US3293090A - Cellulose acetate-ammonium nitrate propellant containing a quaternary ammonium salt of a hexacyclic ureide - Google Patents
Cellulose acetate-ammonium nitrate propellant containing a quaternary ammonium salt of a hexacyclic ureide Download PDFInfo
- Publication number
- US3293090A US3293090A US388274A US38827464A US3293090A US 3293090 A US3293090 A US 3293090A US 388274 A US388274 A US 388274A US 38827464 A US38827464 A US 38827464A US 3293090 A US3293090 A US 3293090A
- Authority
- US
- United States
- Prior art keywords
- ammonium nitrate
- ureide
- composition
- hexacyclic
- quaternary ammonium
- 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
- 239000003380 propellant Substances 0.000 title claims description 35
- 150000007945 N-acyl ureas Chemical class 0.000 title claims description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 15
- 229920002678 cellulose Polymers 0.000 title description 3
- 239000001913 cellulose Substances 0.000 title description 2
- ODFGMSVMKUBHQN-UHFFFAOYSA-O diazanium;acetate;nitrate Chemical compound [NH4+].[NH4+].CC([O-])=O.[O-][N+]([O-])=O ODFGMSVMKUBHQN-UHFFFAOYSA-O 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 49
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 41
- 239000011230 binding agent Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002085 enols Chemical group 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 20
- -1 ammonium dichromate Chemical class 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920002301 cellulose acetate Polymers 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 6
- YIWOOPQOYHKISC-UHFFFAOYSA-N [O-][N+](=O)CC(O)([N+]([O-])=O)OC1=CC=CC=C1 Chemical compound [O-][N+](=O)CC(O)([N+]([O-])=O)OC1=CC=CC=C1 YIWOOPQOYHKISC-UHFFFAOYSA-N 0.000 description 6
- 229940125717 barbiturate Drugs 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 6
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 4
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 229940116269 uric acid Drugs 0.000 description 4
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000002587 enol group Chemical group 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MHQHHBYRYFICDV-UHFFFAOYSA-M sodium;pyrimidin-3-ide-2,4,6-trione Chemical compound [Na+].O=C1CC(=O)[N-]C(=O)N1 MHQHHBYRYFICDV-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- 229940035893 uracil Drugs 0.000 description 3
- XVIRIXVOLLJIPF-UHFFFAOYSA-N 1-nitro-2-(2-nitrophenoxy)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1OC1=CC=CC=C1[N+]([O-])=O XVIRIXVOLLJIPF-UHFFFAOYSA-N 0.000 description 2
- QEVGZEDELICMKH-UHFFFAOYSA-L 2-(carboxylatomethoxy)acetate Chemical compound [O-]C(=O)COCC([O-])=O QEVGZEDELICMKH-UHFFFAOYSA-L 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- WPKMTAGRHJPKHA-UHFFFAOYSA-N (2,3-dinitrophenyl) butanoate Chemical compound C(C)CC(=O)OC1=C(C(=CC=C1)[N+](=O)[O-])[N+](=O)[O-] WPKMTAGRHJPKHA-UHFFFAOYSA-N 0.000 description 1
- AZZUHZQRONMBGM-UHFFFAOYSA-N (2-acetyloxy-1-nitrobutan-2-yl) acetate Chemical compound C(C)(=O)OC(CC)(OC(C)=O)C[N+](=O)[O-] AZZUHZQRONMBGM-UHFFFAOYSA-N 0.000 description 1
- MKEPGIQTWYTRIW-ODZAUARKSA-N (z)-but-2-enedioic acid;ethane-1,2-diol Chemical compound OCCO.OC(=O)\C=C/C(O)=O MKEPGIQTWYTRIW-ODZAUARKSA-N 0.000 description 1
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- SEJFWAWYAJTLJD-UHFFFAOYSA-N 1-(2,3-dinitrophenoxy)-2,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(OC=2C(=C(C=CC=2)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O SEJFWAWYAJTLJD-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- JDTMUJBWSGNMGR-UHFFFAOYSA-N 1-nitro-4-phenoxybenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=CC=C1 JDTMUJBWSGNMGR-UHFFFAOYSA-N 0.000 description 1
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 1
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 1
- FLPPEMNGWYFRSK-UHFFFAOYSA-N 2-(2-acetyloxypropoxy)propyl acetate Chemical compound CC(=O)OCC(C)OCC(C)OC(C)=O FLPPEMNGWYFRSK-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PBXCSOPVWKVVJT-UHFFFAOYSA-N 2-(carboxymethoxy)acetic acid ethane-1,2-diol Chemical compound OCCO.OC(=O)COCC(O)=O PBXCSOPVWKVVJT-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- YJERZJLSXBRUDQ-UHFFFAOYSA-N 2-o-(3,4-dihydroxybutyl) 1-o-methyl benzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OCCC(O)CO YJERZJLSXBRUDQ-UHFFFAOYSA-N 0.000 description 1
- DOUBAFNWVFAWEC-UHFFFAOYSA-N 3-hydroxypropyl acetate Chemical compound CC(=O)OCCCO DOUBAFNWVFAWEC-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 1
- XPEAUXRONRVCDC-UHFFFAOYSA-N C(C(=O)O)(=O)O.C(COCCO)O Chemical compound C(C(=O)O)(=O)O.C(COCCO)O XPEAUXRONRVCDC-UHFFFAOYSA-N 0.000 description 1
- QPGJUXWWUAVSCD-UHFFFAOYSA-N C(COCC(=O)O)(=O)O.C(COCCO)O Chemical compound C(COCC(=O)O)(=O)O.C(COCCO)O QPGJUXWWUAVSCD-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 101000829705 Methanopyrus kandleri (strain AV19 / DSM 6324 / JCM 9639 / NBRC 100938) Thermosome subunit Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- GYTOWSMQXHCYNU-UHFFFAOYSA-N butyl 2-(2-butoxy-2-oxoethoxy)acetate Chemical compound CCCCOC(=O)COCC(=O)OCCCC GYTOWSMQXHCYNU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000013625 clathrin-independent carrier Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- MLQMIKSBTAZNBK-UHFFFAOYSA-N dimethyl 3-nitrobenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC([N+]([O-])=O)=C1C(=O)OC MLQMIKSBTAZNBK-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- DXRFOGXSSDRZFP-UHFFFAOYSA-N tripentyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCOC(=O)CC(O)(C(=O)OCCCCC)CC(=O)OCCCCC DXRFOGXSSDRZFP-UHFFFAOYSA-N 0.000 description 1
- YZWRNSARCRTXDS-UHFFFAOYSA-N tripropionin Chemical compound CCC(=O)OCC(OC(=O)CC)COC(=O)CC YZWRNSARCRTXDS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
Definitions
- This invention relates to ammonium nitrate propellant compositions which contain an ash-free catalyst for promoting the combustion of the ammonium nitrate.
- ammonium nitrate propellant compositions which mainly comprise ammonium nitrate particles and an oxidizable organic binder material, which permits the shaping of the composition into a definite configuration or grain, it is nesessary to promote the combustion of the composition by the use of a catalyst.
- catalysts in the past have been metallic compounds such as ammonium dichromate, the Prussian blues and sodium salts of some organic acids.
- the past history of the use of propellants catalyzed by the above compounds has shown that the resulting gases are detrimental to the hardware in use, such as nozzles of a rocket motor, due to the build-up of deposits and to the erosion caused by metallic compounds, such as sodium carbonate, from the catalyst in the gas streams.
- metallic compounds such as sodium carbonate
- the invention is directed to an ammonium nitrate propellant composition which includes a small catalytic amount of the quaternary ammonium salt of a hexacyclic ureide.
- the propellant composition comprises ammonium nitrate as the major component and between about 10 and 40 weight percent of an oxidizable organic binder material.
- the ammonium nitrate may be the high purity material commonly produced by synthetic plants today, or it may be a technical grade containing small amounts of inorganic impurities. In addition to the ammonium nitrate, for special purposes, small amounts of sodium nitrate or potassium nitrate may be present.
- the decomposition rate of the ammonium nitrate is influenced by the particle size. For gas generation purposes, the ammonium nitrate is finely divided. Particularly suitable ammonium nitrate will contain about 80 weight percent of material having a screen size greater than 80 mesh and smaller than 30 mesh. The more finely powdered ammonium nitrate is used where higher burning rates are desired.
- the propellant composition will contain between about 60 and about 80% (and commonly about 62-73%) of ammonium nitrate. In all cases, the major component present in the composition in ammonium nitrate.
- a matrix former or binder material is present.
- ammonium nitrate decomposes, freeoxygen is released.
- These oxidizable organic materials may contain only carbon and hydrogen, for example, high molecular weight hydrocarbons such as asphalts or resid uums, and rubbers, either natural or synthetic. Or, it may contain other elements in addition to carbon and hydrogen, for example, as in Thiokol rubber and neoprene.
- the stoichi-ome'tr'y' of thcomposition is improved, with respect to smoke production, by the use of organic materials containing combined oxygen as the binder-s.
- the binder or matrix former may be a single compound such as a rubber or asphalt or it may be .a mixture of compounds. The mixtures are particularly suitable when special characteristics are to be imparted to the propellant which can not be obtained by the use of a single compound.
- Multi-component binder consists of a polymeric base material and a plasticizer therefor.
- Particularly suitable polymeric base materials are cellulose esters of alkanoic acids containing from 2 to 4 carbon atoms such as cellulose acetate, cellulose acetate butyrate and cellulose propionate.
- the polyvinyl resins such as polyvinylchloride and polyvinyl acetate are good bases.
- Styreneacrylonitrile is an example of a copolymer which forms a good base material.
- Polyacrylonitrile is another suitable base material.
- the plasticizer component of the binder also, preferably, contains combined oxygen.
- the oxygen may be present in the plasticizer as an ether linkage and/or hydroxyl and/ or carboxyl; also the oxygen may be present as a part of an inorganic substituent, particularly, a nitro group.
- any plasticizer which is adapted to plasticize the particular polymer may be used in the invention.
- a single plasticizing compound may be used; more usually two or more compounds are used in conjunction.
- Exemplary classes of plasticizers which are suitable are set out below. (It is to be understood that these classes are illustrative only and do not limit the types of organic compounds which may be used to plasticize the polymer.)
- Di-lower alkyl-phthalates e.g., dimethyl phthalate, dibutyl phthalate, dioctyl phthalate and dimethyl nitrophthalate.
- Nitrobenzenes e.g., nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, nitroxylene, and nitrodiphenyl.
- Nitrodiphenyl ethers e.g., nitrodiphenyl ether and 2,4-dinitrodiphenyl ether.
- Tri-loweralkyl-citrates e.g., triethyl citrate, tributyl citrate and triamyl citrate.
- Glycerol-lower alkanoates e.g., monoacetin, triacetin,
- Lower alkylene-glycol-lower alkanoates wherein the glycol portion has a molecular weight below about 200 e.g., ethylene glycol diacetate, triethylene glycol dihexoate, triethylene glycol dioctoate, polyethylene glycol dioctoate, dipropylene glycol diacetate, nitromethyl propanediol diacetate, hydroxyethyl acetate and hydroxy propyl acetate (propylene glycol monoacetate).
- Dinitrophenyl-lower alkyl-lower alkanoates e.g., dinitrophenyl ethylacetate, and dinitrophenyl amyloctoate.
- Lower alkylene-glycols wherein the molecular weight is below about 200 e.g., diethylene glycol, polyethylene glycol (200), and tetrapropylene glycol.
- Lower alkylene-glycol oxalates e. g., diethylene glycol oxalate and polyethylene glycol (200) oxalate.
- Lower alkylene-glycol imaleates e. g., ethylene glycol maleate and bis-(diethylene glycol monoethyl ether) maleate.
- Lower alkylene-glycol diglycolates e.g., ethylene glycol diglycolate and diethylene glycol diglycolate.
- Lower alkyl-phthalyl-lower alkyl-glycolate e.g., methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate.
- Di-lower alkyloxy-tetraglycol e.g., dimethoxy tetra glycol and dibuto-xy tetra glycol.
- Nitrophenylether of lower alkylene glycols e.g., dinitrophenyl ether of triethylene glycol and nitrophenyl ether of polypropylene glycol.
- Nitrophenoxy alkanols wherein the alkanol portion is derived from a glycol having a molecular weight of not more than about 200. These may be pure compounds or admixed with major component bis(nitrophenoxy) alkane.
- the catalyst of this invention is the quaternary ammonium salt of a hexacyclic ureide.
- Cyclic uredies are described on pages 244-245 of Organic Chemistry by Fieser and Fieser, third edition, copyright 1956.
- Particular hexacyclic ureides useful for the purposes of this invention have 23 nitrogen atoms in the ring and, in their enol form, have 2-3 hydroxy substituted carbon atoms in the ring.
- the hexacyclic ureides contain only carbon, nitrogen, oxygen and hydrogen.
- Particularly advantageous ureides are barbituric acid, cyanuric acid, uracil, and uric acid,
- the quaternary ammonium portion of the defined catalyst has the formula:
- R groups is alkyl, aryl or combinations of these groups. Particularly useful are the tetra-lower alkyl quaternary ammonium salts, and aryl tri-lower alkyl quaternary ammonium salts, and diaryl di-lower alkyl quaternary ammonium salts.
- Lower alkyl refers to groups containing up to about 6 carbon atoms. Examples of useful alkyl groups are methyl, ethyl, propyl, hexyl, and the like and of useful aryl groups are benzyl, tolulyl, naphthyl, diphenyl and the like.
- the catalytic quaternary ammonium salts are prepared by neutralizing the acids with a stoichiometric amount of the quaternary ammonium hydroxide.
- the amount of the hydroxide used is based on the neutralization of one acidic hydrogen of the acid.
- the catalyst is required in the ammonium nitrate propellant composition to provide the required catalytic effect. Generally the small amount is between about 0.1-15 weight percent of the propellant composition.
- the propellant composition may contain other components.
- a promoter to enhance the activity of the catalyst may be utilized.
- this a carbon component of the type described on pages 34 of copending application S.N, 219,735, filed August 27, 1962 which pages are incorporated into and made a part of this specification by reference.
- the preferred carbons are the highly adsorptive activated carbons and the carbon blacks described in the above reference.
- materials may be present to improve low temperature, ignitability, for instance, oximes or asphalt; and surfactants may be present in order to improve the adhesion of the nitrate and the binder and also to improve the shape retention characteristics of the composition.
- aromatic hydrocarbon amines may be present in order to improve the storage stability, particularly at higher temperatures, of the ammonium nitrate propellant composition. Illustrations of these aromatic amines are toluene diamine, diphenyl amine, naphthalene diamine, and toluene triamine. In general, these are present in an amount between about 0.5 and 5 percent. Better stabilization is obtained with a combination of the aromatic amines and N-phenylmorpholine and N-alkyl propylene diamines where the alkyl group contains about 12-22 carbon atoms. These diamines are available from the Armour Chemical Division, Armour and Company.
- a particularly useful diamine is one identified as Duomeen-T which means that the alkyl group is derived from tallow fatty acids.
- Duomeen-T which means that the alkyl group is derived from tallow fatty acids.
- aromatic hydrocarbon amines when aromatic hydrocarbon amines are also present, between about 0.1% and 1% of N-phenylmorpholine and/or the N-alkyl propylene diamine will be present.
- An illustrative ammonium nitrate propellant composition which provides particularly good properties comprises about 62 to 73% of ammonium nitrate, about 6 to about 14 weight percent of cellulose acetate, about 6 to 14 weight percent of acetyltriethylcitrate, about 5 to about 13 weight percent of dinitrophenoxyethanol, about 0.2 to 3.0 weight percent of toluene diamine, about 0.5 to 7.0 weight percent of carbon, and about 0.5 to 15 weight percent of a quaternary ammonium salt of barbituric acid, cyanuric acid, uracil, or uric acid.
- Example I A propellant composition was prepared from the following components in the following approximate weight percentages:
- Acetyltriethylcitrate 10.30 Dinitrophenoxyethanol 9.40 Toluene diamine 1.00 Ammonium nitrate 65.00 Texas E carbon 2.00 Tetramethyl ammonium barbiturate 2.00
- a one-quart batch of the composition was prepared by mixing the above components for about one hour in a laboratory mixer. The mixing temperature was about C.
- Two plasticizers were used for the cellulose acetate binder. These plasticizers were acetyltriethylcitrate and dinitrophenoxyethanol.
- the resulting pasty mass was compression molded into a slab approximately /2" in thickness.
- the slab was subsequently sawed into strips for the burning rate test which was conducted in the Crawford Bomb pressurized at 1000 p.s.i.a. and at 70 F.
- the pressure exponent n was obtained.
- the pressure exponent is the numerical value equal to the slope of the curve of burning rate in inches per second obtained by plotting the burning rate versus pressure on log-log paper.
- the temperature coefficient at constant pressure, up, was also obtained for the composition.
- the pressure exponents and the temperature coeflicients for both compositions were very similar with the temperature coefiicient of the first composition being slightly higher to that of the second.
- Example II A propellant composition was prepared from the following components in the following approximate weight percentages:
- composition was prepared in essentially the same manner as that described in Example 1, except that -quart batches were made.
- Example 111 Tests were also carried out on propellant compositions catalyzed with the quaternary ammonium salts listed in Table II below.
- the propellant formulation used in these tests was:
- An ammonium nitrate propellant composition comprising ammonium nitrate as the major component, between about 10 and 40 weight percent of an oxidizable organic binder material, and a small catalytic amount of a quaternary ammonium salt of a hexacyclic ureide, said ureide having 2-3 nitrogen atoms in the ring and in its enol form having 23 hydroxy substituted carbon atoms in the ring.
- ammonium nitrate propellant composition of claim 1 wherein said ureide is barbituric acid.
- ammonium nitrate propellant composition of claim 1 wherein said ureide is uric acid.
- ammonium nitrate propellant composition of claim 1 wherein said small amount is between about 01-15 weight percent.
- ammonium nitrate propellant composition of claim 8 wherein said composition includes a promoter for said catalyst.
- An ammonium nitrate propellant composition comprising ammonium nitrate as the major component, about 6 to 14 weight percent of cellulose acetate, about 6 to 14 weight percent of acetyltriethylcitrate, about 5 to about 13 weight percent of dinitrophenoxy ethanol, about 0.2 to 3.0 weight percent of toluene diamine, about 0.5 to 7.0 weight percent of carbon, and about 0.5 to 10 weight percent of a quaternary ammonium salt of a hexacyclic ureide, said ureide having 2-3 nitrogen atoms in the ring and in its enol form having 2-3 hydroxy substituted carbon atoms in the ring.
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Description
United States Patent CELLULOSE ACETATE-AMMONIUM NITRATE PROIELLANT CONTAINING A QUATER- NARY AMMONIUM SALT OF A HEXACY- CLIC UREIDE Lionel A. Henderson, Columbus, Ind., assignor to Standard Oil Company, Chicago, 111., a corporation of Indiana N0 Drawing. Filed Aug. 7, 1964, Ser. No. 388,274
Claims. (Cl. 149-18) This invention relates to ammonium nitrate propellant compositions which contain an ash-free catalyst for promoting the combustion of the ammonium nitrate.
In ammonium nitrate propellant compositions which mainly comprise ammonium nitrate particles and an oxidizable organic binder material, which permits the shaping of the composition into a definite configuration or grain, it is nesessary to promote the combustion of the composition by the use of a catalyst. Commonly used catalysts in the past have been metallic compounds such as ammonium dichromate, the Prussian blues and sodium salts of some organic acids. However, the past history of the use of propellants catalyzed by the above compounds has shown that the resulting gases are detrimental to the hardware in use, such as nozzles of a rocket motor, due to the build-up of deposits and to the erosion caused by metallic compounds, such as sodium carbonate, from the catalyst in the gas streams. For many purposes, particularly in gas generator systems with close tolerances and in turbine power sources where essentially solid-free gases having a low order of erosion are required, there has been a need for an effective ashless organic catalyst for ammonium nitrate propellant compositions.
I have discovered that the quaternary ammonium salts of hexacyclic ureides, such as the tetramethyl ammonium salt of barbituric acid, function as effective combustion catalysts for ammonium nitrate propellant compositions and that the use of these catalysts greatly reduce the above problems encountered with metallic catalysts. These salts are considered unusual because I have found that quaternary ammonium salts of other acids, e.g., picric acid, and another salt of barbituric acid, the guanidine salt, do not function as satisfactory combustion catalysts.
Briefly, the invention is directed to an ammonium nitrate propellant composition which includes a small catalytic amount of the quaternary ammonium salt of a hexacyclic ureide. The propellant composition comprises ammonium nitrate as the major component and between about 10 and 40 weight percent of an oxidizable organic binder material.
The ammonium nitrate may be the high purity material commonly produced by synthetic plants today, or it may be a technical grade containing small amounts of inorganic impurities. In addition to the ammonium nitrate, for special purposes, small amounts of sodium nitrate or potassium nitrate may be present. The decomposition rate of the ammonium nitrate is influenced by the particle size. For gas generation purposes, the ammonium nitrate is finely divided. Particularly suitable ammonium nitrate will contain about 80 weight percent of material having a screen size greater than 80 mesh and smaller than 30 mesh. The more finely powdered ammonium nitrate is used where higher burning rates are desired. Generally the propellant composition will contain between about 60 and about 80% (and commonly about 62-73%) of ammonium nitrate. In all cases, the major component present in the composition in ammonium nitrate.
In order to permit the shaping of the ammonium nitrate composition into definite configurations, a matrix former or binder material is present. When ammonium nitrate decomposes, freeoxygen is released. The existence of this free-oxygen oxidizable organic materals to be used as the binders and thereby obtain additional gas production. These oxidizable organic materials may contain only carbon and hydrogen, for example, high molecular weight hydrocarbons such as asphalts or resid uums, and rubbers, either natural or synthetic. Or, it may contain other elements in addition to carbon and hydrogen, for example, as in Thiokol rubber and neoprene. The stoichi-ome'tr'y' of thcomposition is improved, with respect to smoke production, by the use of organic materials containing combined oxygen as the binder-s. The binder or matrix former may be a single compound such as a rubber or asphalt or it may be .a mixture of compounds. The mixtures are particularly suitable when special characteristics are to be imparted to the propellant which can not be obtained by the use of a single compound.
Multi-component binder, or matrix former, consists of a polymeric base material and a plasticizer therefor. Particularly suitable polymeric base materials are cellulose esters of alkanoic acids containing from 2 to 4 carbon atoms such as cellulose acetate, cellulose acetate butyrate and cellulose propionate. The polyvinyl resins such as polyvinylchloride and polyvinyl acetate are good bases. Styreneacrylonitrile is an example of a copolymer which forms a good base material. Polyacrylonitrile is another suitable base material.
The plasticizer component of the binder also, preferably, contains combined oxygen. The oxygen may be present in the plasticizer as an ether linkage and/or hydroxyl and/ or carboxyl; also the oxygen may be present as a part of an inorganic substituent, particularly, a nitro group. In general, any plasticizer which is adapted to plasticize the particular polymer may be used in the invention. A single plasticizing compound may be used; more usually two or more compounds are used in conjunction. Exemplary classes of plasticizers which are suitable are set out below. (It is to be understood that these classes are illustrative only and do not limit the types of organic compounds which may be used to plasticize the polymer.)
Di-lower alkyl-phthalates, e.g., dimethyl phthalate, dibutyl phthalate, dioctyl phthalate and dimethyl nitrophthalate.
Nitrobenzenes, e.g., nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, nitroxylene, and nitrodiphenyl.
Nitrodiphenyl ethers, e.g., nitrodiphenyl ether and 2,4-dinitrodiphenyl ether.
Tri-loweralkyl-citrates, e.g., triethyl citrate, tributyl citrate and triamyl citrate.
Acyl tri-lower alkyl-citrates where the acyl group contains 2-4 carbon atoms, e.g., acetyl triethyl citrate and acetyl tributyl citrate.
Glycerol-lower alkanoates, e.g., monoacetin, triacetin,
glycerol tripropionate and glycerol tributyrate.
Lower alkylene-glycol-lower alkanoates wherein the glycol portion has a molecular weight below about 200, e.g., ethylene glycol diacetate, triethylene glycol dihexoate, triethylene glycol dioctoate, polyethylene glycol dioctoate, dipropylene glycol diacetate, nitromethyl propanediol diacetate, hydroxyethyl acetate and hydroxy propyl acetate (propylene glycol monoacetate).
Dinitrophenyl-lower alkyl-lower alkanoates, e.g., dinitrophenyl ethylacetate, and dinitrophenyl amyloctoate.
Lower alkylene-glycols wherein the molecular weight is below about 200, e.g., diethylene glycol, polyethylene glycol (200), and tetrapropylene glycol.
Lower alkylene-glycol oxalates, e. g., diethylene glycol oxalate and polyethylene glycol (200) oxalate.
Lower alkylene-glycol imaleates, e. g., ethylene glycol maleate and bis-(diethylene glycol monoethyl ether) maleate.
Lower alkylene-glycol diglycolates, e.g., ethylene glycol diglycolate and diethylene glycol diglycolate.
Miscellaneous diglycolates, e.g., dibutyl diglycolate, di-
methylalkyl diglycolate and methylcarbitol diglycolate.
Lower alkyl-phthalyl-lower alkyl-glycolate, e.g., methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate.
Di-lower alkyloxy-tetraglycol, e.g., dimethoxy tetra glycol and dibuto-xy tetra glycol.
Nitrophenylether of lower alkylene glycols, e.g., dinitrophenyl ether of triethylene glycol and nitrophenyl ether of polypropylene glycol.
Nitrophenoxy alkanols wherein the alkanol portion is derived from a glycol having a molecular weight of not more than about 200. These may be pure compounds or admixed with major component bis(nitrophenoxy) alkane.
The catalyst of this invention is the quaternary ammonium salt of a hexacyclic ureide. Cyclic uredies are described on pages 244-245 of Organic Chemistry by Fieser and Fieser, third edition, copyright 1956. Particular hexacyclic ureides useful for the purposes of this invention have 23 nitrogen atoms in the ring and, in their enol form, have 2-3 hydroxy substituted carbon atoms in the ring. Advantageously, the hexacyclic ureides contain only carbon, nitrogen, oxygen and hydrogen. Particularly advantageous ureides are barbituric acid, cyanuric acid, uracil, and uric acid,
The quaternary ammonium portion of the defined catalyst has the formula:
where one or more of the R groups is alkyl, aryl or combinations of these groups. Particularly useful are the tetra-lower alkyl quaternary ammonium salts, and aryl tri-lower alkyl quaternary ammonium salts, and diaryl di-lower alkyl quaternary ammonium salts. Lower alkyl refers to groups containing up to about 6 carbon atoms. Examples of useful alkyl groups are methyl, ethyl, propyl, hexyl, and the like and of useful aryl groups are benzyl, tolulyl, naphthyl, diphenyl and the like.
The catalytic quaternary ammonium salts are prepared by neutralizing the acids with a stoichiometric amount of the quaternary ammonium hydroxide. The amount of the hydroxide used is based on the neutralization of one acidic hydrogen of the acid.
Normally only a small amount of the catalyst is required in the ammonium nitrate propellant composition to provide the required catalytic effect. Generally the small amount is between about 0.1-15 weight percent of the propellant composition.
In addition to the main components, i.e., ammonium nitrate, binder and catalyst, the propellant composition may contain other components. A promoter to enhance the activity of the catalyst may be utilized. Commonly this a a carbon component of the type described on pages 34 of copending application S.N, 219,735, filed August 27, 1962 which pages are incorporated into and made a part of this specification by reference. The preferred carbons are the highly adsorptive activated carbons and the carbon blacks described in the above reference.
In addition, materials may be present to improve low temperature, ignitability, for instance, oximes or asphalt; and surfactants may be present in order to improve the adhesion of the nitrate and the binder and also to improve the shape retention characteristics of the composition.
Also, aromatic hydrocarbon amines may be present in order to improve the storage stability, particularly at higher temperatures, of the ammonium nitrate propellant composition. Illustrations of these aromatic amines are toluene diamine, diphenyl amine, naphthalene diamine, and toluene triamine. In general, these are present in an amount between about 0.5 and 5 percent. Better stabilization is obtained with a combination of the aromatic amines and N-phenylmorpholine and N-alkyl propylene diamines where the alkyl group contains about 12-22 carbon atoms. These diamines are available from the Armour Chemical Division, Armour and Company. A particularly useful diamine is one identified as Duomeen-T which means that the alkyl group is derived from tallow fatty acids. In general, when aromatic hydrocarbon amines are also present, between about 0.1% and 1% of N-phenylmorpholine and/or the N-alkyl propylene diamine will be present.
An illustrative ammonium nitrate propellant composition which provides particularly good properties comprises about 62 to 73% of ammonium nitrate, about 6 to about 14 weight percent of cellulose acetate, about 6 to 14 weight percent of acetyltriethylcitrate, about 5 to about 13 weight percent of dinitrophenoxyethanol, about 0.2 to 3.0 weight percent of toluene diamine, about 0.5 to 7.0 weight percent of carbon, and about 0.5 to 15 weight percent of a quaternary ammonium salt of barbituric acid, cyanuric acid, uracil, or uric acid.
The present invention will be better understood by reference to the following examples which illustrate the beneficial effects of the invention. It is to be understood that the following example are given for the purpose of illustration only and do not serve in any way to limit the scope of the present invention.
Example I A propellant composition was prepared from the following components in the following approximate weight percentages:
Formulation:
Cellulose acetate 10.30
Acetyltriethylcitrate 10.30 Dinitrophenoxyethanol 9.40 Toluene diamine 1.00 Ammonium nitrate 65.00 Texas E carbon 2.00 Tetramethyl ammonium barbiturate 2.00
A one-quart batch of the composition was prepared by mixing the above components for about one hour in a laboratory mixer. The mixing temperature was about C. Two plasticizers were used for the cellulose acetate binder. These plasticizers were acetyltriethylcitrate and dinitrophenoxyethanol.
After mixing, the resulting pasty mass was compression molded into a slab approximately /2" in thickness. The slab was subsequently sawed into strips for the burning rate test which was conducted in the Crawford Bomb pressurized at 1000 p.s.i.a. and at 70 F. In addition to obtaining the burning rate, the pressure exponent n was obtained. The pressure exponent is the numerical value equal to the slope of the curve of burning rate in inches per second obtained by plotting the burning rate versus pressure on log-log paper. The temperature coefficient at constant pressure, up, was also obtained for the composition.
The results of the above tests are shown below in comparison with those for a similar composition having a metallic catalyst, sodium barbiturate, in place of the tetramethyl ammonium barbiturate.
TABLE I TABLE II Catalyst 1 +70 11 1 +170 1' -05 up Catalyst Weight, 11 R at 70 F.
percent Sodium Barb 0. 0840 0. 04 0.0920 0.0650 0.15 5
'letramcthyl A1mn.Barb .0555 0.66 .0010 .0445 0.13 BZTMA 3 0.08 .0030
BZIMA Barbiturate. 3 0.00 .0068
' TMA Picrate 3 Failed.
The above results demonstrate that the composition 7 g catalyzed by the tetramethyl ammonium barbiturate exhib- %;,1g g 8: 18328 ited good propellant properties in comparison to those of the composition catalyzed by sodium barbiturate. The pressure exponents and the temperature coeflicients for both compositions were very similar with the temperature coefiicient of the first composition being slightly higher to that of the second.
Strands from the composition catalyzed by the tetramethyl ammonium barbiturate Were aged for four successive 24-hour periods at 170 F. and show no change in burning rate. Propellants containing sodium barbiturate generally have shown an increase in burning rate.
Example II A propellant composition was prepared from the following components in the following approximate weight percentages:
Chemical: Percent Cellulose acetate 10.32 Acetyltriethylcitrate 10.30 Dinitrophenoxyethanol 9.40 Texas E carbon 1.40 Toluene diarnine 0.80 N-phenylmorpholine 0.20 Graphite 0.05 Duomeen-T 0.20
Norite carbon 2.20
Ammonium nitrate 62.73 Benzyltrimethyl ammonium barbiturate 2.00
1 As shredded binder.
The composition was prepared in essentially the same manner as that described in Example 1, except that -quart batches were made.
Motor firings were carried out on the above propellant composition. In these tests, it was determined that there was no build-up or formation of ash on the nozzle of the motor and no residue remaining in the motor case, indicating a propellant having clean burning characteristics.
Example 111 Tests were also carried out on propellant compositions catalyzed with the quaternary ammonium salts listed in Table II below. The propellant formulation used in these tests was:
Chemical: Percent Cellulose acetate 10 Acetyltriethylcitrate 9 Dinitrophenoxyethanol 10 Texas E carbon 3 Toluene diamine 1 Ammonium oxalate 0.4 Ammonium nitrate 63.6 Catalyst 3.0
The results of the test are listed in Table II, below, opposite the identification of each catalyst.
The above results show that the quaternary ammonium salts of cyanuric acid, barbituric acid, and uric acid are effective composition catalysts for ammonium nitrate propellant compositions. The results also demonstrate that the above quaternary salts of picric acid were not significantly effective as composition catalyst.
Having thus described the invention, what is claimed is:
1. An ammonium nitrate propellant composition comprising ammonium nitrate as the major component, between about 10 and 40 weight percent of an oxidizable organic binder material, and a small catalytic amount of a quaternary ammonium salt of a hexacyclic ureide, said ureide having 2-3 nitrogen atoms in the ring and in its enol form having 23 hydroxy substituted carbon atoms in the ring.
2. The ammonium nitrate propellant composition of claim 1 wherein said ureide is barbituric acid.
3. The ammonium nitrate propellant composition of claim 1 wherein said ureide is cyanuric acid.
4. The ammonium nitrate propellant composition of claim 1 wherein said ureide is uracil.
5. The ammonium nitrate propellant composition of claim 1 wherein said ureide is uric acid.
6. The ammonium nitrate propellant composition of claim 2 wherein said quaternary ammonium salt is a tetramethyl ammonium salt.
7. The ammonium nitrate propellant composition of claim 2 wherein said quaternary ammonium salt is a benzyltrimethyl ammonium salt.
8. The ammonium nitrate propellant composition of claim 1 wherein said small amount is between about 01-15 weight percent.
9. The ammonium nitrate propellant composition of claim 8 wherein said composition includes a promoter for said catalyst.
10. An ammonium nitrate propellant composition comprising ammonium nitrate as the major component, about 6 to 14 weight percent of cellulose acetate, about 6 to 14 weight percent of acetyltriethylcitrate, about 5 to about 13 weight percent of dinitrophenoxy ethanol, about 0.2 to 3.0 weight percent of toluene diamine, about 0.5 to 7.0 weight percent of carbon, and about 0.5 to 10 weight percent of a quaternary ammonium salt of a hexacyclic ureide, said ureide having 2-3 nitrogen atoms in the ring and in its enol form having 2-3 hydroxy substituted carbon atoms in the ring.
References Cited by the Examiner UNITED STATES PATENTS 3,148,096 9/1964 Butcher 149-19 3,161,550 12/1964 Mosher et a1. 14919 3,180,772 4/1965 OConnor 149-47 BENJAMIN R. PADGETT, Primary Examiner.
LEON D. ROSDOL, Examiner.
Claims (1)
1. AN AMMONIUM NITRATE PROPELLANT COMPOSITION COMPRISING AMMONIUM NITRATE AS THE MAJOR COMPONENT, BETWEEN ABOUT 10 AND 40 WEIGHT PERCENT OF AN OXIDIZABLE ORGANIC BINDER MATERIAL, AND A SMALL CATALYTIC AMOUNT OF A QUATERNARY AMMONIUM SALT OF HEXACYCLIC UREIDE, SAID UREIDE HAVING 2-3 NITROGEN ATOMS IN THE RING AND IN ITS ENOL FORM HAVING 2-3 HYDROXY SUBSTITUTED CARBON ATOMS IN THE RING.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US388274A US3293090A (en) | 1964-08-07 | 1964-08-07 | Cellulose acetate-ammonium nitrate propellant containing a quaternary ammonium salt of a hexacyclic ureide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US388274A US3293090A (en) | 1964-08-07 | 1964-08-07 | Cellulose acetate-ammonium nitrate propellant containing a quaternary ammonium salt of a hexacyclic ureide |
Publications (1)
Publication Number | Publication Date |
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US3293090A true US3293090A (en) | 1966-12-20 |
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Application Number | Title | Priority Date | Filing Date |
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US388274A Expired - Lifetime US3293090A (en) | 1964-08-07 | 1964-08-07 | Cellulose acetate-ammonium nitrate propellant containing a quaternary ammonium salt of a hexacyclic ureide |
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US (1) | US3293090A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2709750A1 (en) * | 1989-08-25 | 1995-03-17 | Hercules Inc | Solid binder propellant containing a non-crystalline polyether and an inert plasticizer. |
WO1997012847A1 (en) * | 1995-10-03 | 1997-04-10 | Atlantic Research Corporation | Extrudable gas-generating compositions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3148096A (en) * | 1958-02-18 | 1964-09-08 | Standard Oil Co | Ammonium nitrate gas generating composition with combustion catalyst |
US3161550A (en) * | 1962-08-27 | 1964-12-15 | Standard Oil Co | Ammonium nitrate propellant composition providing exhaust gases of reduced temperature |
US3180772A (en) * | 1961-12-04 | 1965-04-27 | Standard Oil Co | Ammonium nitrate propellant |
-
1964
- 1964-08-07 US US388274A patent/US3293090A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3148096A (en) * | 1958-02-18 | 1964-09-08 | Standard Oil Co | Ammonium nitrate gas generating composition with combustion catalyst |
US3180772A (en) * | 1961-12-04 | 1965-04-27 | Standard Oil Co | Ammonium nitrate propellant |
US3161550A (en) * | 1962-08-27 | 1964-12-15 | Standard Oil Co | Ammonium nitrate propellant composition providing exhaust gases of reduced temperature |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2709750A1 (en) * | 1989-08-25 | 1995-03-17 | Hercules Inc | Solid binder propellant containing a non-crystalline polyether and an inert plasticizer. |
WO1997012847A1 (en) * | 1995-10-03 | 1997-04-10 | Atlantic Research Corporation | Extrudable gas-generating compositions |
US5734123A (en) * | 1995-10-03 | 1998-03-31 | Atlantic Research Corporation | Extrudable gas-generating compositions |
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