US2979530A - Preparation of alkyl substituted boron hydrides - Google Patents
Preparation of alkyl substituted boron hydrides Download PDFInfo
- Publication number
- US2979530A US2979530A US569945A US56994556A US2979530A US 2979530 A US2979530 A US 2979530A US 569945 A US569945 A US 569945A US 56994556 A US56994556 A US 56994556A US 2979530 A US2979530 A US 2979530A
- Authority
- US
- United States
- Prior art keywords
- alkyl substituted
- preparation
- liquid
- boron hydrides
- diborane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000000217 alkyl group Chemical group 0.000 title description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000446 fuel Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 5
- -1 BORON HYDRIDES Chemical class 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Classifications
-
- 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 System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
- C06B47/10—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant a component containing free boron, an organic borane or a binary compound of boron, except with oxygen
-
- 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
Definitions
- This invention relates to the preparation of a liquid h gh energy fuel composition comprising alkyl substituted higher boron hydrides and more particularly to their preparatron by the reaction of alkyl diboranes with pentaborane-9 (B H Since pentaborane-9 can be prepared by a variety of well known methods and since alkyl diboranes such as diethyl diborane can be prepared by the reaction of ethyl,- ene with diborane, it appeared likely that alkyl substituted higher boron hydrides could be prepared from higher boron hydrides which would have certain desirable properties. It is an object of this invention to provide a new and improved method for the preparation of fuel mixtures comprising alkyl substitutedhigherboron hydrides by the reaction of alkyl diboranes with pentaborane-9.
- This invention is based upon our discovery that liquid products having desirable chemical and physical properties for use as high energy fuels can be prepared by the reaction between a lower alkyl diborane and penta borane-9.
- fraction 2 was mainly unreacted d ethyl diborane
- fraction 3 was a mixture of alkyl boranesconsisting primarily of alkyl higher boranes such as ethyl pentaboranes and contained 26.6 percent boron and 59.2
- the spontaneous ignition temperature of the liquid reaction product obtained in these runs was 65-70 C.
- the liquid products which are produced by the above reactions are useful as high energy fuels in bi-propellant systems.
- These liquid high energy fuels burn readily with conventional oxidizers, including air and oxygen, and are primarily useful in turbojet, ram jet, and rocket engines.
- These fuels may be used alone or in mixtures with other fuels toward which they are chemically inert, e.g. most ordinary hydrocarbon fuels.
- These fuels have a high heat of combustion (greater by 20-50% than the best hydrocarbon fuels), are spontaneously inflammable at high temperature, and have other desirable fuel properties such as low freezing point, large liquidus range, high density, and moderate resistance to hydrolysis.
- a sample of the fuel produced by the above process is introduced into the combustion section of a jet test engine, burned with compressed air, and the efiicency of the combustion and the output of the engine measured.
- 1 H is the volume of hydrogen evolved in complete hydrolysis of the product expressed 11 mllllmols per gram of product.
Description
f at ented PREPARATION OF ALKYL SUBSTITUTED BORON HYDRIDES Myrl Lichtenwalter and Kenneth E. Harwell, Austin,
Tex., assignors to Callery Chemical Company, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed Mar. 6, 19'56, Ser. No. 569,945
3 Claims. (Cl. 260606.5)
This invention relates to the preparation of a liquid h gh energy fuel composition comprising alkyl substituted higher boron hydrides and more particularly to their preparatron by the reaction of alkyl diboranes with pentaborane-9 (B H Since pentaborane-9 can be prepared by a variety of well known methods and since alkyl diboranes such as diethyl diborane can be prepared by the reaction of ethyl,- ene with diborane, it appeared likely that alkyl substituted higher boron hydrides could be prepared from higher boron hydrides which would have certain desirable properties. It is an object of this invention to provide a new and improved method for the preparation of fuel mixtures comprising alkyl substitutedhigherboron hydrides by the reaction of alkyl diboranes with pentaborane-9.
Other objects of this invention will become apparent as described in the specification and the claims hereinafter related. 7
This new and improved method of preparing liquid high energy fuel mixtures will be described more fully in the specification and the novelty thereof will be particularly pointed out and distinctly claimed.
This invention is based upon our discovery that liquid products having desirable chemical and physical properties for use as high energy fuels can be prepared by the reaction between a lower alkyl diborane and penta borane-9.
In a series of experiments diethyl diborane was refluxed with pentaborane-9 for 30 to 240 minutes at a liquid temperature of 25 to 65 C. at a pressure of 70 to 675 millimeters of mercury. The apparatus was arranged so that any diborane produced passed out of the system while higher boiling materials were returned to the reaction as reflux. The following results were obtained:
reacted pentaborane-9; fraction 2 was mainly unreacted d ethyl diborane; fraction 3 was a mixture of alkyl boranesconsisting primarily of alkyl higher boranes such as ethyl pentaboranes and contained 26.6 percent boron and 59.2
percent carbon. The spontaneous ignition temperature of the liquid reaction product obtained in these runswas 65-70 C. Other physical properties of the liquid reaction product obtained were: melting point =101 0., and n =l.4004.
The liquid products which are produced by the above reactions are useful as high energy fuels in bi-propellant systems. These liquid high energy fuels burn readily with conventional oxidizers, including air and oxygen, and are primarily useful in turbojet, ram jet, and rocket engines. These fuels may be used alone or in mixtures with other fuels toward which they are chemically inert, e.g. most ordinary hydrocarbon fuels. These fuels have a high heat of combustion (greater by 20-50% than the best hydrocarbon fuels), are spontaneously inflammable at high temperature, and have other desirable fuel properties such as low freezing point, large liquidus range, high density, and moderate resistance to hydrolysis. In actual tests, a sample of the fuel produced by the above process is introduced into the combustion section of a jet test engine, burned with compressed air, and the efiicency of the combustion and the output of the engine measured.
' When this fuel is burned in a test engine it has a heat of combustion more than 20% greater than the best hydrocarbon fuels. The combustion efliciency is equal to JP-4 .(a standard jet fuel in use for several years past) and the thrust of engine per unit weight of fuel is sub stantially greater than the thrust obtained using the best hydrocarbon fuels. In comparative tests on the fuel produced by the above process and other boron-containing high energy fuels and other hydrocarbon fuels, it has been found that engine output is directly propertional to the heat of combustion per unit weight of fuel. Thus, an aircraft using a high energy boron-containing fuel can travel proportionately further with the same load or can carry proportionately greater loads, than when fueled with conventional fuels.
It should be understood that this invention embraces the reaction of other lower dialkyl diboranes with pentaborane-9 in addition to the reaction of diethyl diborane with pentaborane-9.
While we have described several embodiments of our invention it is to be understood that within the scope of the claims appended hereto this invention may be practiced otherwise than as specifically described.
Analysis of Liquid Percent Reaction Product Run Mols Mols Reaction Temp., Pressure, Conver- No. EhB H, B 119 time 0. mm. slon (mlns) EtQBgH Wt. Wt.
Per- Per- H 1 cent, 13 cent, 0
1 H is the volume of hydrogen evolved in complete hydrolysis of the product expressed 11 mllllmols per gram of product.
In all of the above reactions the gases evolved were condensed in a trap immersed in liquid nitrogen. The
trap was then connected to an infra-red sample cell. The trap was warmed and the resulting gases were passed into the cell and analyzed. These condensed vapors were mainly diborane with some unreacted ethyl diboranes. The liquid product obtained in each case was separated into three fractions by distillation. Vapor pressure and boron analyses indicated that the fraction 1 was mainly unprises contacting a lower alkyl dihoraqe 1 with genteborane-9 at reaction conditions of temperature and pressure and recovering the liquid product thus formed.
2. A method according to clairrrl in which the alkyl diborane is arr ethyl diborane. t
3. A method accordirag to claim 1 in which the alkyl removed is the more volatile product; arid the liquid comprising a mixture of alkyl substituted higher boron hydrides is recovered as the less volatile product.
No references cited.
Claims (1)
1. A METHOD OF PREPARING A LIQUID HIGH ENERGY FUEL MIXTURE COMPRISING LOWER ALKYL SUBSTITUTED HIGHER BORON HYDRIDES CONTAINING 25 TO 55% BORON BY WEIGHT WHICH COMPRISES CONTACTING A LOWER ALKYL DIBORANE WITH PENTABORANE-9 AT REACTION CONDITIONS OF TEMPERATURE AND PRESSURE AND RECOVERING THE LIQUID PRODUCT THUS FORMED.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US569945A US2979530A (en) | 1956-03-06 | 1956-03-06 | Preparation of alkyl substituted boron hydrides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US569945A US2979530A (en) | 1956-03-06 | 1956-03-06 | Preparation of alkyl substituted boron hydrides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2979530A true US2979530A (en) | 1961-04-11 |
Family
ID=24277560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US569945A Expired - Lifetime US2979530A (en) | 1956-03-06 | 1956-03-06 | Preparation of alkyl substituted boron hydrides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2979530A (en) |
-
1956
- 1956-03-06 US US569945A patent/US2979530A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
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