US3011881A - Novel boron compounds and motor fuel containing the same - Google Patents
Novel boron compounds and motor fuel containing the same Download PDFInfo
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- US3011881A US3011881A US26439A US2643960A US3011881A US 3011881 A US3011881 A US 3011881A US 26439 A US26439 A US 26439A US 2643960 A US2643960 A US 2643960A US 3011881 A US3011881 A US 3011881A
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- boron compounds
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- 150000001639 boron compounds Chemical class 0.000 title claims description 15
- 239000000446 fuel Substances 0.000 title description 15
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl lead compound Chemical class 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006079 antiknock agent Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910002923 B–O–B Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
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
- C10L1/30—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
-
- 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
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Definitions
- R represents a radical selected from a group consisting of alkyl, alkenyl, or alicyclic radicals containing from 7 to 21 carbon atoms, and R is selected from a group consisting of hydrogen or an alkyl radical containing up to 5 carbon atoms.
- Gasolines containing one or more of the compounds of the present invention are effective in markedly reducing many of the adverse effects resulting from combustion chamber deposits which accumulate during the prolonged operation of an initially clean engine on a hydrocarbon fuel, and particularly a hydrocarbon fuel which contains tetraethyl lead as an octane improver.
- One of the most serious adverse effects of lead deposits is uncontrolled ignition and a general lack of smoothness in engine operation caused principally by these deposits becoming heated to incandescence within the combustion chamber during engine operation and igniting the fuel either before or after the portion in the cycle at which the charge would normally be ignited by the spark of the sparkplug.
- the boron compounds of the present invention are helpful in overcoming in great part this adverse effect of lead deposits.
- organoboron compounds are effective in minimizing engine operating problems due many of the boron compounds 'previously proposed for such use are not suitable in commercial practice due to the characteristic instability of organoboron compounds toward hydrolysis while in gasoline. Because of this instability, contact with small amounts of water and moist, atmospheric conditions during prolonged storage causes many of the prior art compounds to hydrolyze to solid insoluble products which precipitate out of the gasoline phase, so that the boron content never reaches the engine where it might be efiective. In contradistinction to this general characteristic of boron compounds, the compounds of the present invention are quite stable toward hydrolysis while in gasoline and are well suited for conventional large scale manufacturing and marketing operations.
- gasolines containing boron compounds of the present invention are highly effective in minimizing carburetor icing, usually making it unnecessary to incorporate a speciat additive in the gasoline to guard against this problem.
- Carburetor icing represents a troublesome problem attendant to automotive engines operated in cool, moist, atmospheric conditions. This icing problem is most likely to occur during engine warmup when the engine is temperature. The vaporization of the gasoline in the carburetor during this warmup period produces temperature reduction in the throttle plate and carburetor walls, causing the moisture present in the incoming air on cool, humid days to condense and freeze. Such ice formation restricts the narrow openings in the carburetor, manifesting itself in a rough idling condition and frequent engine stalls.
- the gasoline base stocks to which the present boron compounds are added may be any of those conventionally used in preparing a motor gasoline for a sparkignited internal combustion engine, such as catalytic distillate, motor polymer, alkylate, catalytic reformate, isomerate, naphthas, etc.
- the gasoline will preferably contain a tetra alkyl lead compound as an anti-knock agent and a scavenging agent.
- the amount of anti-knock agent will usually be at a level of approximately 3 ml./ gal. but may range from ml./gal. up to 6 mL/gal.
- the base gasoline may also include other common additives such as anti-oxidants, stabilizers, solvent oils, dyes, and the like.
- the amount of the boron compound added to the fuel may vary and the amount is preferably expressed in terms of boron. Generally an amount of the compound to provide 0.002% by weight of boron (based on the total fuel) is the smallest amount that will give any significant effect. Use of amounts in excess of 0.1% by weight of boron usually cannot be justified economically.
- These compounds may be added directly to the fuel or, if more convenient, they may be dissolved in a suitable solvent to produce a liquid concentrate and the concentrate blended in with the fuel.
- the compounds of the invention are prepared by reacting boric acid with a mono-acylated trialkanol amine compound in an equimolar relationship.
- the monoacylated trialkanol amine compounds employed in this reaction may be characterized by the following general formula:
- R and R are defined as hereinbefore.
- the latter compounds are preferably prepared by reacting a trialkanol amine compound with a fatty acid or naphthenic acid compound containing 8 to 22 carbon atoms in a 1:1 molar ratio under conditions to remove the water of reaction that'is formed.
- Compounds prepared by reacting triethanol amine or triisopropanol amine with oleic acid are particularly desirable for the gasoline compositions of the present invention.
- Commercial grades of the preferred fatty acids which are derived from naturally occurring fats and oils are suitable for the reaction, and hence the R radical in the above formula may correspond to the fatty acid radicals present in such fats and oils.
- the R radical may also be suitably derived from naphthenic acids containing from 8 to 22 carbon atoms.
- the mono-acylated trialkanol amine compound readily undergoes boration under conditions in which the water of reaction is removed from the reaction mixture as it below normal operating 4 is formed.
- the reaction proceeds in accordance with Example 2 the equation: 141 grams (0.5 mole) of oleic acid was mixed wit] (1) 95.8 grams (0.5 mole) of tri-isopropanol amine togethe: H 11' cHr-oH-orr HO with 300 m1. of benzene in a three-necked flask. Th1: N reaction mixture was heated with stirring at the azeotropn P distillation temperature to remove 8.8 ml. of water (9.(
- the resulting product was a trans- API B y 57.8 parent viscous material which was completely soluble in 8 distmflfiml gasoline.
- the product has the following formula: 131,- 91 10% 122 cm 30% 170 0 on. om-dn-o 50% 229 cums- -o-on-car 13-03 38; 281
- the number of surface ignitions in the additive fuel is expressed as percentage of the surface ignitions of the blank fuel with the results as follows:
- the test consisted of running the same number of cycles on each fuel where in each cycle the engine was operated at 2200 r.p.m. for seconds and then decelerated normally to an idle at 450 r.p.m. for a maximum of 30 seconds. Performance of the engine was observed during each idle period, and -a numerical rating based on the degree of rough idling and engine stalls was assigned so that each fuel received a merit rating on a scale ranging from 100 to 0.
- an engine operating with a smooth idle over the idle periods of every test cycle would receive a rating of 100, and an engine which stalled in less than 12 seconds in the idle period of every test cycle would receive a rating of 0.
- the base fuel used had the following composition and specifications.
- X is selected from the group consisting of hydrogen and R, 15 o-hH-on, a o
- CHr-CHg-O where X is selected from the group consisting of hydrogen and in an amount equivalent to 0.002 to 0.1% by weight boron.
- R represents a radical selected from the group consisting of alkyl, allrenyl, and alicyclic radicals containing from 7 to 21 carbon atoms, and R is selected from the group consisting of hydrogen and alkyl radicals containing up to 5 carbon atoms.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Description
. to deposits, but
United States Patent Oflice 3,011,881 Patented Dec. 5, 1981 3,011,881 NOVEL BORON COMPOUNDS AND MOTOR FUEL CONTAININ THE 5 Donald D. Emrick, Shaker Heights, Chien-wei Lino, Beachwood, and Edwin 0. Hook, Chagrin Falls, Ohio, assignors to The Standard Oil Company, Cleveland,
Ohio, a corporation of Ohio No Drawing. Filed May 3, 1960, Ser. No. 26,439 6 Claims. (C1. 44-63) and wherein R represents a radical selected from a group consisting of alkyl, alkenyl, or alicyclic radicals containing from 7 to 21 carbon atoms, and R is selected from a group consisting of hydrogen or an alkyl radical containing up to 5 carbon atoms.
Gasolines containing one or more of the compounds of the present invention are effective in markedly reducing many of the adverse effects resulting from combustion chamber deposits which accumulate during the prolonged operation of an initially clean engine on a hydrocarbon fuel, and particularly a hydrocarbon fuel which contains tetraethyl lead as an octane improver. One of the most serious adverse effects of lead deposits is uncontrolled ignition and a general lack of smoothness in engine operation caused principally by these deposits becoming heated to incandescence within the combustion chamber during engine operation and igniting the fuel either before or after the portion in the cycle at which the charge would normally be ignited by the spark of the sparkplug. The boron compounds of the present invention are helpful in overcoming in great part this adverse effect of lead deposits.
It is well known that organoboron compounds are effective in minimizing engine operating problems due many of the boron compounds 'previously proposed for such use are not suitable in commercial practice due to the characteristic instability of organoboron compounds toward hydrolysis while in gasoline. Because of this instability, contact with small amounts of water and moist, atmospheric conditions during prolonged storage causes many of the prior art compounds to hydrolyze to solid insoluble products which precipitate out of the gasoline phase, so that the boron content never reaches the engine where it might be efiective. In contradistinction to this general characteristic of boron compounds, the compounds of the present invention are quite stable toward hydrolysis while in gasoline and are well suited for conventional large scale manufacturing and marketing operations.
Additionally, gasolines containing boron compounds of the present invention are highly effective in minimizing carburetor icing, usually making it unnecessary to incorporate a speciat additive in the gasoline to guard against this problem. Carburetor icing represents a troublesome problem attendant to automotive engines operated in cool, moist, atmospheric conditions. This icing problem is most likely to occur during engine warmup when the engine is temperature. The vaporization of the gasoline in the carburetor during this warmup period produces temperature reduction in the throttle plate and carburetor walls, causing the moisture present in the incoming air on cool, humid days to condense and freeze. Such ice formation restricts the narrow openings in the carburetor, manifesting itself in a rough idling condition and frequent engine stalls.
The gasoline base stocks to which the present boron compounds are added may be any of those conventionally used in preparing a motor gasoline for a sparkignited internal combustion engine, such as catalytic distillate, motor polymer, alkylate, catalytic reformate, isomerate, naphthas, etc. The gasoline will preferably contain a tetra alkyl lead compound as an anti-knock agent and a scavenging agent. The amount of anti-knock agent will usually be at a level of approximately 3 ml./ gal. but may range from ml./gal. up to 6 mL/gal. The base gasoline may also include other common additives such as anti-oxidants, stabilizers, solvent oils, dyes, and the like.
The amount of the boron compound added to the fuel may vary and the amount is preferably expressed in terms of boron. Generally an amount of the compound to provide 0.002% by weight of boron (based on the total fuel) is the smallest amount that will give any significant effect. Use of amounts in excess of 0.1% by weight of boron usually cannot be justified economically. These compounds may be added directly to the fuel or, if more convenient, they may be dissolved in a suitable solvent to produce a liquid concentrate and the concentrate blended in with the fuel.
The compounds of the invention are prepared by reacting boric acid with a mono-acylated trialkanol amine compound in an equimolar relationship. The monoacylated trialkanol amine compounds employed in this reaction may be characterized by the following general formula:
wherein R and R are defined as hereinbefore. The latter compounds are preferably prepared by reacting a trialkanol amine compound with a fatty acid or naphthenic acid compound containing 8 to 22 carbon atoms in a 1:1 molar ratio under conditions to remove the water of reaction that'is formed. Compounds prepared by reacting triethanol amine or triisopropanol amine with oleic acid are particularly desirable for the gasoline compositions of the present invention. Commercial grades of the preferred fatty acids which are derived from naturally occurring fats and oils are suitable for the reaction, and hence the R radical in the above formula may correspond to the fatty acid radicals present in such fats and oils. The R radical may also be suitably derived from naphthenic acids containing from 8 to 22 carbon atoms.
The mono-acylated trialkanol amine compound readily undergoes boration under conditions in which the water of reaction is removed from the reaction mixture as it below normal operating 4 is formed. The reaction proceeds in accordance with Example 2 the equation: 141 grams (0.5 mole) of oleic acid was mixed wit] (1) 95.8 grams (0.5 mole) of tri-isopropanol amine togethe: H 11' cHr-oH-orr HO with 300 m1. of benzene in a three-necked flask. Th1: N reaction mixture was heated with stirring at the azeotropn P distillation temperature to remove 8.8 ml. of water (9.(
CHPCEFOH HO ml. represents theoretical or 0.5 mole).
31 grams (0.5 mole) of boric acid was then added tc the flask containing the mono-acylated amine and the R CHr-( JH-O reaction mixture was heated again to the azeotropic disg B OH+2H2O tillation temperature and maintained under these conditrons until 2% mols of water of reaction was removed CHPCILO for each mole of mono-acylated amine and boric acid re- 1 acting. The excess solvent was then removed from the or the equation: reaction mixture and the product was a clear plastic III.
N 1 1 CHr-CH-OH HO zit-G-O-OH-OIh-N +2 BOH CHs-CH-OH HO R R H R cm-c'xn-o o-oH-cH| 11' f RCO( JHCH:N B-o-B N-cHr-t m-0-c-R+sm0 CHs-CH-O o-cH-c I depending upon the amount of water that is removed substance which was readily soluble in gasoline. The during the reaction. product has the formula:
CH OH: cm 0Hr-oH-o o-oH-cm CH: f CnHn-C-O-(EH-CHr-N B-O-B -CHr- H--O-C-C17Hs:
cm-cn-o o-cH-c I The water of reaction may be removed by simple boil- The following tests were conducted to show the benefits ing but it is preferable to remove the water by means of available by the use of these compounds in gasoline with azeotropic fractional distillation using preferably benzene, respect to suppressing surface ignition and protecting toluene, or xylene as the solvent. Boric oxide may be against carburetor icing. used in place of the boric acid as the boron source in the To illustrate the improvemcms toward Surface ignition above reactions with the proper adjustment of the molar SIIPPI'QSSiOH, tests in all ASTNFCFR Single cylinder engine relationship With the mohwacyiated triaikanoi amine having a compression ratio adjusted at 12:1 were emcompouni ployed. Preparatory to the test cycle the engine was run The preparation of these compounds will be better thmmiat for 9 minutes to i f the understood in connection with the following examples. engine commons for the test period i' this the engine was operated at open throttle continuously for Examplg 1 three hours,b during vlvhich time the total surface ignition count was 0 served e ectronicall All ex rimental congrams mole) of R1810 flcld was i Wlth ditions were the same for each test except the gasoline. grams mole) of pr p o me 111 the The base fuel in each test was the same and had the presence of 80 ml. of xylene. The reaction mixture was following composition and specifications. heated with stirring at the azeotropic distillation tem- Composition.
perature until 3.2 ml. of water of reaction was removed (3.6 ml. represents theoretical or 0.2 mole). 00 333 5 3? a fi i 12.4 grams (0.2 mole) of boric acid was then added 19% 1 naphtha to the mono-acylated amine and the reaction mixture was 6.5% 1:. alkylatg heated again to azeotrope out 2.0 moles of water for each 4.2% isopentane mole of mono-acylated amine and boric acid reacting. 3.5% butane The reaction mixture was filtered and the excess solvent 5 Tetraethyl lea ------.ml./gal-- 2.4 was then removed. The resulting product was a trans- API B y 57.8 parent viscous material which was completely soluble in 8 distmflfiml gasoline. The product has the following formula: 131,- 91 10% 122 cm 30% 170 0 on. om-dn-o 50% 229 cums- -o-on-car 13-03 38; 281
CHr-CH-O E P Reid vapor pressure 11.24
The number of surface ignitions in the additive fuel is expressed as percentage of the surface ignitions of the blank fuel with the results as follows:
It is obvious from the above table that the boron compounds of the present invention are highly efiective in reducing both total and audible surface ignition with gasoline containing the same.
To demonstrate the carburetor anti-icing virtue of gasoline containing these compounds, 11 test procedure was devised simulating the stop-and-go type of engine operation normally experienced by the motorist during the engine warmup period. The test was conducted in a 1955 Plymouth V-8 engine equipped with a two-barrel carburetor. Carburetor air was supplied at a constant rate of 70 cubic feet per minute by a specially designed air conditioner controlled at 42 F. and 90% relative humidity, which are temperature and humidity conditions considered highly conducive to carburetor icing. test conditions were the same except for the gasoline.
The test consisted of running the same number of cycles on each fuel where in each cycle the engine was operated at 2200 r.p.m. for seconds and then decelerated normally to an idle at 450 r.p.m. for a maximum of 30 seconds. Performance of the engine was observed during each idle period, and -a numerical rating based on the degree of rough idling and engine stalls was assigned so that each fuel received a merit rating on a scale ranging from 100 to 0. By this scheme an engine operating with a smooth idle over the idle periods of every test cycle would receive a rating of 100, and an engine which stalled in less than 12 seconds in the idle period of every test cycle would receive a rating of 0.
The base fuel used had the following composition and specifications.
Composition:
40% 1t. cat. distillate 40% full range reformate 8.3% It. naphtha 8.3 isopentane 3.4% butane It is to be understood that various modifications of the foregoing invention will occur to those skilled in the art upon reading the above description. All such modifications are intended to be included as may be reasonably covered by the appended claims.
We claim:
1. A leaded gasoline for a spark-ignited internal combustion engine containing a boron compound of the following general formula:
where X is selected from the group consisting of hydrogen and R, 15 o-hH-on, a o
-n N-cn -hH-o-o-a o-orr-on,
CHr-CHg-O where X is selected from the group consisting of hydrogen and in an amount equivalent to 0.002 to 0.1% by weight boron.
3. A leaded gasoline for a spark-ignited internal combustion engine containing a boron compound of the following general formula:
0 CH: CH: H-O
C11Hss- -O(!HCH:N B--0X CHr-CHO where X is selected from the group consisting of hydrogen and CH: OJJHCH1 CH; 0 -n NoH,-hH-0o-c"m,
0-CH-C s :1 an amount equivalent to 0.002 to 0.1% by weight oron.
4. A novel boron compound having the following general formula:
to 0 R CHr- H-O R-i'J-O-hH-cm- B-OX CHr-CH-O 7 where X is selected from the group consisting of hydrogen and R! 0HCH, R' f B NcHiJ:H-0-G-R O- CH-CH:
and wherein R represents a radical selected from the group consisting of alkyl, allrenyl, and alicyclic radicals containing from 7 to 21 carbon atoms, and R is selected from the group consisting of hydrogen and alkyl radicals containing up to 5 carbon atoms.
5. A novel boron compound having the following general formula:
CH -CHr-O B-OX cm-cm-o where X is selected from the group consisting of hydrogen and O i CnHsr--O-CHrCHg- 6. A novel boron compound having the following general formula:
References Cited in the file of this patent UNITED STATES PATENTS 2,741,548 Darling et al Apr. 10, 1956 2,939,877 Washburn June 7, 1960 2,942,021 Groszos et al. June 21, 1960 2,948,597 Belden Aug. 9, 1960
Claims (1)
1. A LEADED GASOLINE FOR A SPARK-IGNITED INTERNAL COMBUSTION ENGINE CONTAINING A BORON COMPOUND OF THE FOLLOWING GENERAL FORMULA:
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US26439A US3011881A (en) | 1960-05-03 | 1960-05-03 | Novel boron compounds and motor fuel containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26439A US3011881A (en) | 1960-05-03 | 1960-05-03 | Novel boron compounds and motor fuel containing the same |
Publications (1)
Publication Number | Publication Date |
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US3011881A true US3011881A (en) | 1961-12-05 |
Family
ID=21831825
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US26439A Expired - Lifetime US3011881A (en) | 1960-05-03 | 1960-05-03 | Novel boron compounds and motor fuel containing the same |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3301888A (en) * | 1964-05-12 | 1967-01-31 | Universal Oil Prod Co | Polyhydroxyalkylalkylenepolyamine borate esters |
US3518193A (en) * | 1964-05-12 | 1970-06-30 | Universal Oil Prod Co | Synergistic antioxidant mixture and use thereof |
WO1984001169A1 (en) * | 1982-09-15 | 1984-03-29 | Union Oil Co | Boron-containing heterocyclic compounds and lubricating oils containing same |
US4522632A (en) * | 1983-09-23 | 1985-06-11 | Mobil Oil Corporation | Etherdiamine borates and lubricants containing same |
US4537692A (en) * | 1983-09-23 | 1985-08-27 | Mobil Oil Corporation | Etherdiamine borates and lubricants containing same |
US4557843A (en) * | 1981-11-09 | 1985-12-10 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating compositions containing the same |
US4595514A (en) * | 1983-08-23 | 1986-06-17 | Union Oil Company Of California | Boron-containing heterocyclic compound and lubricating compositions containing same |
US4623474A (en) * | 1981-12-10 | 1986-11-18 | Union Oil Company Of California | Oxidation and corrosion inhibitors for boron-containing lubricants |
US4627930A (en) * | 1980-06-12 | 1986-12-09 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating oil containing same |
US4629579A (en) * | 1980-06-12 | 1986-12-16 | Union Oil Company Of California | Boron derivatives |
US4629580A (en) * | 1980-06-12 | 1986-12-16 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating oil containing same |
US4657686A (en) * | 1980-06-12 | 1987-04-14 | Union Oil Company Of California | Lubricating compositions |
US4724099A (en) * | 1980-06-12 | 1988-02-09 | Union Oil Company Of California | Lubricating compositions |
US4801729A (en) * | 1980-06-12 | 1989-01-31 | Union Oil Company Of California | Lubricating compositions |
US4892670A (en) * | 1985-01-29 | 1990-01-09 | Union Oil Company Of California | Lubricating compositions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2741548A (en) * | 1954-10-15 | 1956-04-10 | Standard Oil Co | Leaded motor fuel containing boron compounds |
US2939877A (en) * | 1959-01-29 | 1960-06-07 | American Potash & Chem Corp | Stable esters of polyboronic acids |
US2942021A (en) * | 1957-10-28 | 1960-06-21 | American Cyanamid Co | Tri-nu-propanolamine borate |
US2948597A (en) * | 1958-12-30 | 1960-08-09 | Standard Oil Co | Novel boron compounds and gasoline containing the same |
-
1960
- 1960-05-03 US US26439A patent/US3011881A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2741548A (en) * | 1954-10-15 | 1956-04-10 | Standard Oil Co | Leaded motor fuel containing boron compounds |
US2942021A (en) * | 1957-10-28 | 1960-06-21 | American Cyanamid Co | Tri-nu-propanolamine borate |
US2948597A (en) * | 1958-12-30 | 1960-08-09 | Standard Oil Co | Novel boron compounds and gasoline containing the same |
US2939877A (en) * | 1959-01-29 | 1960-06-07 | American Potash & Chem Corp | Stable esters of polyboronic acids |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3445422A (en) * | 1964-05-12 | 1969-05-20 | Universal Oil Prod Co | Organic substrates containing borate of polyalkyl - polyhydroxyalkyl - al - kylenepolyamine |
US3518193A (en) * | 1964-05-12 | 1970-06-30 | Universal Oil Prod Co | Synergistic antioxidant mixture and use thereof |
US3301888A (en) * | 1964-05-12 | 1967-01-31 | Universal Oil Prod Co | Polyhydroxyalkylalkylenepolyamine borate esters |
US4629579A (en) * | 1980-06-12 | 1986-12-16 | Union Oil Company Of California | Boron derivatives |
US4801729A (en) * | 1980-06-12 | 1989-01-31 | Union Oil Company Of California | Lubricating compositions |
US4724099A (en) * | 1980-06-12 | 1988-02-09 | Union Oil Company Of California | Lubricating compositions |
US4657686A (en) * | 1980-06-12 | 1987-04-14 | Union Oil Company Of California | Lubricating compositions |
US4629580A (en) * | 1980-06-12 | 1986-12-16 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating oil containing same |
US4627930A (en) * | 1980-06-12 | 1986-12-09 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating oil containing same |
US4557843A (en) * | 1981-11-09 | 1985-12-10 | Union Oil Company Of California | Boron-containing heterocyclic compounds and lubricating compositions containing the same |
US4623474A (en) * | 1981-12-10 | 1986-11-18 | Union Oil Company Of California | Oxidation and corrosion inhibitors for boron-containing lubricants |
WO1984001169A1 (en) * | 1982-09-15 | 1984-03-29 | Union Oil Co | Boron-containing heterocyclic compounds and lubricating oils containing same |
US4595514A (en) * | 1983-08-23 | 1986-06-17 | Union Oil Company Of California | Boron-containing heterocyclic compound and lubricating compositions containing same |
US4537692A (en) * | 1983-09-23 | 1985-08-27 | Mobil Oil Corporation | Etherdiamine borates and lubricants containing same |
US4522632A (en) * | 1983-09-23 | 1985-06-11 | Mobil Oil Corporation | Etherdiamine borates and lubricants containing same |
US4892670A (en) * | 1985-01-29 | 1990-01-09 | Union Oil Company Of California | Lubricating compositions |
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