US3013084A - Purification method for alkylboranes - Google Patents
Purification method for alkylboranes Download PDFInfo
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- US3013084A US3013084A US756055A US75605558A US3013084A US 3013084 A US3013084 A US 3013084A US 756055 A US756055 A US 756055A US 75605558 A US75605558 A US 75605558A US 3013084 A US3013084 A US 3013084A
- Authority
- US
- United States
- Prior art keywords
- pentaborane
- alkyl
- spontaneous ignition
- ignition temperature
- treatment
- 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
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- 238000000034 method Methods 0.000 title claims description 14
- 238000000746 purification Methods 0.000 title description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 aluminum halide Chemical class 0.000 description 17
- 230000002269 spontaneous effect Effects 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 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 Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Definitions
- This invention relates to the purification of alkyl pentaboranes and more particularly to a purification method whereby the spontaneous ignition temperature of these compounds is increased.
- Alkyl pentaboranes are relatively new compounds of boron in which one or more of the hydrogen atoms of pentaborane, B H are replaced with alkyl groups. They may be produced, for example, by the reaction of an alkyl halide or an alkene with pentaborane in the presence of an aluminum halide catalyst, as disclosed in the copending, coassigned application of Wunz and Stang, Serial No. 484,586, filed January 27, 1955, and now abandoned. Many of these compounds as they are obtained from such processes and purified by conventional techniques have a spontaneous ignition temperature, i.e., the temperature at which they ignite spontaneously in air, below ordinary ambient temperature. For these reasons handling of materials, particularly in large volumes, is hazardous and must be attended by extraordinary safety precautions.
- One object of this invention is to provide a method for increasing the spontaneous ignition temperature of alkyl pentaboranes.
- Another object is to provide a method for removing certain impurities from alkyl pentaboranes.
- alkyl pentaboranes which are purified by conventional methods contain certain trace impurities which may be removed by treatment with an active metal or metal oxide, and that such treatment raises the spontaneous ignition temperature of the alkyl pentaborane.
- the spontaneous ignition temperature is the minimum temperature of which a material will ignite spontaneously in air. This temperature may be determined experimentally by a static heated crucible method, such as that described by Setchkin, J. Res. Nat. Bur. Standards, 53, 149 (1954). The spontaneous ignition temperatures mentioned herein were measured by this method.
- alkyl pentaboranes are ordinarily purified by conventional methods such as fractional distillation.
- the product thus obtained is relatively pure and may be used in any desired manner.
- alkyl pentaboranes may be used as high-energy fuels in rocket engines, where they are combusted with conventional oxidizers such as liquid oxygen. It has been found, however, that there remain in the product so purified certain impurities in small or trace amounts.
- the nature of the impurities present depends upon the starting materials used in preparing the alkylpentaborane and the method of preparation. In general, these impurities are acidic or easily oxidized materials. For example, ethylpentaborane,
- C H B H prepared from pentaborane and ethyl bromide in the presonce of an aluminum chloride catalyst, has been found to contain small amounts of hydrogen bromide, hydrogen chloride, ethyl bromide, pentaborane and ethane. While the presence of these impurities in such quantities is not detrimental to ordinary uses of the alkyl pentaborane, their presence causes the alkyl pentaborane to exhibit a relatively low spontaneous ignition temperature thus increasing the hazards of handling and making it necessary to use complex and cumbersome storage apparatus. Treatment of the alkyl pentaborane with an active metal or an oxide of an active metal substantially increases the spontaneous ignition temperature, by removing or decreasing the amount of these acidic and easily oxidized minor impurities.
- the active metals and oxides which may be used in such treatment include iron, magnesium, calcium and aluminum and the oxides of these metals.
- magnesium appears to be the most effective, but the oxides in general seem to be more eflective than the metals.
- ferric oxide For example, when 11.2 grams of ethyl pentaborane having a spontaneous ignition temperature below 25 C. were heated to 50 C. in admixture with 2.5 grams of ferric oxide for one-half hour, the ethyl pentaborane recovered by distillation had a spontaneous ignition temperature of 108 C. Alumina raised the spontaneous ignition temperature from below 25 C. to C., but required treatment for several hours at 25 C. to do so.
- Other metals and oxides, such as magnesium and calcium oxide were generally somewhat less eifective, raising the spontaneous ignition temperature to about 40 C. under similar conditions.
- the conditions for the treatment are not critical. For example, it is not necessary to use elevated temperatures, although moderate heating, e.g., 50 C., may be used if desired in order to minimize the time of treatment. Similarly, the amount of metal or oxide used may be varied; as little at 0.05 gram per milliliter of alkyl pentaborane has been used with good results.
- the purification method described herein is particularly useful in the treatment of the lower-alkyl penta boranes, because these compounds when purified by conventional methods have a spontaneous ignition temperature at or about the range which may be encountered as the ambient temperature under various climatic conditions. Therefore, even a relatively small increase in the spontaneous ignition temperature is desirable since the danger of fire from accidental spilling and other handling is thereby decreased.
- ethyl pentaborane is ordinarily spontaneously inflammable at temperatures below 25 C., the ordinary room temperature, so that this method is especially adapted for treatment of this compound.
- a method of increasing the spontaneous ignition temperature of ethyl pentaborane which comprises contacting said ethyl pentaborane with ferric oxide.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Sttes 3,013,084 Patented Dec. 12, 1961 3,013,084 PURIFICATION METHOD FOR ALKYLBORANE dairies W. Shepherd, Mars, Pa., assignor to Gallery Chemical Company, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed Aug. 12, 1953, Ser. No. 756,055 8 Claims. (Cl. 260-606.5)
This invention relates to the purification of alkyl pentaboranes and more particularly to a purification method whereby the spontaneous ignition temperature of these compounds is increased.
Alkyl pentaboranes are relatively new compounds of boron in which one or more of the hydrogen atoms of pentaborane, B H are replaced with alkyl groups. They may be produced, for example, by the reaction of an alkyl halide or an alkene with pentaborane in the presence of an aluminum halide catalyst, as disclosed in the copending, coassigned application of Wunz and Stang, Serial No. 484,586, filed January 27, 1955, and now abandoned. Many of these compounds as they are obtained from such processes and purified by conventional techniques have a spontaneous ignition temperature, i.e., the temperature at which they ignite spontaneously in air, below ordinary ambient temperature. For these reasons handling of materials, particularly in large volumes, is hazardous and must be attended by extraordinary safety precautions.
One object of this invention, therefore, is to provide a method for increasing the spontaneous ignition temperature of alkyl pentaboranes.
Another object is to provide a method for removing certain impurities from alkyl pentaboranes.
Other objects will become apparent from the following specification and claims.
This invention is based upon the discovery that alkyl pentaboranes which are purified by conventional methods contain certain trace impurities which may be removed by treatment with an active metal or metal oxide, and that such treatment raises the spontaneous ignition temperature of the alkyl pentaborane.
The spontaneous ignition temperature is the minimum temperature of which a material will ignite spontaneously in air. This temperature may be determined experimentally by a static heated crucible method, such as that described by Setchkin, J. Res. Nat. Bur. Standards, 53, 149 (1954). The spontaneous ignition temperatures mentioned herein were measured by this method.
The alkyl pentaboranes are ordinarily purified by conventional methods such as fractional distillation. The product thus obtained is relatively pure and may be used in any desired manner. For example, alkyl pentaboranes may be used as high-energy fuels in rocket engines, where they are combusted with conventional oxidizers such as liquid oxygen. It has been found, however, that there remain in the product so purified certain impurities in small or trace amounts. The nature of the impurities present depends upon the starting materials used in preparing the alkylpentaborane and the method of preparation. In general, these impurities are acidic or easily oxidized materials. For example, ethylpentaborane,
C H B H prepared from pentaborane and ethyl bromide in the presonce of an aluminum chloride catalyst, has been found to contain small amounts of hydrogen bromide, hydrogen chloride, ethyl bromide, pentaborane and ethane. While the presence of these impurities in such quantities is not detrimental to ordinary uses of the alkyl pentaborane, their presence causes the alkyl pentaborane to exhibit a relatively low spontaneous ignition temperature thus increasing the hazards of handling and making it necessary to use complex and cumbersome storage apparatus. Treatment of the alkyl pentaborane with an active metal or an oxide of an active metal substantially increases the spontaneous ignition temperature, by removing or decreasing the amount of these acidic and easily oxidized minor impurities.
The active metals and oxides which may be used in such treatment include iron, magnesium, calcium and aluminum and the oxides of these metals. Of the metals, magnesium appears to be the most effective, but the oxides in general seem to be more eflective than the metals. The best results, i.e., greatest increase in spontaneous ignition temperature in a short time of-treatment, were obtained using ferric oxide. For example, when 11.2 grams of ethyl pentaborane having a spontaneous ignition temperature below 25 C. were heated to 50 C. in admixture with 2.5 grams of ferric oxide for one-half hour, the ethyl pentaborane recovered by distillation had a spontaneous ignition temperature of 108 C. Alumina raised the spontaneous ignition temperature from below 25 C. to C., but required treatment for several hours at 25 C. to do so. Other metals and oxides, such as magnesium and calcium oxide, were generally somewhat less eifective, raising the spontaneous ignition temperature to about 40 C. under similar conditions.
The conditions for the treatment are not critical. For example, it is not necessary to use elevated temperatures, although moderate heating, e.g., 50 C., may be used if desired in order to minimize the time of treatment. Similarly, the amount of metal or oxide used may be varied; as little at 0.05 gram per milliliter of alkyl pentaborane has been used with good results.
The purification method described herein is particularly useful in the treatment of the lower-alkyl penta boranes, because these compounds when purified by conventional methods have a spontaneous ignition temperature at or about the range which may be encountered as the ambient temperature under various climatic conditions. Therefore, even a relatively small increase in the spontaneous ignition temperature is desirable since the danger of fire from accidental spilling and other handling is thereby decreased. For example, ethyl pentaborane is ordinarily spontaneously inflammable at temperatures below 25 C., the ordinary room temperature, so that this method is especially adapted for treatment of this compound.
According to the provisions of the patent statutes, I have explained the principle and mode of practicing my invention, have described what I now consider to be its best embodiments. However, I desire to have it understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.
I claim:
1. In a method of purifying an alkyl pentaborane the step which comprises contacting said alkyl pentaborane with a member selected from the group consisting of iron, magnesium, calcium, aluminum, and their oxides.
2. The step according to claim 1 in which said alkyl pentaborane is a lower alkyl pentaborane.
3. The step according to claim 1 in which said alkyl pentaborane is ethyl pentaborane.
4. The step according to claim 1 in which said member is ferric oxide.
5. The step according to claim 1 in which said mem- 1 her is alumina.
6. The step according to claim 1 in which said member is magnesium.
7. The step according to claim 1 in which said member is calcium oxide.
8. A method of increasing the spontaneous ignition temperature of ethyl pentaborane which comprises contacting said ethyl pentaborane with ferric oxide.
No references cited.
Claims (1)
1. IN A METHOD OF PURIFYING AN ALKYL PENTABORANE THE STEP WHICH COMPRISES CONTACTING SAID ALKYL PENTABORANE WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF IRON, MAGNESIUM, CALCIUM, ALUMINUM, AND THEIR OXIDES.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US756055A US3013084A (en) | 1958-08-12 | 1958-08-12 | Purification method for alkylboranes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US756055A US3013084A (en) | 1958-08-12 | 1958-08-12 | Purification method for alkylboranes |
Publications (1)
Publication Number | Publication Date |
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US3013084A true US3013084A (en) | 1961-12-12 |
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Family Applications (1)
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US756055A Expired - Lifetime US3013084A (en) | 1958-08-12 | 1958-08-12 | Purification method for alkylboranes |
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1958
- 1958-08-12 US US756055A patent/US3013084A/en not_active Expired - Lifetime
Non-Patent Citations (1)
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