US3512932A - Coordination compounds containing trivalent phosphorus compounds and certain metal compounds - Google Patents
Coordination compounds containing trivalent phosphorus compounds and certain metal compounds Download PDFInfo
- Publication number
- US3512932A US3512932A US228009A US3512932DA US3512932A US 3512932 A US3512932 A US 3512932A US 228009 A US228009 A US 228009A US 3512932D A US3512932D A US 3512932DA US 3512932 A US3512932 A US 3512932A
- Authority
- US
- United States
- Prior art keywords
- phosphine
- compounds
- grams
- hydride
- borohydride
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 57
- 150000002736 metal compounds Chemical class 0.000 title 1
- 150000003018 phosphorus compounds Chemical class 0.000 title 1
- -1 PHOSPHORUS COMPOUND Chemical class 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052790 beryllium Inorganic materials 0.000 claims description 19
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 229910052987 metal hydride Inorganic materials 0.000 claims description 7
- 150000004681 metal hydrides Chemical class 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 72
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- 239000000446 fuel Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 239000003380 propellant Substances 0.000 description 18
- 239000007800 oxidant agent Substances 0.000 description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical group CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 150000004678 hydrides Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 5
- WDGZGTCKIDEJGN-UHFFFAOYSA-N P.[N+](=O)(O)[O-] Chemical compound P.[N+](=O)(O)[O-] WDGZGTCKIDEJGN-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- AYBCUKQQDUJLQN-UHFFFAOYSA-N hydridoberyllium Chemical group [H][Be] AYBCUKQQDUJLQN-UHFFFAOYSA-N 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 239000004449 solid propellant Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- BYRBYEZLJWXGTQ-UHFFFAOYSA-N ethene;phosphane Chemical compound P.C=C BYRBYEZLJWXGTQ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 230000001141 propulsive effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NYTOUQBROMCLBJ-UHFFFAOYSA-N Tetranitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O NYTOUQBROMCLBJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 229910012375 magnesium hydride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000004971 nitroalkyl group Chemical group 0.000 description 2
- LSNOMXWFVJKMLN-UHFFFAOYSA-N nitrophosphane Chemical class [O-][N+](P)=O LSNOMXWFVJKMLN-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-AKLPVKDBSA-N Ammonia-N17 Chemical compound [17NH3] QGZKDVFQNNGYKY-AKLPVKDBSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 description 1
- HYWKVFVQRGEFCH-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[PH6+3] Chemical class [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[PH6+3] HYWKVFVQRGEFCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- SOWHJXWFLFBSIK-UHFFFAOYSA-N aluminum beryllium Chemical compound [Be].[Al] SOWHJXWFLFBSIK-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZIOUHCMXEAFYSA-UHFFFAOYSA-N chlorodifluoroamine Chemical compound FN(F)Cl ZIOUHCMXEAFYSA-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- SCESWTHQFQXGMV-UHFFFAOYSA-N ethenylphosphane Chemical compound PC=C SCESWTHQFQXGMV-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 208000007106 menorrhagia Diseases 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 229910000127 oxygen difluoride Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
-
- 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
Definitions
- This invention relates to novel materials suitable for use astrocket propellants and jet fuels and as additives for use in these and allied fields. More particularly, the invention relates to solid and liquid rocket propellants; and liquid jet and internal combustion engine fuels and additives, and to methods for the preparation thereof.
- Illustrative of these compounds are the hydrides of boron, aluminum, beryllium, and the like.
- the principal disadvantages of these compounds have been their high cost and their difliculty in handling during manufacture,.transportation, storage, and use. These compounds have also evidenced a very marked hydrolytic and pyrolytic instability requiring the complete exclusion of even the smallest traces of water and atmospheric oxygen from their presence. Further, these compounds are highly toxic in nature.
- a significant advantage of the propellant compounds of the present invention is the reduction in maximum flame temperature achieved thereby without diminution or loss of impulse thrust when employed in jet and rocket engines. These compounds also provide, as indicated above, valuable additives for use in jet and internal combustion engrnes.
- the present invention involves the stabilization of metal hydrides and organometallic compounds by means of coordination between electron donor and electron acceptor molecules.
- the electron donor compounds comprise nitrogen and phosphorus containing compounds wherein the nitrogen and phosphorus moieties are in the trivalent state.
- the compounds of the invention are therefore coordination complexes formed by virtue of a suitable electron donor-electron acceptor relation found to exist between trivalent phosphorus and nitrogen donor compounds, e.g. phosphine, mono-, diand tri-aryl, alkyl and nitro phosphines, nitroalkyl, alkylene and alkenyl (e.g.
- phosphines nitrated derivatives of phosphines and alkyl phosphines, ammonia, mono-, diand tri-alkyl, aryl, alkenyl and nitroalkyl amines, alkyl alkylene imines, alkylene i imines (e.g., ethylene imine), polyamines, (e.g. alkylene diamines, such as ethylene diamine), hydrazine, monoand di-alkyl hydrazines (e.g. dimethyl hydrazine), aniline, alkenyl, alkyl and aryl nitriles (e.g. acrylonitrile), and. the electronacceptor compounds, that is, beryllium,
- alkyl, alkylene, and alkenyl as employed herein are intended preferably to en compass the corresponding lower hydrocarbons wherein the number of carbon atoms is from 1 to 6 and most desirably from 1 to 3.
- novel metal hydride coordination compounds of the invention may be represented by the formulae: M-(X) and Y-(Z) wherein M is beryllium hydride, BeH lithium hydride, LiH; magnesium hydride, Mgl-i aluminum hydride, AlH lithium-aluminum hydride, LiAlH beryllium borohydride, Be(BI-I lithium borohydride, LiBH aluminum borohydride, AI(BH or magnesium borohydride, Mg(BH.,) as well as aluminum beryllium hydride, lithium beryllium hydride, magnesium berylium hydride, sodium borohydride, potassium borohydride and calcium borohydride;
- X is an alkylene (e.g. ethylene) phosphine,
- n bowl Hz
- R is an
- Y is one of the aforesaid metal hydrides or metal borohydrides or organometallic compounds encompassed by M as recited above, or, in addition, may be a boron hydride or an alkyl derivative thereof containing within the range of 2 to 10 boron atoms, which boranes are encompassed by the formula, B,,R in which each of the R substituents present is a hydrogen atom or an alkyl radical; and when the latter
- each of the R substituents is a hydrogen atom or an alkyl radical, preferably a lower alkyl radical; a is an integer from 2 to 10 inclusive; and c is the integer 4 or 6.
- the expression, (1 to a) refers to the numerical value within the range of 1 to that of the integer symbolized by a as recited above; that is from 1 to 10 inclusive but not in excess of the value of a in any specific instance.
- borane is utilized herein to encompass compounds formed of a plurality of boron atoms (i.e. 2 to 10 in number), having attached thereto hydrogen and/ or alkyl substituents.
- Illustrative of the novel hydride coordination compounds of the invention are aluminum borohydride-phosphine, beryllium borohydride-phosphine, lithium borohydride-methyl phosphine, lithium aluminum hydride-phosphine, aluminum borohydride-dimethyl phosphine, lithium borohydride-phosphine, beryllium hydride-ethylene phosphine, lithium hydride-mono-(methyl nitrate) phosphine, magnesium hydride-di(methyl nitrate) phosphine, aluminum hydride-tri(nitromethyl) phosphine, magnesium borohydride-phosphine nitrate, lithium aluminum hydride-dinitrophosphine, lithium hydride-vinyl phosphine, beryllium borohydride-ethylene phosphine, diborane-vinyl phosphine, tetraborane-vinyl phosphine,
- borane-phosphines are pentaborane-diphosphine, B H (PH decaborane-diphosphine, B H (PH pentaborane-di (trimethylphosphine B H [P (CH decaborane-di(methylphosphine) B H [H PCH tetraborane-phosphine, B H -PH and tetraborane trimethylphosphine, B H -P(CH
- the propellant and fuel additive coordination compounds herein described are formed by admixture of a metal hydride as represented by the symbols M and Y in the above recited formulae with a phosphine encompassed by the symbols X and Z, respectively, of the aforesaid formulae.
- borane-phosphines encompassed by the formula, B R [PR' to is described in the copending application Ser. No. 47,943, filed by the inventors herein on Aug. 8, 1960, now abandoned.
- the procedure comprises reaction of boron hydrides or boranes as represented by the formula B,,R defined above, with a phosphine, PR having the value ascribed thereto hereinabove.
- the mole ratio of hydride to phosphine in the reaction mixtures is within the range of 1:1 to 1:2 respectively; and normally substantially equimolar proportions of hydride and phosphine are utilized.
- the mole ratio of reactants may be extended upward to 1:10, respectively.
- the reaction occurs preferably at a temperature within the range of -30 C. to 50., and takes place most desirably in the presence of a suitable organic solvent, and particularly alkyl ethers, furans, and aliphatic and aromatic hydrocarbon solvents, such as, for example, diethyl ether, tetrahydrofuran, toluene, xylene, isooctane, and the like.
- a suitable organic solvent and particularly alkyl ethers, furans, and aliphatic and aromatic hydrocarbon solvents, such as, for example, diethyl ether, tetrahydrofuran, toluene, xylene, isooctane, and the like.
- the final products, the coordination compounds, like the reactants are readily soluble in these solvents, and are indeed often incorporated in such media to facilitate handling when used particularly as additives for incorporation in internal combustion and jet propulsion engine fuels.
- jet-propulsion it should be noted, as employed throughout this
- the coordination complexes are either liquids, solids, or polymerizable liquids, as where organometallic, organophosphorus or organonitrogen compounds are utilized which contain a polymerizable bond (e.g. a double bond); for example, where the phosphine or nitrogen containing constituent is polymerizable vinyl or ethylene phosphine, ethylene imine or allyl amine, the polymerizable compounds being capable after coordination of reaction to form their own solid matrices when employed as propellant fuels; these solid fuels being formed at the lowest feasible ratio of carbon to metal hydride, thus resulting in fuels capable of releasing substantially more energy in comparison with the standard carbon polymer binder which is of lower energy content than the coordination compounds containing polymerizable bonds, as referred to above.
- the liquid and solid complexes can be incorporated desirably nevertheless in such standard polymer binders, e.g. a polymerized hydrocarbon, in the practice of the invention.
- the formulations of coordination compounds for use in jet or rocket fuel engines are therefore standard and assume a variety of forms. Thus, they may be varied to produce fuels which burn spontaneously when mixed with oxidizer; ignite upon injection into a hot chamber; undergo combustion upon being heated in the presence of a suitable oxidizer; or burn by means of ignition from an external source. Fuel burning rate, as well as the thrust generated, may be continuously varied under close control with the use of bipropellant and hybrid propellant forms. Monopropellant formulations can, of course, also be used effectively.
- the fuel composition includes a liquid coordination compound and oxidizer, each of which is maintained separately from the other prior to use.
- the hybrid propellant form may be used with solid coordination complexes in which case the fuel composition will include, prior to use, some oxidizer, but its firing rate is controlled by a separate liquid oxidizer stream.
- oxygen for example, may be introduced into the fuel disposed, in situ, within the combustion chamber and the mixture ignited from an external source. Liquid or solid fuel is simply combined with the oxidizer in the monopropellant formulation.
- the oxidizers empolyed are conventional within the field and include, as noted, liquid and atmospheric oxygen, ozone, tetranitromethane, nitrogen trifiuoride, chlorine, sodium nitrate, mixed oxides of nitrogen fluorine (gaseous), oxygen difluoride, nitrogen trifiuoride, nitrogen difluoride monochloride, nitrogen trichloride, phosphorus nitrates, fluorine, nitric acid, ammonium perchlorate and mixed oxychlorates and perchlorates, peroxides, e.g. hydrogen peroxide, and oxonides; these materials being particularly well adapted to use in hybrid and bipropellant compositions.
- Thiscombination of oxidizer and propellant is most desirably accomplished where monopropellant compositions are desired, however, by substitution on the carbon, nitrogen, or phosphorus elements of the fuels of the invention, e.g. in the phosphine and/ or hydride moiety of the propellant coordination compound, of nitrate substituents and preferably methyl nitrate for hydrogen or hydrocarbyl substituents; the methyl nitrate thus providing the necessary oxidizer to cause combustion and substantially complete oxidation of the coordinatioucomplex andparticularly the metallic portion thereof without the use of an external oxidizer, with consequent substantially complete utiliziation of the energy of the coordination complex and the metallic moiety thereof.
- a liquid oxidizer for example, nitric acid, could be metered into the combustion chamber to initiate and continue combustion and maintenance of a controlled firing rate.
- the fuels thus formed have been found to exhibit, as noted above, properties which obviate the deficiencies of their individual components (e.g. phosphine and a hydride) while retaining their advantages.
- these compounds are found to be stable both to spontaneous pyrolysis and, hydrolysis, relatively non-toxic due to a reduced vapor pressure and capable of storage for prolongedperiods in the presence of atmospheric oxygen and moisture without visible deterioration.
- the chemical stability of theseicompounds is retained at temperatures well above those normally encountered in storage, handling and processing; nor will they dissociate due to shock or the like.
- the complexes herein described and prepared are manifestly less expensive to produce over the boron-based fuels now receiving wide commercial application.
- these compounds constitute fuels which adhere under conditions of use, such as, for example, in combination with suitable oxidizers if desired, heats of combustion within the range of 6000 to 7000 British thermal units (B.t.u.) per pound thereof.
- Illustrative of the combinations of propellant and oxidizer compositions within the purview of the present invention are beryllium borohydride-phosphine and ammonium perchlorate; lithium aluminum hydride-hydrazine and fuming. nitric acid; diborane-vinyl phosphine and liquid oxygen; magnesium hydride-dimethyl amine and tetranitromethane; aluminum borohydride-dimethyl hydrazine and gaseous fluorine; and aluminum hydrideethylehe imine .and hydrogen peroxide.
- a propellant compound such as diborane-tri (nitromethyl)phosphine oxidizes well in the absence of any additional oxidizer.
- EXAMPLE 1 Preparation of beryllium borohydride-phosphine complex To .a solution of 3.87 grams (0.1 mole) of beryllium borohydride dissolved in 100 grams of tetrahydrofuran at 25 C. is passed phosphine gas (generated from Al-P and water) until absorption is complete. The solvent, tetrahydrofuran, is easily removed by distillation at 50 C. and 30 mm. Hg absolute pressure, leaving the phosphineberyllium borohydride coordination compound which is stable in moist air and is suitable for use as a component of a rocket propellant or a jet engine fuel.
- phosphine gas generated from Al-P and water
- EXAMPLE 4 Preparation of diborane-vinyl phosphine complex
- EXAMPLE 5 Preparation of magnesium borohydride-ethylene phosphine complex Following the procedure of Examples 1 and 4, to a solution of 5.40 grams (0.1 mole) of magnesium borohydride in 100 grams of tetrahydrofuran is added 6.00 grams (0.1 mole) of ethylene phosphine.
- the product, magnesium borohydride-ethylene phosphine complex may be polymerized with traces of acid to form stable polymers which, with other components and an oxidizer, may be used as a solid rocket propellant.
- EXAMPLE 6 Preparation of beryllium hydride-dihydrogen phosphine nitrate complex To a solution of 9.50 grams (0.1 mole) of dihydrogen phosphine nitrate in 100 grams of tetrahydrofuran at -10 C. is added 1.1 grams of beryllium hydride (0.1 mole). The complex, beryllium hydride-dihydrogen phosphine nitrate, remaining after removal of the solvent under vacuum is a suitable component of a liquid or solid fuel in which a part of the oxidizer is furnished by the complex.
- EXAMPLE 7 Preparation of aluminum hydride-tri(methylene nitrate) phosphine complex To a solution of 3.00 grams (0.1 mole) of aluminum hydride polymer dissolved in 100 grams of diethyl ether is added 25.91 grams (0.1 mole) tri(methylene nitrate) phosphine at 25 C. The solvent is removed by vacuum distillation leaving the stable aluminum hydride-tri- (methyl nitrate) phosphine complex which may be utilized in a solid rocket propellant formulation in which a part of the oxidizer is contained in the complex.
- EXAMPLE 10 Preparation of aluminum borohydride-unsym. dimethylhydrazine complex
- Preparation of aluminum borohydride-monomethyl amine complex To a solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200 grams of tetrahydrofuran, there is added 3.1 grams of monomethyl amine at C. The mixture is permitted to warm to room temperature and is maintained at 26 C. for 72 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to result in a substantially quantitative yield of aluminum borohydride-monomethyl amine.
- EXAMPLE 12 Preparation of aluminum borohydride-ethylene imine complex To a solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200 grams of tetrahydrofuran, there is added 4.3 grams of ethylene imine at 20 C. The mixture is permitted to warm to room temperature and is maintained at 26 C. for 72 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to result in a substantially quantitative yield of aluminum borohydride-ethylene imine.
- EXAMPLE 14 Preparation of pentaborane-ethylene imine complex In a similar manner, to a solution of 6.4 grams of pentaborane B H dissolved in 200 grams of tetrahydrofuran, there is added 4.3 grams of ethylene imine. The product secured in substantially quantitative yield is pentaborane-ethylene imine.
- EXAMPLE 20 Preparation of aluminum hydride-ethylene imine complex In a similar manner to that described in the foregoing examples, there is prepared, employing aluminum hydride and ethylene imine as the reactants, the coordination compound, aluminum hydride-ethylene imine.
- a coordination compound composed of a trivalent phosphorus compound as an electron donor compound and an electron acceptor compound selected from the group consisting of a metal hydride and a corresponding borohydride and organo metallic constituent of said metal wherein the metal is selected from the group consisting of beryllium, lithium, magnesium, sodium, calcium, aluminum and potassium.
- the coordination compound beryllium borohydridephosphine.
- the coordination compound beryllium hydride-di hydrogen phosphine nitrate.
- the coordination compound lithium aluminum hydride-hydrazine.
- the coordination compound aluminum dride-monomethyl amine.
- the coordination compound aluminum dride-ethylene imine.
- the coordination compound tetraborane-monovinyl amine.
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Description
United States Patent Int. Cl. c01 1/00 ULS. (:1. 23-190 21 Claims This application is a continuation-in-part of application Ser. No. 47,904, filed Aug. '8, 1960, now abandoned.
This invention relates to novel materials suitable for use astrocket propellants and jet fuels and as additives for use in these and allied fields. More particularly, the invention relates to solid and liquid rocket propellants; and liquid jet and internal combustion engine fuels and additives, and to methods for the preparation thereof.
While propellant fuels employed heretofore have produced an effective propulsive force when employed in jet and rocket engines, many compounds known to be capable of releasing significantly greater amounts of energy per unit and thus capable of effecting markedly enhanced propulsion when employed as fuels, have failed of general acceptance due to certain difiiculties inherent therein. Illustrative of these compounds are the hydrides of boron, aluminum, beryllium, and the like. The principal disadvantages of these compounds have been their high cost and their difliculty in handling during manufacture,.transportation, storage, and use. These compounds have also evidenced a very marked hydrolytic and pyrolytic instability requiring the complete exclusion of even the smallest traces of water and atmospheric oxygen from their presence. Further, these compounds are highly toxic in nature.
We have now discovered, however, compounds which are capable of effecting a propulsive force in rocket and jet engines approximately equivalent to that of the hydridesabove referred to while avoiding substantially the difficulties inherent therein and alluded to above. A significant advantage of the propellant compounds of the present invention is the reduction in maximum flame temperature achieved thereby without diminution or loss of impulse thrust when employed in jet and rocket engines. These compounds also provide, as indicated above, valuable additives for use in jet and internal combustion engrnes.
Thus, the present invention involves the stabilization of metal hydrides and organometallic compounds by means of coordination between electron donor and electron acceptor molecules. For the preparation of high energy fuels by the practice described herein, the electron donor compounds comprise nitrogen and phosphorus containing compounds wherein the nitrogen and phosphorus moieties are in the trivalent state. Accordingly, and more elaborately, the compounds of the invention are therefore coordination complexes formed by virtue of a suitable electron donor-electron acceptor relation found to exist between trivalent phosphorus and nitrogen donor compounds, e.g. phosphine, mono-, diand tri-aryl, alkyl and nitro phosphines, nitroalkyl, alkylene and alkenyl (e.g. vinyl) phosphines, nitrated derivatives of phosphines and alkyl phosphines, ammonia, mono-, diand tri-alkyl, aryl, alkenyl and nitroalkyl amines, alkyl alkylene imines, alkylene i imines (e.g., ethylene imine), polyamines, (e.g. alkylene diamines, such as ethylene diamine), hydrazine, monoand di-alkyl hydrazines (e.g. dimethyl hydrazine), aniline, alkenyl, alkyl and aryl nitriles (e.g. acrylonitrile), and. the electronacceptor compounds, that is, beryllium,
3,512,932 Patented May 19, 1970 ice lithium, magnesium, sodium, calcium, aluminum, potassium, silicon and boron hydrides, and the corresponding borohydrides and alkyl organometallic compounds of the aforesaid metals. These coordination complexes thus provide that compounds capable of high energy release upon combustion, which were, however, unsuitable for use as propulsion agents in rockets or jet engines hitherto because of their hydrolytic and/ or pyrolytic instability, are now made sufficiently stable to permit the use of conventional handling techniques in manufacture, transportation, storage, use, and the like, thus permitting their employment as propulsive agents in high energy fuels.
It is noted that the terms alkyl, alkylene, and alkenyl as employed herein are intended preferably to en compass the corresponding lower hydrocarbons wherein the number of carbon atoms is from 1 to 6 and most desirably from 1 to 3.
Thus, the novel metal hydride coordination compounds of the invention may be represented by the formulae: M-(X) and Y-(Z) wherein M is beryllium hydride, BeH lithium hydride, LiH; magnesium hydride, Mgl-i aluminum hydride, AlH lithium-aluminum hydride, LiAlH beryllium borohydride, Be(BI-I lithium borohydride, LiBH aluminum borohydride, AI(BH or magnesium borohydride, Mg(BH.,) as well as aluminum beryllium hydride, lithium beryllium hydride, magnesium berylium hydride, sodium borohydride, potassium borohydride and calcium borohydride; X is an alkylene (e.g. ethylene) phosphine,
n bowl: Hz
alkenyl (e.g. vinyl) phosphine, H PCH =CH an alkyl nitrate phosphine, such as methyl nitrate phosphine where in the methyl nitrate substituents are within the range of 1 to 3; thus, mono-(methyl nitrate)-phosphine, H PCH NO di(methyl nitrate) phosphine, HP- CH NO tri- (nitro-methyl) phosphine, P [CH (NO tri(methyl nitrate) phosphine, P(CH NO a phosphine nitrate, or a monoor di-nitro substituted phosphine, i.e., H PNO HP(NO phosphine, PH a mono-dior tri-alkyl or aryl phosphine, PR wherein R is an alkyl, aryl or nitro-substituted alkyl; ammonia, NH a. mono-, dior tri-alkyl, nitro alkyl or aryl amine, NH R(3 wherein R retains the same value as recited above; as well as an alkylene imine, alkyl alkylene imine, polyamine (e.g., hexamethylenetetramine, an alkylene diamine such as ethylene diamine), hydrazine, monoor di-alkyl hydrazine, aniline, or an alkenyl, alkyl or aryl nitrile; Y is one of the aforesaid metal hydrides or metal borohydrides or organometallic compounds encompassed by M as recited above, or, in addition, may be a boron hydride or an alkyl derivative thereof containing within the range of 2 to 10 boron atoms, which boranes are encompassed by the formula, B,,R in which each of the R substituents present is a hydrogen atom or an alkyl radical; and when the latter preferably a lower alkyl radical; a.g., diborane, B H tetraborane, B H pentaborane, B H or decaborane, B H Z is phosphine; ethylene phosphine, vinyl phosphine, a methyl nitrate phosphine wherein the methyl nitrate substituents at tached to the phosphorus nucleus are within the range of l to 3; a phosphine nitrate; or a nitrophosphine again, most desirably, a monoor di-nitro substituted phosphine, as defined above; ammonia, an alkyl amine, an alkyl alkylene amine, an alkylene imine, polyamine, hydrazine, dialkyl hydrazine, aniline or an alkenyl, alkyl or aryl nitrile; b is an integer from 1 to 2 inclusive; n is an integer within the range of 1 to 10, and c is either 4 or 6. Other suitable electron acceptor compounds for use herein include the silicon hydrides. Each nitro-alkyl substituent where present contains preferably 1 to 2 nitro groups.
Other coordination compounds, which provide valuable propellants and fuel additives for use in accordance with the invention, are included among the borane-phosphines described in copending application Ser. No. 47,943 filed by the inventors herein on Aug. 8, 1960, now abandoned. Of these the borane-phosphines for use herein may be represented by the general formula:
wherein each of the R substituents is a hydrogen atom or an alkyl radical, preferably a lower alkyl radical; a is an integer from 2 to 10 inclusive; and c is the integer 4 or 6. The expression, (1 to a), refers to the numerical value within the range of 1 to that of the integer symbolized by a as recited above; that is from 1 to 10 inclusive but not in excess of the value of a in any specific instance.
The term borane is utilized herein to encompass compounds formed of a plurality of boron atoms (i.e. 2 to 10 in number), having attached thereto hydrogen and/ or alkyl substituents.
Illustrative of the novel hydride coordination compounds of the invention are aluminum borohydride-phosphine, beryllium borohydride-phosphine, lithium borohydride-methyl phosphine, lithium aluminum hydride-phosphine, aluminum borohydride-dimethyl phosphine, lithium borohydride-phosphine, beryllium hydride-ethylene phosphine, lithium hydride-mono-(methyl nitrate) phosphine, magnesium hydride-di(methyl nitrate) phosphine, aluminum hydride-tri(nitromethyl) phosphine, magnesium borohydride-phosphine nitrate, lithium aluminum hydride-dinitrophosphine, lithium hydride-vinyl phosphine, beryllium borohydride-ethylene phosphine, diborane-vinyl phosphine, tetraborane-vinyl phosphine, tetraborane-ethylene phosphine, tetraborane-di(methylnitrate) phosphine, tetraborane-phosphine nitrate, tetraborane-dinitrophosphine, pentaborane-ethylene phosphine, decaborane-di- (methyl nitrate) phosphine, pentaborane-dinitrophosphine, lithium aluminum hydride-dimethyl amine, lithium aluminum hydride-hydrazine, aluminum borohydride-diethyl hydrazine, aluminum borohydride-monomethyl amine, aluminum borohydride-ethylene imine, aluminum borohydridehydrazine, pentaborane-ethylene imine, tetraborane-monovinyl amine, diborane-polymerized ethylene amine, and beryllium borohydride-ammonia.
Illustrative of the borane-phosphines are pentaborane-diphosphine, B H (PH decaborane-diphosphine, B H (PH pentaborane-di (trimethylphosphine B H [P (CH decaborane-di(methylphosphine) B H [H PCH tetraborane-phosphine, B H -PH and tetraborane trimethylphosphine, B H -P(CH The propellant and fuel additive coordination compounds herein described are formed by admixture of a metal hydride as represented by the symbols M and Y in the above recited formulae with a phosphine encompassed by the symbols X and Z, respectively, of the aforesaid formulae. The preparation of borane-phosphines encompassed by the formula, B R [PR' to is described in the copending application Ser. No. 47,943, filed by the inventors herein on Aug. 8, 1960, now abandoned. In general, the procedure comprises reaction of boron hydrides or boranes as represented by the formula B,,R defined above, with a phosphine, PR having the value ascribed thereto hereinabove. The mole ratio of hydride to phosphine in the reaction mixtures is within the range of 1:1 to 1:2 respectively; and normally substantially equimolar proportions of hydride and phosphine are utilized. The mole ratio of reactants, however, may be extended upward to 1:10, respectively. The reaction occurs preferably at a temperature within the range of -30 C. to 50., and takes place most desirably in the presence of a suitable organic solvent, and particularly alkyl ethers, furans, and aliphatic and aromatic hydrocarbon solvents, such as, for example, diethyl ether, tetrahydrofuran, toluene, xylene, isooctane, and the like. The final products, the coordination compounds, like the reactants, are readily soluble in these solvents, and are indeed often incorporated in such media to facilitate handling when used particularly as additives for incorporation in internal combustion and jet propulsion engine fuels. The term jet-propulsion, it should be noted, as employed throughout this specification and unless otherwise indicated, is intended to encompass rocket as well as jetpropulsion.
The coordination complexes are either liquids, solids, or polymerizable liquids, as where organometallic, organophosphorus or organonitrogen compounds are utilized which contain a polymerizable bond (e.g. a double bond); for example, where the phosphine or nitrogen containing constituent is polymerizable vinyl or ethylene phosphine, ethylene imine or allyl amine, the polymerizable compounds being capable after coordination of reaction to form their own solid matrices when employed as propellant fuels; these solid fuels being formed at the lowest feasible ratio of carbon to metal hydride, thus resulting in fuels capable of releasing substantially more energy in comparison with the standard carbon polymer binder which is of lower energy content than the coordination compounds containing polymerizable bonds, as referred to above. The liquid and solid complexes can be incorporated desirably nevertheless in such standard polymer binders, e.g. a polymerized hydrocarbon, in the practice of the invention.
The formulations of coordination compounds for use in jet or rocket fuel engines are therefore standard and assume a variety of forms. Thus, they may be varied to produce fuels which burn spontaneously when mixed with oxidizer; ignite upon injection into a hot chamber; undergo combustion upon being heated in the presence of a suitable oxidizer; or burn by means of ignition from an external source. Fuel burning rate, as well as the thrust generated, may be continuously varied under close control with the use of bipropellant and hybrid propellant forms. Monopropellant formulations can, of course, also be used effectively. In the bipropellant form, the fuel composition includes a liquid coordination compound and oxidizer, each of which is maintained separately from the other prior to use. The hybrid propellant form may be used with solid coordination complexes in which case the fuel composition will include, prior to use, some oxidizer, but its firing rate is controlled by a separate liquid oxidizer stream. By way of illustrating the foregoing methods, oxygen, for example, may be introduced into the fuel disposed, in situ, within the combustion chamber and the mixture ignited from an external source. Liquid or solid fuel is simply combined with the oxidizer in the monopropellant formulation. The oxidizers empolyed are conventional within the field and include, as noted, liquid and atmospheric oxygen, ozone, tetranitromethane, nitrogen trifiuoride, chlorine, sodium nitrate, mixed oxides of nitrogen fluorine (gaseous), oxygen difluoride, nitrogen trifiuoride, nitrogen difluoride monochloride, nitrogen trichloride, phosphorus nitrates, fluorine, nitric acid, ammonium perchlorate and mixed oxychlorates and perchlorates, peroxides, e.g. hydrogen peroxide, and oxonides; these materials being particularly well adapted to use in hybrid and bipropellant compositions. The mode of employment of the fuels of applicants is also conventional which is, indeed, one of the significant advantages residing in the present invention, as indicated above. Thus, if desired, they may be employed, for example, in the manner described in US. Pats. 2,777,739 and 2,896,403.
One of the principal difficulties known to exist in the use of metal-based fuels known heretofore is the relatively slow rate at which the metallic elements oxidize in these standard fuel formulations. This has resulted in much of such fuels leaving the combustion chamber or area unburned, thus greatly reducing their utility and value. By the use of internal oxidizers in the monopropellant formulations proposed herein, the oxidation or buming rate of the metals can be controlled to give the desired combustion and the need for external oxidizer is substantially eliminated.
Thiscombination of oxidizer and propellant is most desirably accomplished where monopropellant compositions are desired, however, by substitution on the carbon, nitrogen, or phosphorus elements of the fuels of the invention, e.g. in the phosphine and/ or hydride moiety of the propellant coordination compound, of nitrate substituents and preferably methyl nitrate for hydrogen or hydrocarbyl substituents; the methyl nitrate thus providing the necessary oxidizer to cause combustion and substantially complete oxidation of the coordinatioucomplex andparticularly the metallic portion thereof without the use of an external oxidizer, with consequent substantially complete utiliziation of the energy of the coordination complex and the metallic moiety thereof.
If a portion of the required oxidizer is included in the formulation of the solid fuel complex and is insufficient to maintain combustion, then a liquid oxidizer, for example, nitric acid, could be metered into the combustion chamber to initiate and continue combustion and maintenance of a controlled firing rate.
The fuels thus formed have been found to exhibit, as noted above, properties which obviate the deficiencies of their individual components (e.g. phosphine and a hydride) while retaining their advantages. Thus, stored orprocessed according to standard procedures, these compounds are found to be stable both to spontaneous pyrolysis and, hydrolysis, relatively non-toxic due to a reduced vapor pressure and capable of storage for prolongedperiods in the presence of atmospheric oxygen and moisture without visible deterioration. The chemical stability of theseicompounds is retained at temperatures well above those normally encountered in storage, handling and processing; nor will they dissociate due to shock or the like.
Ini addition, the complexes herein described and prepared are manifestly less expensive to produce over the boron-based fuels now receiving wide commercial application. At the same time, however, these compounds constitute fuels which adhere under conditions of use, such as, for example, in combination with suitable oxidizers if desired, heats of combustion within the range of 6000 to 7000 British thermal units (B.t.u.) per pound thereof.
Illustrative of the combinations of propellant and oxidizer compositions within the purview of the present invention are beryllium borohydride-phosphine and ammonium perchlorate; lithium aluminum hydride-hydrazine and fuming. nitric acid; diborane-vinyl phosphine and liquid oxygen; magnesium hydride-dimethyl amine and tetranitromethane; aluminum borohydride-dimethyl hydrazine and gaseous fluorine; and aluminum hydrideethylehe imine .and hydrogen peroxide. As indicated above, a propellant compound such as diborane-tri (nitromethyl)phosphine oxidizes well in the absence of any additional oxidizer. As also indicated above, the production of energy in the form of thrust, heat and/or light by oxidation of these compositions as well as the others described herein is eftected in a standard manner and in any suitable and standard combustion chamber or area of an engine adapted for jet and rocket propulsion.
The following examples are further illustrative of the invention.
EXAMPLE 1 Preparation of beryllium borohydride-phosphine complex To .a solution of 3.87 grams (0.1 mole) of beryllium borohydride dissolved in 100 grams of tetrahydrofuran at 25 C. is passed phosphine gas (generated from Al-P and water) until absorption is complete. The solvent, tetrahydrofuran, is easily removed by distillation at 50 C. and 30 mm. Hg absolute pressure, leaving the phosphineberyllium borohydride coordination compound which is stable in moist air and is suitable for use as a component of a rocket propellant or a jet engine fuel.
EXAMPLE 2 Preparation of pentaborane-phosphine complex Following the procedure of Example 1, to 6.41 grams (0.1 mole) of pentaborane dissolved in grams of tetrahydrofuran is added phosphine gas until absorption at 25 C. is complete. After distilling off the solvent under vacuum, a stable coordination compound, pentaboranephosphine, remains which is a suitable component of a jet engine fuel or rocket propellant.
EXAMPLE 3 Preparation of lithium aluminum hydridephosphine complex Following the procedure of Example 1, phosphine gas is passed into a solution of 3.80 grams (0.1 mole) of lithium aluminum hydride in tetrahydrofuran until one mole (3.4 grams) of phosphine has been absorbed. The product, after solvent removal, is the lithium aluminum hydride-phosphine complex which is stable in moist air, and is suitable for use as a component of a jet engine fuel, or rocket propellant.
EXAMPLE 4 Preparation of diborane-vinyl phosphine complex EXAMPLE 5 Preparation of magnesium borohydride-ethylene phosphine complex Following the procedure of Examples 1 and 4, to a solution of 5.40 grams (0.1 mole) of magnesium borohydride in 100 grams of tetrahydrofuran is added 6.00 grams (0.1 mole) of ethylene phosphine. The product, magnesium borohydride-ethylene phosphine complex may be polymerized with traces of acid to form stable polymers which, with other components and an oxidizer, may be used as a solid rocket propellant.
EXAMPLE 6 Preparation of beryllium hydride-dihydrogen phosphine nitrate complex To a solution of 9.50 grams (0.1 mole) of dihydrogen phosphine nitrate in 100 grams of tetrahydrofuran at -10 C. is added 1.1 grams of beryllium hydride (0.1 mole). The complex, beryllium hydride-dihydrogen phosphine nitrate, remaining after removal of the solvent under vacuum is a suitable component of a liquid or solid fuel in which a part of the oxidizer is furnished by the complex.
EXAMPLE 7 Preparation of aluminum hydride-tri(methylene nitrate) phosphine complex To a solution of 3.00 grams (0.1 mole) of aluminum hydride polymer dissolved in 100 grams of diethyl ether is added 25.91 grams (0.1 mole) tri(methylene nitrate) phosphine at 25 C. The solvent is removed by vacuum distillation leaving the stable aluminum hydride-tri- (methyl nitrate) phosphine complex which may be utilized in a solid rocket propellant formulation in which a part of the oxidizer is contained in the complex.
EXAMPLE 8 Preparation of lithium aluminum hydride-dimethyl amine complex To a solution of lithium aluminum hydride (LiAlH (3.8 grams, 0.1 mole) dissolved in 200 grams of tetrahydrofuran at 30 C., is added 4.5 grams (0.1 mole) of dimethyl amine. The mixture is allowed to warm to room temperature and is maintained at 26 C. for 96 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to yield lithium aluminum hydridedimethyl amine which evidences upon elemental analysis:
Element Found Theory Lithium 8. 27 8. 40 Aluminum 32. 91 32. 6 Carbon 28. 23 28. 9 Nitrogen 17. 16. 9
EXAMPLE 9 Preparation of lithium aluminum hydride-hydrazine complex To a solution of lithium aluminum hydride (3.8 grams) dissolved in 200 grams of tetrahydrofuran, there is added, at 30 C., 3.2 grams of hydrazine. The mixture is permitted to warm to room temperature and is maintained at 26 C. for 96 hours, after which time the solvent is removed in vacuo to yield lithium aluminum hydridehydrazine in a substantially quantitative yield.
EXAMPLE 10 Preparation of aluminum borohydride-unsym. dimethylhydrazine complex Preparation of aluminum borohydride-monomethyl amine complex To a solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200 grams of tetrahydrofuran, there is added 3.1 grams of monomethyl amine at C. The mixture is permitted to warm to room temperature and is maintained at 26 C. for 72 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to result in a substantially quantitative yield of aluminum borohydride-monomethyl amine.
EXAMPLE 12 Preparation of aluminum borohydride-ethylene imine complex To a solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200 grams of tetrahydrofuran, there is added 4.3 grams of ethylene imine at 20 C. The mixture is permitted to warm to room temperature and is maintained at 26 C. for 72 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to result in a substantially quantitative yield of aluminum borohydride-ethylene imine.
EXAMPLE 13 Preparation of aluminum borohydride-hydrazine complex To a solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200 grams of tetrahydrofuran, there is added 3.2 grams of hydrazine at 30 C. The
mixture is permitted to warm to room temperature and is maintained at 26 C. for 72 hours, after which time the solvent, tetrahydrofuran, is removed in vacuo to result in a substantially quantitative yield of aluminum borohydride-hydrazine.
EXAMPLE 14 Preparation of pentaborane-ethylene imine complex In a similar manner, to a solution of 6.4 grams of pentaborane B H dissolved in 200 grams of tetrahydrofuran, there is added 4.3 grams of ethylene imine. The product secured in substantially quantitative yield is pentaborane-ethylene imine.
EXAMPLE 15 Preparation of tetraborane-monovinyl amine complex In a similar manner, to a solution of 5.4 grams of tetraborane, B H dissolved in 200 grams of tetrahydrofuran, there is added 4.3 grams of monovinyl amine. The product secured in substantially quantitative yield is tetraborane-monovinyl amine.
EXAMPLE 16 Preparation of diborane-ethylene diamine complex In a similar manner, to a solution of 2.8 grams of diborane, B H dissolved in 200 grams of tetrahydrofuran, there is added 6.0 grams of ethylene diamine. The prod not secured in substantially quantitative yield is diboraneethylene diamine.
EXAMPLE 17 Preparation of beryllium borohydride-acrylonitrile complex In a similar manner, to a solution of 3.9 grams of beryllium borohydride, Be(BH dissolved in 200 grams of tetrahydrofuran, there is added 5.3 grams of acrylonitrile. The product secured in substantially quantitative yield is beryllium borohydride-acrylonitrile.
EXAMPLE 18 Preparation of magnesium hydride-din1ethylamine complex In a similar manner, to a solution of 2.63 grams of magnesium hydride, MgH dissolved in 200 grams of tetrahydrofuran, there is added 4.5 grams of dimethyl amine. The product secured in substantially quantitative yield is magnesium hydride-dimethyl amine.
EXAMPLE 19 Preparation of diborane-tri(nitromethyl) phosphine complex In a similar manner, employing diborane and tri(nitromethyl) phosphine, there is prepared the coordination compound, diborane-tri(nitromethyl)phosphine.
EXAMPLE 20 Preparation of aluminum hydride-ethylene imine complex In a similar manner to that described in the foregoing examples, there is prepared, employing aluminum hydride and ethylene imine as the reactants, the coordination compound, aluminum hydride-ethylene imine.
What is claimed is:
1. A coordination compound composed of a trivalent phosphorus compound as an electron donor compound and an electron acceptor compound selected from the group consisting of a metal hydride and a corresponding borohydride and organo metallic constituent of said metal wherein the metal is selected from the group consisting of beryllium, lithium, magnesium, sodium, calcium, aluminum and potassium.
2. The coordination compound beryllium borohydridephosphine.
3. The coordination compound lithium aluminum hydride-phosphine.
4. The coordination compound diborane-vinyl phosphine.
5. The coordination compound magnesium borohydride-ethylene phosphine.
6. The coordination compound beryllium hydride-di hydrogen phosphine nitrate.
7. The coordination compound aluminum hydride-tri (methylene nitrate) phosphine.
8.1'The coordination compound lithium aluminum hydride-dimethyl amine.
9. The coordination compound lithium aluminum hydride-hydrazine.
10. The coordination compound aluminum dride-dimethylhydrazine.
11. The coordination compound aluminum dride-monomethyl amine.
12. The coordination compound aluminum dride-ethylene imine.
13. Theqcoordination compound aluminum dride-hydrazine.
14. The coordination compound pentaborane-ethylene mine.
15. The coordination compound tetraborane-monovinyl amine.
16.; The coordination compound diborane-ethylene diamine.
borohyborohyborohyborohy- References Cited UNITED STATES PATENTS 9/1967 Hogsett et al. 149-22 XR 5/1964 Knight 149-36 XR OTHER REFERENCES Ramsey et al.: Nature, vol. 190, May 6, 1961, pp. 528 and 529.
Chatt et al.: J. Chem. Soc. (London), 1959, pp. 4021 and 4026 to 4031.
LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R.
Claims (2)
1. A COORDINATION COMPOUND COMPOSED OF A TRIVALENT PHOSPHORUS COMPOUND AS AN ELECTRON DONOR COMPOUND AND AN ELECTRON ACCEPTOR COMPOUND SELECTED FROM THE GROUP CONSISTING OF A METAL HYDRIDE AND A CORRESPONDING BOROHYDRIDE AND ORGANO METALLIC CONSTITUENT OF SAID METAL WHEREIN THE METAL IS SELECTED FROM THE GROUP CONSISTING OF BERYLLIUM, LITHIUM, MAGNESIUM, SODIUM, CALCIUM, ALUMINUM AND POTASSIUM.
9. THE COORDINATION COMPOUND LITHIUM ALUMINUM HYDRIDE-HYDRAZINE.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3791847A (en) * | 1970-07-27 | 1974-02-12 | Kureha Chemical Ind Co Ltd | Process for the production of incombustible carbonaceous material |
US3912832A (en) * | 1971-07-26 | 1975-10-14 | Toyo Boseki | Oxidation resistant coated carbon articles |
US3920494A (en) * | 1972-09-25 | 1975-11-18 | Us Navy | Propellant pressure burning rate slope modification |
US4532120A (en) * | 1983-12-28 | 1985-07-30 | Ethyl Corporation | Silane purification process |
US6039819A (en) * | 1982-03-04 | 2000-03-21 | Atlantic Research Corporation | Solid propellant containing ferrocenyl phosphine derivatives |
US20180245543A1 (en) * | 2017-02-28 | 2018-08-30 | Alpha Space Test and Research Alliance, LLC | Multi-Stage Solid Rocket Motor |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3132977A (en) * | 1948-10-04 | 1964-05-12 | Aerojet General Co | Hydrazine base fuel |
US3342814A (en) * | 1962-01-15 | 1967-09-19 | Union Carbide Corp | Adducts of metal borohydrides and organic polynitrogen compounds |
-
1962
- 1962-10-03 US US228009A patent/US3512932A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3132977A (en) * | 1948-10-04 | 1964-05-12 | Aerojet General Co | Hydrazine base fuel |
US3342814A (en) * | 1962-01-15 | 1967-09-19 | Union Carbide Corp | Adducts of metal borohydrides and organic polynitrogen compounds |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3791847A (en) * | 1970-07-27 | 1974-02-12 | Kureha Chemical Ind Co Ltd | Process for the production of incombustible carbonaceous material |
US3912832A (en) * | 1971-07-26 | 1975-10-14 | Toyo Boseki | Oxidation resistant coated carbon articles |
US3920494A (en) * | 1972-09-25 | 1975-11-18 | Us Navy | Propellant pressure burning rate slope modification |
US6039819A (en) * | 1982-03-04 | 2000-03-21 | Atlantic Research Corporation | Solid propellant containing ferrocenyl phosphine derivatives |
US4532120A (en) * | 1983-12-28 | 1985-07-30 | Ethyl Corporation | Silane purification process |
EP0198971A1 (en) * | 1983-12-28 | 1986-10-29 | Ethyl Corporation | Process for purification of silane and analysis of contaminants therein |
US20180245543A1 (en) * | 2017-02-28 | 2018-08-30 | Alpha Space Test and Research Alliance, LLC | Multi-Stage Solid Rocket Motor |
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