(2-propyl)-B-trimethylborazole.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Lubricants (AREA)

Priority Applications (7)

Applications Claiming Priority (1)

Publications (1)

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Cited By (12)

Citations (4)

Family Cites Families (2)

• 0
  • NL NL93214D patent/NL93214C/xx active
  • BE BE552505D patent/BE552505A/xx unknown
  • NL NL212110D patent/NL212110A/xx unknown
• 1955
  • 1955-11-14 US US546798A patent/US2821463A/en not_active Expired - Lifetime
• 1956
  • 1956-11-09 FR FR1162767D patent/FR1162767A/fr not_active Expired
  • 1956-11-12 GB GB34583/56A patent/GB818727A/en not_active Expired
  • 1956-11-12 DE DEN12942A patent/DE1022842B/de active Pending

Patent Citations (4)

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